Catalytic composition and process for oligomerizing ethylene into 1-hexene

Patent metadata

Field	Value
Publication number	US-10150108-B2
Application number	US-201514668132-A
Country	US
Kind code	B2
Filing date	Mar 25, 2015
Priority date	Mar 25, 2014
Publication date	Dec 11, 2018
Grant date	Dec 11, 2018

Abstract

A composition is described which comprises at least one chromium compound, at least one aryloxy compound of an element M selected from the group formed by magnesium, calcium, strontium and barium, with general formula [M(RO) 2-n X n ] y , in which RO is an aryloxy radical of a derivative ROH containing 6 to 80 carbon atoms, X is a halogen or a hydrocarbyl radical containing 1 to 30 carbon atoms, n is a whole number which may take the values 0 or 1 and y is a whole number in the range 1 to 10, and at least one additive selected from ether type compounds, which may or may not be cyclic, introduced in a near-stoichiometric quantity with respect to the element M.

First claim

The invention claimed is:

1. A process for the preparation of a kit comprising
a) at least one chromium compound and
b) an intermediate composition comprising:
at least one aryloxy compound of an element M selected from the group consisting of magnesium, calcium, strontium and barium, with general formula [M(RO) 2-n X n ] y , in which RO is an aryloxy radical of a derivative ROH containing 6 to 80 carbon atoms, X is a halogen or a hydrocarbyl radical containing 1 to 30 carbon atoms, n is a whole number which may take the integer values 0 or 1 and y is a whole number in the range 1 to 10;
at least one additive selected from ether compounds, wherein the additive is diethyl ether, dibutyl ether, diisopropylether, 2-methoxy-2-methylpropane, 2-methoxy-2-methylbutane, 2,5-dihydrofuran, tetrahydrofuran, 2-methoxytetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2,3-dihydropyran, tetrahydropyran, 1,3-dioxolane, 1,3-dioxane, 1,4-dioxane, dimethoxyethane, di(2-methoxyethyl)ether or benzofuran, or a mixture thereof, and wherein the molar ratio between the additive and the element M is in the range of 1 to 60, comprising;
a) mixing:

at least one compound MX 2 of an element M selected from the group consisting of magnesium, calcium, strontium and barium, X being a halogen or a hydrocarbyl radical containing 1 to 30 carbon atoms;
at least one derivative ROH in which RO is an aryloxy radical of a derivative ROH containing 6 to 80 carbon atoms;
and at least one additive selected from ether compounds, which may or may not be cyclic, introduced in a near-stoichiometric quantity with respect to the element M to form an intermediate composition, and
b) pairing said intermediate composition with at least one chromium compound.

2. A process for preparing a composition comprising mixing:
at least one chromium compound;
at least one compound MX 2 of an element M selected from the group consisting of magnesium, calcium, strontium and barium, X being a halogen or a hydrocarbyl radical containing 1 to 30 carbon atoms;
at least one derivative ROH in which RO is an aryloxy radical of a derivative ROH containing 6 to 80 carbon atoms; and
at least one additive selected from ether compounds, which may or may not be cyclic, introduced in a near-stoichiometric quantity with respect to the element M;
optionally, at least one aluminium compound selected from the group consisting of tris(hydrocarbyl)aluminium compounds, chlorine- or bromine-containing hydrocarbylaluminium compounds with general formula AIR′ m ,Y 3-m , in which R′ is a hydrocarbyl radical containing 1 to 6 carbon atoms, Y is a chlorine or bromine atom and m is a number from 1 to 3, and aluminoxanes, used alone or as a mixture;

optionally, at least one solvent.

3. The process of claim 2 further comprising contacting the composition with a feed of ethylene to be transformed by an ethylene trimerization reaction.

4. An ethylene trimerization process carried out discontinuously in accordance with the following steps:
introducing
at least one chromium compound;
at least one compound MX 2 of an element M selected from the group consisting of magnesium, calcium, strontium and barium, X being a halogen or a hydrocarbyl radical containing 1 to 30 carbon atoms;
at least one derivative ROH in which RO is an aryloxy radical of a derivative ROH containing 6 to 80 carbon atoms; and
at least one additive selected from ether compounds, which may or may not be cyclic, introduced in a near-stoichiometric quantity with respect to the element Minto a reactor;
introducing ethylene at a desired pressure;
adjusting the temperature to a desired value;
and adding at least one aluminium compound selected from the group consisting of tris(hydrocarbyl)aluminium compounds, chlorine- or bromine-containing hydrocarbylaluminium compounds with general formula AlR′ m ,Y 3-m , in which R′ is a hydrocarbyl radical containing 1 to 6 carbon atoms, Y is a chlorine or bromine atom and m is a number from 1 to 3, and aluminoxanes, used alone or as a mixture.

5. An ethylene trimerization process carried out continuously by simultaneously and separately injecting at least one chromium compound;
at least one compound MX 2 of an element M selected from the group consisting of magnesium, calcium, strontium and barium, X being a halogen or a hydrocarbyl radical containing 1 to 30 carbon atoms;
at least one derivative ROH in which RO is an aryloxy radical of a derivative ROH containing 6 to 80 carbon atoms;

at least one additive selected from ether compounds, which may or may not be cyclic, introduced in a near-stoichiometric quantity with respect to the element M;
at least one aluminium compound selected from the group consisting of tris(hydrocarbyl)aluminium, chlorine- or bromine-containing hydrocarbylaluminium compounds having general formula AlR′ m Y 3-m in which R′ is a hydrocarbyl radical containing 1 to 6 carbon atoms, Y is a chlorine or bromine atom and m is a number from 1 to 3, and aluminoxanes, used alone or as a mixture; and
ethylene into a reactor, the whole system being maintained at a desired temperature and pressure.

6. The process according to claim 4 , in which the ethylene trimerization reaction is carried out at a total pressure of 0.5 to 15 MPa and at a temperature of 20° C. to 180° C.

7. The process of claim 2 , wherein the at least one additive is suitable as a complexing agent for chromium.

Assignees

• Ifp Energies Now

Inventors

• Magna Lionel
• Drochon Sebastien
• Olivier-Bourbigou Helene

Classifications

• Y02P20/52

  using catalysts, e.g. selective catalysts · CPC title

• B01J31/04

  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 title

• B01J31/0214

  Aryloxylates, e.g. phenolates · CPC title

• C07C2/32

  as complexes, e.g. acetyl-acetonates {(complexes of salts of acids of halogen C07C2/20)} · CPC title

• B01J2231/20

  Olefin oligomerisation or telomerisation · CPC title