Method, catalyst, and photocatalyst for the destruction of phosgene

• US 6,464,951 B1
• Filed: 04/20/2002
• Issued: 10/15/2002
• Est. Priority Date: 04/20/2002
• Status: Expired due to Fees

• Current Assignee: KSE Limited
• Original Assignee: KSE Limited
• Inventors: Gerrish, David A., Kittrell, James R., Milazzo, Michael C.
• Primary Examiner(s): Griffin, Steven P.
• Assistant Examiner(s): Strickland, Jonas N.
• Application Number:
  US09/553,627
• Time in Patent Office: 178 Days
• Field of Search: 423/240.R, 423/240.S, 204/158.2, 204/157.3, 204/157.48, 204/157.15, 204/158.21, 210/748, 502/305, 502/306, 502/307, 502/308, 502/309, 502/313, 502/319, 502/321, 502/344, 502/345, 502/349
• US Class Current: 423/240.00R
• CPC Class Codes: B01D 2255/802 Photocatalytic
• CPC Class Codes: B01D 2257/204 Inorganic halogen compounds
• CPC Class Codes: B01D 53/8659 Removing halogens or halogen compounds
• CPC Class Codes: B01J 21/063 Titanium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 21/066 Zirconium or hafnium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 21/18 Carbon
• CPC Class Codes: B01J 23/28 Molybdenum
• CPC Class Codes: B01J 23/6527 Tungsten
• CPC Class Codes: B01J 23/72 Copper
• CPC Class Codes: B01J 23/885 and copper
• CPC Class Codes: B01J 35/30 characterised by their physical properties
• CPC Class Codes: B01J 35/39 Photocatalytic properties
• CPC Class Codes: B01J 37/0201 Impregnation

Abstract

In accordance with the present invention, a catalyst is described which comprises at least one metal selected from the group consisting of copper, zinc, iron, tungsten, molybdenum, and chromium distributed over a catalyst support comprising a material containing at least one of silicon, titanium, zirconium, magnesium, aluminum, and activated carbon. The catalyst is used to remove phosgene from a contaminated gas stream and/or reduce or eliminate phosgene from an effluent of a previously treated gas stream. At least one metal in the catalyst of the present invention is preferably present in an amount from about 0.001 wt % to about 15 wt %. When more than one metal is present, the combined metals preferably do not exceed 20 wt %. Catalysts in accordance with the present invention may be used as Photocatalysts. Processes for using the catalysts and Photocatalysts of the present invention are also described.

Claims

1. A process for treating a contaminated gas stream so as to reduce any phosgene content in said gas stream comprising the steps of:

(a) providing a catalyst comprising at least one metal selected from the group consisting of copper, zinc, iron, tungsten, molybdenum, chromium, and mixtures thereof distributed over a catalyst support comprising a material containing at least one of silicon, titanium, zirconium, magnesium, aluminum, and activated carbon;

(b) operating said catalyst at a temperature from about 0°

C. to about 250°

C. at a pressure from about 0.1 atm. to about 10 atm., and at a contact time of about 0.01 seconds to about 5 minutes; and

(c) reducing said phosgene content in said gas stream by reacting said phosgene in said gas stream by placing said gas stream in contact with said catalyst.

2. A process according to claim 1, wherein said temperature is in a range of from about 25°

C. to about 100°

C.

3. A process according to claim 1, wherein said pressure is in a range from about 0.8 atm. to about 2.0 atm.

4. A process according to claim 1, wherein said contact time is from about 0.1 seconds to about 10 seconds.

5. A process according to claim 1, wherein said step of providing a catalyst comprises providing a photocatalyst comprising said at least one metal selected from the group consisting of copper, zinc, iron, tungsten, molybdenum, chromium, and mixtures thereof distributed over said catalyst support comprising said material containing said at least one of silicon, titanium, zirconium, magnesium, aluminum, and activated carbon and wherein said reducing step comprises placing said gas stream in contact with said photocatalyst so as to reduce said phosgene contact, prevent the formation of any phosgene, and remove any CVOCs from said gas stream.

6. A process according to claim 5, wherein said photocatalyst providing step comprises providing a photocatalyst having said at least one metal present in an amount from 0.001 wt % to about 15 wt %.

7. A process according to claim 5, wherein said photocatalyst providing step comprises distributing at least two of said metals over said catalyst support with the total of said metals not exceeding 20 wt %.

8. A process according to claim 5, wherein said photocatalyst providing step comprises providing a photocatalyst having tungsten or molybdenum in an amount from 0.015 wt % to about 5.0 wt % distributed over said catalyst support.

9. A process according to claim 5, wherein said photocatalyst providing step comprises providing a photocatalyst having a photocatalytically active support comprised primarily of silica, titanium in an amount up to about 5.0 wt %, zirconium in an amount up to 5.0 wt %, and oxygen in an amount consistent with the chemical composition of the oxides of silicon, titanium, and zirconium.

10. A process according to claim 5, wherein said photocatalyst providing step comprises providing a photocatalyst having a photocatalytically active support comprised of silicon in an amount from about 0.1 wt % to about 70 wt %, titanium dioxide in an amount from about 30 wt % to about 90 wt %, tungsten in an amount from about 0.1 wt % to about 50 wt % and at least one of platinum and palladium in an amount from about 0.01 wt % to about 10 wt %.

11. A process according to claim 10, wherein said tungsten is present in an amount from about 1.0 wt % to about 30 wt %.

12. A process according to claim 10, wherein said at least one of platinum and palladium is present in an amount from about 0.1 wt % to 5.0 wt %.

13. A process according to claim 5, wherein said photocatalyst providing step comprises providing a photocatalyst having a photocatalytically active support comprised principally of titania and containing up to 5.0 wt % of at least one of platinum and palladium.

14. A process according to claim 5, wherein said photocatalyst providing step comprises providing a photocatalyst having a photocatalytically active support comprised principally of silica and containing up to 5.0 wt % of at least one of platinum and palladium.

15. A process according to claim 5, wherein said catalyst providing step comprises providing a catalyst having copper and molybdenum distributed over a catalyst support formed from titania.

16. A process according to claim 5, wherein said catalyst providing step comprises providing a catalyst having a support formed from a titanium containing material and further having a material which forms a silicon-tungsten bond deposited on said support.

17. A process according to claim 16, wherein said material forming said silicon-tungsten bond comprises a compound containing silicon and tungsten.

18. A process according to claim 1, further comprising:

providing a photocatalytic stage;

passing said contaminated gas stream through said photocatalytic stage while operating said photocatalytic stage at a temperature from about 0°

C. to about 250°

C. at a pressure from about 0.1 atm. to about 10 atm., and at a contact time of about 0.01 seconds to about 5 minutes to produce a gas stream having a reduced CVOC content; and

reducing any phosgene co-product found in the effluent of the photocatalytic stage by passing said effluent over said catalyst.

19. A process according to claim 18, wherein said temperature of said photocatalytic stage is in a range of from about 25°

C. to about 100°

C. and said operational temperature of said catalyst is in a range of from about 25°

C. to about 100°

C.

20. A process according to claim 18, wherein said pressure in said photocatalytic stage is in a range from about 0.8 atm. to about 2.0 atm. and said catalyst operational pressure is in a range of from about 0.8 atm. to about 2.0 atm.

21. A process according to claim 18, wherein said contact time is from about 0.1 seconds to about 10 seconds.

22. A process according to claim 18, wherein said photocatalytic stage has a photocatalyst bed containing a photocatalyst and a source of UV radiation and said passing step comprises passing said contaminated gas stream over said photocatalyst bed while said photocatalyst is illuminated by said source of UV radiation.

23. A process according to claim 22, wherein said UV radiation has a wavelength of about 100 to 400 nanometers.

24. A process according to claim 22, wherein said UV radiation has a wavelength of about 185 to 375 nanometers.

25. A process according to claim 22, wherein said photocatalyst in said photocatalyst bed used in said photocatalytic stage is comprised of silicon, titanium in an amount from about 0.015 wt % to about 5.0 wt %, zirconium in an amount from about 0.015 wt % to about 5.0 wt %, oxygen in an amount consistent with the chemical composition of the oxides of silicon, titanium, and zirconium, and the balance primarily silica.

26. A process according to claim 22, wherein said photocatalyst in said photocatalyst bed comprises silicon in an amount from about 0.1 wt % to about 70 wt %, titanium oxide in an amount from 30 wt % to about 90 wt %, tungsten in an amount from about 0.1 wt % to about 50 wt % and at least one of platinum and palladium in an amount from about 0.01 wt % to about 10 wt %.

27. A process according to claim 26, wherein said tungsten is present in an amount from about 1.0 wt % to about 30 wt %.

28. A process according to claim 26, wherein said at least one of platinum and palladium is present in an amount from about 0.1 wt % to about 5.0 wt %.

29. A process according to claim 22, wherein said photocatalyst in said photocatalyst bed comprises primarily at least one of silica and titania and at least one of platinum and palladium in an amount from about 0.01 wt % to about 5.0 wt %.

30. A process according to claim 22, wherein said photocatalyst used in said photocatalytic bed is formed primarily from silica.

31. A process according to claim 22, wherein said photocatalyst used in said photocatalytic bed is formed primarily from titania.

32. A process according to claim 18, further comprising providing a photolytic stage prior to said photocatalytic stage and passing said contaminated gas stream through said photolytic stage prior to passing said contaminated gas stream through said photocatalytic stage.

33. A process according to claim 1, further comprising:

providing a photolytic stage;

passing said contaminated gas stream through said photolytic stage; and

said reducing step comprising reducing any phosgene co-product found in the effluent of said photolytic stage by passing said effluent over said catalyst.

34. A process according to claim 1, wherein said catalyst providing step comprises providing a catalyst having copper and molybdenum distributed over a catalyst support formed from titania.

35. A process according to claim 1, wherein said catalyst providing step comprises providing a catalyst having a support formed from a titanium containing material and further having a material which forms a silicon-tungsten bond deposited on said support.

36. A process according to claim 35, wherein said material forming said silicon-tungsten bond comprises a compound containing silicon and tungsten.

37. A process according to claim 1, further comprising:

mixing said catalyst with a photocatalyst; and

said reducing step comprising photocatalytically treating said contaminated gas stream while placing said contaminated gas stream in contact with a bed containing said catalyst-photocatalyst mixture.