Carbon molecular sieves and a process for their preparation and use

• US 4,528,281 A
• Filed: 03/16/1983
• Issued: 07/09/1985
• Est. Priority Date: 03/16/1983
• Status: Expired due to Term

• Current Assignee: Calgon Carbon Corporation (Kuraray Company Limited)
• Original Assignee: Calgon Carbon Corporation (Kuraray Company Limited)
• Inventors: Sutt, Robert F. Jr.
• Primary Examiner(s): Garvin, Patrick P.
• Application Number:
  US06/475,796
• Time in Patent Office: 846 Days
• Field of Search: 502/402, 502/413, 502/416, 502/417, 502/418, 502/423, 502/425, 502/401
• US Class Current: 502/402
• 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 20/0266 Compounds of S
• CPC Class Codes: B01J 20/20 comprising free carbon; comprising carbon obtained by carbonising processes
• CPC Class Codes: B01J 20/26 Synthetic macromolecular compounds
• CPC Class Codes: B01J 20/261 obtained by reactions only involving carbon to carbon unsaturated bonds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds per se C08F
• CPC Class Codes: B01J 20/262 obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds per se C08G
• CPC Class Codes: B01J 20/264 derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
• CPC Class Codes: B01J 20/267 Cross-linked polymers
• CPC Class Codes: B01J 20/28004 Sorbent size or size distribution, e.g. particle size
• CPC Class Codes: B01J 20/28014 characterised by their form
• CPC Class Codes: B01J 20/3021 Milling, crushing or grinding
• CPC Class Codes: B01J 20/3028 Granulating, agglomerating or aggregating
• CPC Class Codes: B01J 20/3078 Thermal treatment, e.g. calcining or pyrolizing
• CPC Class Codes: B01J 20/3204 Inorganic carriers, supports or substrates
• CPC Class Codes: B01J 20/3268 Macromolecular compounds
• CPC Class Codes: B01J 20/327 Polymers obtained by reactions involving only carbon to carbon unsaturated bonds
• CPC Class Codes: B01J 20/3272 Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
• CPC Class Codes: B01J 20/3276 Copolymers
• CPC Class Codes: B01J 20/3282 Crosslinked polymers
• CPC Class Codes: B01J 20/3287 : Layers in the form of a liquid
• CPC Class Codes: B01J 2220/485 : Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss

Abstract

The instant invention is directed to a molecular sieve comprising a carbonaceous substrate selected from the group consisting of molecular sieve carbon, calcined coconut char, oxidized and devolatilized agglomerated coal, calcined agglomerated coal and calcined agglomerated coconut char, impregnated with an organic polymer having a molecular weight of at least 400, as determined by vapor phase osmometry, or with an inorganic polymer at a dosage of at least 0.001 weight percent (based on the substrate weight) up to a maximum dosage which still allows the resulting sieve to separate gas or liquid mixtures containing components of at least two different molecular diameters, molecular weights or molecular shapes.

The instant invention is also directed to a process for preparing the molecular sieve and to a process for using it to separate gas or liquid mixtures.

Claims

1. A molecular sieve comprising a carbonaceous substrate selected from the group consisting of molecular sieve carbon;

calcined char and calcined agglomerated char selected from the group consisting of coconut, peach pits, walnut shells, babassu nut shells, and cherry pits;

oxidized and devolatilized agglomerated coal; and

calcined agglomerated coal;

impregnated with an organic polymer having a molecular weight of at least 400, as determined by vapor phase osmometry, or with an inorganic polymer at a dosage of at least 0.001 weight percent (based on the substrate weight) up to a maximum dosage which still allows the resulting sieve to separate gas or liquid mixtures containing components of at least two different molecular diameters, molecular weights or molecular shapes.

2. The molecular sieve of claim 1, wherein said organic or inorganic polymer is selected from the group consisting of:

polyamides, polyureas, polyurethanes, polyesters, condensation polymers, addition polymers, diene polymers, triene polymers, cyclic polyamides, cyclic polyesters, cyclic poly ethers, silicone polymers, polymerized phosphonitrilic chloride, sulfur polymers, polymerized sulfur nitride, polyphenylene ethers, cross-linked polyesters, phenol formaldehyde resins, epoxy resins, polyethylene glycol, acrylic emulsion polymers or copolymers, asphalt emulsion polymers, and silicates.

3. The molecular sieve of claim 1, wherein said polymeric impregnant is charred at from 250°

to 1100°

C.

4. The molecular sieve of claim 3, wherein said impregnant is charred at from 500°

to 1000°

C.

5. The molecular sieve of claim 1, wherein said carbonaceous substrate has a high percentage of micropores having an Angstrom size of less than 20.

6. The molecular sieve of claim 5, wherein at least 90 percent of said substrate'"'"'s micropores are less than 20 Angstroms.

7. The molecular sieve of claim 1, wherein said carbonaceous substrate is a carbon molecular sieve.

19. The molecular sieve of claim 1, wherein said molecular sieve, after impregnation, has an oxygen/nitrogen selectivity of at least 5.

8. A molecular sieve comprising a carbonaceous substrate selected from the group consisting of molecular sieve carbon;

calcined char and calcined agglomerated char selected from the group consisting of coconut, peach pits, walnut shells, babassu nut shells, and cherry pits;

oxidized and devolatilized agglomerated coal; and

calcined agglomerated coal;

impregnated with an organic polymer having a molecular weight of at least 400, as determined by vapor phase osmometry, or with an inorganic polymer at a dosage of 0.001 to 10.0 weight percent (based on the substrate weight).

9. The molecular sieve of claim 8, wherein the weight percent of said polymer is from 0.001 to 5.0.

10. The molecular sieve of claim 9, wherein the weight percent of said polymer is from 0.01 to 1.0.

20. The molecular sieve of claim 8, wherein said molecular sieve, after impregnation, has an oxygen/nitrogen selectivity of at least 5.

11. A process for preparing a molecular sieve, comprising impregnating a carbonaceous substrate selected from the group consisting of molecular sieve carbons;

calcined char and calcined agglomerated char selected from the group consisting of coconut, peach pits, walnut shells, babassu nut shells, and cherry pits;

oxidized and devolatilized agglomerated coal; and

calcined agglomerated coal with an organic polymer having a molecular weight of at least 400, as determined by vapor phase osmometry, or with an inorganic polymer at a dosage of at least 0.001 weight percent (based on the substrate weight) up to a maximum dosage which still allows the resulting sieve to separate gas or liquid mixtures containing components of at least two different molecular diameters, molecular weights or molecular shapes.

12. The process of claim 11, which further comprises charring said polymer, subsequent to impregnation, at from 250°

C. to 1100°

C.

13. The process of claim 12, wherein said charring is at from 500°

C. to 1000°

C.

14. The process of claim 11, wherein said carbonaceous substrate has a high percentage of micropores having an Angstrom size of less than 20.

15. The process of claim 11, wherein said organic polymer or inorganic polymer is selected from:

polyamides, polyureas, polyurethanes, polyesters, condensation polymers, addition polymers, diene polymers, triene polymers, cyclic polyamides, cyclic polyesters, cyclic poly ethers, silicone polymers, polymerized phosphonitrilic chloride, sulfur polymers, polymerized sulfur nitride, polyphenylene ethers, cross-linked polyesters, phenol formaldehyde resins, epoxy resins, polyethylene glycol, acrylic amulsion polymers or copolymers, and asphalt emulsion polymers.

16. The process of claim 11, wherein said carbonaceous substrate is a carbon molecular sieve.

21. The process of claim 11, wherein said molecular sieve, after impregnation, has an oxygen/nitrogen selectivity of at least 5.

17. A process for preparing a molecular sieve, comprising impregnating a carbonaceous substrate selected from the group consisting of molecular sieve carbon;

calcined char and calcined agglomerated char selected from the group consisting of coconut, peach pits, walnut shells, babassu nut shells, and cherry pits;

oxidized and devolatilized agglomerated coal; and

calcined agglomerated coal;

with an organic polymer having a molecular weight of at least 400, as determined by vapor phase osmometry, at a dosage of 0.001 to 5.0 weight percent (based on the substrate weight).

18. The process of claim 17, wherein the weight percent of the polymeric impregnant is from 0.01 to 1.0.

22. The process of claim 17, wherein said molecular sieve, after impregnation, has an oxygen/nitrogen selectivity of at least 5.