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-10668451-B2
Application number	US-201515317995-A
Country	US
Kind code	B2
Filing date	Jun 9, 2015
Priority date	Jun 13, 2014
Publication date	Jun 2, 2020
Grant date	Jun 2, 2020

Abstract

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

The invention claimed is:

1. A method for preparing a catalyst, comprising
a) a first precipitating step, in an aqueous reaction medium, of at least one basic precursor that is selected from the group consisting of sodium aluminate, potassium aluminate, ammonia, sodium hydroxide, and potassium hydroxide, and at least one acid precursor that is selected from the group consisting of 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, a relative flow rate of the acid and basic precursors of step a) 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) of step a) that contain(s) aluminum is regulated in such a way as to obtain a rate of advance of the first precipitating step of between 5 and 13%, with the rate of advance being defined as being a 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 first precipitation step being performed at a temperature of between 20 and 90° C. and for a period of between 2 and 30 minutes,
b) a heating step of a 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 precipitating step of a 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 the group consisting of sodium aluminate, potassium aluminate, ammonia, sodium hydroxide, and potassium hydroxide, and at least one acid precursor that is selected from the group consisting of 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; a relative flow rate of the acid and basic precursors of step c) 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) of step c) 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 second precipitation step being performed at a temperature of between 40 and 90° C. and for a period of between 2 and 50 minutes,
d) a filtering step of a suspension that is obtained at the end of step c) of second precipitation for obtaining an alumina gel,
e) a drying step of said alumina gel that is obtained in step d) for obtaining a powder,
f) a heat treatment step 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) an impregnating step of said substrate with a solution that comprises salt(s) of precursor(s) of a nickel-based active phase to form an impregnated substrate,
i) a drying step of 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 step of said dried catalyst at a temperature of between 250 and 1000° C. with or without the presence of water;

wherein the catalyst obtained is a 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 macropore volume between 5 and 40% of the total pore volume, 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. A method according to claim 1 , wherein in the obtained catalyst 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. A method according to claim 1 , wherein in the obtained catalyst 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. A method according to claim 1 , wherein in the obtained catalyst the nickel content is between 10 and 34% by weight of said element in relation to the total mass of the catalyst.

5. A method according to claim 1 , wherein in the obtained catalyst the macropore volume of the catalyst is between 10 and 30% of the total pore volume.

6. A method according to claim 1 , wherein in the obtained catalyst the mesopore volume of the catalyst is between 0.45 mL/g and 0.8 mL/g.

7. A method according to claim 1 , wherein the obtained catalyst does not contain micropores.

8. The method according to claim 1 , further comprising at least one step k) of reducing treatment 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.

9. The method according to claim 8 , further comprising a step l) of passivation by a sulfur-containing compound or an oxidized compound or by the CO 2 before or after step k) of reducing treatment.

10. The method according to claim 1 , in which the rate of advance of step a) of first precipitation is between 6 and 12%.

11. The method according to claim 1 , in which the acid precursor of steps a) and c) is selected from the group consisting of aluminum sulfate, aluminum chloride, and aluminum nitrate, and in which the basic precursor of steps a) and c) is selected from the group consisting of sodium aluminate and potassium aluminate.

Assignees

• Ifp Energies Now

Inventors

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

Classifications

• C01P2006/12

  Surface area · CPC title

• B01J35/1066

  Operations & Transport · mapped topic

• B01J23/755 Primary

  Nickel · CPC title

• B01J37/036

  to form a gel or a cogel · CPC title

• C07C5/10

  of aromatic six-membered rings · CPC title