# US 8,465,714 B2 · Catalyst promoters in vanadium-free mobile catalyst > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,465,714 B2 - Document ID: US8465714B2 - Status: Granted - Kind: B2 - Application number: 13/406,098 - Filed: 2012-02-27 - Published: 2012-06-28 - Granted: 2013-06-18 - Earliest claimed: 2009-02-16 - Assignees: Cristal USA Inc. - Applicants: Steven M. Augustine - Inventors: Steven M. Augustine - Web page: https://patentgrep.com/patent/US8465714B2 ## CPC - B01J 21/066: {Zirconium or hafnium; Oxides or hydroxides thereof} - B01D 53/8628: {Processes characterised by a specific catalyst} - B01D 53/9418: {for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas} - B01J 21/063: {Titanium; Oxides or hydroxides thereof} - B01J 23/002: {Mixed oxides other than spinels, e.g. perovskite} - B01J 23/34: Manganese - B01J 37/03: Precipitation; Co-precipitation - B01D 2251/2062: Ammonia - B01D 2255/20707: Titanium - B01D 2255/20715: Zirconium - B01D 2255/2073: Manganese - B01D 2255/30: Silica - B01D 2255/40: Mixed oxides - B01D 2257/404: Nitrogen oxides other than dinitrogen oxide - B01J 2523/00: Constitutive chemical elements of heterogeneous catalysts - 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) ## Abstract Low temperature activity of a vanadium-free selective catalytic reduction catalyst is provided by a mixed metal oxide support containing oxides of titanium and zirconium, the support having a promoter deposited on the surface of the mixed metal oxide support, and further having an active catalyst component deposited over the promoter on the mixed metal oxide support surface. Suitable promoters include oxides of silicon, boron, aluminum, cerium, iron, chromium, cobalt, nickel, copper, tin, silver, niobium, lanthanum, titanium, and combinations thereof. Suitable active catalyst components include oxides of manganese, iron and cerium. ## Claims ### Claim 1 A catalyst composition comprising: a mixed metal oxide support containing oxides of titanium and zirconium and having a mixed metal oxide support surface; a promoter selected from the group consisting of oxides of silicon, boron, aluminum, cerium, iron, chromium, cobalt, nickel, copper, tin, silver, niobium, lanthanum, titanium, and combinations thereof, wherein the promoter is deposited on the mixed metal oxide support surface prior to any calcination of the mixed metal oxide support surface, providing a promoter-containing support surface; and an active catalyst component selected from the group consisting of oxides of manganese, iron and cerium, the active catalyst component deposited on the promoter-containing support surface prior to any calcination of the promoter-containing support surface. ### Claim 2 (depends on 1) The catalyst composition of claim 1, wherein the mixed metal oxide support consists essentially of oxides of titanium and zirconium, the promoter is present in an amount of from about 0.01 wt % to about 15 wt % of the mixed metal oxide, and the active catalyst component consists essentially of manganese oxide. ### Claim 3 (depends on 1) The catalyst composition of claim 1, wherein the mixed metal oxide support is essentially free from vanadium. ### Claim 4 (depends on 3) The catalyst composition of claim 3, wherein the molar ratio of titanium oxide to zirconium oxide in the mixed metal oxide support is in the range of from about 60:40 to about 90:10. ### Claim 5 (depends on 3) The catalyst composition of claim 3, wherein the mixed metal oxide support has a crystalline inner core surrounded by an amorphous metal oxide shell. ### Claim 6 (depends on 5) The catalyst composition of claim 5, wherein the crystalline inner core comprises an oxide selected from the group consisting of anatase, rutile, srilankite, and mixtures thereof, and wherein the promoter is present in an amount of from about 0.01 wt % to about 15 wt % of the mixed metal oxide. ### Claim 7 (depends on 6) The catalyst composition of claim 6, wherein the amorphous metal oxide shell is enriched in zirconium relative to the crystalline inner core. ### Claim 8 (depends on 6) The catalyst composition of claim 6, wherein titanium is deposited on an outer portion of the amorphous metal oxide shell to form a titanium-containing mixed metal oxide support surface. ### Claim 9 (depends on 6) The catalyst composition of claim 6, wherein the mixed metal oxide support surface consists essentially of an outer portion of the amorphous metal oxide shell. ### Claim 10 (depends on 1) The catalyst composition of claim 1, wherein the promoter is silicon oxide. ### Claim 11 (depends on 1) The catalyst composition of claim 1, wherein the promoter is boron oxide. ### Claim 12 A method of making a catalyst for selective catalytic reduction of nitrogen oxide, the method comprising the following steps: contacting a mixed metal oxide support with promoter precursors, the mixed metal oxide support containing titanium oxide and zirconium oxide and having a surface, thereby depositing the promoter on the mixed metal oxide support surface, prior to any calcination of the mixed metal oxide support surface, to form a promoter-containing support surface, the promoter selected from the group consisting of oxides of boron, silicon, aluminum, cerium, iron, chromium, cobalt, nickel, copper, tin, silver, niobium, lanthanum, titanium, and combinations thereof, the promoter present in a range of from about 0.01 wt % to about 15 wt % of the mixed metal oxide; and depositing an outer layer of an active catalyst component onto the promoter-containing support surface, prior to any calcination of the promoter-containing support surface, wherein the active catalyst component is selected from the group consisting of manganese oxide, iron oxide and cerium oxide, and the active catalyst component is present in an amount in a range of from about 0.05 mol % to about 20 mol % of the mixed metal oxide support. ### Claim 13 (depends on 12) The method of claim 12, wherein the promoter contains silicon oxide and the active catalyst component is manganese oxide. ### Claim 14 (depends on 12) The method of claim 12, wherein the mixed metal oxide support is prepared by precipitating titanium and zirconium from an aqueous solution. ### Claim 15 (depends on 12) The method of claim 12 wherein the mixed metal oxide support is provided by precipitating titanium and zirconium oxides from an aqueous solution containing dissolved titanium and zirconium, wherein the precipitation is encouraged by increasing the pH to a range of from about 5 to about 10, and wherein the resulting mixed metal oxide has a TiO2:ZrO2 molar ratio in a range of from about 70:30 to about 85:15. ### Claim 16 (depends on 14) The method of claim 14, further comprising the step of depositing titanium onto the mixed metal oxide support surface from an aqueous solution containing a dissolved compound selected from the group consisting of titanyl sulfate, titanyl chloride, titanium tetrachloride, titanium oxalate, titanium tetraiodide and mixtures thereof. ### Claim 17 (depends on 16) The method of claim 16 wherein titanium is deposited in an amount in a range of from about 0.1 wt % to about 10 wt % of the mixed metal oxide support. ### Claim 18 (depends on 14) The method of claim 14, wherein the promoter is an oxide of silicon and the silicon oxide is deposited onto the mixed metal oxide support surface from an aqueous solution containing a soluble silicon compound. ### Claim 19 (depends on 18) The method of claim 18, wherein the soluble silicon compound is selected from the group consisting of tetramethyl ammonium silicate, tetramethyl ammonium silicate, tetraethyl orthosilicate, tetramethyl orthosilicate, alkali sililcates, alkaline earth silicates, and silicic acid. ### Claim 20 (depends on 14) The method of claim 14, further comprising the step of depositing titanium onto the mixed metal oxide support surface from an aqueous solution containing a dissolved titanium-containing compound to form a titanium-containing mixed metal oxide support surface, and wherein the step of depositing a promoter comprises depositing silicon oxide onto the titanium-containing mixed metal oxide support surface from an aqueous solution containing a soluble silicon compound. ### Claim 21 (depends on 20) The method of claim 20, wherein the titanium-containing compound is selected from the group consisting of titanyl sulfate, titanyl chloride, titanium tetrachloride, titanium oxalate, titanium tetraiodide and mixtures thereof. ### Claim 22 (depends on 14) The method of claim 14, wherein the promoter is an oxide of boron and the boron oxide is deposited onto the mixed metal oxide support surface from an aqueous solution containing a soluble boron compound. ### Claim 23 (depends on 22) The method of claim 22, wherein the soluble boron compound is selected from the group consisting of boron nitrate, boric acid, boracic acid, and boron chloride. ### Claim 24 A method for improving the low temperature conversion activity of manganese-containing mixed metal oxide catalysts used for selective catalytic reduction of nitrogen oxides with ammonia, the method comprising: providing a mixed metal oxide support containing titanium oxide and zirconium oxide; and depositing a promoter onto a surface of the mixed metal oxide support, prior to any calcination of the mixed metal oxide support surface, the promoter selected from the group consisting of oxides of silicon, boron, aluminum, cerium, iron, chromium, cobalt, nickel, copper, tin, silver, niobium, lanthanum, titanium, and combinations thereof, thereby forming a promoter-containing mixed metal oxide support surface; and depositing manganese oxide onto the promoter-containing mixed metal oxide support surface prior to any calcination of the promoter-containing mixed metal oxide support surface; wherein the quantities of promoter and manganese oxide deposited are controlled to provide low temperature catalytic activity. ### Claim 25 (depends on 24) The method of claim 24, wherein the promoter contains silicon oxide. ### Claim 26 A method for selective reduction of nitrogen oxides with ammonia, wherein the nitrogen oxides are present in a gas stream, the method comprising: contacting the gas stream with ammonia in the presence of a catalyst, the catalyst comprising: a mixed metal oxide support containing oxides of titanium and zirconium; and a promoter selected from the group consisting of oxides of silicon, boron, aluminum, cerium, iron, chromium, cobalt, nickel, copper, tin, silver, niobium, lanthanum, and combinations thereof, the promoter deposited on a surface of the mixed metal oxide support, prior to any calcination of the mixed metal oxide support surface, to provide a promoter-containing mixed metal oxide support surface; and an active catalyst component deposited on the promoter-containing mixed metal oxide support surface prior to any calcination of the promoter-containing mixed metal oxide support surface, wherein the active catalyst component is selected from the group consisting manganese oxide, iron oxide and cerium oxide. ### Claim 27 (depends on 26) The method of claim 26, wherein the promoter contains silicon oxide and the active catalyst component is manganese oxide.