Low energy regenerable SO2 scrubbing process

• US 7,214,358 B2
• Filed: 08/13/2003
• Issued: 05/08/2007
• Est. Priority Date: 08/13/2003
• Status: Active Grant

• Current Assignee: Shell Oil Company (Shell Plc)
• Original Assignee: Cansolv Technologies Inc. (Shell Plc)
• Inventors: Sarlis, John Nicolas, Ravary, Patrick M., Parisi, Paul Joseph, Hakka, Leo E.
• Primary Examiner(s): Vanoy; Timothy C.
• Application Number:
  US10/639,678
• Publication Number:
  US 20050034600A1
• Time in Patent Office: 1,364 Days
• Field of Search: 423/242.1, 423/242.2, 423/242.7, 423/243.01, 423/243.11, 423/243.12
• US Class Current: 423/242.1
• CPC Class Codes: B01D 53/1481 Removing sulfur dioxide or sulfur trioxide
• CPC Class Codes: B01D 53/1493 Selection of liquid materials for use as absorbents
• CPC Class Codes: Y02A 50/20 Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

Sulphur dioxide is removed from gas streams by contacting the gas stream with an absorbing medium containing an amine capable of forming an amine salt, heat stable salt and sulfite. The level of heat stable salt is selected such that during the regeneration process of the sulphur dioxide rich amine, the pH of the absorbing medium is at a selected level or below when the level of sulfite in the absorbing medium has been reduced to a specified value. The amine that absorbs the sulphur dioxide has a pKa less than that of sulfite. If the absorbent includes a diamine, then the spent absorbing medium is regenerated under conditions such that at least one amine group remains in salt form.

Claims

1. A cyclic process for the removal of sulphur dioxide from a sulphur dioxide containing gas stream using an amine absorbent medium and for the regeneration of the absorbent medium comprising

a) contacting the gas stream with a lean aqueous absorbing medium containing a sulphur dioxide absorbent to absorb sulphur dioxide from the gas to form a sulphur dioxide lean treated gas stream and spent absorbing medium;

b) steam stripping gaseous sulphur dioxide from the spent absorbing medium at a temperature to form a regenerated aqueous absorbing medium;

c) recovering the gaseous sulphur dioxide;

d) adjusting the level of heat stable salt to maintain the pH of the aqueous absorbing medium during the steam stripping process at 6 or less; and

e) recycling the regenerated aqueous absorbing medium to the contacting step.

2. The process as claimed in claim 1 wherein the pH level is 5 or less.

3. The process as claimed in claim 1 wherein the pH level is determined based on a targeted concentration of total dissolved SO₂ in the regenerated aqueous absorbing medium.

4. The process as claimed in claim 3 wherein the targeted concentration of total dissolved SO₂ in the regenerated aqueous absorbing medium is less than 1.0 wt % based on the total weight of the regenerated aqueous absorbing medium.

5. The process as claimed in claim 3 wherein the targeted concentration of total dissolved SO₂ in the regenerated aqueous absorbing medium is less than 0.5 wt % based on the total weight of the regenerated aqueous absorbing medium.

6. The process as claimed in claim 1 wherein the absorbent is a diamine that is selected so that, in free base form, the diamine has a molecular weight of less than about 300 and the diamine in half salt form has a pKa value for the free nitrogen atom of about 3.0 to about 5.5, the aqueous absorbing medium containing at least 1 mole of water for each mole of sulphur dioxide to be absorbed and having a heat stable salt concentration of greater than 1 equivalents of acid per mole of diamine prior to the lean aqueous absorbing medium contacting the sulphur dioxide containing gas.

7. The process as claimed in claim 1 wherein the absorbent is selected to have a pKa from 3.0 to 5.5 and the selected pH level is 5.5 or less.

8. The process as claimed in claim 1 wherein the absorbent is selected to have a pKa from 3.2 to 5.0 and the selected pH level is 5 or less.

9. The process as claimed in claim 1 wherein the absorbent is selected to have a pKa from 3.5 to 4.5 and the selected pH level is 5 or less.

10. The process as claimed in claim 1 wherein the absorbent has an amine with a lower pKa and an amine with a higher pKa and the aqueous absorbing medium has a heat stable salt concentration to neutralize the amine with a higher pKa prior to the lean aqueous absorbing medium contacting the sulphur dioxide containing gas.

11. The process as claimed in claim 1 wherein the absorbent is a diamine having a weaker amine and a stronger amine and the aqueous absorbing medium has a heat stable salt concentration sufficient to neutralize the stronger amine and a portion of the weaker amine prior to the lean aqueous absorbing medium contacting the sulphur dioxide containing gas.

12. The process as claimed in claim 1 wherein the heat stable salt concentration of the lean aqueous absorbing medium prior to contacting the sulphur dioxide containing gas is selected to be from 1.03 to 1.7 equivalents of acid per mole of diamine.

13. A cyclic process for the removal of sulphur dioxide from a sulphur dioxide containing gas stream using an absorbent medium and for the regeneration of the absorbent medium comprising

a) contacting the gas stream with a lean aqueous absorbing medium containing a water-soluble half salt of a diamine to absorb sulphur dioxide from the gas to form a sulphur dioxide lean treated gas stream and spent absorbing medium, the diamine in free base form having a molecular weight of less than about 300 and the diamine in half salt form having a pKa value for the free nitrogen atom of about 3.0 to about 5.5, the aqueous absorbing medium containing at least 1 mole of water for each mole of sulphur dioxide to be absorbed and having a heat stable salt concentration of greater than 1 equivalents of acid per mole of diamine prior to the lean aqueous absorbing medium contacting the sulphur dioxide containing gas;

b) steam stripping gaseous sulphur dioxide from the spent absorbing medium at a temperature to form a regenerated aqueous absorbing medium;

c) recovering the gaseous sulphur dioxide;

d) recycling the regenerated aqueous absorbing medium to the contacting step

e) adjusting the level of heats stable salts in the aqueous absorbing medium to maintain the pH of the regenerated aqueous absorbing medium at 6 or less during the steam stripping process.

14. The process as claimed in claim 13 wherein the gas stream is contacted with the aqueous absorbing medium at a temperature of from about 10°

to about 60°

C. to absorb sulphur dioxide from the gas stream in amounts of at least about 100 g of sulphur dioxide per kg of absorbing medium, and gaseous sulphur dioxide is stripped from the spent absorbing medium at a temperature of about 50 to about 110°

C. and at least about 30°

C. greater than the contact temperature to form the regenerated aqueous absorbing medium.

15. The process as claimed in claim 13 wherein the heat stable salt concentration of the lean aqueous absorbing medium prior to contacting the sulphur dioxide containing gas is selected to be from 1.03 to 1.7 equivalents of acid per mole of diamine.

16. The process as claimed in claim 13 wherein the heat stable salt concentration of the lean aqueous absorbing medium prior to contacting the sulphur dioxide containing gas is selected to be from 1.05 to 1.45 equivalents of acid per mole of diamine.

17. The process as claimed in claim 13 wherein the heat stable salt concentration of the lean aqueous absorbing medium prior to contacting the sulphur dioxide containing gas is selected to be from 1.1 to 1.3 equivalents of acid per mole of diamine.

18. The process as claimed in claim 13 wherein the heat stable salt concentration is selected to reduce the concentration of sulfur dioxide in the treated gas stream to a selected level.

19. The process as claimed in claim 13 wherein the heat stable salt concentration is selected to reduce steam consumption in the steam-stripping step.

20. The process as claimed in claim 13 wherein the heat stable salt concentration is selected to reduce steam consumption in the steam stripping step to an amount in the range 25 kg steam/kg SO₂ recovered to 2 kg steam/kg SO₂ recovered while producing a sulphur dioxide lean treated gas stream having less than 10 ppm SO₂.

21. The process as claimed in claim 13 wherein the heat stable salt concentration is selected to reduce steam consumption in the steam stripping step to an amount in the range 10 kg steam/kg SO₂ recovered to 2 kg steam/kg SO₂ recovered while producing a sulphur dioxide lean treated gas stream having less than 50 ppm SO₂.

22. The process as claimed in claim 13 wherein the heat stable salt concentration is selected to reduce steam consumption in the steam stripping step to an amount in the range 10 kg steam/kg SO₂ recovered to 2 kg steam/kg SO₂ recovered while producing a sulphur dioxide lean treated gas stream having less than 20 ppm SO₂.

23. The process as claimed in claim 13 wherein the pH level is 5 or less.

24. A method of reducing the concentration of sulfur dioxide in a treated gas stream comprising:

a) contacting a gas stream with an aqueous absorbing medium containing an amine capable of forming an amine salt, heat stable salt and sulfite, the amine having a pKa less than that of sulfite;

b) stripping gaseous sulphur dioxide from the spent absorbing medium at a temperature to form a regenerated aqueous absorbing medium;

c) recovering the gaseous sulphur dioxide;

d) recycling the regenerated aqueous absorbing medium to contacting step (a); and

,

e) adjusting the heat stable salt concentration of the aqueous absorbing medium to have a heat stable salt concentration sufficient to favour dissolved SO₂ being in the form of bisulfite and not sulfite during stripping of gaseous sulphur dioxide from the spent absorbing medium and-the pH of the regenerated aqueous absorbing medium is 6 or less during the steam stripping process.

25. The method as claimed in claim 24 wherein the amine is part of a diamine and the method comprises adjusting the heat stable salt concentration of the aqueous absorbing medium to be greater than 1 equivalents of acid per mole of diamine.

26. The method as claimed in claim 24 wherein the aqueous absorbing medium contains a water-soluble half salt of a diamine to absorb sulphur dioxide from the gas stream to form a sulphur dioxide lean treated gas stream and a spent aqueous absorbing medium, the diamine in free base form having a molecular weight of less than about 300 and the diamine in half salt form having a pKa value for the free nitrogen atom of about 3.0 to about 5.5, the aqueous absorbing medium containing at least 1 mole of water for each mole of sulphur dioxide to be absorbed and comprising less than about 80 wt % of water and the method comprises adjusting the heat stable salt concentration of the aqueous absorbing medium to be from 1.05 equivalents of acid per mole of diamine to 1.45 equivalents of acid per mole of diamine.

27. The method as claimed in claim 24 wherein the method further comprises adjusting the aqueous absorbing medium to have a heat stable salt concentration sufficient such that dissolved SO₂ is at least essentially in the form of bisulfite and not sulfite.

28. The method as claimed in claim 24 wherein the method further comprises adjusting the composition of the aqueous absorbing medium such that the pH of the regenerated aqueous absorbing medium is 5.0 or less.