Gas separation process

• US 8,383,072 B2
• Filed: 06/05/2009
• Issued: 02/26/2013
• Est. Priority Date: 06/05/2008
• Status: Expired due to Fees

• Current Assignee: Callaghan Innovation
• Original Assignee: Industrial Research Limited
• Inventors: Smedley, Stuart, Materic, Vlatko, Henderson, Carolyn Mary
• Primary Examiner(s): McCracken, Daniel C
• Assistant Examiner(s): Berns, Daniel
• Application Number:
  US12/996,501
• Publication Number:
  US 20110158874A1
• Time in Patent Office: 1,362 Days
• Field of Search: 423/220, 423/225, 423/230, 423/430, 423/432, 423/635, 423/636, 423/637, 423/640
• US Class Current: 423/230
• CPC Class Codes: B01D 2251/402 of magnesium
• CPC Class Codes: B01D 2251/404 of calcium
• CPC Class Codes: B01D 2251/602 Oxides
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2258/0283 Flue gases
• CPC Class Codes: B01D 53/1475 Removing carbon dioxide
• CPC Class Codes: B01D 53/62 Carbon oxides
• CPC Class Codes: B01D 53/96 Regeneration, reactivation or recycling of reactants
• CPC Class Codes: B01J 20/041 Oxides or hydroxides
• CPC Class Codes: Y02A 50/20 Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
• CPC Class Codes: Y02C 20/40 of CO2

Abstract

A process for the separation of carbon dioxide from gas mixtures is disclosed in which a metal oxide sorbent, which is used to capture and release carbon dioxide, is recycled. The process incorporates the regeneration of the carbon dioxide capture capacity of the metal oxide to maintain a high capture capacity over many cycles. The regeneration involves hydrating the metal oxide and then heating the resulting metal hydroxide under a gas atmosphere that is effective to suppress the dehydration of the hydroxide so that dehydration occurs at an elevated temperature. The regeneration may also be used independently from the carbon dioxide separation process to produce, from a metal hydroxide, a metal oxide having an enhanced resistance to attrition and fragmentation.

Claims

1. A process for separating CO₂ from a first gas stream comprising CO₂, the process comprising the steps of:

(a) calcining an alkaline earth metal carbonate to generate an alkaline earth metal oxide and produce a first product gas stream comprising CO₂;

(b) contacting the alkaline earth metal oxide with the first gas stream to carbonate the alkaline earth metal oxide and regenerate the alkaline earth metal carbonate;

(c) calcining the alkaline earth metal carbonate regenerated in step (b) to regenerate the alkaline earth metal oxide and produce a second product gas stream comprising CO₂;

(d) optionally repeating steps (b) and (c) using the alkaline earth metal oxide regenerated in step (c);

(e) contacting the alkaline earth metal oxide regenerated in step (c) with water to form an alkaline earth metal hydroxide;

(f) heating the alkaline earth metal hydroxide in a second gas stream comprising CO₂ to a temperature that is higher than the normal decomposition temperature for the alkaline earth metal hydroxide;

(g) dehydrating the alkaline earth metal hydroxide to regenerate the alkaline earth metal oxide;

(h) optionally repeating steps (e) to (g) using the alkaline earth metal oxide regenerated in step (g);

(i) contacting the alkaline earth metal oxide regenerated in step (g) with a third gas stream comprising CO₂ to carbonate the alkaline earth metal oxide and regenerate the alkaline earth metal carbonate;

(j) optionally repeating steps (c) to (i) using the alkaline earth metal carbonate regenerated in step (i); and

(k) repeating steps (a) to (c), (e) to (g), and (i), and one or more of steps (d), (h), and (j) when performed, using the alkaline earth metal carbonate regenerated in step (i).

2. A process as claimed in claim 1, wherein, in step (f), the alkaline earth metal hydroxide is heated in the second gas stream comprising CO₂ to a temperature and for a time and at a concentration of CO₂ effective to suppress the dehydration of the alkaline earth metal hydroxide and reduce the attrition and fragmentation rates, compared to those that would otherwise occur, of the alkaline earth metal oxide formed upon dehydration of the alkaline earth metal hydroxide.

3. A process as claimed in claim 1, wherein the alkaline earth metal oxide is contacted with water vapor to form the alkaline earth metal hydroxide.

4. A process as claimed in claim 3, wherein the alkaline earth metal oxide is contacted with water vapor at a temperature from 100°

C. to 400°

C.

5. A process as claimed in claim 1, wherein the temperature in step (f) is at least about 50°

C. higher than the normal decomposition temperature for the alkaline earth metal hydroxide.

6. A process as claimed claim 1, wherein the temperature in step (f) is from 500°

C. to 600°

C.

7. A process as claimed in claim 1, wherein the temperature in step (f) is maintained constant for a period of time.

8. A process as claimed in claim 1, wherein the total time spent by the alkaline earth metal hydroxide at a temperature that is higher than the normal decomposition temperature for the alkaline earth metal hydroxide is at least about 10 minutes.

9. A process as in claim 1, wherein the alkaline earth metal hydroxide is heated to a temperature from 500°

C. to 800°

C. to dehydrate the alkaline earth metal hydroxide and regenerate the alkaline earth metal oxide.

10. A process as claimed in claim 1, wherein the alkaline earth metal hydroxide is dehydrated in a fourth gas stream to regenerate the alkaline earth metal oxide.

11. A process as claimed in claim 1, wherein at least one step of the process is performed in one or more fluidized or moving bed.

12. A process as claimed in any claim 1, wherein the alkaline earth metal oxide is selected from:

CaO;

MgO; and

mixtures thereof.

13. A process as claimed in claim 12, wherein the alkaline earth metal oxide is CaO.

14. A process as claimed in claim 1, wherein the alkaline earth metal oxide retains an average CO₂ absorption capacity of at least about 40%, measured with respect to the initial capacity, after 75 calcinations.

15. A process as claimed in claim 1, wherein the alkaline earth metal oxide retains an average CO₂ absorption capacity of at least about 315 g CO₂/kg metal oxide after 75 calcinations.

16. A process as claimed in claim 1, wherein the second gas stream comprises 5% to 100% CO₂.

17. A process as claimed in claim 16, wherein the second gas stream comprises 20% to 100% CO₂.

18. A process as claimed in claim 16, wherein the second gas stream comprises 30% to 100% CO₂.

19. A process as claimed in claim 16, wherein the second gas stream comprises 37.5% to 100% CO₂.

20. A process for separating CO₂ from a first gas stream comprising CO₂, the process comprising the steps of:

(a) contacting an alkaline earth metal oxide with the first gas stream to carbonate the alkaline earth metal oxide and form an alkaline earth metal carbonate;

(b) calcining the alkaline earth metal carbonate to regenerate the alkaline earth metal oxide and produce a product gas stream comprising CO₂;

(c) repeating steps (a) and (b) using the alkaline earth metal oxide regenerated in step (b);

(d) contacting the alkaline earth metal oxide regenerated in step (b) with water to form an alkaline earth metal hydroxide;

(e) heating the alkaline earth metal hydroxide in a second gas stream comprising CO₂ to a temperature that is higher than the normal decomposition temperature for the alkaline earth metal hydroxide;

(f) dehydrating the alkaline earth metal hydroxide in a third gas stream to regenerate the alkaline earth metal oxide; and

(g) repeating steps (a) to (f) using the alkaline earth metal oxide regenerated in step (f).

21. A process as claimed in claim 20, wherein step (e) comprises heating the alkaline earth metal hydroxide to a temperature that is at least about 50°

C. higher than the normal decomposition temperature for the alkaline earth metal hydroxide.