Carbon dioxide removal using aminated carbon molecular sieves

• US 4,810,266 A
• Filed: 02/25/1988
• Issued: 03/07/1989
• Est. Priority Date: 02/25/1988
• Status: Expired due to Fees

• Current Assignee: Alliedsignal Inc. (Honeywell International Inc.)
• Original Assignee: Alliedsignal Inc. (Honeywell International Inc.)
• Inventors: Chang, Chin-Hsiung, Oroskar, Anil R., Zinnen, Hermann A.
• Primary Examiner(s): Spitzer, Robert
• Application Number:
  US07/160,442
• Time in Patent Office: 376 Days
• Field of Search: 55/68, 55/74, 55/75, 55/387, 55/389, 423/229, 423/230, 502/437
• US Class Current: 95/139
• CPC Class Codes: B01D 2253/25 Coated, impregnated or composite adsorbents
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 53/02 by adsorption, e.g. preparative gas chromatography solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01
• CPC Class Codes: B01J 20/20 comprising free carbon; comprising carbon obtained by carbonising processes
• CPC Class Codes: Y02C 20/40 of CO2
• CPC Class Codes: Y10S 95/903 Carbon

Abstract

Acid gases such as carbon dioxide are removed from air or other gases using a unique carbon-based material. The material is a carbon molecular sieve prepared from oxygen-free precursors carbonized in the absence of oxygen. The pores of the material are then enlarged as by high temperature steaming. Alcohol amines are then used to impart an amine functionality to the materials. A gas to be treated is contacted with this material at room temperature and atmospheric pressure, with the adsorbed gas being released by heating to a moderate temperature.

Claims

1. A method of removing an acid gas from a vapor which comprises contacting the vapor and adsorbing at an acid gas adsorption-promoting conditions with an adsorbent which is manufactured by a method which comprises:

(a) polymerizing a cross-linking agent and a precursor monomer, with both the cross-linking agent and the monomer being essentially free of molecular oxygen, and producing a cross-linked polymer;

(b) shaping a quantity of the polymer into an article having a desired configuration;

(c) carbonizing the resultant shaped article in a substantially oxygen-free environment and converting polymer into carbon molecular sieves;

(d) increasing the pore volume of the carbonized article by contact with steam at 600-1000 degrees C.; and

,

(e) contacting the carbonized article with a dihydric alcohol amine compound.

2. The method of claim 1 further characterized in that a bulk or solution method of polymerization is employed in the cross-linking step.

3. The method of claim 1 further characterized in that the carbonization step is performed in the substantial absence of oxygen.

4. The method of claim 3 further characterized in that the monomer is a vinyl chloride monomer.

5. The method of claim 4 further characterized in that divinyl benzene is employed as the cross-linking agent.

6. The method of claim 3 further characterized in that the monomer is vinylidene chloride.

7. The method of claim 3 further characterized in that the shaped article is held at a temperature above 800 degrees C. for at least one hour during the carbonization step.

8. The method of claim 7 further characterized in that the weight of the article is reduced by at least 60 percent during the carbonization step.

9. The method of claim 8 further characterized in that the weight of the article is reduced by at least an additional 20 percent during step (d).

10. The method of claim 9 further characterized in that the amine compound is a diethanol amine.

11. The method of claim 10 further characterized in that the acid gas is carbon dioxide.

12. The method of claim 1 further characterized in that the acid gas is carbon dioxide.

13. A method of removing carbon dioxide from a gas comprising water, nitrogen and oxygen which comprises contacting the gas and adsorbing carbon dioxide at adsorption promoting conditions with a shaped product comprising a homogeneous molecular sieve material which is made by a series of steps which comprises:

(a) performing a bulk polymerization of an oxygen-free monomer in the presence of an oxygen-free cross-linking agent, and producing free flow granules of a cross-linked polymer;

(b) producing shaped articles from the granules without the use of a binder material;

(c) carbonizing the resultant shaped articles in a substantially oxygen-free environment in the presence of an inert gas;

(d) reducing the mass of the shaped articles by 25-75 wt. % by contact with steam at an elevated temperature; and

,

(e) contacting the carbonized articles with a mono or dihydric alcohol amine compound under conditions which result in the shaped product containing from about 20 to about 65 weight percent dihydric alcohol amine.

14. The method of claim 13 further characterized in that the monomer is vinylidene chloride.

15. The method of claim 13 further characterized in that the shaped articles are held at a temperature above 800 degrees C. for at least one hour during the carbonization step.

16. The method of claim 13 further characterized in that the dihydric alcohol amine compound is diethanol amine.

17. An adsorbent comprising a secondary amine functionalized carbon support, which carbon support is produced by a series of steps comprising:

(a) performing a polymerization of a monomer in the presence of a cross-linking agent, and producing free flowing granules of a substantially oxygen-free cross-linked polymer;

(b) producing shaped articles from the granules without the use of a binder material;

(c) carbonizing the resultant shaped articles in a substantially oxygen-free environment in the presence of an inert gas;

(d) reducing the mass of the shaped articles by 25-75 wt. % by contact with steam at an elevated temperature; and

,

(e) contacting the shaped particles with a secondary amine under conditions which produce the functionalized carbon support.

18. The adsorbent of claim 17 further characterized in that the shaped articles are held at a temperature above 800 degrees C. for at least one hour during the carbonization step.

19. The adsorbent of claim 18 further characterized in that the mass of the shaped articles is reduced by contact with steam at a temperature of about 750-950 degrees C. for from 10 minutes to 3 hours.

20. The adsorbent of claim 19 further characterized in that the monomer is polymerized via a bulk polymerization.

21. The adsorbent of claim 20 further characterized in that the monomer is a vinyl chloride monomer, and the carbon support is functionalized by contact with a dihydric alcohol amine.

22. The adsorbent of claim 17 further characterized in that the carbon support is functionalized by contact with diethanol amine.

23. The adsorbent of claim 17 further characterized in that the adsorbent contains from about 20 to about 65 weight percent of a dihydric alcohol amine.

24. The adsorbent of claim 23 further characterized in that the adsorbent contains about 40 to about 60 weight percent diethanol amine.