Removal of carbon dioxide from gas streams

• US 5,587,003 A
• Filed: 03/21/1995
• Issued: 12/24/1996
• Est. Priority Date: 03/21/1995
• Status: Expired due to Fees

• Current Assignee: BOC Group, Inc. (Messer Adolf Family)
• Original Assignee: BOC Group, Inc. (Messer Adolf Family)
• Inventors: Dao, Loc, Fitch, Frank R., Bulow, Martin
• Primary Examiner(s): SPITZER, ROBERT H
• Application Number:
  US08/407,817
• Time in Patent Office: 644 Days
• Field of Search: 62/13, 62/18, 95/117-120, 95/123, 95/139, 95/902
• US Class Current: 95/123
• CPC Class Codes: B01D 2253/108 Zeolites
• CPC Class Codes: B01D 2256/10 Nitrogen
• CPC Class Codes: B01D 2256/12 Oxygen
• CPC Class Codes: B01D 2256/18 Noble gases
• CPC Class Codes: B01D 2256/24 Hydrocarbons
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2259/416 involving cryogenic temperature treatment
• 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: B01D 53/04 with stationary adsorbents B01D53/025 takes precedence
• CPC Class Codes: Y02C 20/40 of CO2
• CPC Class Codes: Y10S 95/902 Molecular sieve

Abstract

Carbon dioxide is removed from a gas stream by passing the gas stream through a bed of natural or synthetic clinoptilolite or their chemically-modified derivatives. The process is particularly advantageous when applied to the removal of ppm levels of carbon dioxide from gas streams at temperatures above 20° C.

Claims

1. A method of removing carbon dioxide from a gas stream selected from oxygen, nitrogen, argon and mixtures of these which contains carbon dioxide at a partial pressure not greater than about 10 mbar as an impurity, comprising subjecting said gas stream to adsorption using clinoptilolite as the adsorbent at a temperature in the range of about 20°

to about 80°

C., thereby adsorbing substantially all of the carbon dioxide from the gas stream.

2. The method of claim 1, wherein the adsorption is part of a process selected from temperature swing adsorption, pressure swing adsorption, vacuum swing adsorption and combinations of these.

3. The method of claim 2, wherein said clinoptilolite has exchangeable cations selected from ions of Group 1A, Group 2A, Group 3A, Group 3B, the lanthanide series and mixtures of these.

4. The method of claim 1 or claim 2, wherein said clinoptilolite is selected from natural clinoptilolite, synthetic clinoptilolite, sodium-exchanged clinoptilolite, potassium-exchanged clinoptilolite, lithium-exchanged clinoptilolite, calcium-exchanged clinoptilolite magnesium-exchanged clinoptilolite, barium-exchanged clinoptilolite, and mixtures of these.

5. The method of claim 1 or claim 2, wherein the adsorption is carried out at a temperature in the range of about 30°

to about 60°

C.

6. The method of claim 5 wherein said gas stream is air.

7. The method of claim 1 or claim 2, additionally comprising, prior to removing carbon dioxide from said gas stream, removing water vapor from the gas stream by passing the gas stream through an adsorbent selected from alumina, silica gel, and mixtures of these.

8. A method of separating air comprising the steps:

(a) prepurifying air containing carbon dioxide at a partial pressure not greater than about 10 mbar by subjecting the air to a temperature swing adsorption process comprising an adsorption step carried out at a temperature in the range of about 20°

to about 80°

C. and an adsorbent regeneration step using clinoptilolite as adsorbent, thereby adsorbing substantially all of the carbon dioxide from the air; and

(b) subjecting the prepurified air to cryogenic distillation, thereby producing high purity nitrogen, high purity oxygen or both of these.

9. The method of claim 8, wherein said adsorbent additionally adsorbs water vapor from said air.

10. The method of claim 8, additionally comprising, prior to step (a), the step of removing water vapor from the air by passing the air through an adsorbent selected from alumina, silica gel and mixtures of these.

11. The method of claim 8, wherein the concentration of carbon dioxide in said air is not greater than about 500 ppm.

12. The method of claim 8, wherein said clinoptilolite is selected from natural clinoptilolite, lithium-exchanged clinoptilolite, calcium-exchanged clinoptilolite and mixtures of these.

13. The method of claim 12, wherein said adsorption step is carried out at a temperature in the range of about 30°

to about 60°

C.