Mixed oxides of transition metals, hydrotreatment catalysts obtained therefrom and preparation process

Patent metadata

Field	Value
Publication number	US-10005071-B2
Application number	US-201615357341-A
Country	US
Kind code	B2
Filing date	Nov 21, 2016
Priority date	Mar 30, 2011
Publication date	Jun 26, 2018
Grant date	Jun 26, 2018

Abstract

New sulfide metal catalysts are described, containing Ni, Mo and W, an element Z selected from Si, Al and mixtures thereof, and possibly an organic residue, obtained by sulfidation of mixed oxide precursors, also new, characterized in that they comprise an amorphous phase and a wolframite iso structural crystalline phase, the crystallinity degree of said mixed oxides being higher than 0 and lower than 100%, preferably higher than 0 and lower than 70%. The catalysts of the invention are useful as hydrotreatment catalysts, and in particular as hydrodesulfurization, hydrodenitrogenation and/or hydrodearomatization catalysts.

First claim

The invention claimed is:

1. A process for preparing mixed oxides comprising the following steps:
1) preparing a mixture in water of at least one soluble source of Ni, at least one soluble source of W and a soluble source of Mo, at least one soluble, hydrolyzable or dispersible source of at least one element Z and, as nitrogenated compound N, an amine having formula (A)
R 1 R 2 R 3 N  (A)

wherein
R 1 is a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, and
R 2 and R 3 , equal to or different from each other, are selected from H and linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, said alkyl possibly being equal to or different from R 1 ;
Z is Si, Al, or a mixture thereof;
wherein the molar ratio N/(Ni+Mo+W) is greater than 0 and lower than or equal to 1
2) subjecting the mixture to hydrothermal treatment obtaining a suspension,
3) recovering from the suspension, the solid contained therein,
4) subjecting the solid recovered in step (3) to thermal treatment at a temperature higher than 150° C. and lower than 900° C. obtaining a mixed oxide MO, containing an amorphous phase and a wolframite isostructural crystalline phase, having a crystallinity degree greater than 0 and less than 100%.

2. The process according to claim 1 , wherein, in step (1), the ratios between the reagents, expressed as molar ratios, are the following:
Ni/Mo+W=0.6-1.5,
Mo/W greater than 0.1 and lower than 10,
R 1 R 2 R 3 N/(Ni+Mo+W)=0.1-1,
(Ni+Mo+W)/Z greater than or equal to 0.3 and lower than or equal to 10, H 2 0/(Ni+Mo+W+Z)≥20.

3. The process according to claim 1 , wherein, in step (2), the mixture is subjected to hydrothermal treatment, in a closed reactor, at a temperature ranging from 80 to 150° C.

4. The process according to claim 3 , wherein the hydrothermal treatment is carried out at a temperature lower than or equal to that of the lowest-boiling reagent.

5. The process according to claim 1 , wherein the thermal treatment of step (4) is carried out at a temperature higher than or equal to 150° C. and lower than or equal to 500° C.

6. The process according to claim 1 , wherein the thermal treatment of step (4) is carried out at a temperature higher than 500° C. and lower than 900° C.

7. The process according to claim 2 , wherein the thermal treatment of step (4) is carried out at a temperature higher than 500° C. and lower than 900° C.

8. A process for preparing a mixed oxide, formed, shaped with a binder, comprising the following steps:
1) preparing a mixture in water of at least one soluble source of Ni, at least one soluble source of Mo and a soluble source of W, at least one soluble, hydrolyzable or dispersible source of at least one element Z and, as nitrogenated compound N, an amine having formula (A)
R 1 R 2 R 3 N  (A)

wherein
R 1 is a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, and
R 2 and R 3 , equal to or different from each other, are selected from H and linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, said alkyl possibly being equal to or different from R 1 ;
Z is Si, Al, or a mixture thereof;
wherein the molar ratio N/(Ni+Mo+W) is greater than 0 and lower than or equal to 1,
2) subjecting the mixture to hydrothermal treatment obtaining a suspension,
3) adding to the suspension, a soluble, hydrolyzable or dispersible precursor of an oxide MeO, wherein Me is Si or Al, independently from Z, and possibly adding a mineral or organic acid, mixing, possibly in the presence of heating, for a time sufficient for obtaining a homogeneous paste having a consistency suitable for extrusion,

4) extruding the product obtained from the previous step,
5) subjecting the extruded product to thermal treatment at a temperature higher than or equal to 150° C. and lower than 900° C. obtaining a mixed oxide MO, containing an amorphous phase and a wolframite isostructural crystalline phase, having a crystallinity degree greater than 0 and less than 100%, in a shaped form with a binder MeO.

Assignees

• Eni Spa

Inventors

• Carati Angela
• Gagliardi Maria Federica
• Ferrari Marco Massimo
• Zanardi Stefano
• Marella Marcello
• Tomaselli Michele

Classifications

• B01J23/002 Primary

  Mixed oxides other than spinels, e.g. perovskite · CPC title

• C10G45/08

  in combination with chromium, molybdenum, or tungsten metals, or compounds thereof · CPC title

• B01J37/20

  Sulfiding · CPC title

• B01J37/10

  in the presence of water, e.g. steam · CPC title

• B01J37/04

  Mixing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title