Nano-molecular sieve-polymer mixed matrix membranes with significantly improved gas separation performance

• US 7,897,207 B2
• Filed: 02/26/2007
• Issued: 03/01/2011
• Est. Priority Date: 03/10/2006
• Status: Expired due to Fees

• Current Assignee: UOP Llc (Honeywell International Inc.)
• Original Assignee: UOP Llc (Honeywell International Inc.)
• Inventors: Liu, Chunqing, Wilson, Stephen T.
• Primary Examiner(s): Mulcahy; Peter D.
• Assistant Examiner(s): HU, HENRY S
• Application Number:
  US11/679,155
• Publication Number:
  US 20070209514A1
• Time in Patent Office: 1,464 Days
• Field of Search: 427/244, 427/216, 427/271, 427/273, 427/535, 96/4
• US Class Current: 427/244
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• CPC Class Codes: B01D 67/0079 Manufacture of membranes comprising organic and inorganic components
• CPC Class Codes: B01D 67/00793 Dispersing a component, e.g. as particles or powder, in another component
• CPC Class Codes: B01D 69/148 Organic/inorganic mixed matrix membranes
• CPC Class Codes: B01D 71/028 Molecular sieves carbon B01D71/021
• CPC Class Codes: B01D 71/64 Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: B01D 71/643 Polyether-imides
• CPC Class Codes: Y02C 20/40 of CO2

Abstract

Nano-molecular sieve-polymer mixed matrix membranes (MMMs) for CO₂ removal from natural gas have been prepared by incorporating dispersible template-free nano-molecular sieves into polymer matrices such as Matrimid 5218 polyimide matrix or Ultem 1000 polyetherimide matrix. The nano-molecular sieves used in this invention include template-free nano-AlPO-18, nano-AlPO-5, nano-Silicalite, nano-SAPO-34, and PEG-functionalized nano-Silicalite. These template-free nano-molecular sieves were synthesized by an organic ligand grafting method.

Claims

1. A method of manufacturing a membrane comprising:

(a) selecting a quantity of one or more types of template-containing nano-molecular sieve particles;

(b) functionalizing said template-containing nano-molecular sieve particles by grafting an organic functional group on an outer surface of said template-containing nano-molecular sieve particles using a functional organic linkage;

(c) making template-free nano-molecular sieve particles by high temperature calcination of the said functionalized template-containing nano-molecular sieve particles;

(d) forming a mixture by mixing 5 to 70 wt-% of said template-free nano-molecular sieve particles with a polyimide or polyetherimide polymer; and

(e) making a membrane from said mixture.

2. The method of claim 1 wherein said nano-molecular sieve particles have a particle size from 5 to 1000 nm.

3. The method of claim 1 wherein said nano-molecular sieve particles are selected from the group consisting of nano-AlPO-18, nano-AlPO-14, nano-AlPO-34, nano-UZM-25, nano-CDS-1, nano-Nu-6(2), nano-AlPO-25, nano-AlPO-5, nano-Silicalite, and nano-SAPO-34.

4. The method of claim 1 wherein said functional organic linkage is an organosilane.

5. The method of claim 1 wherein said functional organic linkage is a compound having the formula R(CH₂)_nSi(OR₁)₃ in which R is an organic functional group, n is an integer from 1 to 20, and R₁ is a C₁-C₈ hydrocarbon group.

6. The method of claim 1 wherein said functional organic linkage is a compound having the formula R(CH₂)_nSiR′

(OR₁)₂ in which R is an organic functional group, n is an integer from 1 to 20, R₁ is a C₁-C₈ hydrocarbon group, and R′

is a C₁-C₈ hydrocarbon group.

7. The method of claim 1 wherein said functional organic linkage is a compound having the formula R(CH₂)_nSiR′

(R″

)(OR₁) in which R is an organic functional group, n is an integer from 1 to 20, R₁ is a C₁-C₈ hydrocarbon group, R′

is a C₁-C₈ hydrocarbon group, and R″

is a C₁-C₈ hydrocarbon group.

8. The method of claim 1 wherein said surface-functionalized molecular sieve nanoparticles are dispersible in organic solvents.

9. A mixed matrix membrane made by the method of claim 1.