# US 2019/0169085 A1 · Method for dimerization of ethylene comprising a step for treatment of the reaction effluent > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2019/0169085 A1 - Document ID: US20190169085A1 - Status: Published application - Kind: A1 - Application number: 16/208,749 - Filed: 2018-12-04 - Published: 2019-06-06 - Earliest claimed: 2017-12-05 - Assignees: Ifp Energies Nouvelles - Applicants: IFP Energies Nouvelles - Inventors: Lionel MAGNA; Aurelie CAMARATA - Web page: https://patentgrep.com/patent/US20190169085A1 ## CPC - C07C 2/32: as complexes, e.g. acetyl-acetonates {(complexes of salts of acids of halogen C07C2/20)} - C07C 2/30: containing metal-to-carbon bond; Metal hydrides - C07C 7/10: by extraction, i.e. purification or separation of liquid hydrocarbons with the aid of liquids - C07C 11/08: with four carbon atoms - B01J 31/38: of titanium, zirconium or hafnium - B01J 2531/31: Aluminium - B01J 2531/46: Titanium - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS ## Abstract The invention describes a method for dimerization of ethylene implementing a step for treatment of raw effluent by neutralization, at the outlet of the reactor, of the catalyst for dimerization of ethylene into but-1-ene by a particular alcohol. ## Claims ### Claim 1 Method for treatment of the raw effluent that is obtained directly from a step for dimerization of ethylene into but-1-ene that comprises bringing into contact a catalytic composition that comprises at least one titanium compound of general formula [Ti(OR2)4] and at least one preformed mixture between a Lewis-base (BL)-type additive and an aluminum (Al) compound of general formula Al(R3)mY3-m and an ethylene feedstock, in which the treatment of the effluent comprises a step for neutralization of said raw effluent by adding at least one alcohol of general formula R1OH, in pure form or in solution in a solvent, in which R1 is an alkyl group, linear or branched, which contains from 6 to 20 carbon atoms, an aryl or aralkyl group that contains from 5 to 30 carbon atoms. ### Claim 2 (depends on 1) Method according to claim 1, in which R1 is selected from among an alkyl group that comprises between 6 and 15 carbon atoms, and an aryl or aralkyl group that contains from 6 to 20 C. ### Claim 3 (depends on 1) Method according to claim 1, in which R1 is a branched alkyl group. ### Claim 4 (depends on 1) Method according to claim 1, in which R1OH is selected from among ethyl-2-hexanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-hexanol, 2-ethyl-1-hexanol, 1-heptanol, 2-heptanol, 2-methyl-3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-decanol, 2-decanol, 3-decanol, 2-ethyl-1-decanol, 1-dodecanol, phenol, 2-methylphenol, 2,6-dimethylphenol, 2,4,6-trimethylphenol, 4-methylphenol, 2-phenylphenol, 2,6-diphenylphenol, 2,4,6-triphenylphenol, 4-phenylphenol, 2-tert-butyl-6-phenylphenol, 2,4-di-tert-butyl-6-phenylphenol, 2,6-diisopropylphenol, 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol. ### Claim 5 (depends on 1) Method according to claim 1, in which the alcohol R1OH is used in solution in a solvent or a mixture of solvents that are selected independently from among aliphatic or cycloaliphatic hydrocarbons, such as hexane, cyclohexane, heptane, butane or isobutane, unsaturated hydrocarbons, such as the monoolefins or diolefins that comprise between 4 and 20 carbon atoms, aromatic hydrocarbons, such as benzene, toluene, orthoxylene, mesitylene, ethylbenzene, chlorinated hydrocarbons, such as chlorobenzene or dichloromethane, the solvents of ether type, such as dimethyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane. ### Claim 6 (depends on 1) Method according to claim 1, in which the addition of the alcohol of formula R1OH is carried out at a temperature that is less than or greater than 20° C. relative to the temperature that is used during the dimerization step. ### Claim 7 (depends on 1) Method according to claim 1, in which the addition of the alcohol of formula R1OH is carried out at a pressure that is less than or greater than 2.0 MPa relative to the pressure that is used during the dimerization step. ### Claim 8 (depends on 1) Method according to claim 1, in which the alcohol of formula R1OH is added to the raw effluent at a pressure of between 0.5 and 15.0 MPa. ### Claim 9 (depends on 1) Method according to claim 1, in which the alcohol of formula R1OH is added to the raw effluent that is obtained from the dimerization step in a molar ratio with the aluminum compound that is contained in the effluent (R1OH/Al) that is greater than or equal to 0.1. ### Claim 10 (depends on 1) Method according to claim 1, in which the titanium compound corresponds to the general formula [Ti(OR2)4], in which R2 is independently selected from among a linear or branched alkyl group, containing from 2 to 20 carbon atoms, and optionally substituted by a heteroatom that is selected from among a nitrogen, a phosphorus, a sulfur, or an oxygen, substituted or not, an aryl group comprising from 2 to 30 carbon atoms, substituted or not by alkyl, aryl groups optionally comprising at least one heteroatom that contains nitrogen, phosphorus, sulfur and oxygen. ### Claim 11 (depends on 1) Method according to claim 1, in which the aluminum compound corresponds to the general formula Al(R3)mY3-m, in which R3 is an alkyl or an aryl, preferably alkyl that contains from 1 to 6 carbon atoms, Y is selected from among a chlorine atom or a bromine atom, an alkoxy group that contains from 1 to 6 carbon atoms, and m is a whole number between 1 and 3. ### Claim 12 (depends on 1) Method according to claim 1, in which the Lewis-base-type additive is selected from among the compounds of the following types: ether, amine, phosphine, sulfide, cyclic or non-cyclic, substituted or not by the following groups: alkyl, aryl, aralkyl comprising from 2 to 30 carbon atoms. ### Claim 13 (depends on 1) Method according to claim 1, in which the “BL/Al” molar ratio between a Lewis-base (BL)-type additive and an aluminum compound (Al) is greater than 0.5, preferably is between 0.5 and 20.0. ### Claim 14 (depends on 1) Method according to claim 1, in which the molar ratio between, on the one hand, the preformed mixture that comprises the aluminum compound and the Lewis-base-type additive, and, on the other hand, the titanium compound of the catalytic composition is implemented such that the molar ratio between the aluminum compound and the titanium compound is between 1/1 and 100/1 (mol/mol). ### Claim 15 (depends on 1) Method according to claim 1, in which the titanium compound is used in a mixture with an ether-type additive in a molar ratio between the additive and the titanium compound of between 20/1 and 1/1 (mol/mol).