# US 2018/0021724 A1 · COATED ARTICLES HAVING HIGH KNOx/KSOx RATIOS FOR SELECTIVE CATALYTIC REDUCTION

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- Number: US 2018/0021724 A1
- Document ID: US20180021724A1
- Status: Published application
- Kind: A1
- Application number: 15/694,051
- Filed: 2017-09-01
- Published: 2018-01-25
- Earliest claimed: 2014-06-02
- Assignees: Johnson Matthey Public Limited Company
- Applicants: Johnson Matthey Public Limited Company
- Inventors: Paul Joseph ANDERSEN; Maria BRANDMAIR; Silvia Alcove CLAVE; Rodney FOO; Bruce GOMERSALL; Michael NASH; Alison Mary WAGLAND
- Web page: https://patentgrep.com/patent/US20180021724A1

## CPC

- 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 23/28: Molybdenum
- B01J 23/30: Tungsten
- B01J 23/92: of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J 37/0215: {Coating}
- B01J 37/0225: {of metal substrates}
- B01J 37/0232: {by pulverisation}
- B01J 37/0234: {Impregnation and coating simultaneously}
- B01J 37/0244: {Coatings comprising several layers}
- B01J 38/00: Regeneration or reactivation of catalysts, in general
- B01J 38/485: {Impregnating or reimpregnating with, or deposition of metal compounds or catalytically active elements}
- B01D 53/88: Handling or mounting catalysts
- B01D 53/96: Regeneration, reactivation or recycling of reactants
- B01D 2251/2062: Ammonia
- B01D 2255/20707: Titanium
- B01D 2255/20723: Vanadium
- B01D 2255/20769: Molybdenum
- B01D 2255/20776: Tungsten
- B01D 2255/2092: Aluminium
- B01D 2255/30: Silica
- B01D 2255/40: Mixed oxides
- B01D 2255/9202: Linear dimensions
- B01D 2258/012: Diesel engines and lean burn gasoline engines
- B01D 2258/0283: Flue gases
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 2523/00: Constitutive chemical elements of heterogeneous catalysts
- B01J 2523/41: Silicon
- 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)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

Articles comprising a catalyst film comprising VOx, MoO3 or WO3, and TiO2 deposited on a substrate are disclosed. The articles are useful for selective catalytic reduction (SCR) of NOx in exhaust gases. Methods for producing such articles deposit a catalyst film on the substrate to form a coated substrate, which is then calcined. When used in an SCR process, the coated articles have enhanced activity for NOx conversion, reduced activity for SOx conversion, or both. Light-weight, coated articles having high catalyst loads can be fabricated at the same or reduced dimensions when compared with laminated articles, and increased kNOx/kSOx ratios are available even from coated articles having relatively thin catalyst films. The articles should have particular value for power plant operations, where coal and high-sulfur fuels are commonly used and controlling sulfur trioxide generation is critical.

## Claims

### Claim 1

An article comprising:
(a) a substrate; and
(b) a film deposited on the substrate;
wherein the film comprises VOx, MoO3 or WO3, and TiO2, and the article catalyzes the conversion of nitrogen oxides in a gas containing nitrogen oxides.

### Claim 2 (depends on 1)

The article of claim 1, wherein the film comprises 0.1 to 5 wt. % of VOx, 0.5 to 20 wt. % of MoO3 or WO3, and 75 to 99.4 wt. % of TiO2.

### Claim 3 (depends on 1)

The article of claim 1, wherein the film comprises 0.5 to 2 wt. % of VOx, 1 to 10 wt. % of MoO3 or WO3, and 88 to 98.5 wt. % of TiO2.

### Claim 4 (depends on 1)

The article of claim 1, wherein the film has a thickness of from about 20 μm to about 500 μm.

### Claim 5 (depends on 1)

The article of claim 1, wherein the film has a thickness of from about 50 μm to about 150 μm.

### Claim 6 (depends on 1)

The article of claim 1, wherein the substrates a monolith or a plate.

### Claim 7 (depends on 1)

The article of claim 1, the article having less mass and at least one of: (a) enhanced activity for NOx conversion at a temperature between 350° C. and 400° C.; and (b) reduced activity for SOx conversion at a temperature between 380° C. and 430° C., compared with an article of similar dimensions and composition.

### Claim 8 (depends on 1)

The article of claim 1, wherein the article also catalyzes the conversion of SOx in a gas containing SOx and the conversions of NOx and SOx occur at rates kNOx and kSOx, respectively, and the ratio of kNOx/kSOx is from 0.22 to 0.30.

### Claim 9

An article comprising:
(a) a substrate;
(b) a used catalyst on the surface of a substrate; and
(c) a film deposited over the used catalyst;
wherein the film deposited over the used catalyst comprises VOx, MoO3 or WO3, and TiO2 and the article catalyzes the conversion of nitrogen oxides in a gas containing nitrogen oxides.

### Claim 10

An article comprising:
(a) a substrate; and
(b) a film deposited on the substrate;
wherein the film comprises: (i) VOx or a VOx precursor, (ii) MoO3, a MoO3 precursor, WO3, aWO3 precursor or a mixture thereof, and (iii) TiO2 or a TiO2 precursor, and the article, upon calcination, catalyzes the conversion of nitrogen oxides in a gas containing nitrogen oxides.

### Claim 11 (depends on 10)

The article of claim 10, wherein the film comprises 0.1 to 5 wt. % of VOx or a VOx precursor, 0.5 to 20 wt. % of MoO3, a MoO3 precursor, WO3, aWO3 precursor or a mixture thereof, and 75 to 99.4 wt. % of TiO2 or a TiO2 precursor.

### Claim 12 (depends on 10)

The article of claim 10, wherein the film comprises 0.5 to 2 wt. % of VOx or a VOx precursor, 1 to 10 wt. of MoO3, a MoO3 precursor, WO3, aWO3 precursor or a mixture thereof, and 88 to 98.5 wt. % of TiO2 or a TiO2 precursor.

### Claim 13 (depends on 10)

The article of claim 10, wherein the film has a thickness of from about 20 μm to about 500 μm.

### Claim 14 (depends on 10)

The article of claim 10, wherein the film has a thickness of from about 50 μm to about 150 μm.

### Claim 15 (depends on 10)

The article of claim 10, wherein the substrate is a monolith or a plate.

### Claim 16

An article comprising:
(a) a substrate; and
(b) a used catalyst on the surface of a substrate; and
(c) a film deposited over the used catalyst;
wherein the film comprises: (i) VOx or a VOx precursor, (ii) MoO3, a MoO3 precursor, WO3, aWO3 precursor or a mixture thereof, and (iii) TiO2 or a TiO2 precursor.

### Claim 17 (depends on 16)

The article of claim 16, wherein the film comprises 0.1 to 5 wt. % of VOx or a VOx precursor, 0.5 to 20 wt. % of MoO3, a MoO3 precursor, WO3, aWO3 precursor or a mixture thereof, and 75 to 99.4 wt. % of TiO2 or a TiO2 precursor.

### Claim 18 (depends on 16)

The article of claim 16, wherein the film comprises 0.5 to 2 wt. % of VOx, 1 to 10 wt. % of MoO3 or WO3, and 88 to 98.5 wt. % of TiO2.

### Claim 19 (depends on 16)

The article of claim 16, wherein the film has a thickness of from about 20 μm to about 500 μm.

### Claim 20 (depends on 16)

The article of claim 16, wherein the film has a thickness of from about 50 μm to about 150 μm.

### Claim 21 (depends on 16)

The article of claim 16, wherein the substrate is a monolith or a plate.

### Claim 22

A method for producing an article having selective catalytic reduction activity, the method comprising:
(a) forming a coated substrate by depositing a catalyst film comprising: (i) VOx or a VOx precursor, (ii) MoO3, a MoO3 precursor, WO3, aWO3 precursor or a mixture thereof, and (iii) TiO2 or a TiO2 precursor, onto a substrate, and
(b) calcining the coated substrate.

### Claim 23

A method for producing a selective catalytic reduction catalyst from a used SCR article, the method comprising:
(a) removing particulates from a used article comprising a substrate and a used catalyst on the substrate;
(b) forming a coated substrate by depositing a catalyst film comprising: (i) VOx or V2Ox precursor, (ii) MoO3, a MoO3 precursor, WO3, aWO3 precursor or a mixture thereof, and (iii) TiO2 or a TiO2 precursor onto a substrate, and
(c) calcining the coated substrate.

### Claim 24 (depends on 1)

A process for selectively reducing nitrogen oxides in a gaseous mixture, the method comprising contacting a gaseous mixture comprising nitrogen oxides with a reductant in the presence of an article of claim 1.

### Claim 25 (depends on 24)

The process of claim 24, wherein the process provides at least one of: (a) enhanced activity for NOx conversion at a temperature between 350° C. and 400° C.; and (b) reduced activity for SOx conversion at a temperature between 380° C. and 430° C.