Zeolite DDR membranes

• US 8,673,057 B2
• Filed: 09/12/2012
• Issued: 03/18/2014
• Est. Priority Date: 04/04/2011
• Status: Active Grant

• Current Assignee: Georgia Tech Research Corporation (University System of Georgia)
• Original Assignee: Georgia Tech Research Corporation (University System of Georgia)
• Inventors: Zhou, Zhengzhi, Nair, Sankar
• Primary Examiner(s): Greene, Jason M
• Application Number:
  US13/611,988
• Publication Number:
  US 20130064747A1
• Time in Patent Office: 552 Days
• Field of Search: 95/45, 95/51, 96/4, 96/10, 96/11, 96/12, 502/4, 502/60, 502/62, 502/64, 423/702, 423/709, 423/210, 423/230, 427/372.2
• US Class Current: 95/45
• CPC Class Codes: B01D 2323/08 Specific temperatures applied
• CPC Class Codes: B01D 2323/081 Heating
• CPC Class Codes: B01D 2325/02 Details relating to pores or porosity of the membranes
• CPC Class Codes: B01D 2325/0283 Pore size
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• CPC Class Codes: B01D 67/0051 by controlled crystallisation, e,.g. hydrothermal growth
• CPC Class Codes: B01D 69/10 Supported membranes; Membrane supports
• CPC Class Codes: B01D 69/108 Inorganic support material
• 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 71/0281 Zeolites
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01B 37/02 Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer

Abstract

DDR nanocrystals of uniform size and structure were synthesized using hydrothermal secondary growth and then used to make DDR zeolite membranes and for any other use where uniform, small DDR zeolite crystals are beneficial.

Claims

1. A method for preparing DDR membranes on porous substrates, said method comprising the steps of:

a) preparing seed DDR zeolite crystals in a first growth solution comprising about 6 ADA;

100 SiO2;

50 KF;

8000 H2O, said seed DDR zeolite crystals having a uniform crystal structure and size;

b) seeding a porous substrate with said seed DDR zeolite crystals of 200-600 nm;

c) growing a DDR zeolite membrane by incubation in a second growth solution selected from the group consisting of about 6 ADA;

100 SiO2 50 KF;

10000 H2O, about 6 ADA;

100 SiO2;

x KF;

4000 H2O, where x=60-100 and about 9 ADA;

100 SiO2;

80 KF;

4000 H2O;

d) optionally calcining said DDR zeolite membrane; and

e) optionally sealing any defects in said DDR zeolite membrane by incubation with using a polydimethlysiloxane (PDMS) solution under a pressure differential.

2. The method of claim 1, further comprising washing said DDR zeolite membrane.

3. The method of claim 1, wherein said porous support is α

-alumina.

4. The method of claim 1, wherein said calcining is at 500-700°

C. for 6-24 hours.

5. The method of claim 1, wherein said porous support is organic or inorganic and has 10-60% porosity and pores of 200-500 nm.

6. The method of claim 1, wherein said porous support is selected from the group consisting of polypropylene, polyethylene, polytetrafluoroethylene, polysulphone, polyimide, silica, alpha-alumina, gamma-alumina, mullite, zirconia, titania, yttria, silicon nitride, silicon carbide, iron, bronze and stainless steel, glass, and carbon.

7. The method of claim 1, wherein said porous support is tubular α

-alumina.

8. The method of claim 1, wherein said porous support is tubular α

-alumina having a porosity of 10-50% and a pore size of 100-400 nm.

9. The method of claim 1, wherein said porous support is tubular α

-alumina having a porosity of 30% and a pore size of 200-300 nm.

10. The method of claim 5, wherein said calcining is at 700°

C. for 8 hours.

11. The method of claim 5, wherein said PDMS step is with 2-20 wt % PDMS solution, while a vacuum is applied from the inner bore of said tubular a-alumina, followed by heat curing.

12. The method of claim 5, wherein said PDMS step is with 5% PDMS in n-heptanes for 5-20 minutes, while a vacuum is applied from the inner bore of said tubular α

-alumina, followed by heat curing at about 80°

C. for about 4 hours.

13. A DDR zeolite membrane made by any one of method claims 1-10.

14. A method of separating a small molecule from a mixture of small molecules, said method comprising applying a mixture of small molecules selected from CO₂, CH₄, N₂, O₂, C₂H₄, C₂H₆, C₃H₆, C₃H₈ to a membrane of claim 11, and separating out a small molecule from said mixture.

15. A method of separating a CO2 molecule from a mixture of small molecules, said method comprising applying a mixture of small molecules selected from CO₂, CH₄, N₂, O₂, C₂H₄, C₂H₆, C₃H₆, C₃H₈ to a membrane of claim 11, and separating out CO₂ from said mixture.

16. The method of claim 1, wherein the second growth solution is about 6 ADA:

100 SiO2;

50 KF;

10000 H2O.

17. The method of claim 1, wherein the second growth solution is about 6 ADA:

100 SiO2;

x KF;

4000 H2O, where x=60-100.

18. The method of claim 1, wherein the second growth solution is about 9 ADA:

100 SiO2;

80 KF;

4000 H2O.

19. The method of claim 1, wherein the first growth solution is at temperature of about 130-160°

C., and wherein the second growth solution is at temperature of about 150°

C. or about 160°

C.