Method for forming H2-permselective oxide membranes

• US 5,453,298 A
• Filed: 04/01/1994
• Issued: 09/26/1995
• Est. Priority Date: 11/08/1990
• Status: Expired due to Fees

• Current Assignee: California Institute of Technology
• Original Assignee: California Institute of Technology
• Inventors: Tsapatsis, Michael, Kim, Soojin, Nam, Suk Woo, Gavalas, George R.
• Primary Examiner(s): Beck, Shrive
• Assistant Examiner(s): NOT, DEFINED
• Application Number:
  US08/221,873
• Time in Patent Office: 543 Days
• Field of Search: 427/243, 427/245, 427/255.3, 427/248.1, 55/16, 55/158
• US Class Current: 427/245
• CPC Class Codes: B01D 2323/08 Specific temperatures applied
• CPC Class Codes: B01D 2323/081 Heating
• CPC Class Codes: B01D 67/0072 by deposition from the gaseous phase, e.g. sputtering, CVD, PVD
• CPC Class Codes: B01D 69/141 Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
• CPC Class Codes: B01D 71/02 Inorganic material
• CPC Class Codes: B01D 71/0213 Silicon
• CPC Class Codes: B01D 71/027 Silicium oxide
• CPC Class Codes: C01B 2203/0405 Purification by membrane separation
• CPC Class Codes: C01B 2203/047 the impurity being carbon monoxide
• CPC Class Codes: C01B 2203/0475 the impurity being carbon dioxide
• CPC Class Codes: C01B 2203/0485 the impurity being a sulfur compound
• CPC Class Codes: C01B 2203/0495 the impurity being water
• CPC Class Codes: C01B 3/503 characterised by the membrane
• CPC Class Codes: C23C 16/045 Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
• CPC Class Codes: C23C 16/40 Oxides
• CPC Class Codes: C23C 16/402 Silicon dioxide
• CPC Class Codes: C23C 16/403 of aluminium, magnesium or beryllium
• CPC Class Codes: C23C 16/405 of refractory metals or yttrium
• CPC Class Codes: C23C 16/45523 Pulsed gas flow or change of composition over time

Abstract

Methods of forming permselective oxide membranes that are highly selective to permeation of hydrogen by chemical deposition of reactants in the pore of porous tubes, such as Vycor™ glass or Al₂ O₃ tubes. The porous tubes have pores extending through the tube wall. The process involves forming a stream containing a first reactant of the formula RX_n, wherein R is silicon, titanium, boron or aluminum, X is chlorine, bromine or iodine, and n is a number which is equal to the valence of R; and forming another stream containing water vapor as the second reactant. Both of the reactant streams are passed along either the outside or the inside surface of a porous tube and the streams react in the pores of the porous tube to form a nonporous layer of R-oxide in the pores. The membranes are formed by the hydrolysis of the respective halides. In another embodiment, the first reactant stream contains a first reactant having the formula SiH_n Cl_4-n where n is 1, 2 or 3; and the second reactant stream contains water vapor and oxygen. In still another embodiment the first reactant stream containing a first reactant selected from the group consisting of Cl₃ SiOSiCl₃, Cl₃ SiOSiCl₂ OSiCl₃, and mixtures thereof and the second reactant stream contains water vapor. In still another embodiment, membrane formation is carried out by an alternating flow deposition method. This involves a sequence of cycles, each cycle comprising introduction of the halide-containing stream and allowance of a specific time for reaction followed by purge and flow of the water vapor containing stream for a specific length of time. In all embodiments the nonporous layers formed are selectively permeable to hydrogen.

Claims

1. A method for forming a permselective oxide membrane having hydrogen permselectivity comprising:

(a) forming a first reactant stream containing a first reactant of the formula RX_n wherein R is silicon, titanium, boron or aluminum, X is chlorine, bromine or iodine, and n is a number which is equal to the valence of R;

(b) forming a second reactant stream containing water vapor;

(c) providing a porous tube having an outside surface and an inside surface which define a tube wall and pores extending between the outside surface and inside surface; and

(d) passing both the first and the second reactant streams along one of either the outside of the inside surface, but not both surfaces, of the porous tube and causing said reactant streams to react in the pores of the porous tube to form a nonporous layer of R-oxide in the pores of the porous tube, said nonporous layer being selectively permeable to hydrogen.

2. The method of claim 1, wherein the porous tube has a porosity, and the pores of the porous tube have a diameter, wherein the diameter of the pores of the porous tube are too small for entry of particles of condensed oxides of R, and further comprising minimizing reduction of the porosity of the porous tube outside of the nonporous layer of R-oxide, and minimizing formation of R-oxide particles in the reactant streams outside of the tube wall and on the outside surface and inside surface of the porous tube.

3. The method of claim 1, wherein the first and second reactant streams are both introduced into one end of the porous tube.

4. The method of claim 1, wherein the first and second reactant streams are both along the outside surface of the porous tube.

5. The method of claim 1, wherein X is Cl.

6. The method of claim 1, wherein X is Br.

7. The method of claim 1, wherein X is I.

8. The method of claim 1, wherein R is Si and the two streams react at a temperature between about 400°

C. and about 800°

C.

9. The method of claim 1, wherein R is B and the two streams react at a temperature between about 100°

C. and about 450°

C.

10. The method of claim 1, wherein R is Al and the two streams react at a temperature between about 400°

C. and about 700°

C.

11. The method of claim 1, wherein R is Ti and the two streams react at a temperature between about 300°

C. and about 600°

C.

12. A method for forming a permselective oxide membrane having hydrogen permselectivity comprising:

(a) forming a first reactant stream containing a first reactant of the formula SiH_n Cl_4-n wherein n is 1, 2 or 3;

(b) forming a second reactant stream containing water vapor and oxygen;

(c) providing a porous tube having an outside surface and an inside surface which define a tube wall and pores extending between the outside surface and inside surface; and

(d) passing both the first and the second reactant streams along one of either the outside or the inside surface, but not both surfaces, of the porous tube and causing said reactant streams to react in the pores of the porous tube to form a nonporous layer of silicon oxide in the pores of the porous tube, said nonporous layer being selectively permeable to hydrogen.

13. A method of forming a permselective oxide membrane having hydrogen permselectivity comprising:

(a) forming a first reactant stream containing a first reactant selected from the group consisting of Cl₃ SiOSiCl₃, Cl₃ SiOSiCl₂ OSiCl₃, and mixtures thereof;

(b) forming a second reactant stream containing water vapor;

(c) providing a porous tube having an outside surface and an inside surface which define a tube wall and pores extending between the outside surface and inside surface; and

(d) passing both the first and the second reactant streams along one of either the outside or the inside surface, but not both surfaces, of the porous tube and causing said reactant streams to react in the pores of the porous tube to form a nonporous layer of silicon oxide in the pores of the porous tube, said nonporous layer being selectively permeable to hydrogen.

14. A method for forming a permselective oxide membrane having hydrogen permselectivity comprising:

(a) forming a first reactant stream containing a first reactant of the formula RX_n where in R is silicon, titanium, boron or aluminum, X is chlorine, bromine or iodine, and n is a number which is equal to the valence of R;

(b) forming a second reactant stream containing water vapor as a second reactant;

(c) providing a porous tube having an outside surface and an inside surface which define a tube wall and pores extending between the outside surface and inside surface;

(d) introducing an amount of the first reactant stream along one of either the outside or the inside surface of the porous tube and allowing a length of time for the first reactant to enter and react in the pores of the porous tube;

(e) removing the first reactant which has not entered and reacted in the pores, form the surface of the porous tube along which the first reactant stream was introduced;

(f) introducing the second reactant stream along one of either the outside or the inside surface of the porous tube and allowing the second reactant to react in the pores of the porous tube with the first reactant;

(g) stopping the introducing of the second reactant along said one of either the outside or the inside surface; and

(h) removing the second reactant which has not entered and reacted in the pores form the surface of the porous tube along which the second reactant stream was introduced.

15. The method of claim 14, wherein the introducing of the first reactant stream along said one of either the outside or the inside surface uses a first reactant dosage between about 0.1 to about 1.0 μ

mol/cm² of surface area of said one of either the outside or the inside surface.

16. The method of claim 14, wherein the first reactant has a partial pressure, and wherein the partial pressure of the first reactant immediately after introducing it along one of either the outside or the inside surface of the porous tube is from about 0.01 to about 0.1 atm.

17. The method of claim 14, further comprising repeating the steps of:

introducing the amount of the first reactant stream along said one of either the outside or the inside surface and allowing a length of time for the first reactant to enter and react in the pores of the porous tube,

removing the first reactant which has not entered and reacted in the pores from the surface of the porous tube along which the first reactant stream was introduced,

introducing the second reactant stream along said one of either the ouside or inside surface and allowing the second reactant to react in the pores of the porous tube with the first reactant,

stopping the introducing of the second reactant stream along said one of either the outside or the inside surface, and

removing the second reactant which has not entered and reactant in the pores from the surface of the porous tube along which the second reactant stream was introduced,

a number of times to form a permselective oxide membrane having a hydrogen permselectivity.

18. The method of claim 17, wherein the number of times the steps are repeated is from about 2 to about 100 times.

19. The method of claim 14, wherein the first and second reactant streams are introduced into one end of the porous tube.

20. The method of claim 14, wherein the first and second reactant streams are introduced along the outside surface of the porous tube.

21. The method of claim 14, wherein X is Cl.

22. The method of claim 14, wherein X is Br.

23. The method of claim 14, wherein X is I.

24. The method of claim 14, wherein R is Si and the reactants react at a temperature between about 400°

C. and about 800°

C.

25. The method of claim 14, wherein R is B and the reactants react at a temperature between about 100°

C. and about 450°

C.

26. The method of claim 14, wherein R is Al and the reactants react at a temperature between about 400°

C. and about 700°

C.

27. The method of claim 14, wherein R is Ti and the reactants react at a temperature between about 300°

C. and about 600°

C.

28. A method for forming a permselective oxide membrane having hydrogen permselectivity comprising:

(a) forming a first reactant stream containing a first reactant of the formula RX_n wherein R is silicon, titanium, boron or aluminum, X is chlorine, bromine or iodine, and n is a number which is equal to the valence of R;

(b) forming a second reactant stream containing water vapor as a second reactant;

(c) providing a porous tube having an outside surface and an inside surface which define a tube wall and pores extending between the outside surface and inside surface;

(d) introducing an amount of the first reactant stream along one of either the outside or the inside surface, but not both surfaces, of the porous tube and allowing a length of time for the first reactant to enter and react in the pores of the porous tube;

(e) removing the first reactant which has not entered and reacted in the pores, from said one of either the outside or the inside surface;

(f) introducing the second reactant stream along said one of either the outside or inside surface of the porous tube and allowing the second reactant to react in the pores of the porous tube with the first reactant to form a nonporous layer of R-oxide in the pores of the porous tube, the nonporous layer being selectively permeable to hydrogen;

(g) stopping the introducing of the second reactant along said one of either the outside or the inside surface; and

(h) removing the second reactant which has not entered and reacted in the pores form the surface of the porous tube along which the second reactant stream was introduced.

29. A method for forming a permselective oxide membrane having hydrogen permselectivity comprising:

(a) forming a first reactant stream containing a first reactant of the formula SiH_n Cl_4-n wherein n is 1, 2 or 3;

(b) forming a second reactant stream containing water vapor and oxygen as a second reactant;

(c) providing a porous tube having an outside surface and an inside surface which define a tube wall and pores extending between the outside surface and inside surface; and

(d) introducing an amount of the first reactant stream along one of either the outside or the inside surface, but not both surfaces, of the porous tube and allowing a length of time for the first reactant to enter and react in the pores of the porous tube;

(e) removing the first reactant which has not entered and reacted in the pores, from said one of either the outside or the inside surface;

(f) introducing the second reactant stream along said one of either outside or the inside surface of the porous tube and allowing the second reactant to react in the pores of the porous tube with the first reactant to form a nonporous layer of silicon oxide in the pores of the porous tube, the nonporous layer being selectively permeable to hydrogen;

(g) stopping the introducing of the second reactant along said one of either the outside or the inside surface; and

(h) removing the second reactant which has not entered and reacted in the pores form the surface of the porous tube along which the second reactant stream was introduced.

30. A method for forming a permselective oxide membrane having hydrogen permselectivity comprising:

(a) forming a first reactant stream containing a first reactant selected from the group consisting of Cl₃ SiOSiCl₃, Cl₃ SiOSiCl₂ OSiCl₃, and mixtures thereof;

(b) forming a second reactant stream containing water vapor as a second reactant;

(c) providing a porous tube having an outside surface and an inside surface which define a tube wall and pores extending between the outside surface and inside surface; and

(d) introducing an amount of the first reactant stream along one of either the outside or the inside surface, but not both surfaces, of the porous tube and allowing a length of time for the first reactant to enter and react in the pores of the porous tube;

(e) removing the first reactant which has not entered and reacted in the pores, from said one of either the outside or the inside surface;

(f) introducing the second reactant stream along said one of either the outside or inside surface of the porous tube and allowing the second reactant to react in the pores of the porous tube with the first reactant to form a nonporous layer of silicon oxide in the pores of the porous tube, the nonporous layer being selectively permeable to hydrogen;

(g) stopping the introducing of the second reactant along said one of either the outside or the inside surface; and

(h) removing the second reactant which has not entered and reacted in the pores form the surface of the porous tube along which the second reactant stream was introduced.