Catalytic system and process for the total hydroconversion of heavy oils

Patent metadata

Field	Value
Publication number	US-9700880-B2
Application number	US-201214343007-A
Country	US
Kind code	B2
Filing date	Sep 6, 2012
Priority date	Sep 8, 2011
Publication date	Jul 11, 2017
Grant date	Jul 11, 2017

Abstract

A catalytic system characterized in that it comprises: a first catalyst, having a hydrogenating function, consisting of solid particles of which at least 95% by volume having an equivalent diameter smaller than 20 μm, containing one or more sulfides of metals of group VI and/or VIII B, possibly prepared starting from an oil-soluble precursor of the same; and a second catalyst, having a cracking function, consisting of solid particles of which at least 90% by volume having an equivalent diameter larger than 5 μm and smaller than 5 mm, containing an amorphous silico-aluminate and/or a crystalline silico-aluminate and/or an alumina, the equivalent average diameter of the solid particles of the second catalyst being greater than the equivalent average diameter of the solid particles of the first catalyst. Said catalytic system can be used in a process for the hydroconversion of heavy oils which comprises sending the heavy oil to a hydroprocessing step carried out in one or more slurry reactors, in the presence of hydrogen or a mixture of hydrogen and H 2 S, obtaining a stream of products in vapor or liquid-vapor phase, and extracting at the bottom, in continuous or discontinuous, a liquid stream containing non-converted products together with the two catalysts of said catalytic system, said liquid stream extracted then being separated into a clarified primary stream containing the first catalyst, which is at least partially recycled to the hydroprocessing step, and a stream rich in the second catalyst, which is regenerated in a regeneration step and at least partially recycled to the hydroprocessing step.

First claim

The invention claimed is:

1. A catalytic system which can be used for the hydroconversion of heavy oils comprising a mixture of:
a first catalyst, having a hydrogenating function, consisting of solid particles of which at least 95% by volume having an equivalent diameter smaller than 20 μm, containing one or more sulfides of metals of group VI and/or VIII B; and
a second catalyst, having a cracking function, consisting of solid particles of which at least 90% by volume having an equivalent diameter larger than 5 μm and smaller than 5 mm, containing an amorphous silico-aluminate and/or a crystalline silico-aluminate and/or an alumina, wherein
the equivalent average diameter of the solid particles of the second catalyst is greater than the equivalent average diameter of the solid particles of the first catalyst.

2. The catalytic system according to claim 1 , wherein the first catalyst consists of MoS 2 and/or WS 2 and/or FeS x .

3. The catalytic system according to claim 1 , wherein the first catalyst is obtained from an oil-soluble precursor of metals of group VI and/or VIII B.

4. The catalytic system according to claim 1 , wherein the crystalline silico-aluminate is selected from zeolites having at least one system of channels with an average diameter higher than 5 Angstroms (large-pore zeolites).

5. The catalytic system according to claim 1 , wherein the crystalline silico-aluminate is as MCM-22 zeolite.

6. The catalytic system according to claim 1 , wherein at least 90% by volume of the solid particles forming the second catalyst have a diameter larger than 10 μm and smaller than 1 mm.

7. The catalytic system according to claim 1 , wherein at least 90% by volume of the solid particles forming the second catalyst have a diameter larger than 20 μm and smaller than 0.8 mm.

8. The catalytic system according to claim 1 , wherein at least 95% by volume of the solid particles forming the second catalyst have a diameter smaller than 5 μm.

9. The catalytic system according to claim 1 , wherein the equivalent average diameter of the solid particles of the second catalyst is at least 30 μm greater than the equivalent average diameter of the solid particles of the first catalyst.

10. The catalytic system according to claim 1 , wherein the equivalent average diameter of the solid particles of the second catalyst is at least 50 μm greater than the equivalent average diameter of the solid particles of the first catalyst.

11. The catalytic system according to claim 1 , wherein the second catalyst is a catalyst for FCC (Fluid Catalytic Cracking).

12. A process for the hydroconversion of heavy oils comprising: feeding the heavy oil to a hydroprocessing step carried out in one or more slurry reactors, using a catalytic system according to claim 1 , in the presence of hydrogen or a mixture of hydrogen and H 2 S, so obtaining a stream of products in vapour or liquid-vapour phase, and extracting from the bottom of the reactor(s), in continuous or discontinuous, a liquid stream containing non-converted products together with the two catalysts of the catalytic system used, said extracted liquid stream then being separated into a clarified primary stream containing the first catalyst, which is at least partially recycled to the hydroprocessing step, and a stream rich in the second catalyst, which is regenerated in a regeneration step and at least partially recycled to the hydroprocessing step.

13. The process according to claim 12 , wherein, before being recycled to the hydroprocessing step, the clarified primary stream is at least partially separated into a clarified secondary stream and a solid stream containing part of the first catalyst, optionally metals present in the heavy oil feed and optionally part of the second catalyst, only said clarified secondary stream being at least partially recycled to the hydroprocessing step.

14. The process according to claim 12 , wherein, before being dried, the stream rich in the second catalyst is separated, by addition of a washing solvent, into a liquid stream containing part of the washing solvent and part of the first catalyst, which is recycled to the hydroprocessing step, and into a solid-liquid stream containing part of the solvent and the second catalyst, only said last stream being sent to the regeneration step.

15. The process according to claim 12 , wherein the stream rich in the second catalyst is dried before being regenerated in the regeneration step.

16. The process according to claim 12 , wherein the hydroprocessing step is carried out at a temperature ranging from 360 to 480° C. and a pressure ranging from 80 to 200 atmospheres.

17. The process according to claim 12 , wherein the ratio between the second catalyst and the heavy oil fed to the hydroprocessing step ranges from 1 to 2,000 kg/metric ton.

Assignees

• Molinari Daniele
• Bellussi Giuseppe
• Landoni Alberto
• Pollesel Paolo
• Eni Spa

Inventors

• Molinari Daniele
• Bellussi Giuseppe
• Landoni Alberto
• Pollesel Paolo

Classifications

• B01J29/7876

  MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25 · CPC title

• C10G65/12

  including cracking steps and other hydrotreatment steps · CPC title

• C10G47/16

  Crystalline alumino-silicate carriers · CPC title

• C10G45/12

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

• B01J27/051 Primary

  Molybdenum · CPC title