Carbon molecular sieves and a process for their preparation and use

• US 4,526,887 A
• Filed: 12/13/1983
• Issued: 07/02/1985
• Est. Priority Date: 03/16/1983
• Status: Expired due to Term

• Current Assignee: Calgon Corporation Route 60 & Campbells Run Road Robinson Township Pennsylvania
• Original Assignee: Calgon Carbon Corporation (Kuraray Company Limited)
• Inventors: Sutt, Robert F. Jr.
• Primary Examiner(s): Garvin, Patrick P.
• Application Number:
  US06/561,005
• Time in Patent Office: 567 Days
• Field of Search: 502/416, 502/420, 502/429, 502/437
• US Class Current: 502/420
• CPC Class Codes: B01D 15/00 Separating processes involving the treatment of liquids with solid sorbents using liquid sorbents B01D11/00; ion exchange processes or materials, sorbent materials in general B01J, e.g. sorbents for chromatography B01J20/281; for investigating or analysing materials G01N30/00; Apparatus therefor
• 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

Abstract

The instant invention is directed to carbon molecular sieves which are capable of separating gas or liquid mixtures containing components of at least two different molecular diameters, molecular weights or molecular shapes, said molecular sieve having an average effective pore diameter of from about 3 to about 20 Angstroms and having specified oxygen diffusivities and selectivity ratios.

The instant invention is also directed to a process for preparing carbon molecular sieves having average effective pore diameters of from about 3 to about 20 Angstroms which comprises continuously feeding an agglomerated naturally occurring substrate to a continuous transport type heating means and calcining said agglomerated substrate in a substantially oxygen-free environment under a cocurrent purge of an inert gas at a temperature range of about 250° to 1100° C. for at least 1 minute.

The instant invention is also directed to the use of the carbon molecular sieves in separating gas or liquid mixtures containing components of at least two different molecular diameters, molecular weights or molecular shapes.

Claims

1. A carbon molecular sieve prepared from a naturally occurring substrate which is capable of separating gas or liquid mixtures containing components of at least two different molecular diameters, molecular weights or molecular shapes, said molecular sieve selected from the group consisting of molecular sieves having an average effective pore diameter of from about 3 to about 20 Angstroms and having:

(a)

(i) an oxygen diffusivity of 800×

10^-8 cm² /sec or less and

(ii) a diffusivity ratio or oxygen to nitrogen of 15 to 100;

(b)

(i) an oxygen diffusivity of 600×

10^-8 cm² /sec or less and

(ii) a diffusivity ratio or oxygen to nitrogen greater than 100;

or

(c)

(i) an oxygen diffusivity greater than 800×

10^-8 cm² /sec and

(ii) a diffusivity ratio of oxygen to nitrogen greater than 5.

2. The carbon molecular sieve of claim 1, having an oxygen diffusivity of 500×

10^-8 to 750×

10^-8 cm² /sec and a diffusivity ratio of oxygen to nitrogen of 15 to 75.

3. The carbon molecular sieve of claim 1, having an oxygen diffusivity of 50×

10^-8 to 500×

10^-8 cm² /sec and a diffusivity ratio of oxygen to nitrogen of 100 to 4000.

4. The carbon molecular sieve of claim 3, having a diffusivity ratio of oxygen to nitrogen of 175 to 1550.

5. The carbon molecular sieve of claim 1, having an oxygen diffusivity of 800×

10^-8 to 3000×

10^-8 cm² /sec and a diffusivity ratio of oxygen to nitrogen of 9 to 4000.

6. The carbon molecular sieve of claim 5, having an oxygen diffusivity of 900×

10^-8 to 2100×

10^-8 cm² /sec and a diffusivity ratio of oxygen to nitrogen of 9 to 25.

7. The carbon molecular sieve of claim 1, having an oxygen diffusivity of greater than 800×

10^-8 cm² /sec, a diffusivity ratio of oxygen to nitrogen greater than 5 and a carbon dioxide diffusivity greater than 200×

10^-8 cm² /sec.

8. The carbon molecular sieve of claim 1, having a an oxygen diffusivity of greater than 800×

10^-8 cm² /sec, a diffusivity ratio of oxygen to nitrogen greater than 5 and a methane diffusivity greater than 0.01×

10^-8 cm² /sec.

9. A process for preparing carbon molecular sieves having average effective pore diameters of from about 3 to about 20 Angstroms which comprises continuously feeding an agglomerated naturally occurring carbonaceous substrate to a continuous transport type heating means and calcining said agglomerated substrate under non-activation conditions and under a purge of an inert gas at a rate of 1.2 to 9.2 feet/minute at a temperature range of about 250°

to 1100°

C. for at least 1 minute.

10. The process of claim 9, wherein said agglomerated carbonaceous substrate is calcined at from 525°

to 975°

C. for from 10 to 60 minutes.

11. The process of claim 9, wherein said agglomerated substrate is a mixture of from 30 to 97 percent coconut char, from 1 to 40 percent thermal binder, from 0 to 20 percent cold binder and from 0 to 40 percent water, all percentages being by weight.

12. The process of claim 11, wherein said thermal binder is selected from the group consisting of coal tar pitch, petroleum pitch, asphalt, bitumin and lignin and said cold binder is starch.

13. The process of claim 9, wherein said agglomerated substrate is a mixture of from 30 to 98 percent decoked coal from 1 to 40 percent thermal binder, from 0 to 20 percent cold binder and from 0 to 40 percent water, all percentages being by weight.

14. The process of claim 13, wherein said thermal binder is selected from the group consisting of coal tar pitch, petroleum pitch, asphalt, bitumin and lignin and said cold binder is starch.

15. The process of claim 9, wherein the cocurrent inert purge gas maintains an atmosphere of less than 10,000 ppm oxygen by volume.

16. The process of claim 9, wherein the agglomerated carbonaceous substrate is dried at from 30°

to 200°

C.

17. The process of claim 9, wherein said purge of an inert gas has a linear velocity of 1.2 to 9.2 feet/minute.

18. The product produced by the process of claim 9.