High temperature ammonia SCR catalyst and method of using the catalyst

• US 8,802,582 B2
• Filed: 03/29/2007
• Issued: 08/12/2014
• Est. Priority Date: 01/09/2007
• Status: Active Grant

• Current Assignee: Catalyst Health Solutions Incorporated (UnitedHealth Group Incorporated)
• Original Assignee: Catalyst Health Solutions Incorporated (UnitedHealth Group Incorporated)
• Inventors: Malyala, Rajashekharam, Golden, Stephen J., Iretskaya, Svetlana
• Primary Examiner(s): WOOD, ELIZABETH D
• Application Number:
  US11/731,570
• Publication Number:
  US 20080167178A1
• Time in Patent Office: 2,693 Days
• Field of Search: 502/63, 502/64, 502/65, 502/66, 502/67, 502/69, 502/71, 502/73, 502/74, 502/75, 423/239.1, 423/239.2
• US Class Current: 502/64
• CPC Class Codes: B01D 2251/2062 Ammonia
• CPC Class Codes: B01D 2255/2065 Cerium
• CPC Class Codes: B01D 2255/20738 Iron
• CPC Class Codes: B01D 2255/407 Zr-Ce mixed oxides
• CPC Class Codes: B01D 2255/502 Beta zeolites
• CPC Class Codes: B01D 2255/504 ZSM 5 zeolites
• CPC Class Codes: B01D 2255/908 O2-storage component incorporated in the catalyst
• CPC Class Codes: B01D 53/9418 for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
• CPC Class Codes: B01J 2229/20 to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
• CPC Class Codes: B01J 23/002 Mixed oxides other than spinels, e.g. perovskite
• CPC Class Codes: B01J 2523/36 Yttrium
• CPC Class Codes: B01J 2523/3706 Lanthanum
• CPC Class Codes: B01J 2523/3712 Cerium
• CPC Class Codes: B01J 2523/48 Zirconium
• CPC Class Codes: B01J 29/061 containing metallic elements added to the zeolite
• CPC Class Codes: B01J 29/072 Iron group metals or copper
• CPC Class Codes: B01J 29/076 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
• CPC Class Codes: B01J 29/40 of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
• CPC Class Codes: B01J 29/405 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
• CPC Class Codes: B01J 29/7007 Zeolite Beta
• CPC Class Codes: B01J 29/7057 : Zeolite Beta
• CPC Class Codes: B01J 29/80 : Mixtures of different zeolites
• CPC Class Codes: B01J 37/0242 : Coating followed by impregnation
• CPC Class Codes: B01J 37/0246 : Coatings comprising a zeolite
• CPC Class Codes: Y02T 10/12 : Improving ICE efficiencies

Abstract

A catalyst and a method for selectively reducing nitrogen oxides (“NO_x”) with ammonia are provided. The catalyst includes a first component comprising a zeolite or mixture of zeolites selected from the group consisting of ZSM-5, ZSM-11, ZSM-12, ZSM-18, ZSM-23, MCM-zeolites, mordenite, faujasite, ferrierite, zeolite beta, and mixtures thereof; a second component comprising at least one member selected from the group consisting of cerium, iron, copper, gallium, manganese, chromium, cobalt, molybdenum, tin, rhenium, tantalum, osmium, barium, boron, calcium, strontium, potassium, vanadium, nickel, tungsten, an actinide, mixtures of actinides, a lanthanide, mixtures of lanthanides, and mixtures thereof; optionally an oxygen storage material and optionally an inorganic oxide. The catalyst selectively reduces nitrogen oxides to nitrogen with ammonia at high temperatures. The catalyst has high hydrothermal stability. The catalyst has high activity for conversion of low levels of nitrogen oxides in exhaust streams. The catalyst and the method may have special application to selective reduction of nitrogen oxides in exhaust gas from gas turbines and gas engines, although the catalyst and the method have broad application to a wide range of gas streams that have excess oxygen and high temperatures. The temperature of exhaust gas from gas turbines and gas engines is high. Both the high temperature and the low levels of inlet NO_x are challenging for selective catalytic reduction (SCR) catalysts.

Claims

1. A catalyst for selective catalytic reduction of nitrogen oxides with ammonia at exhaust temperatures greater than about 300°

C., the catalyst comprising;

a first component comprising a zeolite selected from the group consisting of ZSM-5, zeolite beta, and mixtures thereof, wherein the catalyst comprises about 40 to about 80 weight percent zeolite;

a second component comprising at least one member selected from the group consisting of cerium, iron, manganese, and mixtures thereof;

and about 30 to about 60 weight percent of an oxygen storage material, based on the entire catalyst composition, wherein the oxygen storage material composition comprises Ce_1-c-dZr_cLan_dO₂, where Lan is one or more of Y, La, Pr, Nd, Sm, Eu, Gd, Ho, Yb, the weight percent of the oxygen storage material is on the basis of the oxides in the oxygen storage material;

optionally, an inorganic oxide component;

wherein the catalyst comprises about 5 to about 20 weight percent of the second component, where the weight percentage of the second component is calculated based on the total metal content relative to the total weight of the zeolite, oxygen storage material and any inorganic oxide.

2. The catalyst of claim 1 further comprising an inorganic oxide.

3. The catalyst of claim 1, wherein the catalyst comprises the first component, second component, and oxygen storage material in a 50:

10;

30 ratio based on weight, wherein the weight of the second component is on a metal weight basis.

4. The catalyst of claim 1, wherein the catalyst is a powder.

5. The catalyst of claim 4, wherein about 50 weight percent of the zeolite is present in the powder.

6. The catalyst of claim 1, wherein the zeolite is in a form selected from the group consisting of protonic form, ammonia form, sodium form and mixtures thereof.

7. The catalyst of claim 1, wherein the zeolite comprises ZSM-5.

8. The catalyst of claim 1, wherein the zeolite comprises zeolite beta.

9. The catalyst of claim 1, wherein the zeolite comprises zeolite beta and ZSM-5.

10. The catalyst of claim 9, wherein zeolite beta and ZSM-5 are present in a 1:

1 ratio.

11. The catalyst of claim 1, where the second component comprises cerium.

12. The catalyst of claim 1, where the second component comprises iron.

13. The catalyst of claim 1, wherein the second component comprises manganese.

14. The catalyst of claim 1, wherein the catalyst is extruded in the form of a shape.

15. The catalyst of claim 1, wherein the catalyst is coated on a substrate.

16. The catalyst of claim 15, where the substrate is selected from the group consisting of a refractory material, a ceramic substrate, a honeycomb structure, a porcelain substrate, a metallic substrate, a ceramic foam, a reticulate foam, and mixtures thereof, wherein the catalyst is deposited on the substrate, wherein the substrate has a plurality of channels and a porosity.

17. The catalyst of claim 1, wherein the second component is treated with the first component and mixed with the oxygen storage material to obtain a final catalyst.

18. The catalyst of claim 2, wherein the catalyst comprises about 50 weight percent of the first component, about 10 weight percent of the second component, about 30 weight percent of the oxygen storage material, and about 10 weight percent of the inorganic oxide, wherein the weight percent of the second component is on a metal weight basis.

19. The catalyst of claim 2, wherein the inorganic oxide is selected from the group consisting of Al₂O₃, SiO₂, TiO₂, ZrO₂, SnO₂, composites and mixtures thereof.