Cellulose acetate butyrate gas separation membranes

• US 5,096,468 A
• Filed: 06/29/1990
• Issued: 03/17/1992
• Est. Priority Date: 10/19/1987
• Status: Expired due to Term

• Current Assignee: W R Grace & Company - CONN (WR Grace & Company)
• Original Assignee: W R Grace & Company - CONN (WR Grace & Company)
• Inventors: Minhas, Bhupender S.
• Primary Examiner(s): SPITZER, ROBERT H
• Application Number:
  US07/547,549
• Time in Patent Office: 627 Days
• Field of Search: 55/16, 55/68, 55/158, 55/70, 210/500.29, 210/500.30, 264/455, 264/48, 264/49, 264/345, 264/346, 264/DIG. 14
• US Class Current: 95/51
• CPC Class Codes: B01D 53/22 by diffusion manufacturing semi-permeable membranes B01D67/00; form, structure or properties of semi-permeable membranes B01D69/00; material for semi-permeable membranes B01D71/00
• CPC Class Codes: B01D 71/18 Mixed esters, e.g. cellulose acetate-butyrate
• CPC Class Codes: C01C 1/0476 Purge gas treatment, e.g. for removal of inert gases or recovery of H2
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts

Abstract

High performance cellulose acetate butyrate gas separation membranes are prepared from a casting solution containing from about 10 to 30 percent polymer, 35 to 70 percent solvent, and 15 to 30 percent pore-forming agents. A film casting solution is cast onto a substantially flat support surface and a dense layer is formed on the exposed film surface. The film is gelled, washed, and dried to produce a particularly useful gas separation membrane. The cellulose acetate polymers used in this preparation have molecular weights of at least about 20,000, and have about 10 to about 45% butyryl groups, about 2 to about 35% acetyl groups, and about 0.8 to about 2 percent hydroxyl groups, by weight. The membranes may be used for separating a feed gas into a permeate fraction and a residual fraction, and are particularly useful for separating gases in the purge gas stream of ammonia plants to recover a permeate which is relatively rich in hydrogen. Cellulose acetate butyrate membranes may be used to improve the separation of ammonia plant purge gases which contain ammonia as well as hydrogen and nitrogen, especially when there is no pretreatment of the purge gas to remove ammonia gas.

Claims

1. A process for using a gas separation membrane to separate a feed gas stream having at least two components into a permeate fraction which passes through the membrane and is relatively rich in at least one of the feed gas components and residual fraction which does not pass through the membrane and is relatively depleted in at least one of the feed gas components wherein the gas separation membrane comprises a cellulose acetate butyrate polymer having the formula:

##STR2## in which;

R each independently is OH, OOCCH₃, and OOCCH₂ CH₂ CH₃ such that the weight percent of the OOCCH₂ CH₂ CH₃ groups in the polymer is about 10 to 45, the weight percent of OOCCH₃ groups in the polymer is about 2 to about 35, and the weight percent of OH groups in the polymer is about 0.8 to about 2; and

n is selected so that the number average molecular weight of the polymer is at least about 20,000; and

provided that the membrane has a carbon dioxide permeability of at least about 5 SCFH per ft² per 100 psi and a carbon dioxide to methane separation factor of at least about 21.

2. A process of claim 1 wherein the gas separation membrane has a carbon dioxide permeability of at least about 10 SCFH per ft² per 100 psi and a carbon dioxide to methane separation factor of at least about 25.

3. A process of claim 2 wherein the feed gas comprises at least 0.5 volume percent ammonia.

4. A process of claim 1 wherein the cellulose acetate butyrate has a number average molecular weight between about 40,000 and 250,000.

5. A process of claim 1 wherein the weight percent of OOCCH₂ CH₂ CH₃ groups in the polymer is about 15 to 40, the weight percent of OOCCH₃ groups in the polymer is about 10 to 30, or the weight percent of OH groups in the polymer is about 1.5 to 1.8.

6. A process of claim 1 wherein the feed gas stream comprises at least 0.5 volume percent ammonia.

7. An asymmetric gas separation membrane comprising a cellulose acetate butyrate polymer having the formula:

##STR3## in which;

R each independently is OH, OOCCH₃, and OOCCH₂ CH₂ CH₃ such that the weight percent of the OOCCH₂ CH₂ CH₃ group in the polymer is about 10 to 45, the weight percent of OOCCH₃ groups in the polymer is about 2 to about 35, and the weight percent of OH groups in the polymer is about 0.8 to about 2; and

n is selected so that the number average molecular weight of the polymer is at least about 20,000; and

provided that the membrane has a carbon dioxide permeability of at least about 5 SCFH per ft² per 100 psi and a carbon dioxide to methane separation factor of at least about 21.

8. An asymmetric gas separation membrane of claim 7 having a carbon dioxide permeability of at least about 10 SCFH per ft² per 100 psi and a carbon dioxide to methane separation factor of at least about 25.

9. An asymmetric gas separation membrane of claim 7 wherein the cellulose acetate butyrate has a number average molecular weight between about 40,000 and 250,000.

10. An asymmetric gas separation membrane of claim 7 wherein the weight percent of OOCCH₂ CH₂ CH₃ groups in the polymer is about 15 to 40, the weight percent of OOCCH₃ groups in the polymer is about 10 to 30, or the weight percent of OH groups in the polymer is about 1.5 to 1.8.