Process for the selective hydrogenation of a gasoline

Patent metadata

Field	Value
Publication number	US-9505686-B2
Application number	US-201313851258-A
Country	US
Kind code	B2
Filing date	Mar 27, 2013
Priority date	Mar 29, 2012
Publication date	Nov 29, 2016
Grant date	Nov 29, 2016

Abstract

The present application relates to a process for the selective hydrogenation of a gasoline which contains polyunsaturated compounds and sulphurous light compounds, the process allowing conjointly the hydrogenation of polyunsaturated compounds into mono-unsaturated compounds, increasing weight of the sulphurous light compounds by reaction with the unsaturated compounds, and maximization of the isomerization of the monounsaturated compounds comprising an external C═C double bond into their internal C═C double bond isomer, said process implementing a catalyst containing at least one group VIb metal and at least one group VIII metal deposited on a porous support.

First claim

The invention claimed is:

1. A process of selective hydrogenation of a gasoline comprising polyunsaturated compounds and sulphurous light compounds, said process enables, conjointly, hydrogenation of the polyunsaturated compounds into monounsaturated compounds, weighting of the sulphurous saturated light compounds by reaction with the monounsaturated compounds, and isomerisation of the monounsaturated compounds comprising an external C═C double bond into their isomer having an internal C═C double bond, said process is conducted in the presence of a catalyst containing at least one group VIb metal and at least one group VIII metal deposited on a porous support, wherein:
the content by weight of oxide of the group VIb element with reference to the weight of the catalyst is 6 to 18%;
the content by weight of oxide of the group VIII element with reference to the weight of the catalyst is 4 to 12%;
the specific surface area of the catalyst is 200 to 270 m 2 /g;
the density of the group VIb element, expressed as being the ratio of the said content by weight of oxide of the group VIb element to the specific surface area of the catalyst, is 4×10 −4 g/m 2 to 6×10 −4 ; and
the molar ratio between the group VIII metal and the group VIb metal is 0.6 to 3 mol/mol.

2. The process according to claim 1 , wherein the group VIb metal is molybdenum or tungsten.

3. The process according to claim 1 , wherein the group VIII metal is nickel, cobalt or iron.

4. The process according to claim 1 , wherein the group VIII metal is nickel and the group VIb metal is molybdenum.

5. The process according to claim 1 , wherein the content by weight of oxide of the group VIII element is 6 to 10%, with reference to the weight of the catalyst, and wherein the content by weight of oxide of the group VIb element is 8 to 12%, with reference to the weight of the catalyst.

6. The process according to claim 1 , wherein the molar ratio of the group VIII metal to the group VIb metal is 1 to 2 mol/mol.

7. The process according to claim 1 , wherein the density of the group VIb element is 4.3×10 −4 g/m 2 to 5.5×10 −4 g/m 2 .

8. The process according to claim 1 , wherein the sulphuration rate of the group VIb metal and the group VIII metal of the catalyst is greater than 80%.

9. The process according to claim 1 , wherein the catalyst has a total pore volume greater than 0.3 cm 3 /g.

10. The process according to claim 1 , wherein the specific surface area of the catalyst is 220 to 260 m 2 /g.

11. The process according to claim 1 , wherein the support is alumina, silica, silicon carbide or a mixture thereof.

12. The process of selective hydrogenation according to claim 1 , wherein the feed and the hydrogen are put in contact with the catalyst at a temperature of 80° C. to 220° C. and with a liquid hourly space velocity of 1 h −1 and 10 h −1 and a pressure of 0.5 to 5 MPa.

13. A process of desulphuration of gasoline comprising sulphurous compounds, comprising the following steps:
a) a selective hydrogenation step, which is the selective hydrogenation of a gasoline comprising polyunsaturated compounds and sulphurous light compounds to produce a hydrogenated gasoline, said selective hydrogenation step enables, conjointly, hydrogenation of the polyunsaturated compounds into monounsaturated compounds, weighting of the sulphurous saturated light compounds by reaction with the monounsaturated compounds, and isomerisation of the monounsaturated compounds comprising an external C═C double bond into their isomer having an internal C═C double bond, said selective hydrogenation step is conducted in the presence of a catalyst containing at least one group VIb metal and at least one group VIII metal deposited on a porous support, wherein:
the content by weight of oxide of the group VIb element with reference to the weight of the catalyst is 6 to 18%;
the content by weight of oxide of the group VIII element with reference to the weight of the catalyst is 4 to 12%;
the specific surface area of the catalyst is 200 to 270 m 2 /g;
the density of the group VIb element, expressed as being the ratio of the said content by weight of oxide of the group VIb element to the specific surface area of the catalyst, is 4×10 −4 g/m 2 to 6×10 −4 g/m 2 ; and
the molar ratio between the group VIII metal and the group VIb metal is 0.6 to 3 mol/mol;

b) a step of separating the hydrogenated gasoline obtained in step a) into two fractious comprising a light gasoline and a heavy gasoline; and
c) a treatment step of the heavy gasoline separated in step b) on a catalyst allowing sulphurous compounds present in said heavy gasoline to be at least partially broken down to H 2 S.

14. The process according to claim 13 , wherein the treatment step c) is performed in the presence of hydrogen, and a catalyst comprising at least one group VIII element and/or at least one group VIb element at least in part in sulphide form, at a temperature of 210° C. to 350° C., at a pressure of 1 to 4 MPa, and with a space velocity expressed as the volume of liquid per volume of catalyst and per hour of 1 h −1 and 20 h −1 .

15. The process according to claim 13 , wherein the catalyst of step c) comprises a content of group VIII metal expressed in the form of the oxide of 0.5 to 15 wt. %, with reference to the weight of the catalyst, and a content of group VIb metal expressed in the form of the oxide of 1.5 to 60 wt. %, with reference to the weight of the catalyst.

16. The process according to claim 13 , wherein the catalyst of step c) comprises a content of group VIII metal expressed in the form of the oxide of 1 to 10 wt. %, with reference to the weight of the catalyst, and a content of group VIb metal expressed in the form of the oxide of 3 to 50 wt. %, with reference to the weight of the catalyst.

17. The process according to claim 1 , wherein the group VIb metal is molybdenum.

18. The process according to claim 1 , wherein the group VIII metal is nickel.

19. The process according to claim 1 , wherein the content by weight of oxide of the group VIII element is 6 to 8%, with reference to the weight of the catalyst, and wherein the content by weight of oxide of the group VIb element is 10 to 12%, with reference to the weight of the catalyst.

20. The process according to claim 1 , wherein the density of the group VIb element is 4.5×10 −4 g/m 2 to 5×10 −4 g/m 2 .

Assignees

• Ifp Energies Now

Inventors

• Daudin Antoine
• Devers Elodie
• Gornay Julien
• Leflaive Philibert

Classifications

• C10G65/043

  at least one step being a change in the structural skeleton · CPC title

• C10G45/08

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

• C10G45/38 Primary

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

• B01J37/0201

  Impregnation · CPC title

• B01J23/75

  Cobalt · CPC title