Mesoporous and macroporous nickel-based catalyst having a median macropore diameter of between 50 nm and 200 nm and its use with regard to hydrogenation

Patent metadata

Field	Value
Publication number	US-2018207622-A1
Application number	US-201515317995-A
Country	US
Kind code	A1
Filing date	Jun 9, 2015
Priority date	Jun 13, 2014
Publication date	Jul 26, 2018
Grant date	—

Abstract

Disclosed are a supported catalyst, its method of preparation and use in hydrogenation methods, which catalyst contains an oxide substrate that is for the most part calcined aluminum and an active phase that contains nickel, with the nickel content between 5 and 65% by weight in relation to the total mass of the catalyst, with the active phase not containing a metal from group VIB, the nickel particles having a diameter that is less than or equal to 20 nm, the catalyst having a median mesopore diameter of between 14 nm and 30 nm, a median macropore diameter of between 50 and 200 nm, a mesopore volume that is measured by mercury porosimetry that is greater than or equal to 0.40 mL/g, and a total pore volume that is measured by mercury porosimetry that is greater than or equal to 0.42 mL/g.

First claim

1 . Supported catalyst that comprises an oxide substrate that is for the most part calcined aluminum and an active phase that comprises nickel, with the nickel content being between 5 and 65% by weight of said element in relation to the total mass of the catalyst, with said active phase not comprising a metal from group VIB, the nickel particles having a diameter that is less than or equal to 20 nm, said catalyst having a median mesopore diameter of between 14 nm and 30 nm, a median macropore diameter of between 50 and 200 nm, a mesopore volume that is measured by mercury porosimetry that is greater than or equal to 0.40 mL/g, and a total pore volume that is measured by mercury porosimetry that is greater than or equal to 0.42 mL/g.

2 . Catalyst according to claim 1 , in which the substrate has a pore volume that is contained in the pores with a diameter of between 100 and 700 nm that is less than 20% of the total pore volume of the substrate.

3 . Catalyst according to claim 2 , in which the substrate has a pore volume that is contained in the pores with a diameter of between 100 and 700 nm that is less than 15% of the total pore volume of the substrate.

4 . Catalyst according to claim 1 , in which the nickel content is between 10 and 34% by weight of said element in relation to the total mass of the catalyst.

5 . Catalyst according to claim 1 , in which the macropore volume of the catalyst is between 5 and 40% of the total pore volume.

6 . Catalyst according to claim 1 , in which the mesopore volume of the catalyst is between 0.45 mL/g and 0.8 mL/g.

7 . Catalyst according to claim 1 , which does not contain micropores.

8 . Method for preparation of a catalyst according to claim 1 , comprising the following steps:
a) A first precipitation step, in an aqueous reaction medium, of at least one basic precursor that is selected from among sodium aluminate, potassium aluminate, ammonia, sodium hydroxide, and potassium hydroxide, and at least one acid precursor that is selected from among aluminum sulfate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid, and nitric acid, in which at least one of the basic or acid precursors comprises aluminum, the relative flow rate of the acid and basic precursors is selected in such a way as to obtain a pH of the reaction medium of between 8.5 and 10.5, and the flow rate of the acid and basic precursor(s) that contain(s) aluminum is regulated in such a way as to obtain a rate of advance of the first step of between 5 and 13%, with the rate of advance being defined as being the proportion of alumina that is formed into an equivalent of Al 2 O 3 during said first precipitation step in relation to the total quantity of alumina that is formed into an equivalent of Al 2 O 3 at the end of step c) of the preparation method, with said step being performed at a temperature of between 20 and 90° C. and for a period of between 2 and 30 minutes, b) A step of heating the suspension that is obtained in step a) at a temperature of between 40 and 90° C. for a period of between 7 and 45 minutes to obtain an alumina gel, c) A second step for precipitation of the suspension that is obtained at the end of step b) of heating by adding into the suspension at least one basic precursor that is selected from among sodium aluminate, potassium aluminate, ammonia, sodium hydroxide, and potassium hydroxide, and at least one acid precursor that is selected from among aluminum sulfate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid, and nitric acid, in which at least one of the basic or acid precursors comprises aluminum; the relative flow rate of the acid and basic precursors is selected in such a way as to obtain a pH of the reaction medium of between 8.5 and 10.5, and the flow rate of the acid and basic precursor(s) containing aluminum is regulated in such a manner as to obtain a rate of advance of the second step of between 87 and 95%, with the rate of advance being defined as being the proportion of alumina that is formed into an equivalent of Al 2 O 3 during said second precipitation step in relation to the total quantity of alumina that is formed into an equivalent of Al 2 O 3 at the end of step c) of the preparation method, with said step being performed at a temperature of between 40 and 90° C. and for a period of between 2 and 50 minutes, d) A step for filtering the suspension that is obtained at the end of step c) of second precipitation for obtaining an alumina gel, e) A step for drying said alumina gel that is obtained in step d) for obtaining a powder, f) A step for heat treatment at a temperature of between 500 and 1000° C., with or without the presence of an air stream containing up to 60% by volume of water, g) A shaping step to obtain an aluminum porous oxide substrate, h) A step for impregnating said substrate with a solution that comprises the salt(s) of the precursor(s) of the nickel-based active phase, i) A step for drying said impregnated substrate at a temperature of between 15 and less than 250° C., in such a way as to obtain a dried catalyst, j) Optionally a heat treatment of said dried catalyst at a temperature of between 250 and 1000° C. with or without the presence of water.

9 . Method according to claim 8 , in which at least one step k) of reducing treatment is carried out in the presence of a reducing gas after steps i) or j) in such a way as to obtain a catalyst that comprises nickel at least partially in metallic form.

10 . Method according to claim 9 , in which a step l) of passivation by a sulfur-containing compound or an oxidized compound or by the CO 2 is carried out before or after step k) of reducing treatment.

11 . Method according to claim 8 , in which the rate of advance of step a) of first precipitation is between 6 and 12%.

12 . Method according to claim 8 , in which the acid precursor of steps a) and c) is selected from among aluminum sulfate, aluminum chloride, and aluminum nitrate, and in which the basic precursor of steps a) and c) is selected from among sodium aluminate and potassium aluminate.

13 . Hydrogenation method in which the catalyst according to claim 1 is brought into contact in the presence of hydrogen with a hydrocarbon feedstock that contains polyunsaturated molecules and/or aromatic compounds in such a way as to obtain an at least partially hydrogenated effluent.

14 . Hydrogenation method according to claim 13 , in which a selective hydrogenation is carried out at a temperature of between 0 and 500° C., at a pressure of between 0.1 and 20 MPa, at a hydrogen/(polyunsaturated compounds to be hydrogenated) molar ratio of between 0.1 and 10, and at an hourly volumetric flow rate of between 0.1 and 200 h −1 for a liquid feedstock, between 100 and 15000 h −1 for a gaseous feedstock of a hydrocarbon feedstock that contains polyunsaturated compounds that contain at least 2 carbon atoms per molecule and that have a final boiling point that is less than or equal to 250° C.

15 . Hydrogenation method according to claim 13 , in which hydrogenation of the aromatic compounds is carried out 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) molar ratio of between 0.1 and 10, and at an hourly volumetric flow rate of between 0.05 and 50 h −1 of a hydrocarbon feedstock that contains aromatic compounds and that has a final boiling point that is less than or equal to 650° C.

Assignees

• Ifp Energies Now

Inventors

• Boualleg Malika
• Dubreuil Anne Claire
• Maille Emily
• Thomazeau Cecile

Classifications

• C07C5/10

  of aromatic six-membered rings · CPC title

• C07C2601/14

  The ring being saturated · CPC title

• B01J23/755 Primary

  Nickel · CPC title

• C10G2300/1096

  Aromatics or polyaromatics · CPC title

• C07C2523/755

  Nickel · CPC title