Process for metathesis of olefins obtained from Fischer-Tropsch fractions using a ruthenium complex comprising a dissymmetrical N-heterocyclic diaminocarbene

Patent metadata

Field	Value
Publication number	US-9556296-B2
Application number	US-201414261555-A
Country	US
Kind code	B2
Filing date	Apr 25, 2014
Priority date	Apr 26, 2013
Publication date	Jan 31, 2017
Grant date	Jan 31, 2017

Abstract

This invention describes a process for metathesis of olefins from feedstocks obtained from the Fischer-Tropsch process, using as catalyst a ruthenium alkylidene complex comprising a saturated or unsaturated, dissymmetrical N-heterocyclic carbene (NHC) ligand.

First claim

The invention claimed is:

1. A process for metathesis of olefins from a feedstock obtained from a Fischer-Tropsch process, comprising performing said metathesis by a catalyst, which is a ruthenium alkylidene complex of Formula (I) or (II)

in which:
R 1 is an aryl group,
R 2 is a cycloalkyl group,
X 1 and X 2 , identical or different, are anionic ligands,
L is a ligand that is an electron donor and uncharged,
Y represents an alkylidene fragment, which may or may not be substituted, or Y forms a styrenylidene ether with L,
R 3 , R 4 , R 5 , and R 6 —identical or different—are hydrogen, halide, alkyl, cycloalkyl, aryl or arylalkyl groups, each being able to be substituted by alkyl, halide, or alkoxy groups or by a phenyl group that is optionally substituted by halide, alkyl, or alkoxy groups,
and in which the cycloalkyl group is a cyclic secondary aliphatic alkyl.

2. The process according to claim 1 , in which R 1 is an aromatic monocyclic or polycyclic group that has a number of carbon atoms of between 6 and 20.

3. The process according to claim 1 , in which R 2 is a monocyclic cycloalkyl group that has a carbon number of between 3 and 24, or a polycyclic cycloalkyl group that has a carbon number of between 3 and 18.

4. The process according to claim 1 , in which R 3 , R 4 , R 5 , and R 6 can be identical or different and are selected from
a hydrogen atom,
a halide,
a linear or branched alkyl group that has 1 to 15 carbon atoms,
a monocyclic cycloalkyl group that has 3 to 10 carbon atoms, or a polycyclic cycloalkyl group that has 4 to 18 carbon atoms,
an aromatic monocyclic or bicyclic aryl group that has 6 to 20 carbon atoms,
a linear or branched arylalkyl group that carries a monocyclic aromatic cycle that has 7 to 12 carbon atoms, with the aliphatic chain comprising 1 or 2 carbon atoms.

5. The process according to claim 1 , in which X 1 or X 2 is an anionic ligand selected from halides, sulfates, alkyl sulfates, aryl sulfates, alkyl sulfonates, aryl sulfonates, alkyl sulfinates, aryl sulfinates, acyls, carbonates, carboxylates, alcoholates, phenolates, amides, and pyrolides, which may or may not be substituted by one or more groups selected from alkyl groups that have 1 to 12 carbon atoms, alcoholate groups that have 1 to 12 carbon atoms, aryl groups that have 5 to 24 carbon atoms, and halides, said substituent groups, except for halides, themselves being substituted or not by one or more of the groups that are selected from halides, alkyl groups that have 1 to 6 carbon atoms, alcoholate groups that have 1 to 6 carbon atoms, and aryl groups.

6. The process according to claim 1 , in which X 1 or X 2 is selected from halide ligands, benzoates, tosylates, mesylates, trifluoromethane-sulfonates, pyrolides, CF 3 CO 2 trifluoroacetate groups, CH 3 CO 2 acetates, alcoholates, and phenolates.

7. The process according to claim 1 , in which L is a dissymmetrical, saturated or unsaturated, N-heterocyclic diaminocarbene or a phosphorated ligand of formula PR′ 3 , in which P is a phosphorus atom, and R′ is selected from R and (OR), in which R are identical or different and are selected from hydrogen, halides, alkyls, cycloalkyls, aryls and aryalkyls, which may or may not be substituted, each of the groups comprising up to 20 carbon atoms, and the substituents of said groups are selected from halides, alkyl groups, and aryl groups that have up to 20 carbon atoms.

8. The process according to claim 7 , in which L is a trialkylphosphine or a tricycloalkylphosphine selected from tricyclohexylphosphines, triisopropylphosphines, and tricyclopentylphosphines, a dialkylphosphine or a dicycloalkylphosphine selected from dicyclohexylphosphines, dicyclohexylphenylphosphines, di-tert-butylphosphines, and di-tert-butylchlorophosphines, or a triarylphosphine selected from triphenylphosphine, tri(methylphenyl)phosphine, trimesitylphosphine, tri(dimethylphenyl)phosphine, or tri[trifluoromethyl)phenyl]phosphine.

9. The process according to claim 8 , in which X 1 and X 2 are identical and are selected from chloride or bromide ligands, L is a tricyclohexylphosphine, and Y is an indenylidene group that may or may not be substituted.

10. The process according to claim 1 , in which the feedstock comprises linear olefins or linear alpha-olefins that have 3 to 10 carbon atoms.

11. The process according to claim 10 , in which the feedstock also comprises branched olefins and internal olefins or alkanes or oxidized derivatives.

12. The process according to claim 1 , in which the feedstock is selected from fractions that contain more than 20% by weight of olefins that have 4 to 9 carbon atoms, of which more than 70% by weight are linear alpha-olefins, less than 80% by weight of alkanes, and less than 10% oxidized compounds.

13. The process according to claim 1 , in which the quantity of ruthenium complex relative to the linear alpha-olefins, expressed in terms of mols, is between 1 and 10,000 ppm.

14. The process according to claim 1 , which is implemented at a temperature of between 0° C. and 180° C. and at a pressure of between atmospheric pressure and 10 MPa.

15. The process according to claim 1 , which is conducted in a closed system, in a semi-open system, or in a continuous system.

16. The process according to claim 1 , comprising a stage for neutralization of the catalyst after the metathesis reaction.

17. The process according to claim 16 , also comprising a stage for distillation of the products of the metathesis reaction implemented without a preliminary stage for separation of the neutralized ruthenium.

18. The process according to claim 1 , in which Y is an indenylidene group that may or may not be substituted.

19. The process according to claim 1 , in which the ruthenium alkylidene complex is of Formula (I).

20. The process according to claim 1 , in which the ruthenium alkylidene complex is of Formula (II).

21. The process according to claim 1 , in which at least one of R 3 , R 4 , R 5 , and R 6 is selected from
a halide,
a linear or branched alkyl group that has 1 to 15 carbon atoms,
a monocyclic cycloalkyl group that has 3 to 10 carbon atoms, or a polycyclic cycloalkyl group that has 4 to 18 carbon atoms,
an aromatic monocyclic or bicyclic aryl group that has 6 to 20 carbon atoms,
a linear or branched arylalkyl group that carries a monocyclic aromatic cycle that has 7 to 12 carbon atoms, with the aliphatic chain comprising 1 or 2 carbon atoms.

Assignees

• Centre Nat Rech Scient
• Ecole Nat Superieure De Chimie De Rennes
• Ifp Energies Now

Inventors

• Olivier-Bourbigou Helene
• Hugues Francois
• Forget Severine
• Rouen Mathieu
• Mauduit Marc

Classifications

• C07F15/0046 Primary

  Ruthenium compounds · CPC title

• C07C11/02

  Alkenes · CPC title

• C10G2300/1092

  C2-C4 olefins · CPC title

• C10G29/205

  by reaction with hydrocarbons added to the hydrocarbon oil · CPC title

• C10G2400/20

  C2-C4 olefins · CPC title