COBALT CATALYST COMPRISING A SUPPORT COMPRISING A MIXED OXIDE PHASE INCLUDING COBALT AND/OR NICKEL PRODUCED FROM AN ORGANIC COMPOUND FROM THE FAMILY OF CARBOYXYANHYDRIDES

• US 20200129967A1
• Filed: 10/24/2019
• Published: 04/30/2020
• Est. Priority Date: 10/25/2018
• Status: Active Grant

• Current Assignee: IFP Energies Nouvelles
• Original Assignee: IFP Energies Nouvelles
• Inventors: DELCROIX, Damien, CORRAL VALERO, Manuel
• Granted Patent: US 11,161,099 B2
• Time in Patent Office: Days
• CPC Class Codes: B01J 21/04 Alumina
• CPC Class Codes: B01J 21/08 Silica
• CPC Class Codes: B01J 21/12 Silica and alumina
• CPC Class Codes: B01J 2231/648 Fischer-Tropsch-type reactions
• CPC Class Codes: B01J 23/005 Spinels
• CPC Class Codes: B01J 23/75 Cobalt
• CPC Class Codes: B01J 23/755 Nickel
• CPC Class Codes: B01J 2523/00 Constitutive chemical elements of heterogeneous catalysts
• CPC Class Codes: B01J 2523/31 Aluminium
• CPC Class Codes: B01J 2523/41 Silicon
• CPC Class Codes: B01J 2523/845 Cobalt
• CPC Class Codes: B01J 31/0204 Ethers
• CPC Class Codes: B01J 31/0237 Amines
• CPC Class Codes: B01J 31/0245 being derivatives of carboxylic or carbonic acids
• CPC Class Codes: B01J 31/0271 also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
• CPC Class Codes: B01J 31/04 containing carboxylic acids or their salts B01J31/0277 - B01J31/0298 take precedence; multi-metal carboxylate complexes like Pd (II) acetate, i.e. Pd3 (OAc) 6 or Cr(II)acetate, i.e. Cr2(OAc)4 B01J31/2226
• CPC Class Codes: B01J 35/40 characterised by dimensions, e.g. grain size in a colloidal state B01J35/23; crystallite size B01J35/77
• CPC Class Codes: B01J 35/615 100-500 m2/g
• CPC Class Codes: B01J 35/633 less than 0.5 ml/g
• CPC Class Codes: B01J 37/0201 Impregnation
• CPC Class Codes: B01J 37/0203 : the impregnation liquid containing organic compounds
• CPC Class Codes: B01J 37/0205 : in several steps
• CPC Class Codes: B01J 37/0207 : Pretreatment of the support
• CPC Class Codes: B01J 37/0236 : Drying, e.g. preparing a suspension, adding a soluble salt and drying
• CPC Class Codes: B01J 37/088 : Decomposition of a metal salt
• CPC Class Codes: B01J 37/16 : Reducing
• CPC Class Codes: C10G 2/332 : of the iron-group
• CPC Class Codes: C10G 2300/70 : Catalyst aspects

Abstract

The present invention relates to a catalyst containing an active cobalt phase, deposited on a support comprising alumina, silica or silica-alumina, said support containing a mixed oxide phase containing cobalt and/or nickel, said catalyst has been prepared by introducing at least one organic compound of the family of carboxyanhydrides. The invention also relates to the process for the preparation thereof, and to the use thereof in the field of Fischer-Tropsch synthesis processes.

Claims

1. A catalyst containing an active cobalt phase, deposited on a support comprising alumina, silica or silica-alumina, said support containing a mixed oxide phase containing cobalt and/or nickel, said catalyst being prepared by a process comprising at least:

a) a step of bringing a support comprising alumina, silica or silica-alumina into contact with at least one solution containing at least one precursor of cobalt and/or of nickel, then drying at a temperature below 200°

C. and calcining at a temperature of between 700°

C. and 1200°

C., so as to obtain a mixed oxide phase containing cobalt and/or nickel in the support,

then carrying out

b) a step of bringing said support containing said mixed oxide phase into contact with at least one solution containing at least one precursor of cobalt,

c) a step of bringing said support containing said mixed oxide phase into contact with at least one organic compound of the family of carboxyanhydrides,

steps b) and c) being able to be performed separately, in any order, or at the same time,

d) then carrying out a step of drying at a temperature below 200°

C.

2. The catalyst as claimed in claim 1, wherein the content of mixed oxide phase in the support is between 0.1% and 50% by weight relative to the weight of the support.

3. The catalyst as claimed in claim 1, wherein the mixed oxide phase comprises an aluminate of formula CoAl₂O₄ or NiAl₂O₄ in the case of a support based on alumina or on silica-alumina.

4. The catalyst as claimed in claim 1, wherein the mixed oxide phase comprises a silicate of formula Co₂SiO₄ or Ni₂SiO₄ in the case of a support based on silica or on silica-alumina.

5. The catalyst as claimed in claim 1, wherein the silica content of said support is between 0.5% by weight and 30% by weight relative to the weight of the support before the formation of the mixed oxide phase when the support is a silica-alumina.

6. The catalyst as claimed in claim 1, wherein the organic compound of the family of carboxyanhydrides is selected from O-carboxyanhydrides and N-carboxyanhydrides.

7. The catalyst as claimed in claim 6, wherein the organic compound of the family of carboxyanhydrides is selected from the group of O-carboxyanhydrides consisting of 5-methyl-1,3-dioxolane-2,4-dione and 2,5-dioxo-1,3-dioxolane-4-propanoic acid, or from the group of N-carboxyanhydrides consisting of 2,5-oxazolidinedione and 3,4-dimethyl-2,5-oxazolidinedione.

8. The catalyst as claimed in claim 1, wherein the molar ratio of organic compound of the family of carboxyanhydrides introduced during step c) relative to the cobalt element introduced in step b) is between 0.01 mol/mol and 2.0 mol/mol.

9. The catalyst as claimed in claim 1, wherein the content of cobalt element introduced during step b) as active phase is between 2% and 40% by weight expressed as cobalt metal element relative to the total weight of the catalyst.

10. The catalyst as claimed in claim 1, wherein the catalyst further comprises an element selected from groups VIBE, IA, IB, IIA, IIB, IIIA, IIIB and VA.

11. The catalyst as claimed in claim 1, wherein the catalyst further contains an additional organic compound other than the compound of the family of carboxyanhydrides, said additional organic compound containing oxygen and/or nitrogen and preferably comprising one or more chemical functions selected from a carboxylic, alcohol, ether, aldehyde, ketone, amine, nitrile, imide, oxime, urea and amide function.

12. The catalyst as claimed in claim 1, wherein, after the drying step d), a calcining step e) is carried out at a temperature of between 200°

C. and 550°

C. in an inert atmosphere or in an oxygen-containing atmosphere.

13. The catalyst as claimed in claim 12, wherein the catalyst obtained in the drying step d) or obtained in the calcining step e) at a temperature of between 200°

C. and 500°

C., is reduced.

14. A process for preparing a catalyst as claimed in claim 1.

15. A Fischer-Tropsch process for synthesizing hydrocarbons, wherein the catalyst as claimed in claim 1 is brought into contact with a feedstock comprising synthesis gas under a total pressure of between 0.1 MPa and 15 MPa, under a temperature of between 150°

C. and 350°

C., and at an hourly space velocity of between 100 and 20 000 volumes of synthesis gas per volume of catalyst and per hour with an H₂/CO molar ratio of the synthesis gas of between 0.5 and 4.