WO2019117382A1 - Catalyseur de dénitrification à base de structure métallique, pour réduction catalytique sélective, utilisant une suspension d'enrobage et son procédé de préparation - Google Patents

Catalyseur de dénitrification à base de structure métallique, pour réduction catalytique sélective, utilisant une suspension d'enrobage et son procédé de préparation Download PDF

Info

Publication number
WO2019117382A1
WO2019117382A1 PCT/KR2017/014867 KR2017014867W WO2019117382A1 WO 2019117382 A1 WO2019117382 A1 WO 2019117382A1 KR 2017014867 W KR2017014867 W KR 2017014867W WO 2019117382 A1 WO2019117382 A1 WO 2019117382A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal structure
catalyst
oxide
coating
coating slurry
Prior art date
Application number
PCT/KR2017/014867
Other languages
English (en)
Korean (ko)
Inventor
임동하
정해영
이치현
구윤장
임은미
김태용
Original Assignee
한국생산기술연구원
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 한국생산기술연구원 filed Critical 한국생산기술연구원
Publication of WO2019117382A1 publication Critical patent/WO2019117382A1/fr

Links

Images

Classifications

    • 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
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates
    • 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
    • B01J23/16—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
    • B01J23/30—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
    • 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
    • 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
    • B01J35/50—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 monoliths
    • 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
    • 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
    • B01J37/0215—Coating
    • B01J37/0228—Coating in several steps
    • 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
    • B01J37/08—Heat treatment
    • 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
    • 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
    • F01N3/2066—Selective catalytic reduction [SCR]
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the present invention relates to a metal catalyst-based denitration catalyst for selective catalytic reduction using a coating slurry and a method for preparing the same, and more particularly, to a metal catalyst having a single step of coating and heat treatment on a metal structure not subjected to a pretreatment step
  • the present invention relates to a high-efficiency metal structure-based denitration catalyst having high thermal conductivity and thermal stability and having robust and excellent catalytic performance and cost competitiveness, and a method for manufacturing the denitration catalyst.
  • techniques for effectively removing nitrogen oxides include: first, selective catalytic reduction (SCR) using a catalyst and a reducing agent; second, selective non-catalytic reduction using a reducing agent only Catalytic Reduction (SNCR) technology, and third, Low-NOx burner technology that controls the combustion state in the combustion system.
  • SCR selective catalytic reduction
  • SNCR reducing agent only Catalytic Reduction
  • the selective catalytic reduction technology is evaluated as the most effective technology considering the secondary pollution, the removal efficiency, the operation cost, etc.
  • the removal efficiency of nitrogen oxide Is more than 90%, and the endurance period is estimated to be about 2 ⁇ 3 years.
  • the denitration catalyst used in this selective catalytic reduction technique generally consists of an active site and a support.
  • the active metal include oxides such as vanadium, tungsten, and molybdenum. Titanium oxide (TiO 2 ), alumina (Al 2 O 3 ), silica (SiO 2 ) 2 ) and mixtures thereof are mainly used. Particularly, depending on the catalytic activity and toxicity, titania is mainly used as a support for a conventional selective reduction catalyst.
  • the above-described oxide-type active metals are supported on a ceramic carrier to prepare a denitration catalyst, and the prepared catalyst is mixed with various additives such as binders to perform injection molding, and finally, a honeycomb- .
  • Exhaust gas passes through a honeycomb-shaped support denitration catalyst, which is then reacted with a toxic gas such as nitrogen oxides and reduced, thereby converting into a harmless substance.
  • Korean Patent No. 10-0584961 relates to a method for coating a selective reduction catalyst for flue gas denitrification and a support made by the method, and a ceramic honeycomb type support containing an active metal catalyst is disclosed.
  • the denitration catalyst using the honeycomb-shaped ceramic support supports the exhaust gas only in one direction and is purified, the denitrification efficiency is somewhat lowered, and the denitration catalyst is easily broken due to fouling and weak strength due to carbonization or ammonium salt. And has a difficult problem in the regeneration method of the catalyst.
  • a heat treatment or a surface treatment is performed on the metal structure, a modification pretreatment oxide layer is formed on the surface of the metal structure, and a heat treatment process is further performed to form a primer Primer oxide layer was repeated.
  • an object of the present invention is to provide a metal structure-based denitration catalyst having a high efficiency, which is produced through a single process without a pretreatment process and which is excellent in economical efficiency as well as excellent catalytic performance and a method for producing the same.
  • a method for manufacturing a denitration catalyst based on a metal structure is provided.
  • a porous metal structure for forming a plurality of voids between the metal supports to exhaust the exhaust gas in multiple directions through the voids;
  • the metal structure-based denitration catalyst according to the present invention is characterized in that a porous metal structure having a high specific surface area in which a plurality of pores are formed such that exhaust gas or gas penetrates in various directions is formed into a mesh shape, a foil shape, a wire shape or the like instead of a powder or ceramic honeycomb It is possible to easily manufacture, install, maintain and repair the exhaust gas denitrifying equipment for ships, and it is also possible to use a small amount of expensive active metal, And can exhibit high catalytic performance.
  • the coating slurry is coated on the porous metal structure through the coating slurry only once, and is coated on the metal structure without any pretreatment due to the active metal precursor, ceramic powder, modifier, dispersant, binder, etc. contained in the coating slurry It is possible to exhibit excellent catalytic activity and durability without the desorption of the slurry particles containing the catalyst, and the production process is simplified due to the single process, so that productivity and economy are excellent.
  • the NOx removal catalyst according to the present invention can vary the shape of the porous metal structure in various shapes such as a circular shape and a square shape according to the structure of the ship denitrification system, it can be minimized and optimized in a limited space in the ship, And it is convenient to maintenance and management.
  • FIG. 1 is a photograph showing a metal structure-based denitration catalyst for selective catalytic reduction (SCR) coated with a coating slurry on a metal structure according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of a metal-based denitration catalyst coated with a single process according to an embodiment of the present invention and a conventionally used multi-stage process metal-based denitration catalyst.
  • FIG. 3 is an SEM image of a metal structure-based denitration catalyst in which a coating slurry according to one embodiment of the present invention is coated in a single process.
  • FIG. 4 is a view illustrating an entire process for manufacturing a metal structure-based denitration catalyst for coating a coating slurry according to an embodiment of the present invention in a single process.
  • the metal structure-based denitration catalyst according to the present invention is characterized in that a denitration catalyst is produced through a single process using a coating slurry without a pre-oxidation process for metal surface modification.
  • Conventional metal structures are formed by first performing a pretreatment process to form surface roughness through physical or chemical treatment in order to increase the adhesion of a coating material on a metal structure, coating a primer oxide layer, To 1050 < 0 > C for 5 to 30 hours, a catalyst layer containing an active metal was coated on the primer oxidation layer, and heat treatment was performed at about 400 to 550 DEG C for 2 to 5 hours.
  • an electrochemical method such as physical or chemical treatment or anodic oxidation is applied to form a primer oxide layer on a metal structure (see FIG. 2).
  • the present invention relates to a method of coating a slurry containing an active material precursor, a ceramic powder, a modifier, a dispersant, a binder, etc. on a surface of a metal structure that has not undergone a pretreatment process, A selective denitrification reduction catalyst based on a metal structure having excellent productivity and economical efficiency by simplifying a manufacturing process, and a manufacturing method thereof.
  • a slurry containing an active material precursor, a ceramic powder, a modifier, a dispersant, a binder and the like is coated on the metal structure to coat the slurry for coating on the inner and outer surfaces of the metal structure with high dispersion .
  • the porous metal structure according to the present invention is a three-dimensional metal structure which is not in the form of a powder or a ceramic honeycomb, and is a multi-stage process such as kneading, injection molding, or the like using a conventional powder catalyst and additives, It is easy to produce, and it is easy to install or maintain the catalyst.
  • the three-dimensional metal structure can be embodied in various shapes such as a circular shape and a quadrangular shape, the structure and shape of the denitration system can be easily changed according to the limited space, so that a denitration catalyst system optimized for a space, SCR catalyst for ship flue gas denitrification can be produced.
  • the porous metal structure is formed of various metals or alloys such as stainless steel, aluminum, titanium, and nickel.
  • the porous metal structure may be in the form of a mesh, foil or wire.
  • the metal structure in the form of a mesh or a foil may be a single mesh or a foil structure alone or may be a structure in which a plurality of meshes or foil structures are laminated to each other.
  • the wire form may be in the form of a demister in which the wire is arranged in a regular or irregular direction.
  • the physical shape such as the length, height, and width of the metal structure of the mesh, foil or wire can be changed into various shapes such as a circle, a square, and the like.
  • the porous metal structure is a porous metal structure having a high specific surface area in which a plurality of pores are formed so as to communicate with each other so as to pass through the exhaust gas or gas in multiple directions and in which the slurry containing the active catalyst is directly .
  • the porosity of the porous metal structure may be 60% or more, preferably 70 to 95%.
  • porosity of the porous metal structure does not satisfy the above range, fouling may occur due to contamination by carbonization or ammonium salt, or a serious phenomenon such as pressure drop may occur due to a problem in exhaust gas flow So that it can have a degree of porosity above a certain level.
  • the coating slurry is characterized in that distilled water is mixed with an active material precursor, a ceramic powder, a modifier, a dispersant, a binder, and the like.
  • the active material may be composed of a main active material and an auxiliary active material.
  • the main active material is vanadium oxide (V 2 O 5 ) and the auxiliary active material is tungsten oxide (WO 3 ), molybdenum oxide (MoO 3 ), cobalt oxide (Co 2 O 3 ), iron oxide Fe 2 O 3 ), chromium oxide (Cr 2 O 3 ) copper oxide (CuO), manganese oxide (MnO), nickel oxide (NiO), cesium oxide (CsO), niobium oxide (Nb 2 O 5 ) But is not limited thereto.
  • the active material may be contained in an amount of 0.1 to 10.0% by weight based on 100% by weight of the ceramic powder.
  • the modifier is used to adhere the active metal to a metal structure that has not been surface-treated in step (i), and is used for increasing surface roughness through surface modification of the metal structure.
  • the modifier may also act as a dispersant, thereby increasing the degree of dispersion of the ceramic powder in the coating slurry and uniformly coating the active material on the surface of the metal structure.
  • the active material can be firmly adhered to the metal structure, Can exhibit high catalyst performance and long-term stability without desorption of the slurry particles.
  • At least one selected from the group consisting of formic acid, acetylacetone, acetic acid, carboxylic acid, oxalic acid and citric acid may be used.
  • the modifier or dispersant may be included in an amount of 0.1 to 5% by weight based on 100% by weight of the coating slurry.
  • the modifier or the dispersant is contained in an amount of less than 0.1% by weight, the effect of modifying the surface of the metal support is reduced and it is difficult to adhere the slurry on the surface of the metal structure having little surface roughness, The desorption phenomenon of the liver easily occurs.
  • the dispersing agent in the slurry is reduced, the dispersibility of the ceramic powder is decreased, and the added ceramic powder is coagulated in the slurry so that the uniform coating is not formed on the surface of the metal structure.
  • the modifier or dispersant is contained in an amount of more than 5% by weight, the pH of the precursor of the active material in the slurry is affected and the ionic form of the required active material can not be obtained. Further, the metal surface is excessively modified, Since the slurry is not adhered to the metal surface, the coated slurry is easily removed.
  • the ceramic powder serves as a support for supporting the active material and may be formed of a powder of silica (SiO 2 ), alumina (Al 2 O 3 ), zirconia (ZrO 2 ), titania (TiO 2 ) Can be used.
  • the ceramic powder may be contained in an amount of 20 to 50% by weight based on 100% by weight of the coating slurry.
  • the ceramic powder When the ceramic powder is contained in an amount of less than 20% by weight, slurry easily flows down on the metal structure due to low slurry viscosity, or a plurality of repetitive processes need.
  • it When it is contained in an amount exceeding 50% by weight, a large amount of slurry is coated on the metal surface, and after the drying and firing, the slurry is coated on the surface of the oxide catalyst in a form of being cracked and easily broken.
  • the binder has a property of sticking to the surface of the metal structure by fixing the metal structure and the ceramic powder to each other or fixing them to each other between the ceramic powders.
  • the binder is used either singly or in combination with an organic and / or inorganic binder.
  • the organic binder may be at least one selected from the group consisting of acrylate, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl pyrrolidone, ethyl cellulose, methyl cellulose, nitrocellulose, carboxymethyl cellulose, Methylcellulose, methylhydroxyethylcellulose, and an epoxy-based one. Of these, it is preferable to use an acrylic-modified epoxy.
  • the inorganic binder may be at least one selected from the group consisting of silicate sol, alumina sol, titania sol, zirconia sol, ceramic wool, and bentonite. Of these, it is preferable to use a titania-based sol.
  • the organic binder may be contained in an amount of 1 to 10 wt% based on 100 wt% of the entire coating slurry, and the inorganic binder may be included in an amount of 5 to 20 wt% based on 100 wt% of the entire coating slurry.
  • the organic and inorganic binders are not included in the above range, the viscosity and wettability of the slurry deteriorate, so that they do not stick to the surface of the metal structure at the time of coating, but easily flow down and are not coated. Even if some slurry is attached, It falls easily.
  • the coating slurry according to the present invention may contain, in addition to the above-mentioned components, additional additives such as a viscosity agent, a pH adjusting agent and the like.
  • the viscosity of the coating slurry according to the present invention may represent from 20 to 500 mPaS.
  • the viscosity agent at least one selected from the group consisting of polyethylene glycol type, diethylene glycol type, glycerol type, ethylene glycol type, dimethyl sulfoxide type, formamide type and N-methyl formamide type can be used.
  • the viscosity agent may be contained in an amount of 0.5 to 10% by weight based on 100% by weight of the total coating slurry.
  • the pH adjusting agent at least one selected from the group consisting of oxalic acid, citric acid, hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid can be used.
  • the pH adjuster may be contained in an amount of 0.5 to 10% by weight based on 100% by weight of the total coating slurry.
  • an organic solvent such as methanol, ethanol, or acetone may be added as a further added solvent.
  • a metal structure-based denitration catalyst can be produced by a single process through coating, drying, or heat treatment of the coating slurry on the porous metal structure.
  • the coating slurry is subjected to a coating process to deposit the coating slurry on the inner and outer surfaces of the metal structure with high dispersion.
  • the slurry coating process may be performed by various methods such as coating, spraying, and dipping on the surface of the porous metal structure.
  • a typical coating thickness may range from 90 to 130 ⁇ .
  • the slurry-coated porous metal structure is gently dried at 60 to 80 ° C. for about 1 to 3 hours at a slow heating rate of 0.1 to 1 ° C. per minute in a drying furnace, and is then dried at 100 to 120 ° C. for about 1 to 3 hours And is completely dried.
  • porous metal structure having been dried with the coated slurry is subjected to a heat treatment process at 450 to 500 ° C for about 2 to 4 hours.
  • the support and the active material components are subjected to a heat treatment process so that the support has the anatase crystal and the active material has the metal oxide form.
  • the support powder has an anatase crystal phase to improve not only the thermal stability and the active metal dispersion but also to reduce the sulfur poisoning (sulfur deactivation) contained in the exhaust gas. It also reacts with contaminants in the exhaust gas by converting the active material into a metal oxide form.
  • the heat treatment time is preferably 2 to 4 hours.
  • the drying and calcination steps can remove water and impurities contained in the coating slurry solution, and convert the amorphous support and the active metal into a crystalline oxide having activity.
  • a metal structure-based denitration catalyst for selective catalytic reduction (SCR) using a coating slurry according to an embodiment of the present invention comprises
  • a porous metal structure having a plurality of voids formed between metal supports to allow the exhaust gas to penetrate through the voids in multiple directions;
  • a catalyst layer containing an active material formed by coating, drying and heat-treating the coating slurry on the surface of the porous metal structure.
  • Example 1 Manufacture of a metal structure-based denitration catalyst with a slurry coated on a porous metal structure
  • a titanium metal structure in the form of a mesh, foil or wire was impregnated into the prepared coating slurry and coated on the surface of the metal structure. Then, after drying at 60 ° C for 1 hour and at 100 ° C for 1 hour, the slurry was coated on the inner and outer surfaces of the porous metal structure through heat treatment and firing at 500 ° C for 4 hours, Catalyst.
  • vanadium oxide which is an active material
  • X-ray diffraction analysis it was confirmed by Scanning Electron Microscope and Energy Dispersive X-ray Spectrometer analysis that vanadium oxide, which is an active material, was highly dispersed on the surface of the metal structure, and X-ray diffraction analysis In the result, the vanadium precursor was transferred to the crystal structure of the vanadium oxide type.
  • the oxide catalyst is uniformly distributed on the surface of the metal structure, and moisture is evaporated at 100 ⁇ drying, and the organic material is evaporated at a temperature of 400 ⁇ or lower through the sintering process, 3).
  • Conventionally used metal structures include a pretreatment process for forming surface roughness through physical or chemical treatment in order to increase the adhesion of a coating material on a metal structure, coating a primer oxide layer, A catalyst layer containing an active metal is coated on the primer oxide layer for 5 to 30 hours at 950 to 1050 ° C, and then heat treatment is performed at about 400 to 550 ° C for 2 to 5 hours to prepare a denitration catalyst .
  • Example 1 The NO x removal catalysts prepared in Example 1 and Comparative Example 1 were measured for catalyst performance under the conditions shown in Table 1 below, and the results are shown in Table 2 below.
  • Denitrification activity (%) 250 °C 300 ° C 350 °C 400 ° C 450 °C 500 °C
  • the performance of the denitration catalyst was examined at 250 ° C. to 500 ° C. under the same conditions as those shown in Table 1. As a result, it was found that the denitration catalyst according to Example 1 had an 80% Catalytic activity, and the highest activity was found to be 98.5% at 350 °C.
  • the NO x removal catalyst according to Comparative Example 1 showed a catalytic activity of about 80% or more at 250 to 500 ° C, and the maximum activity was 94.2% at 350 ° C.
  • the porous metal structure-based denitration catalyst according to the present invention exhibits excellent denitrification effect even without a pretreatment process for metal surface roughness due to the modifier, dispersant, binder, etc. contained in the coating slurry .
  • the porous metal structure-based denitration catalyst according to the present invention is excellent in productivity and economy and can be used not only for ships but also for power plants, incinerators, paper industry, cement industry, glass industry, large diesel vehicles, diesel farm equipment, railway engines, And the like as a denitration catalyst.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Toxicology (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un catalyseur de dénitrification à base de structure métallique, pour une réduction catalytique sélective, à l'aide d'une suspension d'enrobage et son procédé de préparation et, plus spécifiquement, un catalyseur de dénitrification hautement efficace et son procédé de préparation, le catalyseur de dénitrification hautement économique et présentant d'excellentes performances catalytiques au moyen d'un processus en une étape dans lequel un enrobage en une seule fois et un traitement thermique sont effectués pour une structure métallique pour laquelle un processus de prétraitement n'a pas été effectué.
PCT/KR2017/014867 2017-12-14 2017-12-15 Catalyseur de dénitrification à base de structure métallique, pour réduction catalytique sélective, utilisant une suspension d'enrobage et son procédé de préparation WO2019117382A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2017-0172249 2017-12-14
KR1020170172249A KR102090726B1 (ko) 2017-12-14 2017-12-14 코팅 슬러리를 이용한 선택적 촉매 환원용 금속 구조체 기반 탈질 촉매 및 이의 제조방법

Publications (1)

Publication Number Publication Date
WO2019117382A1 true WO2019117382A1 (fr) 2019-06-20

Family

ID=66819633

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2017/014867 WO2019117382A1 (fr) 2017-12-14 2017-12-15 Catalyseur de dénitrification à base de structure métallique, pour réduction catalytique sélective, utilisant une suspension d'enrobage et son procédé de préparation

Country Status (2)

Country Link
KR (1) KR102090726B1 (fr)
WO (1) WO2019117382A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4212244A1 (fr) * 2020-09-08 2023-07-19 The Chugoku Electric Power Co., Inc. Liquide de revêtement catalytique de réduction des nox
EP4212233A1 (fr) * 2020-09-08 2023-07-19 The Chugoku Electric Power Co., Inc. Corps moulé de catalyseur de dénitration et procédé de fabrication d'un corps moulé de catalyseur de dénitration

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102498427B1 (ko) * 2021-02-01 2023-02-13 주식회사 비에이치피 메탈폼을 이용한 반도체 제조공정의 유해가스 제거용 촉매 및 이의 제조방법
KR102498425B1 (ko) * 2021-02-01 2023-02-13 주식회사 비에이치피 반도체 제조공정의 유해가스 제거용 촉매 및 이의 제조방법
KR102476863B1 (ko) * 2021-11-09 2022-12-14 대영씨엔이(주) 탈질촉매 및 이를 이용한 화력발전용 배기가스 처리 시스템

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001009279A (ja) * 1999-06-29 2001-01-16 Toyota Central Res & Dev Lab Inc 排ガス浄化用触媒とその製造方法及び排ガス浄化方法
KR20060087084A (ko) * 2005-01-28 2006-08-02 주식회사 나노 탈질촉매 압출성형용 티타니아 제조방법
KR20100093823A (ko) * 2009-02-17 2010-08-26 고려대학교 산학협력단 미세 유로에서의 촉매 코팅방법
KR101733171B1 (ko) * 2016-06-21 2017-05-08 한국생산기술연구원 다공극성 금속 구조체 상에 성장된 세라믹 나노튜브를 이용한 선박용 탈질 촉매 및 그의 제조방법

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100584961B1 (ko) 1999-11-10 2006-05-29 에스케이 주식회사 배연탈질용 선택적 환원 촉매의 코팅방법 및 이의방법으로 제조된 지지체
US20010049339A1 (en) 2000-04-11 2001-12-06 Adolf Schafer-Sindlinger Process for the preparation of a vanadia SCR-catalyst supported on titania
KR100781726B1 (ko) 2006-09-15 2007-12-03 한국중부발전(주) 배연탈질용 선택적촉매환원 코팅촉매의 제조방법
KR101891233B1 (ko) * 2015-08-20 2018-08-28 주식회사 에코프로 구조체의 표면에 형성된 촉매층을 포함하는 질소산화물 제거용 촉매, 이의 제조방법 및 용도

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001009279A (ja) * 1999-06-29 2001-01-16 Toyota Central Res & Dev Lab Inc 排ガス浄化用触媒とその製造方法及び排ガス浄化方法
KR20060087084A (ko) * 2005-01-28 2006-08-02 주식회사 나노 탈질촉매 압출성형용 티타니아 제조방법
KR20100093823A (ko) * 2009-02-17 2010-08-26 고려대학교 산학협력단 미세 유로에서의 촉매 코팅방법
KR101733171B1 (ko) * 2016-06-21 2017-05-08 한국생산기술연구원 다공극성 금속 구조체 상에 성장된 세라믹 나노튜브를 이용한 선박용 탈질 촉매 및 그의 제조방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LIU, BO: "Washcoating of cordierite honeycomb with vanadia-tungsta-tita nia mixed oxides for selective catalytic reduction of NO with NH3", CATALYSI S SCIENCE & TECHNOLOGY, vol. 5, no. 2, 2015, pages 1241 - 1250, XP055569474 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4212244A1 (fr) * 2020-09-08 2023-07-19 The Chugoku Electric Power Co., Inc. Liquide de revêtement catalytique de réduction des nox
EP4212233A1 (fr) * 2020-09-08 2023-07-19 The Chugoku Electric Power Co., Inc. Corps moulé de catalyseur de dénitration et procédé de fabrication d'un corps moulé de catalyseur de dénitration

Also Published As

Publication number Publication date
KR102090726B1 (ko) 2020-04-28
KR20190071305A (ko) 2019-06-24

Similar Documents

Publication Publication Date Title
WO2019117382A1 (fr) Catalyseur de dénitrification à base de structure métallique, pour réduction catalytique sélective, utilisant une suspension d'enrobage et son procédé de préparation
WO2017222306A1 (fr) Catalyseur de dénitrification pour navire, utilisant des nanotubes en céramique développés sur une structure métallique poreuse, et procédé de fabrication associé
KR101520009B1 (ko) 연도 가스에서 질소 산화물의 제거를 위한 방법 및 촉매
EP1403231B1 (fr) Procede de production d'un corps ceramique fritté poreux
EP2349950B1 (fr) Corps structural en nid d'abeille pour la purification de gaz d'échappement
WO2014158009A1 (fr) Filtre à nanocatalyseur et son procédé de production
WO2017010775A1 (fr) Catalyseur de réduction catalytique sélective pour l'élimination d'oxydes d'azote et son procédé de production
JPWO2006082684A1 (ja) ハニカム構造体
KR20010081994A (ko) 디젤 배기 가스 필터
WO2020075920A1 (fr) Catalyseur ternaire composite composé d'un support d'oxyde composite et d'un atome unique, et son procédé de préparation
EP0756891A1 (fr) Zéolithe de fer pour la conversion de NOx
US20130316129A1 (en) Silicon carbide material, honeycomb structure, and electric heating type catalyst carrier
KR20060038467A (ko) 탄화규소질 촉매체 및 그 제조 방법
WO2017111350A1 (fr) Filtre revêtu de catalyseur à activité de catalyseur accrue par l'ajout d'un co-catalyseur de lithium
WO2018106021A1 (fr) Catalyseur de dénitrification marine utilisant une structure de réseau tridimensionnel en céramique poreuse et son procédé de production
Shi et al. Evaluation of cordierite–ceria composite ceramics with oxygen storage capacity
CN114011400A (zh) 酸性体系垃圾焚烧scr脱硝催化剂的制备方法、制得的脱硝催化剂
JPH04215853A (ja) 耐熱性金属質モノリス及びその製造方法
KR100784483B1 (ko) 세라믹 필터 및 이의 제조방법
KR20120000980A (ko) 반수석고를 이용한 배연탈질 선택적 환원촉매 제조방법
JP2007117805A (ja) 排ガス中粒子状物質除去フィルタ担体およびフィルタ触媒体
KR101917802B1 (ko) 개선된 촉매 성능을 나타내는 촉매 지지체 및 이의 제조 방법 및 이에 의해 제조된 촉매 지지체
KR20160139473A (ko) 제올라이트 촉매복합체 및 그 제조방법
WO2018056517A1 (fr) Appareil de purification de gaz d'échappement et procédé de purification de gaz d'échappement l'utilisant
WO2010079854A1 (fr) Catalyseur pour retirer des oxydes d'azote de gaz d'échappement, son procédé de préparation, et procédé d'élimination d'oxydes d'azote de gaz d'échappement l'utilisant

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17934637

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17934637

Country of ref document: EP

Kind code of ref document: A1