WO2016039747A1 - Procédés d'oxydation et systèmes de catalyseur zpgm à deux voies et à trois voies et appareil les comprenant - Google Patents

Procédés d'oxydation et systèmes de catalyseur zpgm à deux voies et à trois voies et appareil les comprenant Download PDF

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Publication number
WO2016039747A1
WO2016039747A1 PCT/US2014/055063 US2014055063W WO2016039747A1 WO 2016039747 A1 WO2016039747 A1 WO 2016039747A1 US 2014055063 W US2014055063 W US 2014055063W WO 2016039747 A1 WO2016039747 A1 WO 2016039747A1
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Prior art keywords
washcoat
overcoat
catalyst system
weight
zpgm
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PCT/US2014/055063
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English (en)
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Zahra NAZARPOOR
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Clean Diesel Technologies, Inc.
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Priority to PCT/US2014/055063 priority Critical patent/WO2016039747A1/fr
Publication of WO2016039747A1 publication Critical patent/WO2016039747A1/fr

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    • 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
    • B01D53/92—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
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
    • 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
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • 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
    • B01J23/66—Silver or gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B01J35/19—
    • 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
    • B01D2255/104—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/204—Alkaline earth metals
    • B01D2255/2045—Calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2061—Yttrium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2063—Lanthanum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2065—Cerium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2066—Praseodymium
    • 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
    • B01D2255/20715—Zirconium
    • 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
    • B01D2255/20738—Iron
    • 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
    • B01D2255/20746—Cobalt
    • 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
    • B01D2255/20761—Copper
    • 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
    • B01D2255/2094—Tin
    • 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

  • This disclosure relates generally to catalytic converters, more particularly, to zero platinum group metals catalytic converters.
  • oxi-catalysts and three-way catalysts are used in the exhaust gas lines of internal combustion engines. These catalysts promote the oxidation of unburned hydrocarbons and carbon monoxide as well as the reduction of nitrogen oxides in the exhaust gas stream.
  • TWC three-way catalysts
  • PGM Platinum Group Metals
  • ZPGM catalyst systems may oxidize toxic gases, such as carbon monoxide and hydrocarbons; optionally some ZPGM catalytic converters may as well reduce nitrogen oxides that may be included in exhaust gases.
  • ZPGM catalyst converters may include: a substrate, a washcoat, and an overcoat. Washcoat and overcoat may include at least one ZPGM catalyst, carrier material oxides, and may optionally include OSMs. Suitable known in the art chemical techniques, deposition methods and treatment systems may be employed in order to form the disclosed ZPGM catalyst converters.
  • Materials suitable for use as catalyst include Copper (Cu), Cerium (Ce), Silver (Ag), Tin (Sn), Niobium (Nb), Zirconium (Zr), Lanthanum (La), Iron (Fe), Cobalt (Co), Manganese (Mn), Calcium (Ca) and combinations thereof.
  • Catalytic systems that include combinations of Cu, Ce and Ag in the washcoat or overcoat or both may be suitable for use as Oxidation Catalysts at temperatures below 200°C.
  • Catalytic systems that include Cu-Ce, Cu-Ce-Sn, Cu-Ce-Nb-Zr, and Cu-Ce-Ca may be suitable for use as TWCs at temperatures above 200°C.
  • Catalytic systems that include La-Ce-Mn-Fe-Co and La-Ce-Fe-Co may be suitable for use as Oxidation Catalysts at temperatures above 200°C.
  • Suitable materials for use as substrates may include refractive materials, ceramic materials, metallic alloys, foams, microporous materials, zeolites, cordierites, or combinations.
  • Support materials of use in catalysts containing one or more of the aforementioned combinations may include Cerium Oxide, Alumina, Titanium Oxide, Zirconia, and
  • CZO Ceria/Zirconia
  • Suitable known in the art chemical techniques, deposition methods and treatment systems may be employed in order to form the disclosed ZPGM catalyst systems.
  • FIG. 1 shows a ZPGM catalyst system structure, according to an embodiment.
  • FIG. 2 is a flowchart of a method of preparation of a ZPGM catalyst, according to an embodiment.
  • FIG. 3 shows light-off test results of a ZPGM catalyst system, according to an embodiment.
  • FIG. 4 shows light-off test results of a ZPGM catalyst system, according to an embodiment.
  • FIG. 5 shows light-off test results of a ZPGM catalyst system, according to an embodiment.
  • FIG. 6 shows light-off test results of a ZPGM catalyst system, according to an embodiment.
  • FIG. 7 shows light-off test results of a ZPGM catalyst system, according to an embodiment.
  • FIG. 8 shows light-off test results of a ZPGM catalyst system, according to an embodiment.
  • FIG. 9 shows light-off test results of a ZPGM catalyst system, according to an embodiment.
  • FIG. 10 shows light-off test results of a ZPGM catalyst system, according to an embodiment.
  • FIG. 11 shows light-off test results of a ZPGM catalyst system, according to an embodiment.
  • FIG. 12 shows light-off test results of a ZPGM catalyst system, according to an embodiment.
  • FIG. 13 shows light-off test results of a ZPGM catalyst system, according to an embodiment.
  • FIG. 14 shows light-off test results of a ZPGM catalyst system, according to an embodiment.
  • FIG. 15 shows light-off test results of a ZPGM catalyst system, according to an embodiment.
  • FIG. 16 shows light-off test results of a ZPGM catalyst system, according to an embodiment.
  • FIG. 17 shows the XRD spectra of a fresh sample of a ZPGM catalyst system, according to an embodiment.
  • FIG. 18 shows light-off test results of a ZPGM catalyst system, according to an embodiment.
  • FIG. 19 shows the XRD spectra of fresh and aged samples of a ZPGM catalyst system, according to an embodiment.
  • FIG. 20 shows light-off test results of a ZPGM catalyst system, according to an embodiment.
  • FIG. 21 shows light-off test results of a ZPGM catalyst system, according to an embodiment.
  • Complexing agent refers to a substance capable of promoting the formation of complex compounds.
  • Exhaust refers to the discharge of gases, vapor, and fumes including hydrocarbons, nitrogen oxide, and/or carbon monoxide.
  • Exhaust refers to the discharge of gases, vapor, and fumes including hydrocarbons, nitrogen oxide, and/or carbon monoxide.
  • Exhaust refers to the discharge of gases, vapor, and fumes including hydrocarbons, nitrogen oxide, and/or carbon monoxide.
  • Exhaust refers to the discharge of gases, vapor, and fumes including hydrocarbons, nitrogen oxide, and/or carbon monoxide.
  • “Impregnation” refers to the process of totally saturating a solid layer with a liquid compound.
  • Wash-coat refers to at least one coating including at least one oxide solid that may be deposited on a substrate.
  • “Over-coat” refers to at least one coating including one or more oxide solids or metals that may be deposited on at least one wash-coat or impregnation layer.
  • R Value refers to the number obtained by dividing the reducing potential by the oxidizing potential.
  • Conversion refers to the chemical alteration of at least one material into one or more other materials.
  • T50 refers to the temperature at which 50% of a material is converted.
  • T90 refers to the temperature at which 90% of a material is converted.
  • Three Way Catalyst refers to a catalyst suitable for use in converting at least hydrocarbons, nitrogen oxide, and carbon monoxide.
  • Oxidation Catalyst refers to a catalyst suitable for use in converting at least hydrocarbons and carbon monoxide.
  • ZPGM Zero Platinum Group
  • Platinum Group Metals refers to platinum, palladium, ruthenium, iridium, osmium, and rhodium.
  • Fig. 1 depicts ZPGM Catalyst System 100 configurations, according to various embodiments. As shown in fig. 1 A, ZPGM Catalyst System 100 may include at least a
  • Substrate 102 and a Washcoat 104 where Washcoat 104 may contain active two way or three way ZPGM catalyst components.
  • ZPGM Catalyst System 100 may optionally include an Overcoat 106 applied on over of Washcoat 104. Where Washcoat 104 or Overcoat 106, or both, may include active two way or three way ZPGM catalyst components.
  • Washcoat 104 or Overcoat 106 or both may include at least one ZPGM transition metal catalyst, a ZPGM mixed metal catalyst, a ZPGM zeolite catalyst, or combinations thereof.
  • a ZPGM transition metal catalyst may include one or more transition metals and/or least one rare earth metal, or a mixture; excluding platinum group metals.
  • a ZPGM Catalyst System 100 may include a ZPGM transition metal catalyst.
  • the ZPGM transition metal catalyst may include at least silver oxide and copper oxide distributed in Washcoat 104 or Overcoat 106, or in both.
  • the ZPGM transition metal catalyst may include one or more transition metals that are completely free of platinum group metals.
  • ZPGM transition metal catalyst may include scandium, titanium, chromium, manganese, iron, cobalt, nickel, zinc, yttrium, zirconium, niobium, molybdenum, cadmium, hafnium, tantalum, tungsten, rhenium and gallium.
  • nickel, iron, manganese and cobalt may be preferably added to ZPGM Catalyst System 100.
  • ZPGM Catalyst System 100 may optionally include rare earth metals or rare earth metal oxides, e.g., ceria.
  • Washcoat 104 or Overcoat 106 may include support oxides material referred to as carrier material oxides.
  • Carrier material oxides may include aluminum oxide, doped aluminum oxide, spinel, delafossite, lyonsite, garnet, perovksite, pyrochlore, doped ceria, fluorite, zirconium oxide, doped zirconia, titanium oxide, tin oxide, silicon dioxide, zeolite, and mixtures thereof.
  • carrier material oxides may be doped with one or more lanthanides.
  • ZPGM Catalyst System 100 may include alumina mixed with other metals.
  • Carrier material oxide may be present in Washcoat 104 in a ratio of about 40 to about 60 by weight.
  • Carrier material oxides are normally inert and stable at high temperatures (>1000° C.) and under a range of reducing and oxidizing conditions.
  • Washcoat 104 or Overcoat 106 may include oxygen storage materials (OSM), such as cerium, zirconium, lanthanum, yttrium, lanthanides, actinides, samarium ,and mixtures thereof.
  • OSM oxygen storage materials
  • Washcoat 104 may also include other components such as acid or base solutions or various salts or organic compounds that may be added in order to adjust rheology of the Washcoat 104 and Overcoat 106 slurry and to enhance the adhesion of Washcoat 104 to Substrate 102.
  • Some examples of compounds that can be used to adjust the rheology may include ammonium hydroxide, aluminum hydroxide, acetic acid, citric acid, tetraethyl ammonium hydroxide, other tetralkyl ammonium salts, ammonium acetate, ammonium citrate, glycerol, commercial polymers such as polyethylene glycol, polyvinyl alcohol and other suitable compounds.
  • Preferred solution to enhance binding of Washcoat 104 to Substrate 102 may be tetraethyl ammonium hydroxide.
  • Washcoat 104 may be included in Washcoat 104 or Overcoat 106.
  • ZPGM Catalyst System 100 may include a mixed metal oxide catalyst, which includes at least one transition metal and at least one other metal.
  • the other metals of the mixed metal oxide may include, but are not limited to alkali and alkaline earth metal,lanthanides, or actinides.
  • the mixed metal oxide may include a spinel, a perovskite, adelafossite, a lyonsite, a garnet, or a pyrochlore or combinations thereof.
  • ZPGM Catalyst System 100 may include a mixed metal oxide catalyst that may include a perovskite having the formula AB0 3 or related structures. Partial substitution of the A site with M element will yield the general formula
  • A may include lanthanum, lanthanides, actinides, cerium, magnesium, calcium, barium, strontium, or mixtures thereof.
  • B may include a single transition metal, or a mixture of transition metals and rare earth metals, including iron, manganese, silver, copper, nickel, cobalt, and cerium, chromium or mixture thereof.
  • M may include cerium, strontium, potassium, sodium, iron, and silver or mixtures thereof.
  • the mixed metal oxide catalyst may have the formula AMnl-xCux03, wherein "A” may be lanthanum, cerium, barium, strontium, a lanthanide, or an actinide and "x" may have values from 0 to 1.
  • a mixed metal oxide catalyst may have the formula ACel-xCux03, where "A” may be lanthanum, barium, strontium, or calcium, and "x" is 0 to 1. According to an embodiment, about 40 g/L to about 180 g/L of the formula AB03 may be coupled with Substrate 102.
  • the ZPGM Catalyst System 100 may include a perovskite (AB03) or related structure (with general formula Aa-xBxMOb) and one or more carrier material oxides.
  • the perovskite or related structure may be present in about 5% to about 50% by weight.
  • a mixed metal oxide catalyst that may include a spinel structure having the formula AB204.
  • “A” and “B” of the formula is aluminum, magnesium, manganese, gallium, nickel, copper, silver, cobalt, iron, chromium, titanium, tin, or mixtures thereof.
  • mixed metal oxide catalyst that may include a spinel and a carrier material oxide. The spinel may be present in about 5% to about 50% by weight.
  • ZPGM Catalyst System 100 may include a zeolite catalyst, where the zeolite catalyst may include a zeolite or mixture of zeolites and at least one transition metal catalyst or a mixed metal oxide catalyst.
  • the zeolite catalyst may include ZSM5, heulandite, chabazite, or mixtures thereof.
  • ZPGM Catalyst System 100 includes at least one transition metal catalyst or a mixed metal oxide catalyst
  • the transition metal(s) may be a single transition metal or a mixture of transition metal which may include, chromium, gallium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, tungsten, and silver.
  • the transition metals are selected from the group consisting of copper, nickel, gallium, cobalt, and mixtures
  • transition metals may be present in about 3% to about 25% by weight in any ratio of transition metals.
  • the zeolite catalyst may include support oxides material referred to as carrier material oxides.
  • Carrier material oxides may include aluminum oxide, doped aluminum oxide, pyrochlore, doped ceria, fluorite, zirconium oxide, doped zirconia, titanium oxide, tin oxide, silicon dioxide, zeolite, tin aluminum oxide and mixtures thereof.
  • the zeolite catalyst may include oxygen storage materials (OSM), such as cerium, zirconium, yttrium, lanthanides, actinides, and mixtures thereof.
  • OSM oxygen storage materials
  • the zeolite catalyst may also include other components such as acid or base solutions or various salts or organic compounds that may be added in order to adjust rheology of the Washcoat 104 and Overcoat 106 slurry and to enhance binding of Washcoat 104 or Overcoat 106 to Substrate 102.
  • other components known to one of ordinary skill in the art may be included in ZPGM Catalyst System 100.
  • FIG. 2 is a flowchart of Method for Preparation 200 of Washcoat 104 and
  • Overcoat 106 according to an embodiment.
  • Washcoat 104 or Overcoat 106 may be prepared by following Method for Preparation 200.
  • Method for Preparation 200 Method for Preparation 200.
  • Preparation 200 may be a "co-milling method" which may begin with a Mixing 202 process. In this process, components of Washcoat 104 or Overcoat 106, previously described, may be mixed together. Subsequently, the mixture may undergo a Milling Process 204 in which
  • Washcoat 104 or Overcoat 106 materials may be broken down into smaller particle sizes.
  • a catalyst aqueous slurry may be obtained.
  • Milling Process 204 may take from about 10 minutes to about 10 hours, depending on the batch size, kind of material and particle size desired.
  • suitable average particle size (APSs) of the slurry may be of about 4 microns to about 10 microns, in order to get uniform distribution of Washcoat 104 particles or Overcoat 106 particles. Finer particles may have more coat ability and better adhesion to Substrate 102 and enhanced cohesion between Washcoat 104 and Overcoat 106 layers.
  • Milling Process 204 may be achieved by employing any suitable mill such as vertical or horizontal mills.
  • a laser light diffraction equipment may be employed.
  • aqueous slurries obtained in Milling Process 204 may undergo an Adjusting Rheology 206 step.
  • Adjusting Rheology 206 step acid or base solutions or various salts or organic compounds may be added to the aqueous slurreis.
  • Some examples of compounds that can be used to adjust the rheology may include ammonium hydroxide, aluminum hydroxide, acetic acid, citric acid, tetraethyl ammonium hydroxide, other tetralkyl ammonium salts, ammonium acetate, ammonium citrate, glycerol, commercial polymers such as polyethylene glycol, polyvinyl alcohol and other suitable compounds. All steps included in Method for Preparation 200 may be achieved within room temperature.
  • Washcoat 104 and Overcoat 106 may be synthesized by any chemical techniques known in the art.
  • Washcoat 104 and an Overcoat 106 Washcoat 104 may be deposited on Substrate 102 in at least three different ways. First, depositing all desired components in one step. Or second, by depositing components without a catalyst, then separately depositing at least one impregnation component and heating (this separate deposit is also referred to as an impregnation step).
  • the impregnation component may include, without
  • washcoat 104 that includes at least a catalyst.
  • the third method includes depositing all desired components of Washcoat 104 at once, including metal salts and then heating or calcining ZPGM Catalyst System 100 to convert the metals salts into metal oxides.
  • An Overcoat 106 may be typically applied after treating Washcoat 104, but treating is not required prior to application of Overcoat 106 in every embodiment.
  • washcoats 104 may be coupled with a Substrate 102, preferably an amount that covers most of, or all of, the surface area of a substrate. In an embodiment, about 60 g/L to about 250 g/L of a Washcoat 104 may be coupled with a
  • a Washcoat 104 may be formed on the Substrate 102 by suspending the oxide solids in water to form an aqueous slurry and depositing the aqueous slurry on Substrate 102 as a Washcoat 104.
  • Other components may optionally be added to the aqueous slurry.
  • Other components such as acid or base solutions or various salts or organic compounds may be added to the aqueous slurry to adjust the rheology of the slurry and enhance binding of the Washcoat 104 to the Substrate 102.
  • the slurry may be placed on Substrate 102 in any suitable manner.
  • Substrate 102 may be dipped into the slurry, or the slurry may be sprayed on Substrate 102.
  • Other methods of depositing the slurry onto Substrate 102 known to those skilled in the art may be used in alternative embodiments.
  • a Washcoat 104 may be formed on the walls of the passages.
  • a Washcoat 104 having may be prepared by methods well known in the art.
  • Washcoat 104 may comprise any of the catalysts and additional components described above.
  • Washcoat 104 may be deposited on a Substrate 102 and subsequently treated.
  • the treating may be done at a temperature between 300° C. and 700° C. In some embodiments, at about
  • the treatment may last from about 2 to about 6 hours. In some embodiments, the treatment may last about 4 hours.
  • Substrate 102 coated with Washcoat 104 is treated, Substrate 102 my be cooled to about room temperature. After cooling, Washcoat 104 may be impregnated with at least one impregnation component.
  • the impregnation component may include, at least one transition -metal salt being dissolved in water.
  • ZPGM Catalyst System 100 with the impregnation components may be heat treated. The treating may be performed from about 300° C to about 700° C. In some embodiments, this second heat treatment may be performed at about 550° C.
  • the treating may last from about 2 to about 6 hours, preferably about 4 hours.
  • Washcoat 104 and the impregnation component may be treated before coating.
  • a Washcoat 104 including a transition metal such as Ag may be prepared by methods well known in the art. Washcoat 104 may include only carrier oxide described herein. Washcoat 104 may be deposited on a Substrate 102 and then heat treated. The heat treatment may done at a temperature between 300° C and 700° C. In some embodiments this treatment may be performed at about 550° C. The heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours. After Washcoat 104 and Substrate 102 are treated, they are cooled to about room temperature. After cooling,
  • Washcoat 104 is impregnated with at least one impregnation component such as silver.
  • the impregnation component includes at least silver salts, dissolved in water and capable of being impregnated on the Washcoat 104.
  • Washcoat 104 with the impregnation components may be heat treated.
  • the heat treatment may be performed at about 300° C to about 700° C. In some embodiments this treatment may be performed at about
  • the heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours.
  • Substrate 102, Washcoat 104, and the impregnation components may be treated to form ZPGM Catalyst System 100. In an embodiment, Washcoat 104 and the impregnation component may be heat treated before coating.
  • the method of precipitation includes precipitating transition metal salt or salts on Washcoat 104.
  • the transition metal salt or salts may be precipitated with NH40H,
  • the precipitated transition metal salt or salts and Washcoat 104 may be aged. The aging may take from about 2 hours to about 24 hours. After aging, the precipitated transition metal salt or salts and Washcoat 104 may be deposited on a Substrate 102 followed by a heat treatment that may last from about 2 hours to about 6 hours. In an embodiment the treatment may last about 4 hours. The treatment may be performed at a temperature from about 300° C to about 700° C. In some embodiments, the suitable temperature for the treatment may be of about 550° C.
  • Overcoat 106 may be deposited on the treated precipitated transition metal salt or salts and Washcoat 104.
  • ZPGM Catalyst System 100 may be heat treated. This treatment may be performed at about 300° C to about 700° C. In some embodiments this treatment may be performed at about 550° C. The heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours.
  • a Washcoat 104 including at least one transition metal such as silver may be prepared by methods well known in the art.
  • the method of co -precipitation may include precipitating a silver salt on Washcoat 104.
  • Suitable components for precipitation of the silver salts may include NH40H,(NH4)2C03, tetraethylammonium hydroxide, other tetraalkylammonium salts, ammonium acetate, ammonium carbonate or ammonium citrate.
  • the precipitated silver salt or salts and Washcoat 104 are deposited on a Substrate 102 followed by heat treatment that may last from about 2 hours to about 6 hours.
  • the treatment may last about 4 hours.
  • the treatment may be performed at a temperature from about 300° C to about 700° C.
  • the suitable thermoplastic material may be any suitable thermoplastic material.
  • temperature for the treatment may be of about 550° C.
  • Overcoat 106 may be deposited on the treated precipitated transition metal salt and
  • ZPGM Catalyst System 100 may be heat treated. This treatment may be performed at about 300° C to about 700° C. In some embodiments this treatment may be performed at about 550° C. The heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours.
  • the co-precipitation of silver may optionally be performed on an Overcoat 106. Afterwards, the precipitated silver salt and Overcoat 106 may be heat treated. This heat treatment may be from about 2 hours to about 24 hours.
  • the catalysts and a carrier material oxides are milled together.
  • the catalyst may be previously synthesized by any chemical technique such as solid-state synthesis, precipitation, or any other technique known in the art.
  • the milled catalyst and carrier material oxide may be deposited on a Substrate 102 in the form of a Washcoat 104 and then treated.This treatment may be performed at about 300° C to about 700° C. In some embodiments this treatment may be performed at about 550° C. The heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours.
  • an Overcoat 106 may be deposited on the treated ZPGM catalyst after cooling to about room temperature.
  • the Overcoat 106, Washcoat 104 and Substrate 102 are treated This treatment may be performed at about 300° C to about 700° C. In some embodiments this treatment may be performed at about 550° C.
  • the heat treatment may last from about 2 to about 6 hours.
  • ZPGM catalyst systems 100 including active catalysts prepared by co-milling may be able to have improved performance when compared with ZPGM catalyst systems 100 including active catalysts prepared by other methods due to a better dispersion of the catalysts.
  • a transition metal such as silver and a carrier material oxide may be milled together.
  • the milled catalyst and carrier material oxide are deposited on a Substrate 102 in the form of a Washcoat 104 and then heat treated.
  • This treatment may be performed at about 300° C to about 700° C. In some embodiments this treatment may be performed at about 550° C.
  • the heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours.
  • an Overcoat 106 may be deposited on the treated catalyst after cooling to about room temperature. Subsequently, Overcoat 106, Washcoat 104 and
  • Substrate 102 may be heat treated. This treatment may be performed at about 300° C to about 700° C. In some embodiments this treatment may be performed at about 550° C. The heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours. [0094] Stabilization of catalysts
  • the active catalysts included in ZPGM Catalyst System 100 may need to be stabilized for enhanced effectiveness of dispersion.
  • the stabilized metal particles may include include a transition-metal salt dissolved in a stabilizer solution.
  • Some examples of compounds that can be used as stabilizer solutions for the transition metal ions may include polyethylene glycol, polyvinyl alcohol, poly(N-vinyl-2pyrrolidone) (PVP), polyacrylonitrile, polyacrylic acid, multilayer polyelectrolyte films, poly-siloxane, oligosaccharides,poly(4- vinylpyridine), poly(N,Ndialkylcarbodiimide), chitosan, hyper-branched aromatic polyamides and other suitable polymers.
  • the stabilized transition metal solution may then be impregnated on Washcoat 104, or co-milled with carrier material oxides and deposited on a Substrate 102. After deposition a heat treament may be required. This treatment may be performed at about 300° C to about 700° C. In some embodiments this treatment may be performed at about 550° C. The heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours.
  • a ZPGM Catalyst System 100 including a ZPGM transition metal catalyst having a cordierite Substrate 102, a Washcoat 104 and no Overcoat 106 is prepared.
  • the oxygen storage material and the alumina may be present in this catalyst system.
  • Washcoat 104 in a ratio of 40% to about 60% by weight.
  • the silver in Washcoat 104 is present in about 1% to about 20%, or about 4% to about 10% by weight.
  • the transition metal (silver) and a carrier material oxide are milled together.
  • the catalyst can be synthesized by any suitable chemical technique known in the art.
  • the milled mixture of catalyst and carrier material oxides is deposited on the cordierite Substrate 102 in the form of a Washcoat 104 and then heat treated. This treatment may be performed at about 300° C to about 700° C. In some embodiments this treatment may be performed at about 550° C.
  • the heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hour.
  • FIG. 3 shows the light-off test Results 300 for the ZPGM Catalyst System 100 of example 1.
  • the ZPGM Catalyst System 100 of example 1 Prior to the light off test, the ZPGM Catalyst System 100 of example 1 is aged under dry air condition at 900° C for 4 hours.
  • the hydrocarbon present in the feed stream is propene (C3H6).
  • Carbon monoxide, and hydrocarbons conversion are measured as a function of the ZPGM Catalyst System 100 temperature. Since the light-off test is performed under lean condition (R-values ⁇ l), no nitrogen oxide conversion is measured.
  • the test is performed by increasing the temperature from about 100° C to 580° C at a constant rate of 40° C/min.
  • a ZPGM Catalyst System 100 including a ZPGM transition metal catalyst having a cordierite Substrate 102, a Washcoat 104 and an Overcoat 106 is prepared.
  • Washcoat 104 may include an oxygen storage material (which may be a mixture of cerium and zirconium) and alumina.
  • Overcoat 106 includes copper oxide, ceria, alumina, and at least one oxygen storage material.
  • the oxygen storage material is a mixture of cerium, zirconium, neodymium, and praseodymium.
  • the oxygen storage material and the alumina may be present in Washcoat 104 in a ratio between 40% and about 60% by weight.
  • the alumina and oxygen storage material included in Overcoat 106 are present in a ratio of about 60% to about 40% by weight.
  • the copper and cerium in Overcoat 106 are present in about 5% to about 50% by weight or from about 10% to 16% by weight of Cu and 12% to 20% by weight of Ce.
  • the ZPGM Catalyst System 100 of example 2 is prepared using co-milling techniques previously described. After deposition, Washcoat 104 and Overcoat 106 are treated. This treatment may be performed at about 300° C to about 700° C. In some embodiments this treatment may be performed at about 550° C. The heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours.
  • Figure 4 shows the light-off test Results 400 for the ZPGM Catalyst System 100 of example 2.
  • the ZPGM Catalyst System 100 of example 2 Prior to the light off test, the ZPGM Catalyst System 100 of example 2 is aged under dry air condition at 900° C for 4 hours.
  • the hydrocarbon present in the feed stream is propene (C3H6).
  • Carbon monoxide, and hydrocarbons conversion are measured as a function of the ZPGM Catalyst System 100 temperature. Since the light-off test is performed under lean condition (R-values ⁇ l), no nitrogen oxide conversion is measured.
  • the test is performed by increasing the temperature from about 100° C to 580° C at a constant rate of 40° C/min.
  • a ZPGM Catalyst System 100 including a ZPGM transition metal catalyst having a cordierite Substrate 102, a Washcoat 104 and an Overcoat 106 is prepared.
  • Overcoat 106 includes at least copper oxide, ceria, alumina, and one oxygen storage material.
  • the oxygen storage material material present in Overcoat 106 is a mixture of cerium, zirconium, neodymium, and praseodymium.
  • the oxygen storage material and the alumina may be present in Washcoat 104 in a ratio of 40% to about 60% by weight.
  • the silver in Washcoat 104 is present in about 1% to about 20%, or from about 4% to about 10% by weight.
  • the alumina and oxygen storage material included in Overcoat 106 are present in a ratio of about 60% to about 40% by weight.
  • the copper and cerium in Overcoat 106 are present in about 5% to about 50% by weight or from about 10% to 16% by weight of Cu and 12% to 20% by weight of Ce.
  • the transition metal (silver) and a carrier material oxide are milled together.
  • the catalyst can be synthesized by any suitable chemical technique known in the art.
  • the milled mixture of catalyst and carrier material oxides is deposited on the cordierite Substrate 102 in the form of a Washcoat 104 and then heat treated. This treatment may be performed at about 300° C to about 700° C. In some embodiments this treatment may be performed at about 550° C.
  • the heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours.
  • the Overcoat 106 is prepared following a similar method.
  • FIG. 5 shows the light-off test Results 500 for the ZPGM Catalyst System 100 of example 3.
  • the ZPGM Catalyst System 100 of example 3 Prior to the light off test, the ZPGM Catalyst System 100 of example 3 is aged under dry air condition at 900° C for 4 hours.
  • the hydrocarbon present in the feed stream is propene (C3H6).
  • Carbon monoxide, and hydrocarbons conversion are measured as a function of the ZPGM Catalyst System 100 temperature. Since the light-off test is performed under lean condition (R-values ⁇ l), no nitrogen oxide conversion is measured. The test is performed by increasing the temperature from about 100° C to 580° C at a constant rate of 40° C/min.
  • a ZPGM Catalyst System 100 including a ZPGM transition metal catalyst having a cordierite Substrate 102, a Washcoat 104 and an Overcoat 106 is prepared.
  • Washcoat 104 may include an oxygen storage material (which may be a mixture of cerium and zirconium) and alumina.
  • Overcoat 106 includes copper oxide, silver, ceria, alumina, and at least one oxygen storage material.
  • the oxygen storage material is a mixture of cerium, zirconium, neodymium, and praseodymium.
  • the oxygen storage material and the alumina may be present in Washcoat 104 in a ratio between 40% and about 60% by weight.
  • the alumina and oxygen storage material included in Overcoat 106 are present in a ratio of about 60% to about 40% by weight.
  • the copper in Overcoat 106 is present from about 5% to about 50% by weight or from about 10% to 16% by weight.
  • the silver in Overcoat 106 is present from about 1% to about 20% by weight or from about 4% to 10% by weight.
  • ceria in Overcoat 106 is present from about 5% to about 50% by weight or from about 12% to 20% by weight.
  • the ZPGM Catalyst System 100 of example 4 is prepared by co- precipitation methods described above. After deposition, Washcoat 104 and Overcoat 106 are treated. This treatment may be performed at temperatures from about 300° C to about 700° C. In some embodiments this treatment may be performed at about 550° C. The heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours.
  • FIG. 6 shows the light-off test Results 600 for the ZPGM Catalyst System 100 of example 4.
  • a ZPGM Catalyst System 100 including a ZPGM transition metal catalyst having a cordierite Substrate 102, a Washcoat 104 and an Overcoat 106 is prepared by co-milling using stabilized silver.
  • the oxygen storage material material present in Overcoat 106 is a mixture of cerium, zirconium, neodymium, and praseodymium.
  • the oxygen storage material and the alumina may be present in
  • Washcoat 104 in a ratio of 40% to about 60% by weight.
  • the silver in Washcoat 104 is present in about 1% to about 20%, or from about 4% to about 10% by weight.
  • the copper in Overcoat 106 is present from about 5% to about 50% by weight or from about 10% to 16% by weight. Additionally, ceria in Overcoat 106 is present from about 5% to about 50% by weight or from about 12% to 20% by weight.
  • the silver is stabilized using at least one stabilizer solution, selected from a group includingpolyethylene glycol, polyvinyl alcohol, poly(N-vinyl-2pyrrolidone) (PVP), polyacrylonitrile, polyacrolic acid, multilayer
  • PVP poly(N-vinyl-2pyrrolidone)
  • polyelectrolyte films poly-siloxane, oligosaccharides, poly(4-vinylpyridine), poly(N,N- dialkylcarbodiimide), chitosan, hyper-branched aromatic polyamids and other suitable substances.
  • the silver salt is dissolved in the stabilizer solution with a ratio of silver to stabilizer between 0.1 and 5 by weight or between 0.5 and 1 by weight.
  • the stabilized silver solution and the carrier material oxide are milled together and deposited on Substrate 102 as Washcoat 104.
  • Prior to the application of Overcoat 106 Substrate 102 and Washcoat 104 are heat treated. This treatment may be performed at about 550° C. The heat treatment may last from about 2 to about 6 hours.
  • Overcoat 106 is deposited and Substrate 102 is heat treated at 550° C for 4 hours.
  • Figure 7 shows the light-off test Results 700 for the ZPGM Catalyst System 100 of example 4.
  • a ZPGM Catalyst System 100 including a ZPGM transition metal catalyst having a cordierite Substrate 102, a Washcoat 104 and an Overcoat 106 is prepared.
  • Overcoat 106 includes at least copper oxide, ceria, alumina, and one oxygen storage material.
  • the oxygen storage material material present in Overcoat 106 is a mixture of cerium, zirconium, neodymium, and praseodymium.
  • the oxygen storage material and the alumina may be present in Washcoat 104 in a ratio of
  • the silver in Washcoat 104 is present in about 1% to about
  • Overcoat 106 is present in a ratio of about 40% to about 60% by weight.
  • the copper and cerium in Overcoat 106 are present in about 5% to about 50% by weight or from about 10% to 16% by weight of Cu and 12% to 20% by weight of Ce.
  • the transition metal (silver) and a carrier material oxide are milled together.
  • the catalyst can be synthesized by any suitable chemical technique known in the art.
  • the milled mixture of catalyst and carrier material oxides is deposited on the cordierite Substrate 102 in the form of a Washcoat 104, then Overcoat 106 is deposited and ZPGM Catalyst System 100 is heat at 550° C for 4 hours.
  • Figure 8 shows the light-off test Results 800 for the ZPGM Catalyst System 100 of example 6.
  • Figure 9 shows the light-off test Results 900 for the ZPGM Catalyst System 100 of example 6 having a calcination temperature of 750 ° C. Prior to the light off test, the ZPGM
  • Catalyst System 100 of example 6 is aged under dry air condition at 900° C for 4 hours.
  • the hydrocarbon present in the feed stream is toluene.
  • Carbon monoxide, and hydrocarbons conversion are measured as a function of the ZPGM Catalyst System 100 temperature. Since the light-off test is performed under lean condition (R-values ⁇ l), no nitrogen oxide conversion is measured. The test is performed by increasing the temperature from about 100° C to 500° C at a constant rate of 40° C/min.
  • Figure 10 shows the light-off test Results 1000 for the ZPGM Catalyst System 100 of example 6, having a calcination temperature of 900 ° C.
  • a ZPGM Catalyst System 100 including a ZPGM transition metal catalyst having a cordierite Substrate 102, a Washcoat 104 and an Overcoat 106 is prepared.
  • the oxygen storage material material present in Overcoat 106 is a mixture of cerium, zirconium, neodymium, and praseodymium.
  • the silver in Washcoat 104 is present in about 1% to about 20%, or from about 4% to about 10% by weight.
  • the alumina and oxygen storage material included in Overcoat 106 are present in a ratio of about 60% to about 40% by weight.
  • the copper and cerium in Overcoat 106 are present in about 5% to about 50% by weight or from about 10% to 16% by weight of Cu and
  • the transition metal (silver) and a carrier material oxide are milled together.
  • the catalyst can be synthesized by any suitable chemical technique known in the art.
  • the milled mixture of catalyst and carrier material oxides is deposited on the cordierite Substrate 102 in the form of a Washcoat 104 and then heat treated. This treatment may be performed at about 300° C to about 700° C. In some embodiments this treatment may be performed at about 550° C.
  • the heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours.
  • the Overcoat 106 is prepared following a similar method.
  • FIG 11 shows the light-off test Results 1100 for the ZPGM Catalyst System 100 of example 7.
  • a ZPGM Catalyst System 100 including a ZPGM transition metal catalyst having a cordierite Substrate 102, a Washcoat 104 and an Overcoat 106 is prepared, without including any OSM in Washcoat 104 or Overcoat 106.
  • the Washcoat 104 includes at least silver, and a carrier material oxide such as alumina. There is no OSM in
  • the Overcoat 106 includes at least copper oxide, ceria, and alumina.
  • the silver in Washcoat 104 is present in about 1% to about 20%, or from about 4% to about 10% by weight.
  • the copper and cerium in Overcoat 106 are present in about 5% to about 50% by weight or from about 10% to 16% by weight of Cu and 12% to 20% by weight of Ce.
  • the transition metal (silver) and a carrier material oxide are milled together.
  • the catalyst can be synthesized by any suitable chemical technique known in the art. The milled mixture of catalyst and carrier material oxides is deposited on the cordierite Substrate 102 in the form of a Washcoat 104 and then heat treated.
  • This treatment may be performed at about 300° C to about 700° C. In some embodiments this treatment may be performed at about 550° C.
  • the heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours.
  • the Overcoat 106 is prepared following a similar method.
  • Figure 12 shows the light-off test Results 1200 for the ZPGM Catalyst System 100 of example 8.
  • a ZPGM Catalyst System 100 including a ZPGM transition metal catalyst having a cordierite Substrate 102, a Washcoat 104 and an Overcoat 106 is prepared.
  • the oxygen storage material material present in Overcoat 106 is a mixture of cerium, zirconium and neodymium (CZNd).
  • the silver in Washcoat 104 is present in about 1% to about 20%, or from about 4% to about 10% by weight.
  • the alumina and oxygen storage material included in Overcoat 106 are present in a ratio of about 60% to about 40% by weight.
  • the copper and cerium in Overcoat 106 are present in about 5% to about 50% by weight or from about 10% to 16% by weight of Cu and 12% to 20% by weight of Ce.
  • the transition metal (silver) and a carrier material oxide are milled together.
  • the catalyst can be synthesized by any suitable chemical technique known in the art.
  • the milled mixture of catalyst and carrier material oxides is deposited on the cordierite Substrate 102 in the form of a Washcoat 104 and then heat treated. This treatment may be performed at about 300° C to about 700° C. In some embodiments this treatment may be performed at about 550° C.
  • the heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours.
  • the Overcoat 106 is prepared following a similar method.
  • FIG. 13 shows the light-off test Results 1300 for the ZPGM Catalyst System 100 of example 9.
  • the ZPGM Catalyst System 100 of example 9 Prior to the light of test, the ZPGM Catalyst System 100 of example 9 is aged under dry air condition at 900° C for 4 hours.
  • the hydrocarbon present in the feed stream is toluene. Carbon monoxide, and hydrocarbons conversion are measured as a function of the ZPGM Catalyst System 100 temperature. Since the light-off test is performed under lean condition (R-values ⁇ l), no nitrogen oxide conversion is measured.
  • the test is performed by increasing the temperature from about 100° C to 500° C at a constant rate of 40° C/min.
  • a ZPGM Catalyst System 100 including a ZPGM transition metal catalyst having a cordierite Substrate 102, a Washcoat 104 and no Overcoat 106 is prepared.
  • the oxygen storage material and the alumina may be present in Washcoat 104 in a ratio of 40% to about 60% by weight.
  • the silver in Washcoat 104 is present in about 1% to about 20%, preferably about 4% to about 10% by weight.
  • the amount of lanthanum oxide in alumina may be between 0.1 % and 10 % by weight.
  • the transition metal (silver) and a carrier material oxide are milled together.
  • the catalyst can be synthesized by any suitable chemical technique known in the art.
  • the milled mixture of catalyst and carrier material oxides is deposited on the cordierite Substrate 102 in the form of a Washcoat 104 and then heat treated. This treatment may be performed at about 300° C to about 700° C.
  • This treatment may be performed at about 300° C to about 700° C.
  • this treatment may be performed at about 550° C.
  • the heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours.
  • FIG 14 shows the light-off test Results 1400 for the ZPGM Catalyst System 100 of example 10.
  • a ZPGM Catalyst System 100 including a ZPGM transition metal catalyst having a cordierite Substrate 102, a Washcoat 104 and an Overcoat 106 is prepared.
  • the oxygen storage material material present in Overcoat 106 is a mixture of cerium, zirconium, neodymium, and praseodymium.
  • the silver in Washcoat 104 is present in about 1% to about 20%, or from about 4% to about 10% by weight.
  • the amount of lanthanum oxide in alumina may be between 0.1 % and 10 % by weight.
  • Overcoat 106 are present in a ratio of about 60% to about 40% by weight.
  • the copper and cerium in Overcoat 106 are present in about 5% to about 50% by weight or from about 10% to 16% by weight of Cu and 12% to 20% by weight of Ce.
  • the transition metal (silver) and a carrier material oxide are milled together.
  • the catalyst can be synthesized by any suitable chemical technique known in the art. The milled mixture of catalyst and carrier material oxides is deposited on the cordierite
  • FIG. 15 shows the light-off test Results 1500 for the ZPGM Catalyst System 100 of example 11. Prior to the light of test, the ZPGM Catalyst System 100 of example 11 is aged under dry air condition at 900° C for 4 hours. The hydrocarbon present in the feed stream is toluene.
  • a ZPGM Catalyst System 100 including a ZPGM transition metal catalyst having a cordierite Substrate 102, a Washcoat 104 and an Overcoat 106 is prepared.
  • the oxygen storage material material present in Overcoat 106 is a mixture of cerium, zirconium, neodymium, and praseodymium.
  • the silver in Washcoat 104 is present in about 1% to about 20%, or from about 4% to about 10% by weight.
  • the alumina and oxygen storage material included in Overcoat 106 are present in a ratio of about 60% to about 40% by weight.
  • the copper and cerium in Overcoat 106 are present in about 5% to about 50% by weight or from about 10% to 16% by weight of Cu and 12% to 20% by weight of Ce.
  • Washcoat 104 can be synthesized by any suitable chemical technique known in the art, deposited on the cordierite Substrate 102 and then heat treated.
  • the Overcoat 106 is prepared by co-precipitation. Copper and cerium salts are precipitated with at least one suitable compound. Suitable compounds include NH40H, (NH4)2C03, tetraethylammonium hydroxide, other tetraalkylammonium salts, ammonium acetate, and ammonium citrate. Subsequently, the precipitated transition metal salts are deposited on a Substrate 102 previously coated with Washcoat 104.
  • ZPGM Catalyst System 100 is heat treated, this treatment may be performed at about 300° C to about 700° C. In some embodiments this treatment may be performed at about 550° C. The heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours.
  • FIG 16 shows the light-off test Results 1600 for the ZPGM Catalyst System 100 of example 12.
  • Figure 17 shows the XRD Spectra 1700 of the fresh Overcoat 106 samplesZPGM
  • the XRD analysis is conducted to determine the crystalline phases present in Overcoat 106 materials and to determine the crystallite size of copper oxide.
  • the XRD patterns are measured on a Rigaku® powder diffractometer
  • a ZPGM Catalyst System 100 including a ZPGM transition metal catalyst having a cordierite Substrate 102, a Washcoat 104 and an Overcoat 106 is prepared.
  • the oxygen storage material material present in Overcoat 106 is a mixture of cerium, zirconium, neodymium, and praseodymium.
  • the silver in Washcoat 104 is present in about 1% to about 20%, or from about 4% to about 10% by weight.
  • the alumina and oxygen storage material included in Overcoat 106 are present in a ratio of about 60% to about 40% by weight.
  • the copper and cerium in Overcoat 106 are present in about 5% to about 50% by weight or from about 10% to 16% by weight of Cu and 12% to 20% by weight of Ce.
  • Washcoat 104 can be synthesized by any suitable chemical technique known in the art, deposited on the cordierite Substrate 102 and then heat treated.
  • the Overcoat 106 is prepared by co-milling. Copper and cerium salts are milled with the carrier material oxide, alumina and the OSM. After milling the Overcoat 106 is deposited on a Substrate 102 previously coated with Washcoat 104.
  • ZPGM Catalyst System 100 is then heat treated, this treatment may be performed at about 300° C to about 700° C. In some embodiments this treatment may be performed at about 550° C.
  • the heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours.
  • Figure 18 shows the light-off test Results 1800 for the ZPGM Catalyst System 100 of example 13.
  • Figure 19 shows the XRD Spectra 1900 of the fresh and aged Overcoat 106
  • the XRD spectrum of the fresh sample shows the presence of fluorite structure (filled squares), alumina (A), ceria (C), and CuO (filled diamonds).
  • the XRD pattern of the aged sample shows the presence of fluorite (filled squares), CuAl 2 04 (filled circles), ceria (C), and alumina (A).
  • the fluorite structure is larger in the aged sample as evidenced by the sharper peaks.
  • the XRD spectra of fresh and aged Overcoat 106 samples shows that CuO transfers to CuAl 2 04 spinel phase after aging.
  • the CuO crystallite size for the fresh sample was calculated at about 18 nm and copper dispersion was calculated at about 4.8%.
  • a ZPGM Catalyst System 100 including a ZPGM transition metal catalyst having a cordierite Substrate 102 and a Washcoat 104 and Overcoat 106 is prepared.
  • the Overcoat 106 includes copper, cerium, calcium, a carrier material oxide such as alumina, and an oxygen storage material (which may be a mixture of cerium, zirconium, neodymium and praseodymium) .
  • the oxygen storage material and the alumina may be present in Washcoat 104 in a ratio of 40% to about 60% by weight.
  • Overcoat 106 includes between 5% and 15wt% of copper, between 5% and 15wt% of cerium and between 5% and 15wt% of calcium.
  • the Overcoat 106 is prepared by co-precipitation. Copper, cerium and calcium salts are precipitated with at least one suitable compound.
  • Suitable compounds include NH 4 0H, (NH 4 )2C03, tetraethylammonium hydroxide, other tetraalkylammonium salts, ammonium acetate, and ammonium citrate.
  • the precipitated transition metal salts are deposited on a Substrate 102 previously coated with Washcoat 104.
  • Overcoat 106 is heat treated, this treatment may be performed at about 300° C to about 700° C. In some embodiments this treatment may be performed at about 550° C.
  • the heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours.
  • a ZPGM Catalyst System 100 including a ZPGM transition metal catalyst having a cordierite Substrate 102, a Washcoat 104 and an Overcoat 106 is prepared.
  • Overcoat 106 includes at least copper oxide, ceria, alumina, and one oxygen storage material.
  • the oxygen storage material material present in Overcoat 106 is a mixture of cerium, zirconium, neodymium, and praseodymium.
  • the oxygen storage material and the alumina may be present in Washcoat 104 in a ratio of 40% to about 60% by weight.
  • the calcium in Washcoat 104 is present in about 5% to about 15% by weight.
  • the alumina and oxygen storage material included in Overcoat 106 are present in a ratio of about 60% to about 40% by weight.
  • the copper and cerium in Overcoat 106 are present in about 5% to about 50% by weight or from about 5% to 15% by weight of Cu and 5% to 15% by weight of Ce.
  • the calcium salt is precipitated with at least one suitable compound. Suitable compounds include NH 4 0H, (NH 4 )2C03, tetraethylammonium hydroxide, other tetraalkylammonium salts, ammonium acetate, and ammonium citrate.
  • the precipitated transition metal salts are deposited on a Substrate 102 previously coated with Washcoat 104. Then,
  • Overcoat 106 is heat treated, this treatment may be performed at about 300° C to about 700° C. In some embodiments this treatment may be performed at about 550° C.
  • the heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours.
  • a ZPGM Catalyst System 100 including a ZPGM transition metal catalyst having a cordierite Substrate 102, and Washcoat 104 is prepared.
  • 106 includes at least tin, copper, cerium, a carrier material oxide, an oxygen storage material (which may be a mixture of cerium and zirconium) and alumina.
  • an oxygen storage material which may be a mixture of cerium and zirconium
  • the oxygen storage material and the alumina may be present in
  • Washcoat 104 in a ratio of 40% to about 60% by weight.
  • the tin is present in Overcoat 106 in about 1% to about 10%, or from about 3% to about 6% by weight.
  • the copper and cerium are present in about 5% to about 50% by weight or from about 10% to 16% by weight of Cu and 12% to 20% by weight of Ce.
  • the transition metal salts and a carrier material oxide are milled together.
  • the milled mixture of catalysts and carrier material oxides is deposited on the Substrate 102 previously coated with Washcoat 104 in the form of Overcoat 106 and then heat treated. This treatment may be performed at about 300° C to about 700° C. In some embodiments this treatment may be performed at about 550° C.
  • the heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours.
  • a ZPGM Catalyst System 100 including a ZPGM transition metal catalyst having a cordierite Substrate 102, a Washcoat 104 and an Overcoat 106 is prepared.
  • the Overcoat 106 includes at least calcium, silver, Copper, Cerium a carrier material oxide, an oxygen storage material (which may be a mixture of cerium and zirconium) and alumina.
  • the oxygen storage material material present in Overcoat 106 is a mixture of cerium, zirconium, neodymium, and praseodymium.
  • the oxygen storage material and the alumina may be present in Washcoat 104 in a ratio of 40% to about 60% by weight.
  • the calcium in Overcoat 106 is present in about 5% to about 15% by weight.
  • the silver in Overcoat 106 is present in about 1% to about 20%, or from about 4% to about 10% by weight.
  • Overcoat 106 are present in a ratio of about 60% to about 40% by weight.
  • the copper and cerium in Overcoat 106 are present in about 5% to about 50% by weight or from about 5% to 15% by weight of Cu and 5% to 15% by weight of Ce.
  • the calcium, silver, copper an cerium salts are precipitated with at least one suitable compound. Suitable compounds include NH 4 0H, (NH 4 )2C03, tetraethylammonium hydroxide, other tetraalkylammonium salts, ammonium acetate, and ammonium citrate.
  • the precipitated transition metal salts are deposited on a Substrate 102 previously coated with Washcoat 104.
  • Overcoat 106 is heat treated, this treatment may be performed at about 300° C to about 700° C. In some embodiments this treatment may be performed at about 550° C. The heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours.
  • a ZPGM Catalyst System 100 including a ZPGM transition metal catalyst having a cordierite Substrate 102, a Washcoat 104 and an Overcoat 106 is prepared.
  • the Washcoat 104 includes at least Niobium oxide and zirconium oxide and mixture of metal oxide carrier such as alumina and ceria.
  • the Overcoat 106 includes at least copper oxide, ceria, alumina, and one oxygen storage material.
  • the oxygen storage material material present in Overcoat 106 is a mixture of cerium, zirconium, neodymium, and praseodymium.
  • the oxygen storage material and the alumina may be present in Washcoat 104 in a ratio of 40% to about 60% by weight.
  • the niobium in Washcoat 104 is present in about 10% to about 20% by weight.
  • the zirconium in Washcoat 104 is present in about 30% to about 60% by weight.
  • the alumina and oxygen storage material included in Overcoat 106 are present in a ratio of about 60% to about 40% by weight.
  • the copper and cerium in Overcoat 106 are present in about 5% to about 50% by weight or from about 5% to 15% by weight of Cu and 5% to 15% by weight of Ce.
  • the metal salt solutions are precipitated with at least one suitable compound. Suitable compounds include NH 4 0H, (NH 4 )2C03, tetraethylammonium hydroxide, other tetraalkylammonium salts, ammonium acetate, and ammonium citrate.
  • the precipitated transition metal salts are deposited on a Substrate 102 previously coated with Washcoat 104.
  • Overcoat 106 is heat treated, this treatment may be performed at about 300° C to about 700° C. In some embodiments this treatment may be performed at about 550° C.
  • the heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours.
  • a ZPGM Catalyst System 100 including a mixed metal oxide catalyst having a cordierite Substrate 102, a Washcoat 104 and impregnation is prepared.
  • the impregnation solution includes at least lanthanum, cerium, iron and cobalt. Lanthanum is present in about 10 % to 30 % by weight, cerium is present in about 6% to 20% by weight, iron is present in about 3 % to 15% by weight and cobalt is present in about 5% to 10% by weight.
  • the liquid solution of cobalt salt iron salt is added to the mixture of lanthanum and cerium salts which were already dissolved in dionized water.
  • citric acid is added with a molar ratio of total metal to citric acid of 1:1.5.
  • the pH of mixture is adjusted to approximately neutral condition.
  • the mixture of metal soultion is impregnated to the substare already coated with Washcoat 104.
  • the impregnated catalyst is heat treated, this treatment may be performed at about 700° C.
  • the heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours.
  • the ZPGM Catalyst System 100 of example 19 has a perovskite structure (Lao.8Ceo.2)(Feo.sCoo.5)03.
  • a ZPGM Catalyst System 100 including a mixed metal oxide catalyst having a cordierite Substrate 102, a Washcoat 104 and impregnation is prepared.
  • Washcoat 104 includes at least a carrier metal oxide.
  • the impregnation solution includes at least lanthanum, cerium, iron, manganese and cobalt. Lanthanum is present in about 10 % to 30 % by weight, cerium is present in about 6% to 20% by weight, iron is present in about 3 % to 15% by weight, manganese is present about 4% to 10% by weight, and cobalt is present in about 5% to 10% by weight.
  • citric acid is added with a molar ratio of total metal to citric acid of 1: 1.5.
  • the pH of mixture is adjusted to approximately neutral condition.
  • the mixture of metal solution is impregnated to the Substrate 102 already coated with Washcoat 104.
  • the impregnated catalyst is heat treated, this treatment may be performed at about 700° C.
  • the heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours.
  • the catalyst of example 20 has a mixed phase perovskite and bixbyite structure of La(Feo.6Coo.4)0 3 and FeMn0 3 .
  • a ZPGM Catalyst System 100 including a mixed metal oxide catalyst having a cordierite Substrate 102, a Washcoat 104 and impregnation is prepared.
  • Washcoat 104 includes at least a carrier metal oxide.
  • the impregnation solution includes at least iron and mangase. Iron is present in about 3 % to 15% by weight and mangase is present in about 4% to 10% by weight.
  • To prepare the ZPGM Catalyst System 100 of example 21 the iron salt iron salt is added to manganse salt in dionized water. Subsequently, citric acid is added with a molar ratio of total metal to citric acid of 1: 1.5. The pH of mixture is adjusted to approximately neutral condition. The mixture of metal soultion is impregnated to the substare already coated with Washcoat 104.
  • the impregnated catalyst is heat treated, this treatment may be performed at about 700° C. The heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours.
  • the ZPGM Catalyst System 100 of example 21 has a bixbyite structure Mn1.4Feo.7O3.
  • a ZPGM Catalyst System 100 including a mixed metal oxide catalyst having a cordierite Substrate 102, Washcoat 104 and Overcoat 106 is prepared.
  • Washcoat 104 includes at least a carrier metal oxide.
  • the Overcoat 106 includes at least lanthanum, cerium, iron and cobalt, and a mixed metal oxide carrier such as zirconia and ceria.
  • the Overcoat 106 is heat treated at 700C for 4 hrs.
  • the ZPGM Catalyst System 100 of example 22 has a perovskite structure (Lao.8Ceo.2)(Feo.5Coo.5)0 3 .
  • a ZPGM Catalyst System 100 including a a mixed metal oxide catalyst having a cordierite Substrate 102, Washcoat 104 and Overcoat 106 is prepared.
  • the liquid solution of cobalt salt and iron salt is added to the mixture of manganese, lanthanum and cerium salts which were already dissolved in di-ionized water.
  • citric acid is added with a molar ratio of total metal to citric acid of 1: 1.5.
  • the mixture of metal solution precipitated to the mixed metal oxide carrier with a suitable compounds.
  • the Overcoat 106 slurry is coated to the Substrate 102 already coated with Washcoat 104.
  • Overcoat 106 is heat treated at 700C for 4 hr.
  • the ZPGM Catalyst System 100 of example 23 has a mixed phase perovskite and bixbyite structure of
  • a ZPGM Catalyst System 100 including a ZPGM transition metal catalyst having a metallic Substrate 102, a Washcoat 104 and an Overcoat 106 is prepared.
  • the Substrate 102 has a length of 60mm, a diameter of 40mm and a cell density of 300 cells per square inch (cpsi).
  • the Washcoat 104 includes at least silver, a carrier material oxide such as alumina. There is no OSM in Washcoat 104.
  • the Overcoat 106 includes at least copper oxide, ceria, alumina, and one oxygen storage material.
  • the oxygen storage material material present in Overcoat 106 is a mixture of cerium, zirconium, neodymium, and praseodymium.
  • the silver in Washcoat 104 is present in about 1% to about 20%, or from about 4% to about 10% by weight.
  • Overcoat 106 are present in a ratio of about 60% to about 40% by weight.
  • the copper and cerium in Overcoat 106 are present in about 5% to about 50% by weight or from about 10% to 16% by weight of Cu and 12% to 20% by weight of Ce.
  • the transition metal (silver) and a carrier material oxide are milled together.
  • the catalyst can be synthesized by any suitable chemical technique known in the art. The milled mixture of catalyst and carrier material oxides is deposited on the metallic
  • Substrate 102 in the form of a Washcoat 104 and then heat treated. This treatment may be performed at about 300° C to about 700° C. In some embodiments this treatment may be performed at about 550° C.
  • the heat treatment may last from about 2 to about 6 hours. In an embodiment the treatment may last about 4 hours.
  • the Overcoat 106 is prepared following a similar method.
  • Figure 20 shows light-off test Results 2000 for a fresh sample of the ZPGM Catalyst System 100 of example 24.
  • Figure 21 shows the light-off test Results 2100 for an aged sample of the ZPGM Catalyst System 100 of example 24.
  • the ZPGM Catalyst System 100 of example 34 Prior to the light of test, the ZPGM Catalyst System 100 of example 34 is aged under dry air condition at 900° C for 4 hours.
  • the hydrocarbon present in the feed stream is toluene. Carbon monoxide, and hydrocarbons conversion are measured as a function of the ZPGM Catalyst System 100 temperature. Since the light-off test is performed under lean condition (R-values ⁇ l), no nitrogen oxide conversion is measured.
  • the test is performed by increasing the temperature from about 100° C to 500° C at a constant rate of 40° C/min.

Abstract

L'invention concerne des systèmes de catalyseur ZPGM d'oxydation et des systèmes de catalyseur ZPGM à trois voies. Les systèmes de catalyseur ZPGM peuvent oxyder des gaz toxiques, tels que le monoxyde de carbone et des hydrocarbures, éventuellement certains systèmes de catalyseur ZPGM peuvent également réduire des oxydes d'azote qui peuvent être inclus dans des gaz d'échappement. Les systèmes de catalyseur ZPGM peuvent comprendre : un substrat, une couche d'imprégnation, et une couche de revêtement. La couche d'imprégnation peut comprendre au moins un catalyseur ZPGM et des oxydes de matériau de support. De même, la couche de revêtement peut comprendre au moins un catalyseur ZPGM, des oxydes de matériau de support et des OSM. Des techniques chimiques, des procédés de dépôt et des systèmes de traitement convenables, connus dans la technique, peuvent être utilisés pour former les systèmes de catalyseurs de type ZPGM décrits.
PCT/US2014/055063 2014-09-11 2014-09-11 Procédés d'oxydation et systèmes de catalyseur zpgm à deux voies et à trois voies et appareil les comprenant WO2016039747A1 (fr)

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US9700841B2 (en) 2015-03-13 2017-07-11 Byd Company Limited Synergized PGM close-coupled catalysts for TWC applications
US9951706B2 (en) 2015-04-21 2018-04-24 Clean Diesel Technologies, Inc. Calibration strategies to improve spinel mixed metal oxides catalytic converters
US10533472B2 (en) 2016-05-12 2020-01-14 Cdti Advanced Materials, Inc. Application of synergized-PGM with ultra-low PGM loadings as close-coupled three-way catalysts for internal combustion engines
US9861964B1 (en) 2016-12-13 2018-01-09 Clean Diesel Technologies, Inc. Enhanced catalytic activity at the stoichiometric condition of zero-PGM catalysts for TWC applications
US10265684B2 (en) 2017-05-04 2019-04-23 Cdti Advanced Materials, Inc. Highly active and thermally stable coated gasoline particulate filters
CN113083286A (zh) * 2021-04-08 2021-07-09 安徽元琛环保科技股份有限公司 一种超高温脱硝催化剂的制备方法

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