Hydrogenation catalyst and method for producing same

Patent metadata

Field	Value
Publication number	US-9737883-B2
Application number	US-201214349105-A
Country	US
Kind code	B2
Filing date	Oct 22, 2012
Priority date	Oct 24, 2011
Publication date	Aug 22, 2017
Grant date	Aug 22, 2017

Abstract

A hydrotreating catalyst includes a hydrogenation active metal supported on a alumina-phosphorus support and satisfies: a specific surface area being 100 m 2 /g or more; a total pore volume measured by mercury intrusion being in a range 0.80-1.50 ml/g; a maximum value of pore distribution being present in a pore diameter range 10-30 nm; a ratio of a pore volume of pores with a pore diameter within a range of ±2 nm of a pore diameter at the maximum value to a pore volume of pores with a pore diameter in a range 5-100 nm being 0.40 or less; a pressure capacity being 10 N/mm or more; 0.4-10.0 mass % of phosphorus being contained in the catalyst in terms of P 2 O 5 concentration based on a total amount of the catalyst; and a hydrogenation active metal being at least one metal selected from metals of VIA and VIII groups of the periodic table.

First claim

The invention claimed is:

1. A hydrotreating catalyst comprising:
an alumina-phosphorus support, where the alumina-phosphorus support is shaped in the form of a column, and
a hydrogenation active metal supported on the alumina-phosphorus support, wherein:
(1) a specific surface area of the hydrotreating catalyst is 100 m 2 /g or more;
(2) a total pore volume (PV T ) of the hydrotreating catalyst measured according to a mercury intrusion method is in a range from 0.80 to 1.50 ml/g;
(3) the hydrotreating catalyst has a maximum value of pore distribution in a pore diameter range from 10 to 30 nm;
(4) a ratio (ΔPV/PVme) of a pore volume (ΔPV) of pores with a pore diameter within a range of ±2 nm of a pore diameter at the maximum value to a pore volume (PVme) of pores with a pore diameter in a range from 5 to 100 nm is 0.40 or less;
(5) a pressure capacity of the hydrotreating catalyst is 10 N/mm or more;
(6) 0.4 to 10.0 mass % of phosphorus is contained in the hydrotreating catalyst in terms of P 2 O 5 concentration based on a total amount of the hydrotreating catalyst; and
(7) the hydrogenation active metal is at least one metal selected from metals of VIA and VIII groups of the periodic table.

2. The hydrotreating catalyst according to claim 1 ,
wherein
the alumina-phosphorus support contains 0.5 to 7.0 mass % of phosphorus in terms of P 2 O 5 concentration based on a total amount of the support.

3. The hydrotreating catalyst according to claim 1 ,
wherein
the hydrotreating catalyst contains 1 to 25 mass % of the hydrogenation active metal in terms of oxide concentration based on the total amount of the hydrotreating catalyst.

4. The hydrotreating catalyst according to claim 1 ,
wherein
the hydrotreating catalyst has a second maximum value of the pore distribution in a pore diameter range from 100 to 1000 nm.

5. The hydrotreating catalyst according to claim 4 , wherein
a ratio (PVma/PVme) of a pore volume (PVma) of pores having a pore diameter in the range from 100 to 1000 nm to the pore volume (PVme) of pores having the pore diameter in the range from 5 to 100 nm is in a range from 0.1 to 0.5.

6. The hydrotreating catalyst according to claim 1 ,
wherein
the hydrotreating catalyst is used for treating a heavy hydrocarbon oil.

7. The hydrotreating catalyst according to claim 1 ,
wherein
the specific surface area of the hydrotreating catalyst is in a range from 150 to 250 m 2 /g.

8. The hydrotreating catalyst according to claim 1 ,
wherein
the maximum value of pore distribution of the hydrotreating catalyst is in a pore diameter range from 12 to 25 nm.

9. The hydrotreating catalyst according to claim 1 ,
wherein
the ΔPV/PVme ratio is 0.30 or less.

10. The hydrotreating catalyst according to claim 1 ,
wherein
the maximum value of pore distribution of the hydrotreating catalyst is in a pore diameter range from 10 to 20 nm.

11. The hydrotreating catalyst according to claim 1 ,
wherein
the maximum value of pore distribution of the hydrotreating catalyst is in a pore diameter range from 15.2 to 18.5 nm, and
the ΔPV/PVme ratio is in a range from 0.22 to 0.30.

12. The hydrotreating catalyst according to claim 1 ,
wherein
the hydrotreating catalyst is comprised in a fixed-bed apparatus.

13. A method for producing the hydrotreating catalyst of claim 1 , the method comprising:
producing an alumina-phosphorus support; and
supporting a hydrogenation active metal on the alumina-phosphorus support, wherein
the producing of the support comprises:
a first step of obtaining an alumina hydrate by preparing an acidic aluminum aqueous solution of which pH is adjusted in a range from 2.0 to 5.0 and, while agitating the acidic aluminum aqueous solution, adding a basic aluminum aqueous solution so that the pH falls in a range from 7.5 to 10.0;
a second step of obtaining an alumina-phosphorus hydrate by adding phosphorus to the alumina hydrate from which a residual product salt of the alumina hydrate is removed; and
a third step of obtaining an alumina-phosphorus support by aging, kneading, molding, drying and calcining the alumina-phosphorus hydrate in turn.

14. The method for producing the hydrotreating catalyst according to claim 13 ,
wherein
phosphorus is added to the alumina hydrate in the second step so that 3.0 to 7.0 mass % of phosphorus in terms of P 2 O 5 concentration based on a total amount of the support is contained in the alumina hydrate.

15. The method for producing the hydrotreating catalyst according to claim 13 ,
wherein
phosphorus is added to the alumina hydrate in the second step so that 0.5 to 2.5 mass % of phosphorus in terms of P 2 O 5 concentration based on a total amount of the support is contained in the alumina hydrate.

Assignees

• Jgc Catalysts & Chemicals Ltd
• Jgc Catalysis And Chemicals Ltd

Inventors

• Yamane Kenji
• Ohama Kouichi
• Tagawa Shogo

Classifications

• B01J37/033

  Using Hydrolysis · CPC title

• B01J27/16

  containing oxygen {, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr} · CPC title

• B01J37/0203

  the impregnation liquid containing organic compounds · CPC title

• B01J37/28

  Phosphorising · CPC title

• C10G45/04

  characterised by the catalyst used · CPC title