Catalyst comprising an active nickel sulfur phase distributed in a shell

Patent metadata

Field	Value
Publication number	US-12064751-B2
Application number	US-202017631094-A
Country	US
Kind code	B2
Filing date	Jul 16, 2020
Priority date	Jul 31, 2019
Publication date	Aug 20, 2024
Grant date	Aug 20, 2024

Abstract

Catalyst comprising nickel and sulfur on an alumina support, said catalyst being characterized in that:
the nickel is distributed both on a crust at the periphery of the support, and in the core of the support, the thickness of said crust being between 2% and 15% of the diameter of the catalyst; the nickel density ratio between the crust and the core is strictly greater than 3; said crust comprises more than 25% by weight of nickel element relative to the total weight of nickel contained in the catalyst, the size of the nickel particles in the catalyst, measured in oxide form, is between 7 and 25 nm.

First claim

The invention claimed is:

1. A catalyst comprising nickel and sulfur on an alumina support, said catalyst comprising 5% to 25% by weight of elemental nickel relative to the total weight of the catalyst, between 0.05% and 10% by weight of elemental sulfur relative to the total weight of said catalyst, said catalyst having the following characteristics:
the nickel is distributed both on a crust at the periphery of the support, and in the core of the support, the thickness of said crust being between 2% and 15% of the diameter of the catalyst;
the nickel density ratio between the crust and the core is strictly greater than 3;
said crust comprises more than 25% by weight of nickel element relative to the total weight of nickel contained in the catalyst,
wherein the nickel in the catalyst is in the form of particles, and wherein the size of the nickel particles in the catalyst, measured in oxide form, is between 7 and 25 nm.

2. The catalyst as claimed in claim 1 , wherein the nickel density ratio between the crust and the core is greater than or equal to 3.5.

3. The catalyst as claimed in claim 1 , wherein said crust comprises more than 40% by weight of nickel element relative to the total weight of nickel contained in the catalyst.

4. The catalyst as claimed in claim 1 , wherein the transition interval between the core and the crust of the catalyst is between 0.05% and 3% of the diameter of the catalyst.

5. The catalyst as claimed in claim 1 , wherein the size of the nickel particles in the catalyst is between 8 and 23 nm.

6. The catalyst as claimed in claim 1 , wherein the sulfur content of the alumina support is between 0.001% and 2% by weight relative to the total weight of the alumina support, and the sodium content of said alumina support is between 0.001% and 2% by weight relative to the total weight of said alumina gel.

7. The catalyst as claimed in claim 1 , wherein the thickness of said crust is between 2.5% and 12% of the diameter of the catalyst.

8. The catalyst as claimed in claim 1 , wherein the nickel density ratio between the crust and the core is between 3.8 and 15.

9. A process for preparing a catalyst as claimed in claim 1 , said process comprises the following steps:
a) an alumina gel is provided;
b) the alumina gel from step a) is shaped;
c) the shaped alumina gel obtained at the end of step b) is subjected to a heat treatment comprising at least one hydrothermal treatment step in an autoclave in the presence of an acid solution, at a temperature of between 100° C. and 800° C., and at least one calcining step, at a temperature of between 400° C. and 1500° C., carried out after the hydrothermal treatment step, in order to obtain an alumina support;
d) the following sub-steps are carried out:
d1) the alumina support is brought into contact with at least one precursor of the nickel active phase in order to obtain a catalyst precursor;
d2) the catalyst precursor obtained at the end of step d1) is dried at a temperature below 250° C.;

e) the following sub-steps are carried out:
e1) the catalyst precursor is brought into contact with at least one solution containing at least one organic additive chosen from aldehydes containing 1 to 14 carbon atoms per molecule, ketones or polyketones containing 3 to 18 carbon atoms per molecule, ethers and esters containing 2 to 14 carbon atoms per molecule, alcohols or polyalcohols containing 1 to 14 carbon atoms per molecule and carboxylic acids or polycarboxylic acids containing 1 to 14 carbon atoms per molecule, the mole ratio between the organic additive and the nickel being greater than 0.05 mol/mol;
e2) a hydrothermal treatment of the catalyst precursor obtained at the end of step e1) is carried out at a temperature between 100° C. and 200° ° C. under a gas stream comprising between 5 and 650 grams of water per kg of dry gas;

f) the following sub-steps are carried out:
f1) the catalyst precursor is brought into contact with at least one aqueous or organic solution comprising at least one sulfur-containing compound;
f2) optionally, the catalyst precursor obtained at the end of step f1) is dried at a temperature between 100° ° C. and 200° ° C.,

steps e) and f) being carried out in any order, or steps e1) and f1) being carried out at the same time.

10. The process as claimed in claim 9 , wherein the sulfur-containing compound is an organic polysulfide or an organic disulfide.

11. The process as claimed in claim 9 , wherein the sulfur-containing compound provided in step f1) is 2,2′-dithiodiethanol.

12. The process as claimed in claim 9 , which process further comprises a step e3) of drying the catalyst precursor obtained at the end of step e2) at a temperature between 50° C. and 200° ° C. under a gas stream comprising an amount of water strictly less than 5 grams of water per kg of dry gas.

13. The process as claimed in claim 9 , which process further comprises a step d2′) of calcining the dried catalyst precursor obtained at the end of step d2), under a gas stream comprising an amount of water strictly less than 150 grams of water per kg of dry gas at a temperature between 250° C. and 1000° ° C.

14. The process as claimed in claim 9 , in which, in step d3), the organic additive is chosen from formic acid, formaldehyde, acetic acid, citric acid, oxalic acid, glycolic acid, malonic acid, ethanol, methanol, ethyl formate, methyl formate, paraldehyde, acetaldehyde, gamma-valerolactone, glucose, sorbitol and trioxane.

15. A process for the selective hydrogenation of polyunsaturated compounds containing at least 2 carbon atoms per molecule, contained in a hydrocarbon feedstock having a final boiling point below or equal to 300° C., said process being carried out at a temperature of between 0° ° C. and 300° C., at a pressure of between 0.1 and 10 MPa, at a hydrogen/(polyunsaturated compounds to be hydrogenated) mole ratio of between 0.1 and 10 and at an hourly space velocity of between 0.1 and 200 h −1 when the process is carried out in the liquid phase, or at a hydrogen/(polyunsaturated compounds to be hydrogenated) mole ratio of between 0.5 and 1000 and at an hourly space velocity of between 100 and 40 000 h −1 when the process is carried out in the gas phase, in the presence of a catalyst as claimed in claim 1 .

16. The catalyst as claimed in claim 1 , wherein the catalyst comprises 5% to 15% by weight of elemental nickel relative to the total weight of the catalyst.

17. The catalyst as claimed in claim 1 , wherein the catalyst comprises 15% to 25% by weight of elemental nickel relative to the total weight of the catalyst.

18. The catalyst as claimed in claim 1 , wherein the catalyst comprises 5% by weight of elemental nickel relative to the total weight of the catalyst.

19. The catalyst as claimed in claim 1 , wherein the catalyst comprises 15% by weight of elemental nickel relative to the total weight of the catalyst.

20. The catalyst as claimed in claim 1 , wherein the catalyst comprises 0.1% to 2.5% by weight of elemental sulfur relative to the total weight of the catalyst.

Assignees

• Ifp Energies Now

Inventors

• Dubreuil Anne-Claire
• Coupard Vincent
• Boualleg Malika

Classifications

• B01J35/45

  Nanoparticles · CPC title

• C10G45/36

  containing nickel or cobalt metal, or compounds thereof · CPC title

• C07C2523/755

  Nickel · CPC title

• C07C2521/04

  Alumina · CPC title

• C07C5/11

  Partial hydrogenation · CPC title