Process for preparing a catalytic composition for the hydroconversion of petroleum fractions

Patent metadata

Field	Value
Publication number	US-9776174-B2
Application number	US-201414560983-A
Country	US
Kind code	B2
Filing date	Dec 4, 2014
Priority date	Aug 31, 2005
Publication date	Oct 3, 2017
Grant date	Oct 3, 2017

Abstract

The invention relates to a method of preparing a catalytic composition comprising at least one non-noble metal from group VIII and at least one metal from group VIB of the periodic table. The invention also relates to the catalytic composition thus produced, which has a high specific activity in reactions involving the hydroprocessing of light and intermediate fractions, preferably in reactions involving the hydrotreatment of hydrocarbon streams, including hydrodesulphurisation (HDS), hydrodenitrogenation (HDN) and hydro-dearomatisation (HDA).

First claim

What is claimed is:

1. A catalytic component consisting of at least one Group VIII non-noble metal, a single Group VIB metal and carbon, said catalytic component obtained by the process of reacting a solution of at least one soluble Group VIII metal precursor, a single soluble Group VIB metal precursor and a tetraalkyl quaternary ammonium salt at pH 5-14;
evaporating the solution to form a crystallized complex; thermally treating the crystallized complex; and
sulfiding the thermally treated crystallized complex to obtain the catalytic component wherein said catalytic component consists of at least one Group VIII metal sulfide, a Group VIB metal sulfide, and a surface area of 50 to 300 m 2 /g, a pore volume of 0.05 to 2.5 cm 3 /g and a pore diameter of 2-20 nm, and carbon in an amount of up to 5 wt. % based on the total weight of the Group VIII metal sulfide and Group VIB metal sulfide.

2. The catalytic component of claim 1 , wherein said tetraalkyl quaternary ammonium salt is a carbon precursor and is included in an amount to provide a carbon content of up to 5 wt % based on the weight of the Group VIII non-noble metal sulfide and the Group VIB metal sulfide.

3. The catalytic component of claim 2 , wherein the carbon is present in an amorphous state in an amount of 0.05 and 5 wt. % based on the total weight of the Group VIB and Group VIII metal sulfides.

4. The catalytic component of claim 2 , wherein the carbon is present as carbides in an amount of 0.05 and 5 wt. % based on the total weight of the Group VIB and Group VIII metal sulfides.

5. The catalytic component of claim 1 , wherein said catalytic component comprises fullerene nanoparticles with a laminae of 2 to 20 layers.

6. The catalytic component of claim 1 , wherein said tetraalkyl quaternary ammonium salt is a carbon precursor and is included in an amount to provide carbon in the catalytic component in an amount of 0.05 wt % to 5.0 wt % based on the total weight of the Group VIB and Group VIII metal sulfides.

7. The catalytic component of claim 1 , wherein the Group VIB and Group VIII metal sulfides have a surface area of 70 to 150 m2/g, a pore volume of 0.1 to 0.7 cm3/g, and a pore diameter of 3-10 nm.

8. A catalyst comprising a catalytic component consisting essentially of at least one Group VIII non-noble metal sulfide, a single Group VIB metal sulfide and carbon, and a surface area of 50 to 300 m2/g, a pore volume of 0.05 to 2.5 cm3/g and a pore diameter of 2-20 nm, said catalytic component obtained by the process comprising:
a) forming a solution of precursor salts in a solvent selected from the group consisting of water, methanol, ethanol, propanol, butanol, and mixtures thereof, said precursor salt being salts of at least one Group VIII non-noble metal and a single Group VIB metal;
b) forming a solution of a tetraalkyl quaternary ammonium salt carbon precursor in a solvent;
c) forming a mixture of the solutions obtained in steps (a) and (b);
d) adding a basic hydroxide solution and/or ammonium carbonate to the solution (c) at a pH between 5 and 14;
e) heating the solution obtained in step (d) to a temperature between 50 and 200° C.;
f) homogenizing the solution in step (e);
g) crystallizing the solution obtained in step (f) through evaporation of the solvent;
h) filtering or centrifugation of the resulting crystallized suspension obtained in step (g) for the separation of the crystals and recovery of mother liquors in the event that the evaporation has not been completed;
i) washing the solid obtained in step (h) with sufficient deionized water and/or water/alcohol mixture;
j) drying the solid obtained in step (i) at a temperature between 50 and 300° C.;
k) thermally treating the solid obtained in step (j) in inert atmosphere of nitrogen, helium, or argon, at a temperature between 200 and 1000° C.;
I) sulfiding of the material obtained step (i) or in step (j) in a gas flow made up of 10 vol. % hydrogen sulfide or with a hydrocarbon fraction containing at least 0.2 wt. % sulfur under a hydrogen flow at a temperature between 200 and 600° C., and a pressure between 1 and 100 Kg/cm2 to obtain said catalytic component.

9. The catalyst in accordance with claim 8 , where the Group VIII non-noble metal is selected from the group consisting of nickel, cobalt, and/or iron, and mixtures thereof.

10. The catalyst in accordance with claim 9 , where the nickel and/or cobalt represent 100 wt. % of the Group VIII non-noble metals calculated as oxides.

11. The catalyst in accordance with claim 8 , where the Group VIB metal is one selected from the group consisting of molybdenum, tungsten and chromium.

12. The catalyst in accordance with claim 8 , further comprising an inorganic oxide binder selected from the group consisting of alumina, silica, titania, silica-alumina, alumina-titania, zirconia, zirconia-titania, zirconia-alumina, amorphous silico-aluminates, and/or crystalline clays in the homogenization step of the mixture of precursor salts.

13. The catalyst in accordance with claim 8 , further comprising the addition of an inorganic oxide binder, after the crystallization stage in the wet and/or dry material.

14. The catalyst in accordance with claim 8 , further comprising the addition of an inorganic oxide as a binder, after the material has been thermally treated and/or sulfided.

15. The catalytic component of claim 8 , wherein said tetraalkyl quaternary ammonium salt carbon precursor is included in an amount to provide a carbon content of up to 5 wt % based on the weight of the Group VIII non-noble metal sulfide and the Group VIB metal sulfide.

Assignees

• Mexicano Inst Petrol

Inventors

• Toledo Antonio Jose Antonio
• Perez Luna Miguel
• Cortes Jacome Maria Antonia
• Escobar Aguilar Jose
• Mosqueira Mondragon Maria De Lourdes
• Angeles Chavez Carlos
• Lopez Salinas Esteban
• Perez Moreno Victor
• Ferrat Torres Gerardo
• Mora Vallejo Rodolfo Juventino
• Lozada Y Cassou Marcelo

Classifications

• B01J23/883

  and nickel · CPC title

• B01J37/084

  Decomposition of carbon-containing compounds into carbon · CPC title

• B01J37/03

  Precipitation; Co-precipitation · CPC title

• B01J23/85 Primary

  Chromium, molybdenum or tungsten · CPC title

• B01J37/0018

  Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat) · CPC title