Porous 4 group metal oxide and method for preparation thereof

• US 20040238410A1
• Filed: 01/26/2004
• Published: 12/02/2004
• Est. Priority Date: 07/27/2001
• Status: Active Grant

• Current Assignee: Chiyoda Corporation (Mitsubishi Corporation)
• Original Assignee: Chiyoda Corporation (Mitsubishi Corporation)
• Inventors: Mutou, Akihiro, Ono, Tateo, Takatsuka, Toru, Nomura, Hisashi, Inoue, Shinichi, Makabe, Toshiji
• Granted Patent: US 7,943,115 B2
• Time in Patent Office: Days
• US Class Current: 208/213
• CPC Class Codes: B01J 21/06 Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
• 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 23/28 Molybdenum
• CPC Class Codes: B01J 23/85 Chromium, molybdenum or tungsten
• CPC Class Codes: B01J 23/88 Molybdenum
• CPC Class Codes: B01J 23/882 and cobalt
• CPC Class Codes: B01J 23/883 and nickel
• CPC Class Codes: B01J 23/888 Tungsten
• CPC Class Codes: B01J 27/188 with chromium, molybdenum, tungsten or polonium
• CPC Class Codes: B01J 35/60 characterised by their surface properties or porosity
• CPC Class Codes: B01J 35/613 10-100 m2/g
• CPC Class Codes: B01J 35/615 100-500 m2/g
• CPC Class Codes: B01J 35/633 less than 0.5 ml/g
• CPC Class Codes: B01J 35/635 0.5-1.0 ml/g
• CPC Class Codes: B01J 35/67 monomodal
• 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 37/036 to form a gel or a cogel
• CPC Class Codes: C01G 23/04 Oxides; Hydroxides
• CPC Class Codes: C01G 23/0536 by hydrolysing chloride-containing salts
• CPC Class Codes: C01G 25/02 : Oxides
• CPC Class Codes: C01P 2002/72 : by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2006/12 : Surface area
• CPC Class Codes: C01P 2006/14 : Pore volume
• CPC Class Codes: C01P 2006/17 : Pore diameter distribution
• CPC Class Codes: C01P 2006/21 : Attrition-index or crushing strength of granulates
• CPC Class Codes: C01P 2006/82 : water content
• CPC Class Codes: C10G 45/08 : in combination with chromium, molybdenum, or tungsten metals, or compounds thereof

Abstract

This invention relates to a 4 group metal oxide and to a method for preparation thereof and the 4 group metal oxide prepared by adding a particle growth inhibiter to a hydrosol a hydrogel or a dried product of a hydrous 4 group metal oxide represented by MO_(2-x)(OH)_2x (wherein M denotes a 4 group metal and x is a number greater than 0.1 or x>0.1) followed by drying and calcining has a specific surface area of 80 m²/g or more, a pore volume of 0.2 ml/g or more and a pore sharpness degree of 50% or more and excellent heat stability and is useful for a catalyst or a catalyst carrier in which a catalyst metal is dispersed to a high degree. This invention further relates to a porous 4 group metal oxide and to a method for preparation thereof and the 4 group metal oxide prepared by application of a pH swing operation is characterized by a large specific surface area, excellent heat stability, high dispersion of a catalyst metal and a controlled and sharp pore distribution and is useful for a catalyst or a catalyst carrier of excellent reaction selectivity.

Claims

1. A porous 4 group metal oxide which is characterized in that it is prepared by adding a particle growth inhibiter to a hydrosol, a hydrogel or a dried product of a hydrous 4 group metal oxide represented by the general formula MO_(2-x) (OH)_2x (wherein M denotes a 4 group metal and x is a number greater than 0.1 or x>

0.1) followed by drying and calcining and has a specific surface area of 80 m²/g, a pore volume of 0.2 ml/g or more and a pore sharpness degree of 50% or more.

2. A porous 4 group metal oxide as described in claim 1 wherein the 4 group metal M is titanium (Ti).

3. A porous 4 group metal oxide as described in claim 1 wherein the 4 group metal M is zirconium (Zr).

4. A porous 4 group metal oxide as described in claim 1 wherein the hydrous 4 group metal oxide is hydrous titanium oxide represented by the composition formula TiO_(2-x) (OH)_2x.yH₂O (wherein 0.1≦

x<

2.0 and 0.3≦

y≦

40).

5. A porous 4 group metal oxide as described in claim 1 wherein the hydrous 4 group metal oxide is hydrous titanium oxide represented by the composition formula TiO_(2-x) (OH)_2x.yH₂O (wherein 0.2≦

x<

1.0 and 0.3≦

y≦

40).

6. A porous 4 group metal oxide as described in any one of claims 1 through 5 wherein the hydrous 4 group metal oxide is prepared by using a 4 group metal compound as a raw material and a pH adjusting agent and performing a pH swing operation alternately plural times between the precipitating pH range and the dissolving pH range of the hydrous 4 group metal oxide in a synthesis solvent.

7. A porous 4 group metal oxide as described in any one of claims 1 through 5 wherein the 4 group metal M is titanium (Ti) and the hydrous titanium oxide is synthesized by using a raw material titanium compound and a pH adjusting agent and performing a pH swing operation in a synthesis solvent in the non-dissolving pH range of the hydrous titanium oxide alternately plural times between the range on the low pH side (1<

pH≦

4) and the pH range near the isoelectric point of the hydrous titanium oxide (5.1≦

pH≦

7.1) or between the pH range near the isoelectric point of the hydrous titanium oxide (5.1≦

pH≦

7.1) and the range on the high pH side (8≦

pH≦

12).

8. A porous 4 group metal oxide as described in any one of claims 1 through 5 wherein the 4 group metal M is titanium (Ti) and the hydrous titanium oxide is synthesized by using a raw material titanium compound and a pH adjusting agent and performing a pH swing operation in a synthesis solvent in the non-dissolving pH range of the hydrous titanium oxide between the range on the low pH side (1<

pH≦

4) and the range across the pH range near the isoelectric point of the hydrous titanium oxide (5.1≦

pH≦

7.1) or between the range on the high pH side (8≦

pH≦

12) and the range across the pH range near the isoelectric point of the hydrous titanium oxide (5.1≦

pH≦

7.1) while allowing a sufficient aging time for growth of particles in the pH range near the isoelectric point (5.1≦

pH≦

7.1).

9. A porous 4 group metal oxide as described in any one of claims 1 through 5 wherein the metal oxide is hydrous titanium oxide and wherein the pore asymmetric coefficient N of the hydrous titanium oxide defined by N=(A−

C)/(B−

A) (wherein A is the logarithmic value of the median diameter, B is the logarithmic value of the pore diameter of the 2% pore volume and C is the logarithmic value of the pore diameter of the 98% pore volume) falls in the range of 1.5≦

N≦

4.

10. A porous 4 group metal oxide as described in any one of claims 1 through 5 wherein the particle growth inhibiter is a compound yielding ions containing an element selected from silicon (Si), phosphorus (P), magnesium (Mg), calcium (Ca), manganese (Mn), aluminum (Al) and zirconium (Zr).

11. A porous 4 group metal oxide as described in any one of claims 1 through 5 wherein the particle growth inhibiter is a compound yielding ions containing an element selected from sulfur (S), molybdenum (Mo), tungsten (W), vanadium (V) and boron (B).

12. A porous 4 group metal oxide as described in any one of claims 1 through 5 wherein the particle growth inhibiter is a compound yielding ions containing an element selected from iron (Fe), nickel (Ni), cobalt (Co), platinum (Pt), palladium (Pd), rhodium (Rh) and ruthenium (Ru).

13. A porous 4 group metal oxide described in any one of claims 1 through 5 wherein the particle growth inhibiter is added together with the 4 group metal compound as a raw material to the reaction solvent during the synthesis of the hydrous 4 group metal oxide, after the synthesis and before the dehydration of the hydrous 4 group metal oxide, or after the dehydration and before the calcination of the hydrous 4 group metal oxide.

14. A porous 4 group metal oxide as described in any one of claims 1 through 5 wherein the particle growth inhibiter is added in the steps for filtration and washing of the hydrous 4 group metal oxide.

15. A porous 4 group metal oxide as described in any one of claims 1 through 5 wherein the particle growth inhibiter is added at a pH less than the isoelectric point of the hydrous 4 group metal oxide in case it is anions, added at a pH more than the isoelectric point in case it is cations or added at a pH corresponding to the isoelectric point ±

1.0 in case it is simultaneously anions and cations.

16. A porous 4 group metal oxide described in any one of claims 1 through 5 wherein the element contained in the particle growth inhibiter has catalytic activity for hydrotreating and the hydroxyl groups of the hydrous 4 group metal oxide are exchanged by the ions of said element.

17. A porous 4 group metal oxide as described in claims 1 through 5 wherein the porous 4 group metal oxide has a purity of 97 wt % or more on the oxide (MO₂) basis.

18. A porous 4 group metal oxide as described in claim 17 wherein the element originating in the particle growth inhibiter is contained in the range from 0.1 wt % to not more than 3 wt % on the oxide basis.

32. A hydrotreating catalyst for hydrocarbon oils comprising the porous 4 group metal oxide described in claim 16.

33. A hydrotreating catalyst for hydrocarbon oils as described in claim 32 wherein the 4 group metal M is titanium (Ti).

34. A hydrotreating catalyst for hydrocarbon oils as described in claim 32 wherein the element having catalytic activity for hydrotreating is the principal catalyst element molybdenum (Mo) and/or tungsten (W) and one kind or more of promoter elements selected from 9, 10, 11, 13 and 15 groups.

35. A hydrotreating catalyst for hydrocarbon oils as described in claim 34 wherein the promoter element is one kind or more of elements selected from cobalt (Co), nickel (Ni), phosphorus (P) and boron (B).

36. A hydrotreating catalyst for hydrocarbon oils as described in claim 32 wherein the amount of ion exchange of the principal catalyst element is 0.06-0.46 atom per 1 atom of titanium, that of the promoter element is 0.02-0.26 atom per 1 atom of titanium and the sum total of the amounts of ion exchange of the principal catalyst element and the promoter element is 0.08-0.82 atom per 1 atom of titanium.

37. In the preparation of the hydrotreating catalyst described in claim 32, a method for preparing a hydrotreating catalyst for hydrocarbon oils which comprises bringing the hydrous 4 group metal oxide into contact with the ions containing the principal catalyst element and the ions containing the promoter element, either together or separately, to effect an ion exchange, finally regulating the pH in the range of 3-9, molding, drying and calcining.

38. In the preparation of the hydrotreating catalyst described in claim 32, a method for preparing a hydrotreating catalyst for hydrocarbon oils which comprises adding the hydrous 4 group metal oxide to a impregnating solution of the ions containing the principal catalyst element and the ions containing the promoter element at pH 1-7 or pH 9-11 to effect an ion exchange, filtering, molding, drying and calcining.

39. In the preparation of the hydrotreating catalyst described in claim 32, a method for preparing a hydrotreating catalyst for hydrocarbon oils which comprises effecting the ion exchange involving the ions containing the principal catalyst element molybdenum (Mo) and/or tungsten (W) and the ions containing one kind or more of the promoter elements selected from cobalt (Co), nickel (Ni), phosphorus (P) and boron (B), filtering, molding, drying and calcining.

40. A method for hydrotreating of hydrocarbon oils which comprises contacting the hydrotreating catalyst described in claim 32 with hydrocarbon oils in the presence of hydrogen at a reaction temperature of 280-400°

C., a reaction pressure of 2-15 MPa, an LHSV of 0.3-10 hr<sup>−

1</sup> and a hydrogen/oil ratio of 50-500 Nl/l to remove sulfur components and nitrogen components from the hydrocarbon oils.

19. A method for preparing a porous 4 group metal oxide which comprises adding a particle growth inhibiter to a hydrosol, a hydrogel or a dried product of a hydrous 4 group metal oxide obtained by the reaction of a 4 group metal compound as a raw material with a pH adjusting agent in an aqueous solvent and represented by the general formula MO_(2-x)(OH)_2x (wherein M denotes a 4 group metal and x is a number greater than 0.1 or x>

0.1) followed by drying and calcining thereby yielding a 4 group metal oxide which has a specific surface area of 80 m²/g or more, a pore volume of 0.2 ml/g or more and a pore sharpness degree of 50% or more.

20. A method for preparing a porous 4 group metal oxide as described in claim 19 wherein the hydrous 4 group metal oxide is hydrous titanium oxide or the 4 group metal M is titanium (Ti).

21. A method for preparing a porous 4 group metal oxide as described in claim 19 wherein the hydrous 4 group metal oxide is hydrous zirconium oxide or the 4 group metal M is zirconium (Zr).

22. A method for preparing a porous 4 group metal oxide as described in claim 19 wherein the hydrous 4 group metal oxide is hydrous titanium oxide represented by the composition formula TiO_(2-x)(OH)_2x.yH₂O (wherein 0.1≦

x<

2.0 and 0.3≦

y≦

40).

23. A method for preparing a porous 4 group metal oxide as described in claim 19 wherein the hydrous 4 group metal oxide is hydrous titanium oxide represented by the composition formula TiO_(2-x)(OH)_2x .yH₂O (wherein 0.2≦

x<

1.0 and 0.3≦

y≦

40).

24. A method for preparing a porous 4 group metal oxide as described in any one of claims 19 through 23 wherein the hydrous 4 group metal oxide is obtained by using a 4 group metal compound as a raw material and a pH adjusting agent and performing a pH swing operation alternately between the precipitating pH range and the dissolving pH range of the hydrous 4 group metal oxide plural times in a synthesis solvent.

25. A method for preparing a porous 4 group metal oxide as described in any one of claims 19 through 23 wherein the 4 group metal M is titanium (Ti) and hydrous titanium oxide is synthesized by using a raw material titanium compound and a pH adjusting agent and performing a pH swing operation in a synthesis solvent in the non-dissolving pH range of the hydrous titanium oxide alternately plural times between the range on the low pH side (1<

pH≦

4) and the pH range near the isoelectric point of the hydrous titanium oxide (5.1≦

pH≦

7.1) or between the pH range near the isoelectric point of the hydrous titanium oxide (5.1≦

pH≦

7.1) and the range on the high pH side (8≦

pH≦

12).

26. A method for preparing a porous 4 group metal oxide as described in any one of claims 19 through 23 wherein the 4 group metal M is titanium (Ti) and hydrous titanium oxide is synthesized by using a raw material titanium compound and a pH adjusting agent and performing a pH swing operation in a synthesis solvent in the non-dissolving pH range of the hydrous titanium oxide between the range on the low pH side (1<

pH≦

4) and the range across the pH range near the isoelectric point (5.1≦

pH≦

7.1) or between the range on the high pH side (8≦

pH≦

12) and the range across the pH range near the isoelectric point (5.1≦

pH≦

7.1) while allowing a sufficient aging time for growth of particles in the range near the isoelectric point (5.1≦

pH≦

7.1).

27. A method for preparing a porous 4 group metal oxide as described in any one of claims 19 through 23 wherein the particle growth inhibiter is added together with the 4 group metal compound as a raw material to the reaction solvent during the synthesis of the hydrous 4 group metal oxide, after the synthesis and before the dehydration of the hydrous 4 group metal oxide or after the dehydration and before the calcination of the hydrous 4 group metal oxide.

28. A method for preparing a porous 4 group metal oxide as described in any one of claims 19 through 23 wherein the particle growth inhibiter is added at a pH less than the isoelectric point of the hydrous 4 group metal oxide in case it is anions, added at a pH more than the isoelectric point in case it is cations or added at a pH corresponding to the isoelectric point ±

1.0 in case it is simultaneously anions and cations.

29. A method for preparing a porous 4 group metal oxide as described in any one of claims 19 through 23 wherein the particle growth inhibiter is added in the steps for filtration and washing of the hydrous 4 group metal oxide.

30. A method for preparing a porous 4 group metal oxide as described in claim 29 wherein washing water to be used in the steps for filtration and washing of the hydrous 4 group metal oxide contains a particle growth inhibiter in an amount in the range of 1-100 ppm on the oxide basis of the metal contained in the particle growth inhibiter.

31. A method for preparing a porous 4 group metal oxide as described in any one of claims 19 through 23 wherein the metal contained in a particle growth inhibiter has catalytic activity for hydrotreating and the hydroxyl groups of the hydrous 4 group metal oxide are exchanged by the ions of this metal.