Process for the selective dimerisation of ethylene to 1-butene

Patent metadata

Field	Value
Publication number	US-2016002123-A1
Application number	US-201514790734-A
Country	US
Kind code	A1
Filing date	Jul 2, 2015
Priority date	Jul 4, 2014
Publication date	Jan 7, 2016
Grant date	—

Abstract

The invention concerns a process for the selective dimerization of ethylene to 1-butene employing a catalytic composition comprising at least one alkoxy or aryloxy titanium compound, at least one additive selected from ether type compounds and at least one aluminium compound.

First claim

1 . A process for the selective dimerization of ethylene to 1-butene using a catalytic composition comprising at least one alkoxy or aryloxy titanium compound, at least one additive selected from ether type compounds and at least one aluminium compound, in which the molar ratio between the additive and the alkoxy or aryloxy titanium compound is strictly more than 10 and the molar ratio between the aluminium compound and the alkoxy or aryloxy titanium compound is strictly more than 4.

2 . The process according to claim 1 , in which the molar ratio between the additive and the alkoxy or aryloxy titanium compound of the catalytic composition is in the range 11 to 19.

3 . The process according to claim 1 , in which the molar ratio between the aluminium compound and the alkoxy or aryloxy titanium compound of the catalytic composition is in the range 5 to 15.

4 . The process according to claim 1 , in which the alkoxy titanium compound has the general formula [Ti(OR) 4 ], in which R is a linear or branched alkyl radical containing 2 to 30 carbon atoms.

5 . The process according to claim 1 , in which the aryloxy titanium compound has the general formula [Ti(OR′) 4 ], in which R′ is an aryl radical which may or may not be substituted with alkyl, aryl or aralkyl groups containing 2 to 30 carbon atoms.

6 . The process according to claim 1 , in which the aluminium compound is selected from the group formed by hydrocarbylaluminium compounds, tris(hydrocarbyl)aluminium compounds, chlorine-containing or bromine-containing hydrocarbylaluminium compounds and aluminoxanes.

7 . The process according to claim 6 , in which the aluminium compound is selected from the group formed by dichloroethylaluminium (EtAlCl 2 ), ethylaluminium sesquichloride (Et 3 Al 2 Cl 3 ), chlorodiethylaluminium (Et 2 AlCl), chlorodiisobutylaluminium (i-Bu 2 AlCl), triethylaluminium (AlEt 3 ), tripropylaluminium (Al(n-Pr) 3 ), and triisobutylaluminium (Al(i-Bu) 3 ).

8 . The process according to claim 1 , using a composition in which the titanium compound is [Ti(O n Bu) 4 ], the additive is THF and is in a molar ratio with respect to the titanium compound (THF/Ti) which is strictly more than 10, and the aluminium compound is triethylaluminium in a molar ratio with respect to the titanium compound (AlEt 3 /Ti) which is strictly more than 4.

9 . The process according to claim 1 , in which the additive is selected from the group formed by diethyl 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 and benzofuran, used alone or as a mixture.

10 . The process according to claim 1 , in which the catalytic composition is used as a mixture with a solvent selected from the group formed by aliphatic and cycloaliphatic hydrocarbons, by an unsaturated hydrocarbon such as a monoolefin or a diolefin containing 4 to 20 carbon atoms, for example, by a hydrocarbon or by a chlorine-containing hydrocarbon, pure or as a mixture.

11 . The process according to claim 1 , carried out under a total pressure of 0.5 to 20 MPa and at a temperature of 20° C. to 180° C.

12 . The process according to claim 1 , carried out in a batch or continuous implementational mode.

13 . The process according to claim 1 , in which a selected volume of the catalytic composition is introduced into a reactor provided with stirring, heating and cooling means, then pressurising using ethylene and adjusting the temperature.

14 . The process for the selective dimerization of ethylene to 1-butene according to claim 1 , carried out such that on the one hand a solution containing the titanium compound and the additive and on the other hand a solution containing the aluminium compound are introduced separately into a reactor maintained under a constant pressure of ethylene in a manner so as to produce the catalytic composition.

15 . The process for the selective dimerization of ethylene to 1-butene according to claim 1 , carried out such that on the one hand a solution containing the titanium compound and the additive and on the other hand a solution containing the aluminium compound are introduced into a first reactor/mixer in a manner so as to produce the catalytic composition, said composition then being continuously introduced into a reactor maintained under a constant pressure of ethylene.

16 . The process for the preparation of the catalytic composition according to claim 1 , in which the aluminium compound is added to a solution containing the additive and the alkoxy or aryloxy titanium compound present in a molar ratio strictly more than 10, the molar ratio of the aluminium compound to the titanium compound being strictly more than 4.

Assignees

• IFP Energies Nouvelles

Inventors

• Magna Lionel
• Olivier-Bourbigou Helene

Classifications

• B01J2531/31

  Aluminium · CPC title

• B01J31/0204

  Ethers · CPC title

• C07C2531/02

  containing organic compounds or metal hydrides · CPC title

• C07C2/30 Primary

  containing metal-to-carbon bond; Metal hydrides · CPC title

• B01J2531/46

  Titanium · CPC title