Methods for preventing formation of sulfuric acid and related products in combustion effluents

• US 4,849,192 A
• Filed: 03/16/1988
• Issued: 07/18/1989
• Est. Priority Date: 04/08/1987
• Status: Expired due to Term

• Current Assignee: Energy & Environmental Research Center (GE Aerospace)
• Original Assignee: Energy & Environmental Research Center (GE Aerospace)
• Inventors: Lyon, Richard K.
• Primary Examiner(s): Heller, Gregory A.
• Application Number:
  US07/169,211
• Time in Patent Office: 489 Days
• Field of Search: 423/235, 423/235 D, 423/239, 423/242 R, 423/242 A
• US Class Current: 423/235
• CPC Class Codes: B01D 53/34 Chemical or biological purification of waste gases
• CPC Class Codes: B01D 53/60 Simultaneously removing sulfur oxides and nitrogen oxides
• CPC Class Codes: Y02A 50/20 Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The present invention is related to a method for preventing the formation of NH₄ HSO₄ during the noncatalytic reduction of nitric oxide by ammonia or ammonia precursors in combustion effluents. The present invention is also related to a method for preventing the formation of H₂ SO₄ in the absence of ammonia or its precursors. The formation of these corrosive substances is extremely detrimental. NH₄ HSO₄ formation is a limitation upon the usefulness of nitric oxide reduction processes, particularly in boilers, furnaces, and other combustion devices. The formation of H₂ SO₄ limits effective heat recovery in combustion equipment.

The present invention specifically teaches the use of methanol to reduce SO₃ in the effluent stream to SO₂. The noncatalytic reduction of SO₃ by methanol is selective in that a large fraction of the SO₃ is converted to SO₂, while on a percentage basis very little oxygen is consumed. In addition, the process of the present invention allows the amount of methanol to be limited such that significant amounts of carbon monoxide are not produced and emitted with the effluent stream. By eliminating SO₃, the formation of NH₄ HSO₄ and H₂ SO₄ can be blocked.

The present invention teaches contacting the methanol with the combustion effluent at a temperature ranging from approximately 500° C. to about 950° C. in order to assure proper operation of the process. It is also important to limit the reaction time used so that the carbon monoxide produced by the methanol oxidation is not itself oxidized to carbon dioxide.

Claims

1. A process for minimizing the formation of H₂ SO₄ in a combustion effluent having NO, at least 1 ppm SO₃, and water vapor, the process comprising the step of contacting the combustion effluents with methanol, in an amount such that the mole ratio of the methanol to the sum of NO and SO₃ is in the range of from about 0.8 to about 2.0, at a temperature in the range from about 500°

C. to about 950°

C., said methanol reducing the SO₃ in the combustion effluent to SO₂, thereby minimizing the formation of H₂ SO₄.

2. A process as defined in claim 1 wherein the environment comprises at least 50 ppm SO_x.

3. A process as defined in claim 1 wherein the methanol injected comprises less than approximately 1,000 ppm of the total combustion effluents.

4. A process as defined in claim 1 wherein the methanol injected comprises less than approximately 500 ppm of the total combustion effluents.

5. A process as defined in claim 1 wherein the ratio of moles of methanol to the sum of moles of NO and SO₃ is in the range of from approximately 0.9 to approximately 1.5.

6. A process as defined in claim 1 wherein the temperature of the combustion effluents at the point of contacting the methanol is at least 900°

C. and wherein the period between the time at which the methanol is introduced into the effluents and the time in which the effluents cool to below 900°

C. is no greater than approximately 0.05 seconds.

7. A process as defined in claim 1 wherein the temperature of the combustion effluents at the point of contacting with methanol is between approximately 800°

C. and approximately 900°

C. and wherein the period between the time at which the methanol is introduced into the effluents and the time when the effluents cool to below 800°

C. is no greater than approximately 0.2 seconds.

8. A method of reducing SO₃ to SO₂ in a stream of combustion effluents, wherein the stream of effluents is at a temperature between approximately 500°

C. and approximately 950°

C. and wherein the stream of effluents comprises at least 50 ppm SO_x, water, and NO, comprising the step of introducing methanol into the stream of effluents such that the ratio of moles of methanol to the sum of the moles of SO₃ and NO is in the range of from approximately 0.8 to approximately 2.0.

9. A method of reducing SO₃ to SO₂ in a stream of combustion effluents as defined in claim 8 wherein the methanol is in liquid form.

10. A method of reducing SO₃ to SO₂ in a stream of combustion effluents as defined in claim 8 wherein the methanol is atomized and propelled into the stream of effluents by a jet of gas.

11. A method of reducing SO₃ to SO₂ in a stream of combustion effluents as defined in claim 10 wherein the jet of gas comprises ammonia.

12. A method of reducing SO₃ to SO₂ in a stream of combustion effluents as defined in claim 8 wherein the ratio of moles of methanol to the sum of the moles of NO and SO₃ is in the range of from approximately 0.8 to approximately 1.5.

13. A method of reducing SO₃ to SO₂ in a stream of combustion effluents as defined in claim 8 wherein the temperature of the combustion effluents at the point of contacting the methanol is at least 900°

C. and wherein the period between the time at which the methanol is introduced into the effluents and the time in which the effluent is cooled to below 900°

C. is no greater than approximately 0.05 seconds.

14. A method of reducing SO₃ to SO₂ in a stream of combustion effluents as defined in claim 8 wherein the temperature of the combustion effluents at the point of contacting with methanol is between approximately 800°

C. and approximately 900°

C. and wherein the period between the time at which the methanol is introduced into the effluent and the time when the effluents cool to below 800°

C. is no greater than approximately 0.2 seconds.

15. A method of reducing SO₃ to SO₂ in a stream of combustion effluents as defined in claim 8 wherein the methanol introduced into the stream of effluents comprises less than approximately 1000 ppm of the total combustion effluents.

16. A method of reducing SO₂ to SO₃ in a stream of combustion effluents as defined in claim 8 wherein the methanol introduced into the stream of effluents comprises less than approximately 500 ppm of the total combustion effluents.

17. A method for preventing the formation of H₂ SO₄ by reducing SO₃ to SO₂ in a stream of combustion effluents wherein the stream of combustion effluents comprises at least 1 ppm SO₃, NO, and water vapor wherein the temperature of the stream of effluents is between approximately 500°

C. and approximately 950°

C. comprising introducing methanol into the stream of effluents such that the ratio of the moles of methanol to the sum of the moles of SO₃ and NO is in the range of approximately 0.8 to approximately 1.5.

18. A method for preventing the formation of H₂ SO₄ as defined in claim 17 wherein the temperature of the combustion effluents is at least 900°

C. and wherein the period between the time at which the methanol is introduced into the effluents and the time when the effluents cool to below 900°

C. is no greater than approximately 0.05 seconds.

19. A method for preventing the formation of H₂ SO₄ as defined in claim 17 wherein the temperature of the combustion effluents is between approximately 800°

C. and approximately 900°

C. and wherein the period between the time at which the methanol is introduced into the effluents and the time when the effluents cool to below 800°

C. is no greater than approximately 0.2 seconds.

20. A process for removing SO₃ a precursor of H₂ SO₄, in a combustion effluent having NO, at least 1 ppm SO₃ and water vapor, the process comprising the step of contacting the combustion effluent with methanol in an amount such that the mole ratio of methanol to the sum of NO and SO₃ is in the range of from about 0.8 to about 2.0, at a temperature in the range from about 500°

C. to about 950°

C., said methanol contacting the combustion effluent in order to reduce the SO₂ to SO₃, thereby minimizing the formation of H₂ SO₄, the methanol being present in an amount insufficient to increase the amount of CO formed to unacceptable emission levels by the oxidation of methanol.

21. A process for removing SO₃, a precursor of H₂ SO₄, in a combustion effluent as defined in claim 20 wherein the methanol injected comprises less than approximately 1,000 ppm of the total combustion effluents.

22. A process for removing SO₃ a precursor of H₂ SO₄, in a combustion effluent as defined in claim 20 wherein the ratio of moles of methanol to the sum of the moles of NO and SO₃ is in the range of from approximately 0.9 to approximately 1.5 such that the production of CO is minimized.

23. A process for removing SO₃, a precursor of H₂ SO₄, in a combustion effluent as defined in claim 20 wherein the temperature of the combustion effluents at the point of contacting the methanol is at least 900°

C. and wherein the period between the time at which the effluents cool to below 900°

C. is no greater than approximately 0.05 seconds.

24. A process for removing SO₃, a precursor of H₂ SO₄, in a combustion effluent as defined in claim 20 wherein the temperature of the combustion effluents at the point of contacting with methanol is between approximately 800°

C. and approximately 900°

C. and wherein the period between the time at which the methanol is introduced into the effluents and the time when the effluents cool to below 800°

C. is no greater than approximately 0.2 seconds.