Method for separation of substances

• US 5,378,440 A
• Filed: 02/11/1993
• Issued: 01/03/1995
• Est. Priority Date: 01/25/1990
• Status: Expired due to Term

• Current Assignee: Mobil Oil Corporation (Exxon Mobil Corporation)
• Original Assignee: Mobil Oil Corporation (Exxon Mobil Corporation)
• Inventors: Herbst, Joseph A., Vartuli, James C., Wang, Daniel I. C., Olson, David H., Schmitt, Kirk D., Kresge, Charles T.
• Primary Examiner(s): MCFARLANE, ANTHONY R
• Application Number:
  US08/016,402
• Time in Patent Office: 691 Days
• Field of Search: 585/820, 210/500.25, 210/500.21, 210/660, 210/679, 55/75, 55/386, 423/210, 502/407, 502/415
• US Class Current: 423/210
• CPC Class Codes: B01D 53/8628 Processes characterised by a specific catalyst
• CPC Class Codes: B01J 20/041 Oxides or hydroxides
• CPC Class Codes: B01J 20/06 comprising oxides or hydroxides of metals not provided for in group B01J20/04
• CPC Class Codes: B01J 20/08 comprising aluminium oxide or hydroxide; comprising bauxite
• CPC Class Codes: B01J 20/103 comprising silica
• CPC Class Codes: B01J 20/12 Naturally occurring clays or bleaching earth
• CPC Class Codes: B01J 20/18 Synthetic zeolitic molecular sieves
• CPC Class Codes: B01J 20/3078 Thermal treatment, e.g. calcining or pyrolizing
• CPC Class Codes: B01J 2229/26 to stabilize the total catalyst structure
• CPC Class Codes: B01J 2229/32 Reaction with silicon compounds, e.g. TEOS, siliconfluoride
• CPC Class Codes: B01J 2229/34 Reaction with organic or organometallic compounds with organo-silicium compounds B01J2229/32
• CPC Class Codes: B01J 2229/36 Steaming
• CPC Class Codes: B01J 2229/40 Special temperature treatment, i.e. other than just for template removal
• CPC Class Codes: B01J 2229/42 Addition of matrix or binder particles
• CPC Class Codes: B01J 2229/64 in or on refractory materials
• CPC Class Codes: B01J 29/0308 Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
• CPC Class Codes: B01J 29/041 Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
• CPC Class Codes: B01J 29/043 Noble metals
• CPC Class Codes: B01J 29/40 of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
• CPC Class Codes: B01J 29/70 of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
• CPC Class Codes: B01J 29/82 : Phosphates B01J29/005 takes precedence
• CPC Class Codes: B01J 29/83 : Aluminophosphates [APO compounds]
• CPC Class Codes: B01J 29/85 : Silicoaluminophosphates [SAPO compounds]
• CPC Class Codes: C01B 37/00 : Compounds having molecular sieve properties but not having base-exchange properties
• CPC Class Codes: C01B 37/02 : Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
• CPC Class Codes: C01B 37/08 : Silicoaluminophosphates [SAPO compounds] , e.g. CoSAPO
• CPC Class Codes: C01B 39/00 : Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination treatment to modify the sorption properties, e.g. shaping using a binder, B01J20/10; treatment to modify the catalytic properties, e.g. combination of treatments to make the zeolites appropriate to their use as a catalyst, B01J29/04; treatment to improve the ion-exchange properties B01J39/14
• CPC Class Codes: C10G 11/05 : Crystalline alumino-silicates, e.g. molecular sieves
• CPC Class Codes: C10G 47/16 : Crystalline alumino-silicate carriers

Abstract

Methods for separation of substances are provided. The methods include contacting a mixture of at least two components in flowable conditions with mesoporous, crystalline materials termed M41S which also include MCM-41 materials. The mesoporous crystalline materials may be used in separations as is or functionalized.

Claims

1. A method for separating substances comprising contacting a mixture of components having different sorption characteristics including at least a first and a second component in a flowable condition with an inorganic, porous, non-layered crystalline phase material consisting essentially of a material exhibiting after calcination and/or functionalization, an X-ray diffraction pattern with at least one peak at a d-spacing greater than about 18 Å

Units with a relative intensity of 100 and having a benzene adsorption capacity of greater than 15 grams per 100 grams anhydrous crystal at 50 torr and 25°

C., said contact occurring for a sufficient time and under conditions suitable for inducing a retention of said first component within said material, whereby said first component is separated from said second component.

2. A method according to claim 1, further comprising providing said components in a gaseous form.

3. A method according to claim 1, further comprising providing said components in a gaseous carrier medium.

4. A method according to claim 1, further comprising providing said components in a liquid form.

5. A method according to claim 1, further comprising providing said components in a liquid carrier medium.

6. A method according to claim 1, further comprising providing the pores of said material with a specified size and shape so as to allow said first component of said mixture to pass into the pores for retention therein while excluding entry of said second component, whereby said first component becomes separated from said second component.

7. A method according to claim 6, further comprising providing said material in a gel matrix suitable for performing gel permeation chromatography.

8. A method according to claim 6, further comprising providing said material in a system selected from the group consisting of flat-bed, batch and column chromatography systems.

9. The method according to claim 1, wherein said crystalline phase material is in the form of a separation membrane.

10. The method according to claim 9, further comprising forming said material into a thin, cohesive continuous unsupported membrane under crystallization conditions by inducing crystallization of said material in a continuous layer upon a non-porous forming surface and removing the resulting crystallized layer in order to obtain a thin, non-composite membrane prior to contact with said feedstream mixture.

11. A method according to claim 9, further comprising depositing said material onto a porous, inorganic substrate in order to form a thin-layer composite membrane prior to contact with said feedstream mixture.

12. A method according to claim 9, further comprising providing said components in a gaseous form.

13. A method according to claim 9, further comprising providing said components in a gaseous carrier medium.

14. A method according to claim 9, further comprising providing said components in a liquid form.

15. A method according to claim 9, further comprising providing said components in a liquid carrier medium.

16. A method according to claim 10, wherein said non-composite membrane is loaded with a gas permeable metal.

17. The method according to claim 11, wherein said thin-layer membrane is loaded with a gas permeable metal.

18. A chromatographic substance for use in size exclusion-based separations, said substance comprising:

a gel matrix; and

an inorganic, porous, non-layered crystalline phase material, said material exhibiting after calcination and/or functionalization, an X-ray diffraction pattern with at least one peak at a d-spacing greater than about 18 Å

Units with a relative intensity of 100 and having a benzene adsorption capacity of greater than 15 grams per 100 grams anhydrous crystal at 50 torr and 25°

C., wherein said material is disposed within said matrix.

19. A method for chromatographic separation comprising contacting a stationary phase with a fluid mobile phase and a mixture of at least a first component and a second component having different partition or retention characteristics with respect to said stationary phase, said stationary phase comprising an inorganic, porous, non-layered crystalline phase material consisting essentially of a material exhibiting after calcination and/or functionalization, an X-ray diffraction pattern with at least one peak at a d-spacing greater than about 18 Å

Units with a relative intensity of 100 and having a benzene adsorption capacity of greater than 15 grams per 100 grams anhydrous crystal at 50 torr and 25°

C., said contacting occurring for a sufficient time and under conditions suitable for inducing a retention of said first component within said stationary phase, whereby said first component is separated from said second component.

20. The method of claim 19, wherein said partition or retention characteristics are caused by physical characteristics selected from the group consisting of molecular weight, molecular size, solubility, ion exchange and binding affinity.

21. A method for membrane separation comprising contacting a separation membrane including an inorganic, porous, non-layered crystalline phase material consisting essentially of a material exhibiting after calcination and/or functionalization, an X-ray diffraction pattern with at least one peak at a d-spacing greater than about 18 Å

Units with a relative intensity of 100 and having a benzene adsorption capacity of greater than 15 grams per 100 grams anhydrous crystal at 50 torr and 25°

C., with a feedstream mixture of components having different permeability characteristics including at least a first component at a first concentration and a second component at a second concentration, said contacting occurring under separation conditions such that said separation membrane affords greater permeability to said first component through said membrane than said second component, thereby producing an effluent stream wherein the concentration of said second component has been substantially reduced.

22. A method according to claim 21, further comprising providing the pores of said material with a specified pore size and shape so as to allow said first component to enter the pores and permeate therethrough while restricting the passage of said second component therethrough.

23. A chromatographic system which comprises a stationary phase, a fluid mobile phase, and a mixture of at least a first and second component having different sorption characteristics with respect to said stationary phase, said stationary phase comprising an inorganic, porous, non-layered crystalline phase material, said material exhibiting after calcination and/or functionalization, an X-ray diffraction pattern with at least one peak at a d-spacing greater than about 18 Å

Units with a relative intensity of 100 and having a benzene adsorption capacity of greater than 15 grams per 100 grams anhydrous crystal at 50 torr and 25°

C., said fluid mobile phase being in contact with said stationary phase for a sufficient time under conditions suitable for separating said first component from second component.

24. A chromatographic substance according to claim 23, wherein said material includes a separating agent supported upon its pore walls, said separating agent capable of a retentive association with at least one of a plurality of components present within a sample mixture to be separated.

25. A chromatographic system according to claim 24, wherein said separating agent is disposed upon the pore walls of said material by way of absorption.

26. A chromatographic system according to claim 25, wherein said material includes functional groups attached to the pore walls by way of a treatment comprising

contacting said material with a treatment composition comprising M'"'"'X'"'"'Y'"'"'_n wherein,

M'"'"' is selected from a group consisting of Periodic Table Groups IIA, IIIA, IVA, VA, VIA, VIIIA, IB, IIB, IIIB, IVB, VB and VIB;

X'"'"' is selected from a group consisting of halides, hydrides, alkoxides of C_1-6, alkyls of C_1-18, alkenyls of C_1-18, aryls of C_1-18, aryloxides of C_1-18, sulfonates, nitrates, and acetates;

Y'"'"' is selected from a group consisting of X'"'"', amines, phosphines, sulfides, carbonyls and cyanos; and

n=1-5;

said contacting of said material with said treatment composition occurring under such conditions so that the pore walls of said crystalline phase material become functionalized.

27. A chromatographic system according to claim 26, wherein a specialized moiety is coupled to the functionalized pore walls to serve as said separating agent.

28. A chromatographic system according to claim 27, wherein said specialized moiety is an ion exchanging moiety.

29. A chromatographic system according to claim 27, wherein said specialized moiety is selected from the group consisting of peptides, peptide fragments and peptide conjugates.

30. A membrane system which comprises a separation membrane including an inorganic, porous, non-layered crystalline phase material, said material exhibiting after calcination and/or functionalization, an X-ray diffraction pattern with at least one peak at a d-spacing greater than about 18 Å

Units with a relative intensity of 100 and having a benzene adsorption capacity of greater than 15 grams per 100 grams anhydrous crystal at 50 tort and 25°

C., and a feedstream mixture of components having different permeability characteristics with respect to said separation membrane such that said membrane affords greater permeability to at least one component of said mixture.

31. A membrane system according to claim 30, wherein said material is present in a thin, cohesive, continuous, unsupported non-composite membrane.

32. A membrane system according to claim 30, wherein said material is deposited onto a porous, inorganic substrate to form a thin-layer composite membrane.

33. A membrane system according to claim 30, wherein said material further comprises pores of a predetermined size and shape so as to exclude passage of at least one component in a mixture.

34. A membrane system according to claim 30, wherein said material further comprises a separating agent disposed upon the pore walls of said material, said separating agent capable of a retentive association with at least one of a plurality of components present within a sample mixture to be separated.

35. A separation membrane according to claim 34, wherein said material includes functional groups attached to the pore walls by way of a treatment comprising:

contacting said material with a treatment composition comprising M'"'"'X'"'"'Y'"'"'_n wherein,

M'"'"' is selected from a group consisting of Periodic Table Groups IIA, IIIA, IVA, VA, VIA, VIIIA, IB, IIB, IIIB, IVB, VB and VIB;

X'"'"' is selected from a group consisting of halides, hydrides, alkoxides of C_1-6, alkyls of C_1-18, alkenyls of C_1-18, aryls of C_1-18, aryloxides of C_1-18, sulfonates, nitrates and acetates;

Y'"'"' is s elected from a group consisting of X'"'"', amines, phosphines, sulfides, carbonyls and cyanos; and

n=1-5;

said contacting of said material with said treatment composition occurring under such conditions so that the pore walls of said crystalline phase material become functionalized.

36. A separation membrane according to claim 35, wherein a specialized moiety is coupled to the pore walls to serve as said separating agent.

37. A separation membrane according to claim 36, wherein said specialized moiety is an ion exchanging moiety.

38. A separation membrane according to claim 37, wherein said specialized moiety is selected from the group consisting of peptide fragments and peptide conjugates.

39. A separation membrane according to claim 31, wherein said non-composite membrane is loaded with a gas permeable metal.

40. A separation membrane according to claim 32, wherein said thin-layer membrane is loaded with a gas permeable metal.

41. A method for separating substances comprising contacting a mixture of components having different sorption characteristics including at least a first and a second component in a flowable condition with an inorganic, porous, non-layered crystalline phase material having a separating agent supported upon the pore walls of said material, said material exhibiting after calcination and/or functionalization, an X-ray diffraction pattern with at least one peak at a d-spacing greater than about 18 Å

Units with a relative intensity of 100 and having a benzene adsorption capacity of greater than 15 grams per 100 grams anhydrous crystal at 50 torr and 25°

C., said contact occurring for a sufficient time and under conditions suitable for inducing a retention of said first component within said material, whereby said mixture enters the pores and said first component becomes retained therein by way of a retentive association with said separating agent, thereby separating said first component from said second component.

42. A method according to claim 41, further comprising providing said separating agent upon the pore walls by way of adsorption.

43. A method according to claim 42, further comprising providing said material in a system selected from the group consisting of flat-bed, batch and column chromatography systems.

44. A method according to claim 42, further comprising providing said separating agent in a fluid condition, said fluid being adsorbed upon the pore walls.

45. The method according to claim 41, wherein said crystalline phase material having a separating agent supported upon the pore walls of said material is in the form of a separation membrane.

46. A method according to claim 45, further comprising selecting said moiety from the group consisting of ion exchanging moieties, whereby said first component is retained within said material via an ion exchange mechanism.

47. A method according to claim 45, further comprising selecting said moiety from the group consisting of, peptide fragments and peptide conjugates, whereby said first component is retained within said material via a binding affinity for said moiety.

48. A method for separating substances comprising contacting a mixture of components having different sorption characteristics including at least a first and a second component in a flowable condition with an inorganic, porous, non-layered crystalline phase material having a specialized moiety coupled to functionalized pore walls of said material, wherein prior to contact with said mixture said material has been treated by contacting said material with a treatment composition comprising M'"'"'X'"'"'Y'"'"'_n wherein,

M'"'"' is selected from a group consisting of Period Table Groups IIA, IIIA, IVA, VA, VIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB;

X'"'"' is selected from a group consisting of halides, hydrides, alkoxides of C_1-6, alkyls of C_1-18, alkenyls of C_1-18, aryls of C_1-18, aryloxides of C_1-18, sulfonates, nitrates, and acetates;

Y'"'"' is selected from a group consisting of X'"'"', amines, phosphines, sulfides, carbonyls and cyanos; and

n=1-5;

said contacting of said material with said treatment composition occurring under such conditions so that the pore walls of said crystalline phase material become functionalized.

49. A method according to claim 48, further comprising selecting said moiety from the group consisting of ion exchanging moieties, whereby said first component is retained within said material via an ion exchange mechanism.

50. A method according to claim 49, further comprising providing said material in a system selected from the group consisting of flat-bed, batch and column chromatography systems.

51. A method according to claim 48, further comprising selecting said moiety from the group consisting of peptide fragments and peptide conjugates, whereby said first component is retained within said material via a binding affinity for said moiety.

52. A method according to claim 51, further comprising providing said material in a system selected from the group consisting of flat-bed, batch and column chromatography systems.

53. The method according to claim 48, wherein said crystalline phase material having a specialized moiety coupled to functionalized pore walls of said material is in the form of a separation membrane.