Method for hydrogenating aromatics using a catalyst obtained by impregnation comprising a specific support

Patent metadata

Field	Value
Publication number	US-11370976-B2
Application number	US-201816630042-A
Country	US
Kind code	B2
Filing date	Jun 13, 2018
Priority date	Jul 13, 2017
Publication date	Jun 28, 2022
Grant date	Jun 28, 2022

Abstract

Process for hydrogenating at least one aromatic or polyaromatic compound contained in a hydrocarbon feedstock having a final boiling point of less than or equal to 650° C., said process being performed in the gas phase or in the liquid phase at a temperature of between 30 and 350° C., at a pressure of between 0.1 and 20 MPa, at a hydrogen/(aromatic compounds to be hydrogenated) mole ratio of between 0.1 and 10 and at an hourly space velocity (HSV) of between 0.05 and 50 h−1, in the presence of a catalyst comprising an active phase comprising nickel, said active phase not comprising any group VIB metal, and a support comprising an amorphous mesoporous alumina having a connectivity (Z) of greater than 2.7, the connectivity being determined from the nitrogen adsorption/desorption isotherms.

First claim

The invention claimed is:

1. A process comprising hydrogenating at least one aromatic or polyaromatic compound contained in a hydrocarbon feedstock having a final boiling point of less than or equal to 650° C., said process being performed in the gas phase or in the liquid phase, at a temperature of between 30 and 350° C., at a pressure of between 0.1 and 20 MPa, at a hydrogen/(aromatic or polyaromatic compound) mole ratio of 0.1 to 10 and at an hourly space velocity HSV of 0.05 to 50 h −1 , in the presence of a catalyst comprising an active phase comprising nickel, said active phase not comprising any group VIB metal, and a support comprising an amorphous mesoporous alumina having a connectivity (Z) of greater than 2.7, the connectivity being determined from nitrogen absorption/desorption isotherms, and a mesopore volume of greater than or equal to 0.40 mL/g.

2. The process as claimed in claim 1 , in which the nickel content of said catalyst is 5% to 65% by weight relative to the total weight of the catalyst.

3. The process as claimed in claim 1 , in which said alumina support has a connectivity (Z) of 2.7 to 10.

4. The process as claimed in claim 1 , in which the support has mesopores with a median mesopore diameter of 8 to 25 nm.

5. The process as claimed in claim 1 , in which the support has the following pore distribution:
the volume percentage included in the pores of 2 to 6 nm in size is 1% to 25% of the total pore volume;
the volume percentage included in the pores greater than 6 nm and less than 15 nm in size represents 40% to 95% of the total pore volume;
the volume percentage included in the pores 15 to 50 nm in size represents 0 to 50% of the total pore volume; and
the volume percentage included in the pores 50 to 7000 nm in size, which corresponds to the macropore volume, represents 0 to 20% of the total pore volume.

6. The process as claimed in claim 1 , in which the support does not contain any micropores.

7. The process as claimed in claim 1 , in which the active phase comprising nickel comprises nickel particles having a size of less than 20 nm.

8. The process as claimed in claim 1 , in which said catalyst is prepared by at least the following:
a) obtaining a suspension by at least one precipitation of alumina, in aqueous reaction medium, from at least one basic precursor that is sodium aluminate, potassium aluminate, ammonia, sodium hydroxide or potassium hydroxide and from at least one acidic precursor that is aluminum sulfate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid or nitric acid, in which at least one of the basic or acidic precursors comprises aluminum, the relative flow rate of the acidic and basic precursors is chosen so as to obtain a pH of the reaction medium of 8.5 to 10.5 and the flow rate of the acidic and basic precursor(s) containing aluminum is adjusted so as to obtain a rate of progress of said first step of 40% to 100%, the rate of progress being defined as being the proportion of alumina formed as Al 2 O 3 equivalent during said first precipitation step relative to the total amount of alumina formed on conclusion of c) of the preparation process, said first precipitation taking place at a temperature of 10 to 50° C., and for a time of 2 minutes to 30 minutes,
b) heat treatment of the suspension formed in a) heated to a temperature of 50 to 200° C. for a time of between 30 minutes and 5 hours allowing the production of an alumina gel,
c) filtering the gel obtained on conclusion of the heat treatment b), followed by at least one washing the gel obtained,
d) drying the alumina gel obtained on conclusion of c) to obtain a powder,
e) forming the powder obtained on conclusion of d) to obtain a crude material,
f) heat treatment of the crude material obtained on conclusion of e) at a temperature of 500 to 1000° C., in the presence or absence of an air stream containing up to 60% by volume of water, to obtain a calcined aluminous porous oxide support,
g) impregnating said support obtained on conclusion of f) with a solution comprising salt(s) of precursor(s) of the active phase comprising nickel,
h) a step of drying the impregnated support at a temperature below 250° C., so as to obtain a dried catalyst.

9. The process as claimed in claim 8 , in which, in the case where the degree of progress obtained on conclusion of the first precipitation a) is less than 100%, said preparation process comprises a second precipitation a′) after the first precipitation a).

10. The process as claimed in claim 9 , in which the sulfur content of the alumina gel obtained on conclusion of step b) is 0.001% to 2% by weight relative to the total weight of the alumina gel, and the sodium content of said alumina gel is 0.001% to 2% by weight relative to the total weight of said alumina gel.

11. The process as claimed in claim 9 , in which at least one heat treatment i) of the dried catalyst obtained on conclusion of h) is performed at a temperature of 250 to 1000° C., in the presence or absence of water.

12. The process as claimed in claim 11 , in which at least one reductive treatment j) is performed in the presence of a reducing gas after h) or i) so as to obtain a catalyst comprising nickel at least partially in metallic form.

13. The process as claimed in claim 1 , comprising hydrogenation of benzene as the aromatic compound, at a temperature of 30 to 250° C., at a pressure of 0.1 to 10 MPa, at a hydrogen/(benzene) mole ratio of 0.1 to 10 and at an hourly space velocity HSV of 0.05 to 50 h −1 .

14. The process as claimed in claim 1 , wherein said hydrocarbon feedstock is a reformate obtained from catalytic reforming.

Assignees

• Ifp Energies Now

Inventors

• Boualleg Malika
• Dubreuil Anne-Claire

Classifications

• B01J35/77

  Compounds characterised by their crystallite size · CPC title

• B01J2235/15

  X-ray diffraction · CPC title

• B01J35/80

  characterised by their amorphous structures · CPC title

• B01J2235/00

  Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties · CPC title

• B01J35/45

  Nanoparticles · CPC title