EP4149661A1 - Catalyseur de réduction catalytique sélective et article catalytique le comprenant - Google Patents

Catalyseur de réduction catalytique sélective et article catalytique le comprenant

Info

Publication number
EP4149661A1
EP4149661A1 EP21803037.7A EP21803037A EP4149661A1 EP 4149661 A1 EP4149661 A1 EP 4149661A1 EP 21803037 A EP21803037 A EP 21803037A EP 4149661 A1 EP4149661 A1 EP 4149661A1
Authority
EP
European Patent Office
Prior art keywords
scr catalyst
scr
weight
antimony
support
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21803037.7A
Other languages
German (de)
English (en)
Other versions
EP4149661A4 (fr
Inventor
Yuchao ZHANG
Renjie QIU
Jia Di Zhang
Liang Chen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Corp
Original Assignee
BASF Corp
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 BASF Corp filed Critical BASF Corp
Publication of EP4149661A1 publication Critical patent/EP4149661A1/fr
Publication of EP4149661A4 publication Critical patent/EP4149661A4/fr
Pending legal-status Critical Current

Links

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
    • 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
    • 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
    • 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
    • B01J21/08—Silica
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • 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
    • B01J37/0215—Coating
    • B01J37/0221—Coating of particles
    • 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
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0246—Coatings comprising a zeolite
    • 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
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0248—Coatings comprising impregnated particles
    • 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
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia
    • 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
    • B01D2255/209—Other metals
    • B01D2255/2098—Antimony
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/30—Silica
    • 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
    • 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 selective catalytic reduction (SCR) catalyst comprising a support, vanadium and antimony, a catalytic article comprising the SCR catalyst, and an exhaust treatment system for an internal combustion engine comprising the SCR catalyst.
  • SCR selective catalytic reduction
  • Nitrogen oxides also referred to as NOx, emitted as exhaust gases from mobile source such as vehicles and stationary source such as power plants would be harmful to environment and human beings.
  • catalytic reduction methods have heretofore been developed.
  • SCR selective catalytic reduction
  • the catalytic reduction methods are suitable for dealing with large quantities of exhaust gases, and of these, selective catalytic reduction (SCR) is a means of converting NOx with the aid of an SCR catalyst into nitrogen (N 2 ) and water (H 2 O) in the presence of a reductant source.
  • the reductant source can be hydrocarbon, ammonia, urea, etc. that exists in the exhaust gas of a diesel engine or is added to a stream of exhaust gas of a diesel engine.
  • the reductant source is usually automotive-grade urea, otherwise known as Diesel Exhaust Fluid (DBF).
  • DBF Diesel Exhaust Fluid
  • the urea undergoes the hydrolysis reaction (urea plus water produces ammonia and carbon dioxide) to deliver ammonia into the exhaust flow.
  • a process comprising adding ammonia (or urea) as a reducing agent to catalytically reduce NOx selectively to N 2 was reported to be superior.
  • Various catalysts useful for selective catalytic reduction, also called SCR catalysts have been developed for abatement of NOx from the stationary and mobile sources.
  • the SCR catalysts are required to reduce NOx over a broad temperature range and especially at a temperature as low as possible below 300 °C.
  • V SCR catalysts a group of catalysts with vanadium oxides as active species
  • V SCR catalysts comprise one or more promoters to provide improved catalyst performances.
  • V SCR catalysts containing an oxide of tungsten or molybdenum as a promoter have been widely studied for several decades, as described in US3279884A, EP0272620A2, EP0348768A2,
  • V SCR catalysts with alternative promoters were developed.
  • One of the alternative promoters of interest is antimony.
  • Such V SCR catalysts with antimony as a promoter were described, for example, in KR101065242B1, US2009/143225A1 , and W02017101449A1.
  • KR101065242B1 discloses a V SCR catalyst prepared by a process which comprises mixing a vanadium precursor and an antimony precursor into a slurry containing TiO 2 sol and calcining the obtained slurry at 500°C or lower temperature. It was described that the V SCR catalyst with antimony as the promoter has good NOx abatement efficiency and sulfur poisoning resistance at low temperatures.
  • V SCR catalyst comprising metal oxide supporters, vanadium as the active material and antimony as the promoter.
  • the V SCR catalyst was prepared by impregnation of TiO 2 with precursors containing vanadium and antimony or other conventional catalyst synthesis methods such as sol gel method. It was described that the V SCR catalyst can promote reduction of NOx at low temperatures and increase sulfur poisoning resistance.
  • W02017101449A1 discloses a SCR catalyst prepared from a process which comprises mixing a vanadium/antimony oxide and optionally a silicon source with a support comprising TiO 2 in a solvent to obtain a suspension, drying and calcining.
  • the vanadium/antimony oxide was prepared by providing a suspension comprising vanadium oxide(s) and antimony oxide(s), and drying.
  • the present invention relates to a selective catalytic reduction (SCR) catalyst comprising a support, vanadium and antimony.
  • SCR selective catalytic reduction
  • SCR catalysts for reduction of nitrogen oxides comprising: a support, and an active material on the support.
  • SCR catalytic articles comprising the SCR catalysts
  • exhaust treatment systems for internal combustion engines are also aspects.
  • the present invention provides an SCR catalyst for reduction of nitrogen oxides (NOx), comprising: a support, and an active material on the support;
  • the support calculated as its oxide, is present in the SCR catalyst in an amount of 40 to 99% by weight, relative to the total weight of the SCR catalyst;
  • the active material comprises vanadium and antimony
  • the vanadium, calculated as V 2 O 5 is present in the SCR catalyst in an amount of 1 to 15% by weight, relative to the total weight of the SCR catalyst
  • the antimony, calculated as Sb 2 O 3 is present in the SCR catalyst in an amount of 0.5 to 20% by weight, relative to the total weight of the SCR catalyst
  • the SCR catalyst after hydrothermally aged at 550°C for 100 hours with 10% water, has a 200-300°C denitrification efficiency of at least 60%, with 60,000tr 1 space velocity and an ammonia to NOx molar ratio of 1:1.
  • the SCR catalyst after thermally aged at 600°C for 50 hours, has a 200-300°C denitrification efficiency of at least 50%, with 60,000h -1 space velocity and an ammonia to NOx molar ratio of 1:1.
  • the support can be a metal oxide of Ti, Si, W, Al, Ce, Zr, Mg, Ca, Ba, Y, La, Pr, Nb, Mo, Mn, Fe, Co, Ni, Cu, Zn, Ga, Sn, Bi, or a mixture of any two or more of these oxides.
  • the support can comprise a molecular sieve.
  • the molecular sieve can be a silicate zeolite, an aluminosilicate zeolite, a metal-substituted aluminosilicate zeolite or a non-zeolitic molecular sieve.
  • At least a portion of the metal oxides listed above in the support can also act as additives such as binder, dispersant, filler, stabilizers, promoter, etc.
  • the amount of the additive depends on the form of the finished catalysts.
  • the amount of the additive expressed as the oxides of respective species to be incorporated into the SCR catalyst in total, is generally in the range of 1 to 30 wt%, preferably 1 to 15 wt% in the case that the finished SCR catalysts are in form of coated substrate which will be described hereinbelow, and is generally in the range of 1 to 90 wt% preferably 5 to 60 wt%, more preferably 10 to 50 wt% in the case that the finished catalysts are in form of shaped bodies.
  • Respective amount of each additive, if more than one additive is used, is not critical for the purpose of the present invention.
  • the support comprises at least one of TiO 2 , SiO 2 , WO 3 , CeO 2 , AI 2 O 3 and ZrC>2.
  • the support comprises TiO 2 , and/or SiO 2 .
  • the support comprises TiO 2 and SiO 2 , the SiO 2 , is present in an amount of 1 to 20% by weight, preferably 2.5 to 15% by weight, and more preferably 3 to 10% by weight, relative to the total weight of the support.
  • the support consists of TiO 2 , of TiO 2 and SiO 2 , of TiO 2 and WO 3 , of TiO 2 , SiO 2 and WO 3 , of TiO 2 and CeO 2 , of TiO 2 , WO 3 and CeO 2 , of TiO 2 and AI2O 3 or of TiO 2 and TiO 2 .
  • TiO 2 to be used in the present invention may be commercially available or prepared via conventional methods known in the art. In specific embodiments, TiO 2 to be used in the present invention is in the form of anatase.
  • the amount of SiO 2 is in a range of 1 to 20% by weight, preferably 2.5 to 15% by weight, and more preferably 3 to 10% by weight, relative to the total weight of the support.
  • the molecular sieve belongs to structure type AFG, AST, DOH, FAR, FRA, GIU, LIO, LOS, MAR, MEP, MSO, MTN, NON, RUT, SGT, SOD, SW, TOL, UOZ, AJBW, ACO, AEI, AEN, AFN, AFT, AFV, AFX, ANA, ARC, APD, ATN, ATT, ATV, AVL, AWO, AWW, BCT, BIK, BRE, CAS, CDO, CHA, DDR, DFT, EAB, EDI, EEI, EPI, ERI, ESV, ETL, GIS, GOO, IFY, IHW, IRN, ITE, ITW, JBW, JNT, JOZ, JSN, KFI, LEV, -LIT, LTA, LTJ, LTN, MER, MON, MTF, MWF, NPT, NSI
  • the support calculated as metal oxides or molecular sieves is present in the SCR catalyst in an amount of 50 to 90% by weight, preferably 60 to 85% by weight, including 65, 70, 75 and 80% by weight, relative to the total weight of the SCR catalyst.
  • the vanadium calculated as V 2 O 5
  • the vanadium is present in the SCR catalyst in an amount of 4 to 12% by weight, preferably 5 to 10% by weight, including 6, 7, 8 and 9% by weight, relative to the total weight of the SCR catalyst.
  • the antimony calculated as Sb 2 O 3
  • the antimony is present in the SCR catalyst in an amount of 3 to 16% by weight, preferably 4 to 14% by weight, including 5, 6, 7, 8, 9, 10, 11, 12 and 13% by weight, relative to the total weight of the SCR catalyst.
  • vanadium and antimony are present in a molar ratio V/Sb in the range of from 8:1 to 1:8, preferably from 4:1 to 1:4, more preferably from 2:1 to 1 :2, calculated as respective elements.
  • the SCR catalyst further comprises a platinum group metal (PGM).
  • PGM platinum group metal
  • the PGM is selected from the group consisting of platinum (Pt), palladium (Pd), rhodium (Rh) and mixtures thereof. It is to be understood that these terms embrace not only the metallic form of these PGMs, but also any metal oxide forms that are catalytically active for emissions reduction. Combinations of metallic and catalytically active metal oxide forms are also contemplated by the invention.
  • the present invention also provides a method for preparing an SCR catalyst, comprising steps of:
  • step 2) adding a vanadium precursor into the antimony suspension obtained in step 1), and stirring to obtain an active material suspension in a temperature range of 50 to 150°C;
  • the vanadium precursor and antimony precursor are intended to mean compounds containing vanadium and compounds containing antimony respectively, which may be converted to the vanadium species and anatomy species, such as metal oxide, composite oxide, salt, sulfate, phosphate, vanadate, antimonate, etc.
  • Typical vanadium precursor can be at least one of ammonium vanadate, vanadium oxalate, vanadyl oxalate, vanadium oxides (e.g. vanadium pentoxide), vanadium monoethanolamine, vanadium chloride, vanadium trichloride oxide, vanadyl sulfate, vanadium sulfate, vanadium antimonite, vanadium antimonate and vanadium oxides.
  • vanadium oxides e.g. vanadium pentoxide
  • vanadium monoethanolamine vanadium chloride
  • vanadium trichloride oxide vanadyl sulfate
  • vanadium sulfate vanadium antimonite
  • vanadium antimonate vanadium oxides.
  • Typical antimony precursor can be at least one of antimony acetate, ethylene glycol antimony (antimony ethylene glycoxide), antimony sulfate, antimony nitrate, antimony chloride, antimonous sulfide, antimony oxides (e.g. Sb 2 O 3 ) and antimony vanadate.
  • the drying in step 3) is preferably conducted at a temperature in the range of 100 °C to 250 °C, more preferably 110 °C to 180 °C.
  • the drying can be conducted in any ways known in the art without particular limitations.
  • the mixture from step 4 which may be dry or wet, may be prepared in various ways known in the art, depending on the precursors to be used in this step.
  • the wet mixture may be prepared by incipient wetness impregnation techniques, also called capillary impregnation or dry impregnation.
  • the wet mixture is prepared by a method comprising preparation of a mixture of support and Sb 2 O 3 and then incorporating a solution of vanadium precursor via incipient wetness impregnation.
  • the present invention also provides an SCR catalytic article comprising an SCR catalyst described above, the SCR catalyst is applied onto a substrate having a monolithic structure.
  • the substrate is not particularly limited, and for example, a flow-through substrate or a wall-flow substrate.
  • the substrate may be any of those materials typically used for preparing such catalysts, such as ceramic or metal, and will preferably have a ceramic honeycomb structure.
  • Any suitable substrates may be employed, such as a monolithic substrate of the type having fine, parallel gas flow passages extending therethrough from an inlet or an outlet face of the substrate, such that passages are open to fluid flow therethrough (i.e., flow-through substrates).
  • the passages which are essentially straight paths from their fluid inlet to their fluid outlet, are defined by walls on which the catalytic material is applied as a washcoat so that the gases flowing through the passages contact the catalytic material.
  • the flow passages of the monolithic substrate are thin-walled channels, which can be of any suitable cross-sectional shape and size, such as trapezoidal, rectangular, square, sinusoidal, hexagonal, oval, circular, etc.
  • Such monolithic substrates may contain up to about 900 or more flow passages (or "cells") per square inch of cross section, although far fewer may be used.
  • the substrates may have about 50 to 600, more usually about 200 to 600, and most usually about 300 to 600 cells per square inch (“cpsi").
  • the load of the SCR catalyst on the substrate is generally in the range of 0.5 to 10 g/in 3 , preferably 1 to 7 g/in 3 , and more preferably 2 to 5.5 g/in 3 .
  • the SCR catalyst may be shaped into beads, spheres, pellets, or honeycomb bodies and the like, according to various techniques known in the art. Any conventional auxiliaries may be incorporated during the shaping process as desired, such as binders, fillers and/or plasticizers. It is to be understood that the shaped bodies will be dried and calcined so as to be ready for service.
  • the SCR catalyst is shaped into a honeycomb body by extrusion, dried and calcined to provide the finished catalysts in form of extruded honeycomb bodies.
  • Such catalysts in form of extruded honeycomb bodies contain the catalytic material itself as the skeleton without an additional inert substrate. By dispensing the use of inert substrate, significantly more amount of catalytic material per volume of the catalyst body is available and thus better NOx abatement performance may be provided especially at low temperatures, compared with the finished catalysts in form of coated substrate.
  • the extruded SCR catalytic article further comprises at least one binder and/or matrix material and/or the precursors thereof.
  • the binder and/or matrix components may improve the mechanical strength of the final extruded products.
  • the binder and/or matrix materials can be, but not limited to, selected from cordierite, nitrides, carbides, borides, intermetallic, aluminosilicate, spinel, alumina and/or doped alumina, silica, titania, zirconia, titania-zirconia, glass fiber and mixtures of any two or more thereof.
  • the extruded SCR catalytic article may be prepared by a process, in which additives such as plasticizer and/or dispersant and/or acid and/or pore forming agent, etc., can be added.
  • the vanadium calculated as V 2 O 5
  • the vanadium is present in the extruded SCR catalytic article in an amount of 0.5 to 15% by weight, relative to the total weight of the extruded SCR catalytic article.
  • the antimony calculated as Sb 2 O 3
  • the antimony is present in the extruded SCR catalytic article in an amount of 0.25 to 20% by weight, relative to the total weight of the extruded SCR catalytic article.
  • the SCR catalyst on the substrate, or the extruded SCR catalyst is then dried at a temperature in the range of -20 °C to 300 °C, preferably 20 °C to 250 °C, more preferably 20 °C to 200 °C.
  • the drying can be conducted in any ways known in the art without particular limitations.
  • the SCR catalyst on the substrate, or the extruded SCR catalyst after drying is further calcinated at a temperature of from 350°C to 700 °C, preferably in the range of 400 °C to 700 °C, more preferably 450 °C to 600 °C, 500 °C and 550 °C included.
  • the calcination is generally conducted for a period of no more than 5 hours, particularly no more than 3 hours, for example 0.5 or 1 or 2 hours in the case that the finished catalysts are in form of coated substrate, and for a period of no more than 20 hours, particularly no more than 10 hours, for example 1 , 2, 3, 4, 5, 6, 7, 8, or 9 hours in the case that the finished catalysts are in a form of shaped bodies.
  • the present invention relates to a method for treatment of exhaust gas from an internal combustion engine comprising:
  • the exhaust gases which can be treated by the SCR catalysts according to the present invention are any exhaust gases containing NOx to be removed or reduced.
  • the exhaust gases are from for example, but not limited to an internal combustion engine such as lean-bum engines, diesel engines, natural gas engines, power plants, incinerators, generator sets, or gasoline engines.
  • the exhaust gases are contacted with the SCR catalysts according to the present invention at a temperature in the range of 150 °C to 650 °C, or 170 to 625 °C, or 180 to 600 °C, or 200 to 550 °C, 250°C, 300°C, 350°C, 400°C, 450°C and 500°C included.
  • the contact of the exhaust gases with the SCR catalysts according to the present invention is conducted in the presence of a reductant.
  • the reductant that can be used in the present invention may be any reductants known in the art per se for reducing NOx, for example NH 3 .
  • NH 3 may be derived from urea.
  • the present invention relates to a method for testing NOx conversion comprising contacting an exhaust gas comprising NOx with a reductant in the presence of an SCR catalyst described above, the method selectively reduces at least a portion of the NOx to N 2 and H 2 O.
  • the present invention relates to an exhaust treatment system for an internal combustion engine comprising a reductant injector, and an SCR catalyst described above.
  • the exhaust treatment system further comprises at least one catalyst selected from a Diesel Oxidation Catalyst (DOC), a Catalyzed Soot Filter (CSF), and an Ammonia Oxidation Catalyst (AMOx).
  • DOC Diesel Oxidation Catalyst
  • CSF Catalyzed Soot Filter
  • AMOx Ammonia Oxidation Catalyst
  • Oxidation catalysts comprising a precious metal, such as one or more platinum group metals (ROMs), dispersed on a refractory metal oxide support, such as alumina, are known for use in treating the exhaust of diesel engines in order to convert both hydrocarbon and carbon monoxide gaseous pollutants by catalyzing the oxidation of these pollutants to carbon dioxide and water.
  • ROMs platinum group metals
  • DOC diesel oxidation catalysts
  • the diesel oxidation catalysts are formed on ceramic or metallic substrates upon which one or more catalyst coating compositions are deposited.
  • SOF portion oxidation catalysts that contain one or more ROMs promote the oxidation of NO to NO 2 .
  • DOC diesel oxidation catalyst
  • the DOC catalyst mainly contains PGM, alumina, zeolite and titania on ceramic or metallic substrates, preferably contain Pt and/or Pd, alumina and/or titania, as well as optionally silica as additives on ceramic or metallic substrates.
  • particulate filters are used to achieve high particulate matter reduction in exhaust treatment systems.
  • Known filter structures that remove particulate matter from exhaust include honeycomb wall flow filters, wound or packed fiber filters, open cell foams, sintered metal filters, etc. These filters can remove over 90% of the particulate material from the exhaust.
  • the soot filter is coated with a catalyst to promote soot combustion and thereby promoting filter regeneration. In one or more embodiments, the soot filter is coated with a catalyst to promote NOx conversion. In one or more embodiments, the soot filter is coated with a catalyst to have at least one function of CO oxidation, hydrocarbon storage, hydrocarbon oxidation, NOx storage, NO oxidation, and fuel light-off.
  • Ammonia slip from the ammonia-SCR catalyst presents a number of problems.
  • the odor thresh-old for NH 3 is 20 ppm in air. Eye and throat irritation are noticeable above 100 ppm, skin irritation occurs above 400 ppm, and the IDLH is 500 ppm in air.
  • NH 3 is caustic, especially in its aqueous form. Condensation of NH 3 and water in cooler regions of the exhaust line downstream of the exhaust catalysts will give a corrosive mixture. Therefore, it is desirable to eliminate the ammonia before it can slip out of the tailpipe.
  • a selective ammonia oxidation catalyst (AMOx) is employed for this purpose, with the objective to convert the excess ammonia to N 2 . It is desirable to provide a catalyst for selective ammonia oxidation that is able to convert ammonia at a wide range of temperatures where ammonia slip occurs in the vehicles driving cycle, and can produce minimal nitrogen oxide byproducts.
  • the AMOx catalyst should also produce minimal N 2 0, which is a potent greenhouse gas.
  • An ammonia oxidation catalyst or AMOx refers to a catalyst that promotes the oxidation of NH 3 .
  • the ammonia oxidation catalyst (AMOx) is used to convert ammonia to N 2 as major product, and to produce minimal nitrogen oxide byproducts.
  • the SCR catalyst can optionally be integrated with other functions such as DOC, CSF, AMOx, CO oxidation, hydrocarbon storage, hydrocarbon oxidation, NOx storage, NO oxidation, etc. as one catalyst or in one “brick”.
  • the SCR catalyst can optionally be integrated with other functions as one catalyst or in one "brick” via different layouts (zoning, layering, homogeneous, etc.).
  • rick refers to a single article such as a monolith, such as flow through monolith or a filter, such as wall flow filter.
  • An SCR catalyst for reduction of nitrogen oxides comprising: a support, and an active material on the support; wherein the support, calculated as its oxide, is present in the SCR catalyst in an amount of 40 to 99% by weight, relative to the total weight of the SCR catalyst; wherein the active material comprises vanadium and antimony, the vanadium, calculated as V 2 O 5 , is present in the SCR catalyst in an amount of 1 to 15% by weight, relative to the total weight of the SCR catalyst and the antimony, calculated as Sb 2 O 3 , is present in the SCR catalyst in an amount of 0.5 to 20% by weight, relative to the total weight of the SCR catalyst; wherein the SCR catalyst, after hydrothermally aged at 550°C for 100 hours with 10% water, has a 200-300°C denitrification efficiency of at least 60%, with 60,000h "1 space velocity and an ammoni
  • the SCR catalyst according to embodiment 1 wherein the support comprises a metal oxide of Ti, Si, W, Al, Ce, Zr, Mg, Ca, Ba, Y, La, Pr, Nb, Mo, Mn, Fe, Co, Ni, Cu, Zn, Ga, Sn, Bi, or a mixture of any two or more of the metal oxides, or a molecular sieve.
  • step 2) adding a vanadium precursor into the antimony suspension obtained in step 1), and stirring to obtain an active material suspension in a temperature range of 50 to 150°C;
  • An SCR catalytic article comprising an SCR catalyst according to any one of embodiments 1 to 11, wherein the SCR catalyst is applied onto a substrate having a monolithic structure.
  • An SCR catalytic article comprising an SCR catalyst according to any one of embodiments 1 to 11, wherein the SCR catalyst further comprises a matrix material, the SCR catalyst is shaped into a honeycomb body by extrusion.
  • a method for treatment of exhaust gas from an internal combustion engine comprising:
  • a method for testing NOx conversion comprising: contacting an exhaust gas comprising NOx with a reductant in the presence of an SCR catalyst according to any one of embodiments 1 to 11, wherein the method selectively reduces at least a portion of the NOx to N 2 and H 2 O.
  • An exhaust treatment system for an internal combustion engine comprising a reductant injector, an SCR catalyst according to any one of embodiments 1 to 11.
  • the exhaust treatment system for an internal combustion engine according to embodiment 18 further comprises at least one catalyst selected from a Diesel Oxidation Catalyst (DOC), a Catalyzed Soot Filter (CSF), and an Ammonia Oxidation Catalyst (AMOx).
  • DOC Diesel Oxidation Catalyst
  • CSF Catalyzed Soot Filter
  • AMOx Ammonia Oxidation Catalyst
  • SCR catalytic article 2 was analogous to that of SCR catalytic article in Example 1 , except that the amounts of SiO 2 /TiO 2 powder and active material 1 were adjusted to 79.5 g and 10.8 g respectively. After cooling to room temperature, SCR catalytic article 2 with an SCR catalyst containing 4.0% V 2 O 5 was obtained. The total loading of washcoat on the substrate is 4.5 g/in 3 .
  • SCR catalytic article 3 was analogous to that of SCR catalytic article in Example 1 , except that the amounts of SiO 2 /TiO 2 powder and active material 1 were adjusted to 76.8 g and 13.5 g respectively. After cooling to room temperature, SCR catalytic article 3 with an SCR catalyst containing 5.0% V 2 O 5 was obtained. The total loading of washcoat on the substrate is 4.5 g/in 3 .
  • SCR catalytic article 4 was analogous to that of SCR catalytic article in Example 1 , except that the amounts of SiO 2 /TiO 2 powder and active material 1 were adjusted to 74.1 g and 16.2 g respectively. After cooling to room temperature, SCR catalytic article 4 with an SCR catalyst containing 6.0% V 2 O 5 was obtained. The total loading of washcoat on the substrate is 4.5 g/in 3 .
  • SCR catalytic article 5 was analogous to that of SCR catalytic article in Example 1 except that the amounts of SiO 2 /TiO 2 powder and active material 1 were adjusted to 76.4 g and 19.0 g respectively. No further treatment at 550°C in 10% steam / air for 100 hours was applied. After cooling to room temperature, SCR catalytic article 5 with SCR catalyst containing 7.0% V 2 O 5 was obtained. The total loading of washcoat on the substrate is 3.0 g/in 3 .
  • SCR catalytic article 5 was further treated at 550°C in 10% steam / air for 100 hours. After cooling to room temperature, SCR catalytic article 6 was obtained. The total loading of washcoat on the substrate is 3.0 g/in 3 .
  • SCR catalytic article 5 was further treated at 600°C in air for 50 hours. After cooling to room temperature, SCR catalytic article 7 was obtained. The total loading of washcoat on the substrate is 3.0 g/in 3 .
  • SCR catalytic article 8 was analogous to that of the SCR catalytic article in Example 5 except that the amounts of SiOa/TiC ⁇ powder and active material 1 were adjusted to 63.3 g and 27.0 g respectively. After cooling to room temperature, SCR catalytic article 8 with SCR catalyst containing 10.0% V 2 O 5 was obtained. The total loading of washcoat on the substrate is 3.0 g/in 3 .
  • SCR catalytic article 8 was further treated at 550°C in 10% steam / air for 100 hours. After cooling to room temperature, SCR catalytic article 9 was obtained. The total loading of washcoat on the substrate is 3.0 g/in 3 .
  • Comparative SCR catalytic article 2 was analogous to that of SCR catalytic article in Comparative Example 1 except that the amounts of SiO 2 /TiO 2 powder, vanadyl oxalate solution and Sb 2 O 3 were adjusted to 83.1 g, 38.1 g and 6.0 g respectively. After cooling to room temperature, Comparative SCR catalytic article 2 with SCR catalyst containing 4.0% V 2 O 5 was obtained. The total loading of washcoat on the substrate is 4.5 g/in 3 .
  • Example 12 Comparative Example 3
  • Comparative SCR catalytic article 3 was analogous to that of SCR catalytic article in Comparative Example 1 except that the amounts of SiO 2 /TiO 2 powder, vanadyl oxalate solution and Sb 2 O 3 were adjusted to 80.5 g, 47.6 g and 7.5 g respectively. After cooling to room temperature, Comparative SCR catalytic article 3 with SCR catalyst containing 5.0% V 2 O 5 was obtained. The total loading of washcoat on the substrate is 4.5 g/in 3 .
  • Example 13 (Comparative Example 4) he synthesis procedure for Comparative SCR catalytic article 4 was analogous to that of SCR catalytic article in Comparative Example 1 except that the amounts of SiO 2 /TiO 2 powder, vanadyl oxalate solution and Sb 2 O 3 were adjusted to 78.1 g, 57.1 g and 9.0 g respectively. After cooling to room temperature, Comparative SCR catalytic article 4 with SCR catalyst containing 6.0% V 2 O 5 was obtained. The total loading of washcoat on the substrate is 4.5 g/in 3 .
  • Comparative SCR catalytic article 5 was analogous to that of SCR catalytic article in Comparative Example 1 except that the amounts of SiO 2 /TiC> 2 powder, vanadyl oxalate solution and Sb 2 O 3 were adjusted to 75.5 g, 66.7 g and 10.5 g respectively. No further treatment at 550°C in 10% steam / air for 100 hours was applied. After cooling to room temperature, Comparative SCR catalytic article 5 with SCR catalyst containing 7.0% V 2 O 5 was obtained. The total loading of washcoat on the substrate is 3.0 g/in 3 .
  • Comparative SCR catalytic article 5 was further treated at 550°C in 10% steam / air for 100 hours. After cooling to room temperature, Comparative SCR catalytic article 6 was obtained. The total loading of washcoat on the substrate is 3.0 g/in 3 .
  • Comparative SCR catalytic article 5 was further treated at 600°C in air for 50 hours. After cooling to room temperature, Comparative SCR catalytic article 7 was obtained. The total loading of washcoat on the substrate is 3.0 g/in 3 .
  • Comparative SCR catalytic article 8 was analogous to that of SCR catalytic article in Comparative Example 5 except that the amounts of SiO 2 /TiO 2 powder, vanadyl oxalate solution and Sb 2 O 3 were adjusted to 68.1 g, 95.2 g and 15.5 g respectively. After cooling to room temperature, Comparative SCR catalytic article 8 with SCR catalyst containing 10.0% V 2 O 5 was obtained. The total loading of washcoat on the substrate is 3.0 g/in 3 .
  • Example 18 Comparative Example 9
  • Comparative SCR catalytic article 8 was further treated at 550°C in 10% steam / air for 100 hours. After cooling to room temperature, Comparative SCR catalytic article 9 was obtained. The total loading of washcoat on the substrate is 3.0 g/in 3 .
  • the SCR performance was characterized by the conversion of NOx, which was calculated according to the following equation.

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)
  • Analytical Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Toxicology (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Exhaust Gas After Treatment (AREA)

Abstract

La présente invention concerne un catalyseur de réduction catalytique sélective (SCR) comprenant un support, du vanadium et de l'antimoine, un article catalytique comprenant le catalyseur SCR, et un système de traitement d'échappement destiné à un moteur à combustion interne comprenant le catalyseur SCR.Dans un mode de réalisation, l'invention concerne un catalyseur SCR destiné à la réduction d'oxydes d'azote, comprenant : un support, et un matériau actif sur le support ;le support, calculé comme son oxyde, étant présent dans le catalyseur SCR à une teneur de 40 à 99 % en poids, par rapport au poids total du catalyseur SCR ; le matériau actif comprend du vanadium et de l'antimoine ; le vanadium, calculé comme du V2O5, étant présent dans le catalyseur SCR à une teneur de 1 à 15 % en poids, par rapport au poids total du catalyseur SCR ; l'antimoine, calculé comme du Sb2O3, étant présent dans le catalyseur SCR à une teneur de 0,5 à 20 % en poids, par rapport au poids total du catalyseur SCR ; le catalyseur SCR, après vieillissement hydrothermique à 550 °C pendant 100 heures avec 10 % d'eau, ayant une efficacité de dénitrification à 200 à 300 °C d'au moins 60 %, avec une vitesse spatiale de 60 000 h-1 et un rapport molaire ammoniac/NOx de 1:11.
EP21803037.7A 2020-05-15 2021-04-26 Catalyseur de réduction catalytique sélective et article catalytique le comprenant Pending EP4149661A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2020090595 2020-05-15
PCT/US2021/029084 WO2021231070A1 (fr) 2020-05-15 2021-04-26 Catalyseur de réduction catalytique sélective et article catalytique le comprenant

Publications (2)

Publication Number Publication Date
EP4149661A1 true EP4149661A1 (fr) 2023-03-22
EP4149661A4 EP4149661A4 (fr) 2024-05-22

Family

ID=78526031

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21803037.7A Pending EP4149661A4 (fr) 2020-05-15 2021-04-26 Catalyseur de réduction catalytique sélective et article catalytique le comprenant

Country Status (6)

Country Link
EP (1) EP4149661A4 (fr)
JP (1) JP2023528232A (fr)
KR (1) KR20230012001A (fr)
CN (1) CN115551618A (fr)
BR (1) BR112022022827A2 (fr)
WO (1) WO2021231070A1 (fr)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6971985B6 (ja) * 2015-12-17 2021-12-22 ビーエーエスエフ コーポレーション Ｖ及びＳｂを含む複合酸化物を含む選択的触媒還元（ＳＣＲ）触媒、その製造方法、及び窒素酸化物除去のためのその使用方法
KR20190098762A (ko) * 2016-12-30 2019-08-22 바스프 에스이 압출된 벌집형 촉매
EP3482825A1 (fr) * 2017-11-14 2019-05-15 Umicore Ag & Co. Kg Catalyseur rcs
CN112423864A (zh) * 2018-07-30 2021-02-26 巴斯夫公司 钒基选择性催化还原催化剂
KR20210075195A (ko) * 2018-11-02 2021-06-22 바스프 코포레이션 희박 연소 엔진용 배기가스 처리 시스템

Also Published As

Publication number Publication date
JP2023528232A (ja) 2023-07-04
BR112022022827A2 (pt) 2022-12-13
KR20230012001A (ko) 2023-01-25
CN115551618A (zh) 2022-12-30
EP4149661A4 (fr) 2024-05-22
WO2021231070A1 (fr) 2021-11-18

Similar Documents

Publication Publication Date Title
JP7314225B2 (ja) 低温排出制御のためのｓｃｒとｐｎａの組み合わせ
US10322372B2 (en) NH3 overdosing-tolerant SCR catalyst
RU2743125C2 (ru) Однослойный или двухслойный катализатор устранения проскока аммиака
US9273578B2 (en) Catalytic converter for the selective catalytic reduction of nitrogen oxides in the exhaust gas of diesel engines
JP2020513297A (ja) 排ガス処理のための骨格外の鉄及び／又はマンガンを有するｌｔａ触媒
KR20180075480A (ko) 배기 가스 처리 촉매
CN111801164A (zh) 具有原位Pt固定的氨漏失催化剂
US11511228B2 (en) Exhaust treatment system for a lean burn engine
WO2022188808A1 (fr) Article catalytique comprenant un catalyseur à base de vanadium et un catalyseur à base de tamis moléculaire
CN113646065A (zh) 选择性氨氧化催化剂
EP4149661A1 (fr) Catalyseur de réduction catalytique sélective et article catalytique le comprenant
US20230347288A1 (en) Selective catalytic reduction catalyst and catalytic article comprising the same
KR20220110755A (ko) 복합재에서 공동-교환된 Cu 및 Pd를 갖는 제올라이트
EP3936221A1 (fr) Filtre à particules catalysé ayant une fonctionnalité de suie passive améliorée
US20230035318A1 (en) Zoned ammonia slip catalyst for improved selectivity, activity and poison tolerance
EP3775510B1 (fr) Système d'échappement comprenant un catalyseur scrf avec zone d'oxydation
RU2776705C2 (ru) Каталитическое изделие с активным субстратом scr, слоем катализатора нейтрализации проскока аммиака и слоем scr для использования в системе обработки выхлопов
WO2024017252A1 (fr) Article catalytique comprenant un catalyseur contenant du vanadium et un catalyseur d'oxydation
WO2024008077A1 (fr) Article catalytique comprenant un catalyseur d'oxydation d'ammoniac
WO2023046146A1 (fr) Système catalytique comprenant un catalyseur contenant de l'antimoine
WO2021262966A1 (fr) Procédé de préparation d'une zéolite activée par du cuivre
EP4171811A1 (fr) Catalyseur scr contenant une zéolite

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

Free format text: ORIGINAL CODE: 0009012

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20221215

AK Designated contracting states

Kind code of ref document: A1

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

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Free format text: PREVIOUS MAIN CLASS: B01D0053560000

Ipc: B01J0023220000

A4 Supplementary search report drawn up and despatched

Effective date: 20240418

RIC1 Information provided on ipc code assigned before grant

Ipc: B01D 53/56 20060101ALI20240412BHEP

Ipc: B01D 53/94 20060101ALI20240412BHEP

Ipc: B01J 37/10 20060101ALI20240412BHEP

Ipc: B01J 37/02 20060101ALI20240412BHEP

Ipc: B01J 35/56 20240101ALI20240412BHEP

Ipc: B01J 21/08 20060101ALI20240412BHEP

Ipc: B01J 21/06 20060101ALI20240412BHEP

Ipc: B01J 29/89 20060101ALI20240412BHEP

Ipc: B01J 29/076 20060101ALI20240412BHEP

Ipc: B01J 23/22 20060101AFI20240412BHEP