IP Library Granted Patent US 7,718,153
Granted Patent B2
US 7,718,153 · App. 12/122,116 · Granted May 18, 2010

Catalytic process for control of NO

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Quick Facts
Patent No.
US 7,718,153
App. No.
12/122,116
Granted
May 18, 2010
Kind
B2
Abstract

A selective catalytic reduction process with a palladium catalyst for reducing NOx in a gas, using hydrogen as a reducing agent. A zirconium sulfate (ZrO 2 )SO 4 catalyst support material with about 0.01-2.0 wt. % Pd is applied to a catalytic bed positioned in a flow of exhaust gas at about 70-200° C. The support material may be (ZrO 2 —SiO 2 )SO 4 . H 2 O and hydrogen may be injected into the exhaust gas upstream of the catalyst to a concentration of about 15-23 vol. % H 2 O and a molar ratio for H 2 /NO x in the range of 10-100. A hydrogen-containing fuel may be synthesized in an Integrated Gasification Combined Cycle power plant for combustion in a gas turbine to produce the exhaust gas flow. A portion of the fuel may be diverted for the hydrogen injection.

Claims (37)

1. A process for selective catalytic reduction of nitrogen oxides (NOx) in a gas stream using H2, comprising contacting the gas stream with a catalyst comprising (ZrO2)SO4 and palladium,

wherein the catalyst further comprises tungsten.

2. A process according to claim 1 , wherein a tungsten loading of the catalyst is between 0.5 and 5 wt. %.

3. A process according to claim 1 wherein the catalyst further comprises SiO2.

4. A process according to claim 3 wherein a mass ratio of SiO2 to (ZrO2+SiO2) in the catalyst is between 0.05 and 0.90.

5. A process according to claim 3 wherein a mass ratio of SiO2 to (ZrO2+SiO2) in the catalyst is between 0.25 and 0.50.

6. A process according to claim 1 wherein the palladium loading of the catalyst is between 0.01 and 2.0 wt %.

7. A process according to claim 1 wherein the atomic S/Zr ratio of the catalyst is between 0.01 and 0.15.

8. A process according to claim 1 , wherein a catalyst bed comprising the catalyst is installed in a flow path of an exhaust gas stream of a gas turbine, wherein the exhaust gas stream comprises NOx, H2O, O2, and SO2.

9. A process according to claim 8 wherein H2O and hydrogen are injected into the exhaust gas between the gas turbine and the catalytic bed, to a concentration of about 5-25 vol. % H2O and a molar ratio for H2/NOx in the range of 10 to 100 in the exhaust gas.

10. A process of claim 8 wherein the process comprises passing the exhaust gas over the catalytic bed at a temperature between 70-250° C.

11. A process according to claim 8 , wherein the exhaust gas is passed over the catalytic bed at a temperature maintained in a range of 110-140° C.

12. A process according to claim 8 , wherein the catalyst bed is installed in the flow path of exhaust gas of the gas turbine in an integrated gasification combined cycle (IGCC) power generation plant that synthesizes a hydrogen-containing fuel for the gas turbine, and further comprising:

diverting a portion of the hydrogen-containing fuel to supply the H2 as a NOx reducing agent;

injecting water and the diverted portion of the hydrogen-containing fuel into the exhaust gas between the gas turbine and the catalytic bed to a concentration of about 15-25 vol. % H2O and a molar ratio for H2/NOx in the range of 10-100 in the exhaust gas; and

passing the exhaust gas over the catalytic bed at a temperature between 70-250° C.

13. A process according to claim 12 , wherein the H2O is injected to a concentration of about 17-21 vol. %.

14. A system for implementing a process for selective catalytic reduction of nitrogen oxides (NOx) in an exhaust gas from a gas turbine in an integrated gasification combined cycle power plant, comprising:

a fuel gas synthesizer that produces a fuel gas containing at least 10 vol. % H2 and at least 10 vol. % nitrogen;

a gas turbine that burns a portion of the fuel gas, producing the exhaust gas;

a catalytic bed installed in a flow path of the exhaust gas, the catalytic bed comprising a catalyst comprising (ZrO2)SO4 and palladium;

a hydrogen injector that mixes a diverted portion of the fuel gas into the exhaust gas between the gas turbine and the catalytic bed;

an H2O injector that mixes H2O into the exhaust gas between the gas turbine and the catalytic bed; and

sensors and valves at control points in the system connected to a controller that maintains operational conditions in the exhaust gas at the catalytic bed, wherein the operational conditions comprise a temperature between 70-250° C., a molar ratio for H2/NOx in the range of 10-100, and H2O at a concentration of about 15-23 vol. %.

15. A system for implementing a process according to claim 14 , wherein the catalyst further comprises SiO2, and a mass ratio of SiO2 to (ZrO2+SiO2) in the catalyst is between 0.25 and 0.50.

16. A system for implementing a process according to claim 15 , wherein the catalyst further comprises a tungsten loading of between 0.5 and 5 wt. %.

17. A system for implementing a process according to claim 16 , wherein a palladium loading of the catalyst is between 0.01 and 2.0 wt. %.

18. A process for selective catalytic reduction of nitrogen oxides (NOx) in a gas stream using a hydrogen reducing agent, comprising:

preparing a catalyst on a catalyst bed, wherein the catalyst comprises Pd/W(ZrO2-SiO2)SO4, wherein a ratio of SiO2 to (ZrO2+SiO2) in the catalyst is 25 to 50 wt %, a proportion of Pd in the catalyst is 0.3 to 1.1 wt %, an atomic S/Zr ratio of the catalyst is 0.01 to 0.15, and a tungsten loading of the catalyst is 0.5 to 5 wt %;

positioning the catalyst bed in an exhaust stream of a gas turbine;

injecting the hydrogen reducing agent into the exhaust stream upstream of the catalyst bed to a molar ratio for H2/NOx in the exhaust stream in the range of 20-100;

injecting H2O into the exhaust stream upstream of the catalyst bed to maintain an H2O concentration in the exhaust stream of about 15-23 vol. %; and

passing the exhaust stream over the catalyst bed at an operating temperature range of 70-250° C.

19. The process of claim 18 , wherein the gas turbine is installed in an integrated gasification combined cycle plant (IGCC), and further comprising:

producing a hydrogen-containing fuel in a gasifier of the IGCC for the gas turbine;

diverting a portion of the hydrogen-containing fuel as the hydrogen reducing agent; and

cooling the exhaust stream to the operating temperature range of the catalyst bed by means of a heat recovery steam generator in the IGCC, wherein a lower bound of the operating temperature range is established above a dewpoint in the exhaust stream.

Assignments (3)
CONFIRMATORY LICENSE Recorded Mar 22, 2010
From: SIEMENS ENERGY, INC.
To: ENERGY, UNITED STATES DEPARTMENT OF
Reel/Frame 024115/0316 →
CHANGE OF NAME Recorded Mar 31, 2009
From: SIEMENS POWER GENERATION, INC.
To: SIEMENS ENERGY, INC.
Reel/Frame 022488/0630 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 20, 2008
From: SOBOLEVSKIY, ANATOLY; ROSSIN, JOSEPH A.; KNAPKE, MICHAEL J.
To: SIEMENS POWER GENERATION, INC.
Reel/Frame 020970/0344 →