WO2017072138A1 - Catalyseur d'oxydation monolithique en nid d'abeille et son procédé de préparation - Google Patents

Catalyseur d'oxydation monolithique en nid d'abeille et son procédé de préparation Download PDF

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Publication number
WO2017072138A1
WO2017072138A1 PCT/EP2016/075723 EP2016075723W WO2017072138A1 WO 2017072138 A1 WO2017072138 A1 WO 2017072138A1 EP 2016075723 W EP2016075723 W EP 2016075723W WO 2017072138 A1 WO2017072138 A1 WO 2017072138A1
Authority
WO
WIPO (PCT)
Prior art keywords
monolithic honeycomb
group
oxidation catalyst
inert
top layer
Prior art date
Application number
PCT/EP2016/075723
Other languages
English (en)
Inventor
Kim Hougaard PEDERSEN
Francesco Castellino
Viggo Lucassen Hansen
Original Assignee
Haldor Topsøe A/S
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
Priority claimed from DKPA201600583A external-priority patent/DK180289B1/en
Application filed by Haldor Topsøe A/S filed Critical Haldor Topsøe A/S
Priority to CN201680058965.3A priority Critical patent/CN108136372B/zh
Publication of WO2017072138A1 publication Critical patent/WO2017072138A1/fr

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Classifications

    • B01J35/56—
    • 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
    • B01D53/864—Removing carbon monoxide or hydrocarbons
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6527—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
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • 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
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1023—Palladium
    • 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
    • B01D2255/20776—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the invention relates to a monolithic honeycomb catalyst for the oxidation of carbon monoxide and volatile organic compounds (VOCs) in exhaust gases and flue gases from stationary flue gas sources including gas turbines and power plants.
  • VOCs volatile organic compounds
  • the invention is in particular directed to a monolithic honeycomb shaped oxidation catalyst with a core layer comprising inert clay material and a top layer comprising one or more platinum group metals (PGM)coated on a monolithic honeycomb shaped substrate for use in the removal of carbon monoxide and VOCs in flue gas formed in stationary sources in the combustion of fossil fuel like natural gas, coal or oil.
  • PGM platinum group metals
  • the invention is additionally directed a method for the preparation of an oxidation cata- lyst with a core layer of inert clay material coated on a monolithic honeycomb substrate and a top layer of catalytic material active in the oxidation of CO and VOCs.
  • palladium promoted vanadium oxide catalysts offer a very high CO and VOC oxidation activity in combination with a high sulfur resistance.
  • catalysts are in particular preferred where there is a risk of exposure to high sulfur containing flue gases and where high sulfate emissions and fouling of downstream equipment and/or risk of catalyst deactivation has to be minimized.
  • the advantage of palladium based oxidation catalysts is that these catalysts have a relatively low sulfur oxidation activity, which is particularly important when employed in the cleaning of sulfur oxide containing flue gas.
  • the catalyst is washcoated on a monolithic honeycomb substrate, typically consisting of stacked up corrugated sheets of ceramic material or non-woven glass fibers forming a monolithic honeycomb structure with a plurality of parallel flow through channels.
  • Monolithic honeycomb shaped catalysts of the above type are typically prepared by coating the monolithic honeycomb substrate with a washcoat containing a catalyst carrier material and impregnating the coated substrate with a solution of precursors of the catalytic active metal oxides.
  • the washcoat can also contain the precur- sors.
  • Washcoating of a monolithic honeycomb substrate is usually performed by slurry pickup in the substrate by pouring the slurry into the channels of the substrate, by dipping the substrate at one side into the washcoat slurry and optionally applying vacuum at the opposite side or by pumping the washcoat slurry into the channels and optionally applying vacuum.
  • the substrate After having been coated with the washcoat, the substrate is dried and finally calcined for activation of the catalytic components in the coat.
  • the PGM catalyst is distributed throughout the whole wall cross section.
  • the PGM catalyst distributed beneath surface of the walls does not participate in the catalytic CO and reactive VOC oxidation.
  • the problem is solved by the present invention, when providing the walls of the substrate with a core layer of inert clay materials and applying a washcoat comprising PGM on the surface of the core layer.
  • a washcoat comprising PGM on the surface of the core layer.
  • diffusion of PGM can be eliminated or substantially diminished when decreasing the rate of diffusion of PGM on the substrate.
  • the precursor compounds are added to an aqueous slurry containing vanadium compounds, which act as a carrier for PGM and which is used for the coating of the inert clay core layer on the substrate.
  • the PGM compounds are adsorbed on the supported vanadium compound particles and are thereby not dissolved in the aqueous phase of the aqueous slurry, which otherwise would result in undesired diffusion into the walls of the substrate and/or clay core layer.
  • this invention provides a monolithic honeycomb oxidation catalyst with a plurality of flow through channels confined by walls, the walls consisting of one or more corrugated sheets of inert material, optionally provided with flat liners, coated with a core layer comprising an inert clay material, the core layer is coat- ed with a top layer comprising at least one metal selected from the group of platinum group metals and vanadium pentoxide.
  • the catalyst according to the invention has the advantage that it shows at least as good structure stability as conventional monoliths since the overall thickness of the monolith wall is preserved due to the inert clay core layer.
  • the present invention reduces additionally the catalyst load per unit volume of monolith leading to a reduced SO2 oxidation.
  • Specific features of the catalyst according to the invention are alone or in combination thereof that the top layer further comprises an oxide of tungsten and titania;
  • the at least one metal selected from the group of platinum group metals is palladium;
  • the one or more corrugated sheets of inert material, and the optional flat liners comprise entangled non-woven fibers;
  • the entangled non-woven fibers comprise glass fibers
  • the inert clay material is selected from the kaolin group, hydrous alumina silicates, the chlorite group, the pyrophillite group, bentonite or mixtures thereof; the top layer comprises 0.1 to 10 % by weight vanadium pentoxide;
  • the top layer comprises 100 to 30000 ppm by weight palladium
  • a further aspect of the present invention is a method of preparing a monolithic honey- comb oxidation catalyst comprising the steps of
  • step (d) coating the core layer with a top layer by applying the washcoat prepared in step (c);
  • step(c) is prepared by
  • the washcoat further comprises titania and an oxide of tungsten
  • the finished SCR catalyst product comprising vanadium pentoxide further comprises titania and an oxide of tungsten;
  • the platinum group metal is palladium
  • the entangled non-woven fibers are glass fibers
  • the inert clay material is selected from the kaolin group, hydrous alumina silicates, the chlorite group, the pyrophillite group, bentonite or mixtures thereof;
  • the top layer comprises 0.1 to 10 % by weight vanadium pentoxide; the top layer comprises 100 to 30000 ppm by weight palladium.
  • int material and "inert clay material” as used hereinbefore or in the following description and claims it should be understood that the material is not catalyti- cally active.
  • An Pd-V205-W03-TiC>2 based oxidation catalyst on an inert clay core was prepared as follows.
  • a monolithic honeycomb substrate made of a number of corrugated sheets made of glass fibers and provide each with a flat liner were coated with a core layer of kaolin by dipping the substrate into a slurry of kaolin and butanol until the wall thickness of the coated substrate was 0.4 mm.
  • the thus prepared monolithic honeycomb substrate was then allowed to drain for 10 minutes, dried for three days and fired for two hours at 550°C in N2 atmosphere.
  • the substrate with the kaolin core layer was coated with a wash coat prepared as fol- lows:
  • the monolithic honeycomb substrate with an inert core layer of kaolin as prepared above was dipped into the slurry for 1 .5 minutes and the slurry was afterwards allowed to drain from the substrate for 15 minutes.
  • the resulting monolithic honeycomb catalyst was then calcined for two hours at 400°C.

Abstract

L'invention concerne un catalyseur d'oxydation monolithique en nid d'abeille et un procédé de préparation de celui-ci, le catalyseur d'oxydation en nid d'abeilles possède une pluralité de canaux traversants d'écoulement confinés par des parois, les parois étant constituée d'un matériau inerte revêtu d'une couche d'âme comprenant un matériau d'argile inerte, la couche d'âme est revêtue d'une couche supérieure comprenant au moins un métal choisi parmi le groupe des métaux du groupe du platine et du pentoxyde de vanadium.
PCT/EP2016/075723 2015-10-28 2016-10-26 Catalyseur d'oxydation monolithique en nid d'abeille et son procédé de préparation WO2017072138A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201680058965.3A CN108136372B (zh) 2015-10-28 2016-10-26 整料式蜂窝状氧化催化剂及其制备方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DKPA201500661 2015-10-28
DKPA201500661 2015-10-28
DKPA201600583A DK180289B1 (en) 2016-10-03 2016-10-03 Monolithic honeycomb oxidation catalyst and process for its preparation
DKPA201600583 2016-10-03

Publications (1)

Publication Number Publication Date
WO2017072138A1 true WO2017072138A1 (fr) 2017-05-04

Family

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Application Number Title Priority Date Filing Date
PCT/EP2016/075723 WO2017072138A1 (fr) 2015-10-28 2016-10-26 Catalyseur d'oxydation monolithique en nid d'abeille et son procédé de préparation

Country Status (2)

Country Link
CN (1) CN108136372B (fr)
WO (1) WO2017072138A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK201600583A1 (en) * 2016-10-03 2018-04-23 Haldor Topsoe As Monolithic honeycomb oxidation catalyst and method of preparation thereof
CN110560058A (zh) * 2018-06-06 2019-12-13 科莱恩国际有限公司 蜂窝体催化剂、借助于其氧化一氧化碳和有机空气污染物的方法以及蜂窝体催化剂的用途
EP3616786A1 (fr) * 2018-08-28 2020-03-04 Umicore Ag & Co. Kg Catalyseur destiné à être utilisé dans la réduction catalytique sélective (scr) d'oxydes d'azote
WO2020043662A1 (fr) * 2018-08-28 2020-03-05 Umicore Ag & Co. Kg Catalyseur destiné à être utilisé dans la réduction catalytique sélective d'oxydes d'azote

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5198403A (en) * 1989-02-28 1993-03-30 Degussa Ag Process for producing a catalyst for selective reduction of nitrous oxides with ammonia
US20070122330A1 (en) * 2005-11-29 2007-05-31 Dae Young C & E Co., Ltd. Composition, catalytic module element, and catalytic module for selective catalytic reduction of nitrogen oxides in gaseous medium containing oxygen
US20070209350A1 (en) * 2006-03-09 2007-09-13 Keld Johansen Process for purification of sulphur-containing exhaust gas
EP1524024B1 (fr) * 2003-10-15 2010-02-24 Haldor Topsoe A/S Support de catalyseur, catalyseur préparé avec ce support et procédé pour le traitement d'effluents gazeux

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3906136C1 (fr) * 1989-02-28 1990-08-09 Degussa Ag, 6000 Frankfurt, De

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5198403A (en) * 1989-02-28 1993-03-30 Degussa Ag Process for producing a catalyst for selective reduction of nitrous oxides with ammonia
EP1524024B1 (fr) * 2003-10-15 2010-02-24 Haldor Topsoe A/S Support de catalyseur, catalyseur préparé avec ce support et procédé pour le traitement d'effluents gazeux
US20070122330A1 (en) * 2005-11-29 2007-05-31 Dae Young C & E Co., Ltd. Composition, catalytic module element, and catalytic module for selective catalytic reduction of nitrogen oxides in gaseous medium containing oxygen
US20070209350A1 (en) * 2006-03-09 2007-09-13 Keld Johansen Process for purification of sulphur-containing exhaust gas

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK201600583A1 (en) * 2016-10-03 2018-04-23 Haldor Topsoe As Monolithic honeycomb oxidation catalyst and method of preparation thereof
CN110560058A (zh) * 2018-06-06 2019-12-13 科莱恩国际有限公司 蜂窝体催化剂、借助于其氧化一氧化碳和有机空气污染物的方法以及蜂窝体催化剂的用途
EP3616786A1 (fr) * 2018-08-28 2020-03-04 Umicore Ag & Co. Kg Catalyseur destiné à être utilisé dans la réduction catalytique sélective (scr) d'oxydes d'azote
WO2020043662A1 (fr) * 2018-08-28 2020-03-05 Umicore Ag & Co. Kg Catalyseur destiné à être utilisé dans la réduction catalytique sélective d'oxydes d'azote
US11426709B2 (en) 2018-08-28 2022-08-30 Umicore Ag & Co. Kg Catalyst for use in the selective catalytic reduction (SCR) of nitrogen oxides
US11772075B2 (en) 2018-08-28 2023-10-03 Umicore Ag & Co. Kg Catalyst for use in the selective catalytic reduction (SCR) of nitrogen oxides
JP7436456B2 (ja) 2018-08-28 2024-02-21 ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト 窒素酸化物の選択的触媒還元（ｓｃｒ）で使用するための触媒

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Publication number Publication date
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CN108136372A (zh) 2018-06-08

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