Catalyst for removing organic halogen compounds, preparation method therefor and method for removing organic halogen compounds

• US 6,120,747 A
• Filed: 12/19/1997
• Issued: 09/19/2000
• Est. Priority Date: 12/27/1996
• Status: Expired due to Fees

• Current Assignee: Nippon Shokubai Company Limited
• Original Assignee: Nippon Shokubai Company Limited
• Inventors: Morita, Atsushi, Sugishima, Noboru, Kobayashi, Motonobu
• Primary Examiner(s): Straub, Gary P.
• Assistant Examiner(s): Wong, Melanie C.
• Application Number:
  US08/995,099
• Time in Patent Office: 1,005 Days
• Field of Search: 502/350, 502/353, 502/309, 502/242, 423/240 S, 588/206
• US Class Current: 423/240.00S
• 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 23/30 Tungsten
• CPC Class Codes: B01J 2523/00 Constitutive chemical elements of heterogeneous catalysts
• CPC Class Codes: B01J 2523/47 Titanium
• CPC Class Codes: B01J 2523/55 Vanadium
• CPC Class Codes: B01J 2523/69 Tungsten
• CPC Class Codes: B01J 35/30 characterised by their physical properties
• CPC Class Codes: B01J 35/40 characterised by dimensions, e.g. grain size in a colloidal state B01J35/23; crystallite size B01J35/77
• CPC Class Codes: B01J 35/56 Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
• CPC Class Codes: B01J 35/613 10-100 m2/g
• CPC Class Codes: B01J 35/615 100-500 m2/g
• CPC Class Codes: B01J 35/66 Pore distribution
• CPC Class Codes: B01J 35/69 bimodal
• CPC Class Codes: B01J 37/0009 Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
• CPC Class Codes: B01J 37/031 Precipitation

Abstract

The present invention provides a catalyst having excellent capability of removing organic halogen compounds such as dioxins, a method for preparing the catalyst, and a method for removing organic halogen compounds using the catalyst. A catalyst for removing organic halogen compounds comprises titanium oxide as a catalyst component and has pores including a group of pores having a pore diameter distribution peak in a range of 0.01 to 0.05 gm and another group of pores having a pore diameter distribution peak in a range of 0.1 to 0.8 μm. Another catalyst for removing organic halogen compounds comprises titanium oxide and a titanium-silicon composite oxide as catalyst components and has pores including a group of pores having a pore diameter distribution peak in a range of 0.01 to 0.05 μm and another group of pores having a pore diameter distribution peak in a range of 0.8 to 4 μm.

Claims

1. A method for removing organic halogen compounds, which method comprises the step of bringing a catalyst component into contact with organic halogen compounds, wherein the catalyst component comprises titanium oxide and "said titanium oxide having a bimodal pore distribution wherein the first group of pores having a pore diameter distribution peak in a range of 0.01 to 0.05 μ

m and the second group of pores having a pore diameter distribution peak in a range of 0.1 to 0.8 μ

m with essentially all the pore volume of the titanium oxide being in said ranges".

2. A method according to claim 1, wherein the total pore volume measured by a mercury press-fit method is in a range of 0.2 to 0.6 cc/g, the pore volume of the group of pores having a pore diameter distribution peak in a range of 0.01 to 0.05 μ

m accounts for 10 to 60% of the total pore volume, and the pore volume of the group of pores having a pore diameter distribution peak in a range of 0.1 to 0.8 μ

m accounts for 10 to 60% of the total pore volume, said pores'"'"' groups providing essentially 100% of the pore volume of the titanium oxide.

3. A method according to claim 2, further comprising either or both of vanadium oxide and tungsten oxide as catalyst components.

4. A method for removing organic halogen compounds, which comprises the step of bringing an exhaust gas containing an organic halogen compound into contact with a catalyst as recited in claim 2.

5. A method according to claim 1, further comprising either or both of vanadium oxide and tungsten oxide as catalyst components.

6. A method for removing organic halogen compounds, which comprises the step of bringing an exhaust gas containing an organic halogen compound into contact with a catalyst as recited in claim 5.

7. The method according to claim 5, wherein either of vanadium oxide and tungsten oxide is added as a catalyst component in an amount of 0.1 to 25 wt % relative to an amount of titanium oxide.

8. The method according to claim 5, wherein both of vanadium oxide and tungsten oxide are added as catalyst components, with vanadium oxide being added in an amount of 0.1 to 25 wt % relative to an amount of titanium oxide, and with tungsten oxide being added in an amount of 0.1 to 25 wt % relative to the amount of titanium oxide.

9. The method according to claim 5, wherein the catalyst components of titanium oxide and tungsten oxide are mixed together to a high degree so as to obtain a uniformly dense mixture and such that an X-ray diffraction of said mixture produces substantially no peak derived from tungsten oxide.

10. A method for removing organic halogen compounds, which comprises the step of bringing an exhaust gas containing an organic halogen compound into contact with a catalyst as recited in claim 1.

11. The method according to claim 1, wherein the catalyst component comprises a catalyst in the shape of a particle, with the particle having a specific surface area measured by a BET method of 30 to 250 m₂ /g.

12. The method according to claim 1, wherein each of the pore diameter distribution peaks includes a pore diameter distribution that is substantially uniform.

26. A method for removing organic halogen compounds according to claim 1, wherein said pore groups provide about 90% or more of the pore volume of the titanium oxide.

27. A method of removing organic halogen compounds according to claim 1, wherein:

a) each of the pore diameter distribution peaks is produced by plotting pore diameter on an "x" axis against the number of pores having a certain pore diameter on a "y" axis to obtain a graph showing a bimodal pore distribution;

b) the graph includes each of the pore diameter distribution peaks;

c) each of the peaks is produced by a first line representing an increase in the number of pores having a certain pore diameter and a second line representing a decrease in the number of pores having a certain pore diameter, with said peak being between the first and second lines; and

d) said phrase "essentially all the pore volumes of the titanium oxide being in said range" includes the following;

i) for the first group of pores, those pores having a pore diameter slightly less than the value of 0.01 μ

m where said pores are on or below the first line;

ii) for the first group of pores, those pores having a pore diameter slightly greater than the value of 0.05 μ

m where said pores are on or below the second line;

iii) for the second group of pores, those pores having a pore diameter slightly less than the value of 0.1 μ

m where said pores are on or below the first line; and

iv) for the second group of pores, those pores having a pore diameter slightly greater than the value of 0.8 μ

m where said pores are on or below the second line.

13. A method for removing organic halogen compounds, which method comprises the step of bringing catalyst components into contact with organic halogen compounds, wherein one of the catalyst components comprises titanium oxide and the other catalyst component comprises a titanium-silicon composite oxide, "having a bimodal pore distribution wherein each of the catalyst components comprises two groups of pores, wherein the first group of pores has a pore diameter distribution peak in a range of 0.01 to 0.05 μ

m and wherein the second group of pores has a pore diameter distribution peak in a range of 0.8 to 4 μ

m with essentially all the pore volume of the said components being in said ranges."

14. A method according to claim 13, wherein the total pore volume measured by a mercury press-fit method is in a range of 0.2 to 0.6 cc/g, the pore volume of the group of pores having a pore diameter distribution peak in a range of 0.01 to 0.05 μ

m accounts for 20 to 60% of the total pore volume, and the pore volume of the group of pores having a pore diameter distribution peak in a range of 0.8 to 4 gm accounts for 10 to 50% of the total pore volume, said pores'"'"' groups providing essentially 100% of the pore volume of said components.

15. A method according to claim 14, further comprising either or both of vanadium oxide and tungsten oxide as catalyst components.

16. A method for removing organic halogen compounds, which comprises the step of bringing an exhaust gas containing an organic halogen compound into contact with a catalyst as recited in claim 14.

17. A method according to claim 14, wherein the pore volume of the group of pores having a pore diameter distribution peak in a range of 0.8 to 4 μ

m accounts for 31 to 50% of the total pore volume.

18. A method according to claim 13, further comprising either or both of vanadium oxide and tungsten oxide as catalyst components.

19. The method according to claim 18, wherein either of vanadium oxide and tungsten oxide is added as a catalyst component in an amount of 0.1 to 25 wt % relative to an amount of titanium oxide.

20. The method according to claim 18, wherein both of vanadium oxide and tungsten oxide are added as catalyst components, with vanadium oxide being added in an amount of 0.1 to 25 wt % relative to a total amount of titanium oxide and titanium-silicon composite oxide, and with tungsten oxide being added in an amount of 0.1 to 25 wt % relative to the total amount of titanium oxide and titanium-silicon composite oxide.

21. The method according to claim 18, wherein the catalyst components of titanium oxide and titanium-silicon composite oxide and tungsten oxide are mixed together to a high degree so as to obtain a uniformly dense mixture and such that an X-ray diffraction of said mixture produces substantially no peak derived from tungsten oxide.

22. A method for removing organic halogen compounds, which comprises the step of bringing an exhaust gas containing an organic halogen compound into contact with a catalyst as recited in claim 13.

23. The method according to claim 13, wherein the catalyst components comprise a catalyst in the shape of a particle, with the particle having a specific surface area measured by a BET method of 30 to 250 m² /g.

24. The method according to claim 13, wherein each of the pore diameter distribution peaks includes a pore diameter distribution that is substantially uniform.

25. The method according to claim 13, wherein an amount of titanium-silicon composite oxide is 0.01 to 5 times by weight an amount of titanium oxide.

28. A method for removing organic halogen compounds according to claim 13, wherein said pore groups provide about 89% or more of the pore volume of said components.

29. A method for removing organic halogen compounds according to claim 13, wherein:

a) each of the pore diameter distribution peaks is produced by plotting pore diameter on an "x" axis against the number of pores having a certain pore diameter on a "y" axis to obtain a graph showing a bimodal pore distribution;

b) the graph includes each of the pore diameter distribution peaks;

c) each of the peaks is produced by a first line representing a increase in the number of pores having a certain pore diameter and a second line representing a decrease in the number of pores having a certain pore diameter, with said peak being between the first and second lines; and

d) said phrase "essentially all the pore volumes of said components being in said ranges" includes the following;

i) for the first group of pores, those pores having a pore diameter slightly less than the value of 0.01 μ

m where said pores are on or below the first line;

ii) for the first group of pores, those pores having a pore diameter slightly greater than the value of 0.05 μ

where said pores are on or below the second line;

iii) for the second group of pores, those pores having a pore diameter slightly less than the value of 0.8 μ

m where said pores are on or below the first line; and

iv) for the second group of pores, those pores having a pore diameter slightly greater than the value of 4 μ

m where said pores are on or below the second line.

30. A method for removing organic halogen compounds, which method comprises the step of bringing a catalyst component into contact with organic galogen compounds wherein the catalyst component comprises titanium oxide, said titanium oxide having a bimodal pore distribution, wherein the first group of pores define a first pore diameter distribution curve and a first pore volume and wherein the second group of pores define a second pore diameter distribution curve and a second pore volume, with all of the pores and thus all of the pore volumes being on or under said two pore diameter distribution curves, wherein each of the pores of said first group of pores has a diameter in a range of about 0.01 to about 0.05 μ

m, and wherein each of the pores of the second group of pores has a diameter in a range of about 0.1 to about 0.8 μ

m, with about 90% or more of the pore volumes of the titanium oxide being in ranges of exactly 0.01 to exactly 0.05 μ

m and exactly 0.1 to exactly 0.8 μ

m.

31. A method for removing organic halogen compounds, which method comprises the step of bringing catalyst components into contact with organic halogen compounds, wherein one of the catalyst components comprises titanium oxide and the other catalyst components comprises a titanium-silicon composite oxide having a bimodal pore distribution, wherein each of the catalyst components comprises first and second groups of pores, wherein the first group of pores define a first pore diameter distribution curve and a first pore volume and wherein the second group of pores define a second pore diameter distribution curve and a second pore volume, with all of the pores and thus all of the pore volumes being on or under said first and second pore diameter distribution curves, wherein each of the pores of said first group of pores has a diameter ina range of about 0.01 to about 0.05 μ

m and wherein each of the pores of said second group pores has a diameter in a range of about 0.8 to about 4 μ

m, with about 89% or more of the pore volumes of said components being in ranges of exactly 0.01 to exactly 0.05 μ

m and exactly 0.8 to exactly 4 μ

m.