# US 12,179,186 B2 · Layered catalysts composition and catalytic article and methods of manufacturing and using the same > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,179,186 B2 - Document ID: US12179186B2 - Status: Granted - Kind: B2 - Application number: 17/309,746 - Filed: 2019-12-16 - Published: 2022-01-06 - Granted: 2024-12-31 - Earliest claimed: 2018-12-19 - Assignees: BASF Mobile Emissions Catalysts LLC - Applicants: BASF Mobile Emissions Catalysts LLC - Inventors: Xiaolai Zheng; Michel Deeba; Dinh Dang - Web page: https://patentgrep.com/patent/US12179186B2 ## CPC - B01J 35/19: {Catalysts containing parts with different compositions} - B01D 53/945: {characterised by a specific catalyst} - B01J 21/04: Alumina - B01J 23/63: with rare earths or actinides - B01J 23/83: with rare earths or actinides - B01J 35/57: Honeycombs - B01J 37/0244: {Coatings comprising several layers} - B01J 37/0248: {Coatings comprising impregnated particles} - F01N 3/035: with catalytic reactors - F01N 3/101: {Three-way catalysts} - F01N 3/2807: {Metal other than sintered metal (F01N3/2832 and F01N3/2835 take precedence)} - F01N 3/281: {Metallic honeycomb monoliths made of stacked or rolled sheets, foils or plates} - F01N 3/2828: {Ceramic multi-channel monoliths, e.g. honeycombs} - B01D 2255/1023: Palladium - B01D 2255/2065: Cerium - B01D 2255/20753: Nickel - B01D 2255/2092: Aluminium - B01D 2255/9022: Two layers - B01D 2255/908: O2-storage component incorporated in the catalyst - B01J 2523/00: Constitutive chemical elements of heterogeneous catalysts - F01N 2370/02: used in catalytic reactors - F01N 2510/0684: having more than one coating layer, e.g. multi-layered coatings - Y02T 10/12: Improving ICE efficiencies - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28) - F01N: GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES (arrangements in connection with gas exhaust of propulsion units in vehicles B60K13/00; combustion-air intake silencers specially adapted for, or arranged on, internal-combustion engines F02M35/00; protecting against, or damping, noise in general G10K11/16) - Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION ## Abstract The presently claimed invention provides a layered catalytic article comprising a first layer comprising a nickel component and a ceria component, wherein the amount of the nickel component is 1.0 to 50 wt. %, calculated as nickel oxide, based on the total weight of the first layer, and wherein the first layer is essentially free of copper; a second layer comprising a platinum group metal component, an oxygen storage component, and an alumina component, wherein the platinum group metal component comprises platinum, rhodium, palladium, or any combination thereof, and wherein the amount of the platinum group metal component is 0.0 to 5 wt. %, based on the total weight of the second layer; and a substrate. The presently claimed invention also provides a process for preparing the layered catalytic article. It further provides an exhaust system for internal combustion engines comprising a layered catalytic article. ## Claims ### Claim 1 A layered catalytic article comprising: a) a first layer comprising a nickel component supported on a ceria component, wherein the amount of the nickel component ranges from 1.0 wt. % to 50 wt. %, calculated as nickel oxide, based on the total weight of the first layer, and wherein the first layer is essentially free of copper, wherein the amount of copper is <0.001 wt. %, wherein the ceria component comprises ceria having a specific surface area ranging from 15 m2/g to 60 m2/g after calcination at 950° C. for 12 hours in air, and the amount of the ceria component ranges from 20 wt. % to 80 wt. %, based on the total weight of the first layer; b) a second layer comprising a platinum group metal component supported on an oxygen storage component and an alumina component, wherein the platinum group metal component is chosen from a group consisting of platinum, rhodium, palladium, and any combination thereof, and wherein the amount of the platinum group metal component ranges from 0.01 wt. % to 5 wt. %, based on the total weight of the second layer; and c) a substrate, wherein the first or the second layer is deposited as a top layer or bottom layer on a substrate. ### Claim 2 (depends on 1) The layered catalytic article according to claim 1, wherein the amount of the nickel component in the first layer ranges from 10 wt. % to 40 wt. %, calculated as nickel oxide, based on the total weight of the first layer. ### Claim 3 (depends on 1) The layered catalytic article according to claim 1, wherein the ceria component of the first layer comprises a dopant chosen from a group consisting of zirconia, yttria, praseodymia, lanthana, neodymia, samaria, gadolinia, alumina, titania, baria, strontia, and combinations thereof, and wherein the amount of the dopant ranges from 1.0 wt. % to 20 wt. %, based on the total weight of the ceria component. ### Claim 4 (depends on 1) The layered catalytic article according to claim 1, wherein the first layer comprises a transition metal chosen from a group consisting of manganese, iron, zinc, and combinations thereof, and wherein the amount of the transition metal ranges from 1.0 wt. % to 10 wt. %, calculated as the corresponding transition metal oxide, based on the total weight of the first layer. ### Claim 5 (depends on 4) The layered catalytic article according to claim 4, wherein the transition metal is iron, and wherein the amount of iron ranges from 1.0 wt. % to 10 wt. %, calculated as iron oxide, based on the total weight of the first layer. ### Claim 6 (depends on 1) The layered catalytic article according to claim 1, wherein the amount of the platinum group metal component in the second layer ranges from 0.02 wt. % to 1.0 wt. %, based on the total weight of the second layer. ### Claim 7 (depends on 1) The layered catalytic article according to claim 1, wherein the platinum group metal component comprises i) 0.02 wt. % to 1 wt. % rhodium, based on the total weight of the second layer, ii) palladium and rhodium, or iii) platinum and rhodium, and wherein the ratio of palladium or platinum to rhodium ranges from 100:1 to 1:5. ### Claim 8 (depends on 1) The layered catalytic article according to claim 1, wherein the oxygen storage component is chosen from a group consisting of ceria-zirconia, ceria-zirconia-lanthana, ceria-zirconia-yttria, ceria-zirconia-lanthana-yttria, ceria-zirconia-neodymia, ceria-zirconia-praseodymia, ceria-zirconia-lanthana-neodymia, ceria-zirconia-lanthana-praseodymia, ceria-zirconia-lanthana-neodymia-praseodymia, and any combination thereof, wherein the amount of the oxygen storage component ranges from 20 wt. % to 80 wt. %, based on the total weight of the second layer; and wherein the alumina component is chosen from a group consisting of alumina, lanthana-alumina, ceria-alumina, ceria-zirconia-alumina, zirconia-alumina, lanthana-zirconia-alumina, baria-alumina, baria-lanthana-alumina, baria-lanthana-neodymia-alumina, and combinations thereof; wherein the amount of the alumina component ranges from 10 to 80 wt. %, based on the total weight of the second layer. ### Claim 9 (depends on 1) The layered catalytic article according to claim 1, wherein the oxygen storage component comprises ceria content and the ceria content of the oxygen storage component in the second layer ranges from 5 wt. % to 50 wt. %, based on the total weight of the oxygen storage component. ### Claim 10 (depends on 1) The layered catalytic article according to claim 1, wherein the second layer further comprises at least one alkaline-earth metal oxide chosen from a group consisting of barium oxide, strontium oxide, and any combination thereof, and wherein the amount of the alkaline-earth metal oxide ranges from 1 wt. % to 20 wt. %, based on the total weight of the second layer. ### Claim 11 (depends on 1) The layered catalytic article according to claim 1, wherein the first layer is deposited as a bottom layer on the substrate and the second layer is deposited as a top layer on the first layer. ### Claim 12 (depends on 1) The layered catalytic article according to claim 1, wherein the substrate has a flow-through ceramic honeycomb structure, a wall-flow ceramic honeycomb structure, or a metal honeycomb structure. ### Claim 13 (depends on 1) The layered catalytic article according to claim 1, wherein the second layer is deposited as a bottom layer on the substrate and the first layer is deposited as a top layer on the second layer. ### Claim 14 (depends on 1) The layered catalytic article according to claim 1, wherein at least one of the first and the second layer comprises a zonal arrangement comprising a first zone and a second zone, wherein the first or second zone covers from 45% to 90% of the length of the substrate. ### Claim 15 (depends on 1) A process for the preparation of the layered catalytic article according to claim 1, comprising: preparing a bottom layer slurry; depositing the bottom layer slurry on a substrate to obtain a bottom layer; preparing a top layer slurry; and depositing the top layer slurry on the bottom layer to obtain a top layer followed by calcination at a temperature ranging from 400° C. to 700° C., wherein the step of preparing the bottom layer slurry or top layer slurry comprises a technique chosen from a group consisting of incipient wetness impregnation, incipient wetness co-impregnation, and post-addition. ### Claim 16 (depends on 1) An exhaust system for internal combustion engines, comprising: i) the layered catalytic article according to claim 1; and ii) optionally, a platinum group metal based three-way conversion (TWC) catalytic article comprising from 50 g/ft3 to 300 g/ft3 of a platinum group metal chosen from a group consisting of platinum, palladium, rhodium and combinations thereof. ### Claim 17 (depends on 16) The exhaust system according to claim 16, wherein the system comprises a platinum group metal based three-way conversion (TWC) catalytic article and the layered catalytic article, wherein the platinum group metal based three-way conversion (TWC) catalytic article is positioned downstream from an internal combustion engine and the catalytic article is positioned downstream in fluid communication with the platinum group metal based three-way conversion (TWC) catalytic article. ### Claim 18 (depends on 16) The exhaust system according to claim 16, wherein the system comprises a platinum group metal based three-way conversion (TWC) catalytic article and the layered catalytic article, wherein the layered catalytic article is positioned downstream from an internal combustion engine and the platinum group metal based three-way conversion (TWC) catalytic article is positioned downstream in fluid communication with the three-way conversion (TWC) catalytic article. ### Claim 19 (depends on 1, 16) A method of reducing hydrocarbons, carbon monoxide, and nitrogen oxide levels in a gaseous exhaust stream, comprising contacting the gaseous exhaust stream with the layered catalytic article according to claim 1 or an exhaust system according to claim 16 to reduce the levels of hydrocarbons, carbon monoxide, and nitrogen oxide in the exhaust gas. ### Claim 20 A layered catalytic article comprising: a) a first layer comprising a nickel component supported on a ceria component, wherein the amount of the nickel component ranges from 1.0 wt. % to 50 wt. %, calculated as nickel oxide, based on the total weight of the first layer, and wherein the first layer is essentially free of copper, wherein the amount of copper is <0.001 wt. %; b) a second layer comprising a platinum group metal component supported on an oxygen storage component and an alumina component, wherein the platinum group metal component is chosen from a group consisting of platinum, rhodium, palladium, and any combination thereof, and wherein the amount of the platinum group metal component ranges from 0.01 wt. % to 5 wt. %, based on the total weight of the second layer; and c) a substrate, wherein the first or the second layer is deposited as a top layer or bottom layer on a substrate; wherein at least one of the first and the second layer comprises a zonal arrangement comprising a first zone and a second zone, wherein the first or second zone covers from 45% to 90% of the length of the substrate.