Catalytic system and process for the hydroconversion of heavy oil products

Patent metadata

Field	Value
Publication number	US-9765266-B2
Application number	US-99678209-A
Country	US
Kind code	B2
Filing date	Jun 8, 2009
Priority date	Jun 11, 2008
Publication date	Sep 19, 2017
Grant date	Sep 19, 2017

Abstract

Catalytic system which can be used in processes for the hydroconversion of heavy oils by means of hydrotreatment in slurry phase, characterized in that it comprises: a catalyst, having the function of hydrogenating agent, containing MoS 2 or WS 2 or mixtures thereof in lamellar form or an oil-soluble precursor thereof; a co-catalyst, having nanometric or micronic particle-sizes, selected from cracking and/or denitrogenation catalysts. The co-catalyst preferably consists of zeolites having small-sized crystals and with a low aggregation degree between the primary particles, and/or oxides or sulfides or precursors of sulfides of Ni and/or Co in a mixture with Mo and/or W.

First claim

The invention claimed is:

1. A catalytic system, comprising:
a catalyst, as a hydrogenating agent; and
a nanometric or micronic co-catalyst, that is a cracking catalyst, a denitrogenation catalyst, or a combination thereof,
wherein the catalytic system is suitable for hydroconversion of a heavy oil,
wherein the catalyst consists of MoS 2 , WS 2 , or a mixture thereof, in lamellar form, or an oil-soluble precursor thereof,
wherein the catalyst is not supported, and
wherein the co-catalyst consists of zeolites having small-sized crystals and with a low aggregation degree between primary particles.

2. The catalytic system according to claim 1 wherein the zeolites comprise medium or large pores.

3. The catalytic system according to claim 2 , wherein the zeolites are Beta, Y, or MCM-22.

4. The catalytic system according to claim 1 , wherein the co-catalyst is supported on solid particles with micronic or submicronic dimensions.

5. The catalytic system according to claim 4 , wherein the solid particles on which the co-catalyst is supported are alumina, silica, silico-alumina, talc, mica, or a combination thereof.

6. The catalytic system according to claim 1 , wherein the catalyst and co-catalyst are in a weight ratio from 100:1 to 1:70.

7. The catalytic system according to claim 6 , wherein the catalyst and co-catalyst are in a weight ratio from 75:1 to 1:50.

8. A process for hydroconversion of a heavy oil, the process comprising:
sending the heavy oil to a hydrotreatment in slurry phase with a catalytic system as in claims 2 - 5 , or 6 ,
wherein the heavy oil is a crude oil, a heavy crude oil, a bitumen from a tar sand, a distillation residue, a heavy distillation cut, a deasphalted distillation residue, a vegetable oil, an oil deriving from coal or oil shale, an oil obtained by a process comprising thermo-decomposition of a waste product, a polymer, a biomass, a distillate, or a combination thereof.

9. The process according to claim 8 , further comprising:
separating an effluent stream from the hydrotreatment downstream of the hydrotreatment, thereby obtaining a heavier liquid fraction comprising dispersed catalyst and co-catalyst, and
recycling the heavier liquid fraction to the hydrotreatment.

10. The process according to claim 9 ,
wherein the sending comprises feeding hydrogenation catalyst dispersed in a feedstock, comprising the heavier liquid fraction of the recycling, to the hydrotreatment, and
wherein a concentration of the hydrogenation catalyst, based on a concentration of a metal or metals, is from 100 to 30,000 ppm.

11. The process according to claim 8 , wherein the hydrotreatment is at a temperature of from 350 to 480° C. and a pressure of from 80 to 220 atmospheres.

12. The process of claim 8 , wherein sending the heavy oil to the hydrotreatment in slurry phase with the catalytic system comprises hydrogenating the heavy oil, demetallizing the heavy oil, and cracking and denitrogenation of the heavy oil.

Assignees

• Bellussi Giuseppe
• Rispoli Giacomo
• Carati Angela
• Eni Spa

Inventors

• Bellussi Giuseppe
• Rispoli Giacomo
• Carati Angela

Classifications

• C10G2300/1074

  Vacuum distillates · CPC title

• C10G45/04 Primary

  characterised by the catalyst used · CPC title

• C10G45/12

  containing crystalline alumino-silicates, e.g. molecular sieves · CPC title

• B01J29/041

  Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 · CPC title

• C10G45/54

  containing crystalline alumino-silicates, e.g. molecular sieves · CPC title