WO2021104925A1 - Procede de neutralisation d'une composition catalytique contenu dans un effluent issu d'une etape d'oligomerisation - Google Patents

Procede de neutralisation d'une composition catalytique contenu dans un effluent issu d'une etape d'oligomerisation Download PDF

Info

Publication number
WO2021104925A1
WO2021104925A1 PCT/EP2020/082322 EP2020082322W WO2021104925A1 WO 2021104925 A1 WO2021104925 A1 WO 2021104925A1 EP 2020082322 W EP2020082322 W EP 2020082322W WO 2021104925 A1 WO2021104925 A1 WO 2021104925A1
Authority
WO
WIPO (PCT)
Prior art keywords
vaporization
mpa
effluent
pressure
chosen
Prior art date
Application number
PCT/EP2020/082322
Other languages
English (en)
French (fr)
Inventor
Pierre-Alain Breuil
Nicolas ARIBERT
Olivier COTTE
Original Assignee
IFP Energies Nouvelles
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by IFP Energies Nouvelles filed Critical IFP Energies Nouvelles
Publication of WO2021104925A1 publication Critical patent/WO2021104925A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/005—Processes comprising at least two steps in series
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/09—Purification; Separation; Use of additives by fractional condensation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/14875—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/14875—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with organic compounds
    • C07C7/14891—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with organic compounds alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24—Phosphines

Definitions

  • the present invention relates to a process for neutralizing a catalytic composition contained in an effluent from an oligomerization step in a vaporization step.
  • the oligomerization step is a step of dimerization of ethylene to 1-butene by a nickel-based catalyst system.
  • octenes or hexenes or nonenes are produced respectively by dimerization of butenes or oligomerization of propylene by the Dimersol TM process from Axens (Revue de Institut für du Pperile, Vol. 37, No. 5, September- October 1982, p 639).
  • the octenes can be converted in good yields by hydroformylation reaction followed by hydrogenation to isononanols.
  • C9 alcohols that is to say comprising 9 carbon atoms
  • Hexenes or nonenes can also be used as a base for very good octane fuel.
  • Application FR3061175A1 describes a process for treating an effluent resulting from an olefin oligomerization step in the presence of a nickel-based catalyst and an alkylaluminum halide comprising a neutralization step with a solution containing a nitrile compound. Said method preferably comprises an additional step of washing with a basic or acidic aqueous solution.
  • the Applicant in its research has developed a new process for neutralizing an oligomerization effluent comprising a catalytic composition for oligomerization of olefins comprising an alkylaluminum halide, by bringing said oligomerization effluent into contact with a neutralization system comprising an alcohol and an amine.
  • the process according to the invention makes it possible, synergistically, by the use of an amine and an alcohol, to prevent the resumption of activity of the neutralized catalytic composition during the subsequent stages of purification of the liquid. 'effluent while limiting the corrosion phenomena due to the used catalytic composition.
  • the process according to the invention makes it possible to maximize the production of desired olefins.
  • the method according to the invention also makes it possible to limit the costs associated with the maintenance of production units.
  • the present invention relates to a process for treating an effluent resulting, preferably, directly from an oligomerization step using a catalytic composition comprising an alkylaluminum halide and a nickel precursor, comprising a neutralization step to deactivate said catalytic composition by bringing said effluent into contact with a neutralization system comprising
  • an alkyl group linear or branched, containing from 1 to 20 carbon atoms, and optionally substituted by an NH 2 group.
  • the R 1 group is an alkyl group, substituted by one or more substituent (s) chosen from a hydroxyl group (-OH), and an amine group (-NH2).
  • At least one of the groups R 2 , R 3 and R 4 is chosen from hydrogen.
  • the molar ratio of amine to alcohol is between 1.0 and 100.
  • the effluent, resulting from an oligomerization step contains a chlorine content of between 0.01 and 100,000 ppm by weight, preferably between 1.0 and 1,000 ppm by weight.
  • the molar ratio of the alkylaluminum halide to the nickel precursor, denoted Al / Ni, is preferably greater than or equal to 5, and preferably less than or equal to 30.
  • the effluent resulting directly from an oligomerization step contains an alkylaluminum halide content of between 0.01 and 100,000 ppm by weight.
  • the molar ratio of the neutralization system (corresponding to the sum of the alcohol (R 1 OH) and of the amine (NR 2 R 3 R 4 )) relative to the halide of alkylaluminum is between 0.5 and 100.
  • the alkylaluminum halide has the formula [Al m R 5 n X 3-n ] o in which
  • - R 5 is an alkyl group, linear or branched, containing from 1 to 12 carbon atoms, - X is a chlorine or bromine atom, and preferably a chlorine atom, and
  • - m is chosen from 1 or 2
  • - n is chosen from 0, 1 or 2
  • - o is chosen from 1 or 2
  • the temperature of contacting the neutralization system and the effluent from the oligomerization step is that at which said oligomerization step takes place.
  • the method comprises a step of thermal separation of an effluent obtained at the end of the neutralization step, said separation being carried out at a pressure of between 0.1 and 5.0 MPa and at a temperature between 70 and 200 ° C.
  • the step of thermal separation of the effluent from the neutralization step comprises two vaporization substeps in series:
  • a first vaporization step implemented at a pressure between 2.0 and 5.0 MPa and at a temperature between 70 and 200 ° C, making it possible to obtain a liquid fraction sent to a second vaporization step , and a gas fraction, preferably sent to a distillation section,
  • said second vaporization step is carried out at a pressure between 0.5 and 3.0 MPa and at a temperature between 70 and 200 ° C, making it possible to obtain a liquid fraction and a gas fraction , preferably, said gaseous fraction is sent to the distillation section, in which the pressure of the first vaporization stage is greater than the pressure of the second vaporization stage, preferably at least 0.5 MPa, of preferably at least 1.0 MPa, more preferably at least 1.5 MPa.
  • the thermal separation step implements a third vaporization step into which is sent the liquid fraction resulting from the second vaporization step, said third vaporization step is carried out at a pressure between 0.1 and 1.5 MPa and at a temperature between 70 and 200 ° C, making it possible to obtain a liquid fraction and a gaseous fraction, preferably said gaseous fraction is sent to the distillation section, and the pressure of the second vaporization step is greater than the pressure of the third vaporization step, preferably at least 0.5 MPa, preferably at least 0.8 MPa.
  • the gaseous fraction resulting from the first vaporization stage and / or the gaseous fraction resulting from the second vaporization stage and / or the gaseous fraction resulting from the third vaporization stage are liquefied by reducing the temperature. , so as to achieve a pressure between 2.0 and 5.0 MPa and preferably to be sent to the distillation section.
  • the temperature making it possible to liquefy the gaseous fraction (s) resulting from the vaporization stages is between 0 and 60 ° C.
  • the different parameter ranges for a given step such as the pressure ranges and the temperature ranges can be used alone or in combination.
  • a preferred pressure value range can be combined with a more preferred temperature value range.
  • An object according to the invention is therefore a process for treating an effluent resulting directly from an oligomerization step comprising a neutralization step by bringing said effluent into contact with a neutralization system comprising
  • R 1 OH an alcohol of general formula R 1 OH, in which the group R 1 is chosen from * an alkyl group, linear or branched, containing from 2 to 20 carbon atoms,
  • an alkyl group linear or branched, containing from 1 to 20 carbon atoms, and optionally substituted by an NH 2 group.
  • the Applicant has surprisingly discovered that the use of an alcohol associated with an amine makes it possible synergistically to prevent the resumption of activity of the neutralized catalytic composition during the subsequent stages of purification of the effluent while limiting the phenomena of corrosion due to the presence of the spent catalytic composition.
  • an advantage of the neutralization process according to the invention is to limit the corrosion phenomena of equipment located in particular downstream of the oligomerization unit due to the presence of the used catalytic composition.
  • Another advantage of the neutralization process according to the invention is to maximize the selectivity to but-1-ene.
  • the method according to the invention therefore relates to the treatment of an effluent, resulting directly from an oligomerization step, in a neutralization step by bringing said effluent into contact with a neutralization system comprising, preferably consisting of,
  • an alkyl group linear or branched, containing from 1 to 20 carbon atoms, and optionally substituted by an NH 2 group.
  • the neutralization step makes it possible to obtain an effluent in which the catalytic composition is neutralized, that is to say deactivated.
  • said composition no longer exhibits catalytic activity for the oligomerization reaction.
  • the R 1 group can be an alkyl group containing from 3 to 15 carbon atoms, preferably from 4 to 14 carbon atoms, preferably from 6 to 12 carbon atoms and preferably between 7 and 10 carbon atoms .
  • the group R 1 can be an aryl group containing from 5 to 30 carbon atoms, preferably from 5 to 20 carbon atoms, preferably 6 to 18 carbon atoms, and preferably from 6 to 15 carbon atoms. .
  • the group R 1 is a branched alkyl.
  • the R 1 group is a linear alkyl.
  • the group R 1 can be an alkyl substituted by one or more substituent (s) chosen from a hydroxyl group (-OH), or an amine group (-NH 2 ).
  • the alcohol of general formula R 1 OH is chosen from 1-propanol, 2-propanol, iso-propanol, 1-butanol, 2-butanol, iso-butanol, sec- butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3- heptanol, 4-heptanol, 1-octanol, 2-octanol, 3- octanol, 4-octanol, 2-ethyl-1-hexanol, 2-methyl-3-heptanol, 1-decanol, 2-decanol, 3-decanol, 4-decanol, 5-decanol, 1-undecanol, 2-undecanol, 7-methyl-2- decanol, 1-doc
  • the groups R 2 , R 3 and R 4 which are identical or different, are chosen independently from a hydrogen, an alkyl group, linear or branched, containing from 2 to 20 carbon atoms, preferably from 4 to 14 carbon atoms. carbon, preferably 6 to 12 carbon atoms and more preferably 7 to 10 carbon atoms.
  • At least one of the groups R 2 , R 3 and R 4 is chosen from hydrogen. In an even more preferred embodiment, at least two of the groups R 2 , R 3 and R 4 are chosen from hydrogen.
  • the amine is a poly-amine such as a diamine.
  • at least one of the groups R 2 , R 3 and R 4 is substituted by an amino group (-NH 2 ).
  • one of the groups R 2 , R 3 and R 4 is substituted by an amino group (-NH 2 ).
  • the amine of general formula NR 2 R 3 R 4 is chosen from 1-propylamine, 2-propylamine, iso-propylamine, 1-butylamine, 2-butylamine, iso-butylamine, sec-butylamine, tert-butylamine, 1-pentylamine, 2-pentylamine, 3-pentylamine, 1-hexylamine, 2-hexylamine, 3-hexylamine, 1-heptylamine, 2-heptylamine, 3-heptylamine, 4-heptylamine, 1-octylamine, 2-octylamine, 3-octylamine, 4- octylamine, 2-ethyl-1 -hexylamine, 2-methyl-3-heptylamine, 1 -decylamine, 2-decylamine, 3-decylamine, 4-decylamine, 5-decylamine, 1-undecylamine, 2- undecylamine,
  • the neutralization system comprises, preferably consists of, a mixture of 2-ethyl-1-hexanol and 2-hexylamine.
  • an alcohol R 1 OH and an amine NR 2 R 3 R 4 as a neutralization system makes it possible to effectively deactivate the catalytic composition present in the treated effluent, resulting directly from a step of oligomerization, by overcoming the problems associated with corrosion and by preventing a resumption of activity of said catalytic composition which leads to a decrease in selectivity.
  • the effluent, resulting directly from an oligomerization step is advantageously brought into contact with a mixture of alcohol and amine.
  • the effluent, resulting directly from an oligomerization step is advantageously brought into contact simultaneously with an alcohol of formula R 1 OH and with an amine of formula NR 2 R 3 R 4 .
  • the molar ratio of the amine relative to the alcohol is between 1.0 and 100, preferably between 1.1 and 90, preferably between 1.2 and 80, preferably between 1.5 and 70, preferably between 2.0 and 60, and more preferably between 2.2 and 50.
  • the molar ratio of the amine relative to the alcohol is between 1.0 and 40, from preferably between 1.1 and 30, preferably between 1.2 and 20, preferably between 1.5 and 15, preferably between 2.0 and 10, and more preferably between 2.2 and 5.0.
  • the molar ratio of the neutralization system (corresponding to the sum of the molar quantities of the alcohol (R 1 OH) and of the amine (NR 2 R 3 R 4 )) relative to the halide of alkylaluminum is between 0.5 and 100, preferably between 1.0 and 90, preferably between 1.5 and 80, preferably between 2.0 and 70, preferably between 3.0 and 60, preferably between 3.5 and 50.
  • the molar ratio of the neutralization system (corresponding to the sum of the molar quantities of the alcohol (R 1 OH) and of the amine (NR 2 R 3 R 4 )) relative to the alkylaluminum halide is between 0.5 and 50, preferably between 1.0 and 40, preferably between 1.5 and 30, preferably between 2.0 and 20, preferably between 3.0 and 15, preferably between 3.5 and 10.0.
  • the effluent resulting directly from an oligomerization step contains an alkylaluminum halide content of between 0.01 and 100,000 ppm by weight, preferably between 0.1 and 10,000 ppm by weight, preferably between 1, 0 and 1000 ppm by weight, preferably between 2.0 and 600 ppm, preferably between 3.0 and 400 ppm, preferably between 5.0 and 200 ppm, preferably between 6.0 and 100 ppm, preferably between 8.0 and 50 ppm, preferably between 10 and 40 ppm and preferably between 12 and 30 ppm by weight, relative to the total weight of said effluent.
  • an alkylaluminum halide content of between 0.01 and 100,000 ppm by weight, preferably between 0.1 and 10,000 ppm by weight, preferably between 1, 0 and 1000 ppm by weight, preferably between 2.0 and 600 ppm, preferably between 3.0 and 400 ppm, preferably between 5.0 and 200 ppm, preferably between 6.0 and 100 ppm, preferably between
  • the effluent resulting directly from an oligomerization step, contains a chlorine content of between 0.1 and 100,000 ppm by weight, preferably between 1.0 and 10,000 ppm by weight, preferably between 2.0 and 1 000 ppm by weight, preferably between 3.0 and 600 ppm, preferably between 4.0 and 400 ppm, preferably between 5.0 and 200 ppm, preferably between 8.0 and 100 ppm, preferably between 10 and 80 ppm, preferably between 12 and 70 ppm and preferably between 15 and 60 ppm by weight, relative to the total weight of said effluent.
  • a chlorine content of between 0.1 and 100,000 ppm by weight, preferably between 1.0 and 10,000 ppm by weight, preferably between 2.0 and 1 000 ppm by weight, preferably between 3.0 and 600 ppm, preferably between 4.0 and 400 ppm, preferably between 5.0 and 200 ppm, preferably between 8.0 and 100 ppm, preferably between 10 and 80 ppm, preferably between 12 and 70 pp
  • the neutralization system is preferably brought into contact with the effluent resulting from the oligomerization step at a temperature between -40 and 250 ° C, preferably between -20 ° C and 150 ° C, preferably between 20 ° C and 100 ° C, preferably between 30 and 80 ° C and very preferably between 40 and 60 ° C.
  • the temperature for bringing the neutralization system into contact with the effluent resulting from the oligomerization step is that at which said oligomerization step takes place.
  • the alcohol of general formula R 1 OH and the amine of general formula NR 2 R 3 R 4 can be used in an identical or different solvent.
  • Said solvent may be chosen from any solvent capable of diluting or dissolving the amine and / or the alcohol according to the invention.
  • said solvent can be chosen from one or more solvents as described below for the catalytic composition. "Optional" oligomerization step
  • the effluent treated in the process according to the invention is obtained at the end of an oligomerization step, preferably ethylene to olefin using a catalytic composition comprising an alkylaluminum halide, and of preferably a metal precursor, in particular a nickel precursor, said step making it possible to obtain said effluent treated in the process according to the invention, preferably in liquid form and comprising unconverted ethylene, the products formed during the oligomerization step, said catalytic composition and optionally a solvent.
  • a catalytic composition comprising an alkylaluminum halide, and of preferably a metal precursor, in particular a nickel precursor
  • the olefins obtained at the end of the oligomerization step are but-1-ene, but-2-ene, hex-1-ene and / or oct-1-ene, alone or in combination.
  • the oligomerization step is preferably carried out in the presence of said catalytic composition preferably comprising an alkylaluminum halide and a nickel precursor, with a nickel concentration advantageously between 10 12 and 1.0 mol / L, and preferably between 10 9 and 0.4 mol / L.
  • the oligomerization step is advantageously carried out at a pressure between 0.1 and 20.0 MPa, preferably between 0.1 and 15.0 MPa, and preferably between 0.5 and 8.0 MPa , and at a temperature between -40 and 250 ° C, preferably between -20 ° C and 150 ° C, preferably between 20 ° C and 100 ° C, and preferably between 30 to 80 ° C.
  • the oligomerization step is a step of dimerization of ethylene into but-1-ene and / or into but-2-ene, of trimerization of ethylene into hex-1-ene, or of tetramerization of ethylene to oct-1-ene.
  • the oligomerization step can be carried out continuously or discontinuously.
  • the constituents of the catalytic composition are injected into a reactor stirred by conventional mechanical means or by external recirculation, in which the olefin reacts, preferably with temperature control.
  • the alkylaluminum halide and a solution comprising the nickel precursor and optionally a ligand are injected into a reactor stirred by conventional mechanical means or by external recirculation, in which the olefin reacts, of preferably with temperature control.
  • the effluent treated in the process according to the invention therefore results from a step of oligomerization of ethylene to olefin using a catalytic composition comprising an alkylaluminum halide and preferably a nickel precursor.
  • the nickel precursor is chosen from nickel (II) chloride, nickel (II) chloride (dimethoxyethane), nickel bromide (II), nickel (II) bromide (dimethoxyethane), fluoride nickel (ll), nickel iodide (ll), nickel sulphate (ll), nickel carbonate (ll), nickel dimethylglyoxime (ll), nickel hydroxide (ll), nickel (ll) hydroxyacetate, nickel (ll) oxalate, nickel (ll) carboxylates such as for example nickel 2-ethylhexanoate, nickel (ll) phenates, nickel (ll) naphthenates , nickel acetate (ll), nickel trifluoroacetate (ll), nickel triflate (ll), nickel stearate (ll), nickel formate (ll), nickel acetylacetonate (ll) , nickel hexafluoroacetylacetonate (ll), TT-allylnickel (ll) chloride, TT-ally
  • the nickel precursor is chosen from nickel sulfate (II), nickel carbonate (II), nickel dimethylglyoxime (II), nickel hydroxide (II), nickel hydroxyacetate (II ), nickel oxalate (II), nickel carboxylates (II) such as for example 2- nickel ethylhexanoate, nickel phenates (ll), nickel naphthenates (ll), nickel acetate (ll), nickel trifluoroacetate (ll), nickel triflate (ll), nickel acetylacetonate (ll), nickel hexafluoroacetylacetonate (ll), TT-allylnickel (l I) chloride, TT-allylnickel (ll) bromide, methallylnickel (ll) chloride dimer, h 3 hexafluorophosphate - allylnickel (ll), the hexafluorophosphate of r
  • the alkylaluminum halide corresponds to the formula [Al m R 5 n X3- n ] 0 in which
  • R 5 is an alkyl group, linear or branched, containing from 1 to 12 carbon atoms,
  • - X is a chlorine or bromine atom, and preferably a chlorine atom
  • - m is chosen from 1 or 2
  • - n is chosen from 0, 1 or 2
  • R 5 groups can be identical or different.
  • R 5 is chosen from a linear or branched alkyl group containing from 2 to 10 carbon atoms, preferably from 2 to 6 carbon atoms, and preferably from 2 to 4 carbon atoms.
  • R 5 is an alkyl group chosen from methyl, ethyl, propyl, i-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl.
  • R 5 is an alkyl group chosen from ethyl, propyl, i-propyl, isopropyl, n-butyl, and tert-butyl.
  • the alkylaluminum halide is chosen from the group formed by methylaluminum dichloride (MeAICI 2 ), ethylaluminum dichloride (EtAICI 2 ), ethylaluminum sesquichloride (Et 3 Al 2 CI 3 ), chloride of diethylaluminum (Et 2 AICI), diisobutylaluminum chloride (iBu 2 AICI), isobutylaluminum dichloride (iBuAICI 2 ), taken alone or as a mixture.
  • MeAICI 2 methylaluminum dichloride
  • EtAICI 2 ethylaluminum dichloride
  • EtAICI 2 ethylaluminum sesquichloride
  • Et 3 Al 2 CI 3 chloride of diethylaluminum
  • iBu 2 AICI diisobutylaluminum chloride
  • iBuAICI 2 isobutylaluminum dichloride
  • the molar ratio of the alkylaluminum halide to the nickel precursor, denoted Al / Ni, is preferably greater than or equal to 5, more preferably greater than or equal to 6, and preferably less than or equal to 30, preferably less than or equal to 25, more preferably less than or equal to 20.
  • the catalytic composition can also comprise a ligand chosen from a phosphine.
  • the catalytic composition comprises a ligand chosen from a phosphine of formula PR 6 R 7 R 8 in which the groups R 6 , R 7 and R 8 , identical or different to each other, linked or not to each other, are chosen
  • the catalytic composition comprises at least one phosphine ligand of formula PR 6 R 7 R 8 in which the groups R 6 , R 7 and R 8 are identical to one another.
  • the aromatic groups R 6 , R 7 and R 8 of the phosphine ligand PR 6 R 7 R 8 are preferably chosen from the group formed by the phenyl, o-tolyl, m-tolyl, p-tolyl, mesityl, 3,5 groups.
  • the R 6 , R 7 and R 8 alkyl groups of the phosphine ligand PR 6 R 7 R 8 advantageously comprise 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, preferably between 3 and 10 carbon atoms.
  • the alkyl groups R 6 , R 7 and R 8 of the phosphine ligand PR 6 R 7 R 8 are chosen from the group formed by the methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclopentyl groups, cyclohexyl, benzyl, adamantyl.
  • the molar ratio between the phosphine ligand of formula PR 6 R 7 R 8 and the nickel precursor is between 5 and 25, preferably between 5 and 20, more preferably between 5 and 15.
  • this ratio molar range is between 6 and 30, preferably between 6 and 25, more preferably between 6 and 20, even more preferably between 6 and 15, and even more preferably between 7 and 14.
  • each constituent or mixture of constituents of the catalytic composition can be used in a solvent.
  • the solvent (s) are advantageously chosen from
  • - ethers alcohols, halogenated solvents and hydrocarbons, saturated or unsaturated, cyclic or not, aromatic or not, comprising between 1 and 20 carbon atoms, preferably between 1 and 15 carbon atoms and preferably between 4 and 15 carbon atoms, - ionic liquids.
  • the solvent is chosen from pentane, hexane, cyclohexane, methylcyclohexane, heptane, butane or isobutane, cycloocta-1,5-diene, benzene, toluene, ortho -xylene, mesitylene, ethylbenzene, diethyl ether, tetrahydrofuran, 1,4-dioxane, dichloromethane, dichloroethane, chlorobenzene, dichlorobenzene, methanol, ethanol, pure or in mixture and liquids ionic.
  • the solvent is an unsaturated hydrocarbon
  • it can be advantageously chosen from the products of the oligomerization reaction.
  • the solvent is an ionic liquid
  • it is advantageously chosen from N-butyl-pyridinium hexafluorophosphate, N-ethyl-pyridinium tetrafluoroborate, pyridinium fluorosulphonate, butyl-3-methyl-1 tetrafluoroborate -imidazolium, butyl-3-methyl-1-imidazolium bis-trifluoromethane-sulfonyl amide, triethylsulfonium bis-trifluoromethane-sulfonyl amide, butyl-3-methyl-1-imidazolium hexafluoro-antimonate , butyl-3-methyl-1-imidazolium hexafluorophosphate, butyl-3-methyl-1-imidazolium trifluoroacetate, butyl-3-methyl-1-imidazolium trifluoromethylsulfonate, trimethylphenylammonium
  • the treatment process can comprise, preferably comprises, a thermal separation step, commonly called vaporization, of the effluent obtained at the end of the neutralization step, said separation is carried out at a pressure between 0.1 and 5.0 MPa and at a temperature between 70 and 200 ° C.
  • a thermal separation step commonly called vaporization
  • Said separation step advantageously makes it possible to remove an effluent comprising the neutralized catalyst and the neutralization system and to send the reaction effluent containing unconverted ethylene, the products formed during the oligomerization step and optionally the solvent. in a distillation section in order to purify them.
  • the effluent comprising the neutralized catalyst separated in the vaporization step is sent to an incinerator.
  • the step of thermal separation of the effluent from the neutralization step comprises two vaporization substeps in series:
  • a first vaporization step implemented at a pressure between 2.0 and 5.0 MPa and at a temperature between 70 and 200 ° C, making it possible to obtain a liquid fraction sent to a second vaporization step , and a gas fraction, preferably sent to a distillation section,
  • said second vaporization step is carried out at a pressure between 0.5 and 3.0 MPa and at a temperature between 70 and 200 ° C, making it possible to obtain a liquid fraction and a gas fraction , preferably, said gaseous fraction is sent to the distillation section,
  • the pressure of the first vaporization step is greater than the pressure of the second vaporization step, preferably at least 0.5 MPa, preferably at least 1.0 MPa, preferably at least 1.5 MPa.
  • the gas fractions sent to the distillation section include unconverted ethylene, products formed during the oligomerization step and optionally solvent.
  • the thermal separation step makes it possible to remove the neutralized catalyst by vaporization of the compounds of interest (that is to say the products formed from the oligomerization step and of unconverted ethylene) at moderate temperature.
  • the implementation of at least two vaporization steps at moderate temperature with a decreasing pressure gradient makes it possible to further reduce the risk of resumption of activity of the neutralized catalyst and therefore to improve or at least optimize the selectivity for the desired olefins.
  • the first vaporization step is carried out at a pressure between 2.0 and 4.5 MPa, preferably 2.5 and 4.0 MPa, and more preferably between 2.5 and 3.5 MPa and at a temperature between 70 and 180 ° C, preferably between 75 and 160 ° C, preferably between 80 and 150 ° C, preferably between 85 and 140 ° C, preferably between 80 and 130 ° C, and so preferred between 95 and 120 ° C.
  • the second vaporization step is carried out at a pressure between 0.8 and 3.0 MPa, preferably 1.0 and 2.0 MPa, preferably between 1.1 and 1.8 MPa, and very preferably between 1.2 and 1.5 MPa and at a temperature between 70 and 180 ° C, preferably between 75 and 160 ° C, preferably between 80 and 150 ° C, preferably between 85 and 140 ° C preferably between 80 and 130 ° C, and more preferably between 95 and 125 ° C.
  • the thermal separation step implements a third vaporization step into which the liquid effluent from the second vaporization step is sent, said third vaporization step being carried out at a pressure between 0.1 and 1.5 MPa and at a temperature between 70 and 200 ° C.
  • Said third vaporization step makes it possible to obtain a liquid fraction and a gas fraction, preferably said gas fraction is sent to the distillation section.
  • the pressure of the second vaporization step is higher than the pressure of the third vaporization step, preferably at least 0.5 MPa, preferably at least 0.8 MPa, preferably at least 1.0 MPa, and preferably at least 1.5 MPa.
  • the last liquid fraction obtained at the end of the second or third vaporization step corresponds to a stream comprising the neutralized catalyst and the neutralization system which is preferably sent to an incinerator.
  • the gas fraction resulting from the second or the third vaporization step is sent to the distillation section.
  • the third vaporization step is carried out at a pressure between 0.3 and 1.2 MPa, preferably between 0.4 and 1.0 MPa, preferably between 0.5 and 0.8 MPa, and at a temperature between 70 and 180 ° C, preferably between 75 and 160 ° C, preferably between 80 and 150 ° C, preferably between 85 and 140 ° C preferably between 80 and 130 ° C, preferably between 85 and 130 ° C, preferably between 90 and 120 ° C and more preferably between 95 and 110 ° C.
  • flash is understood to mean a gas / liquid separation carried out by a change in pressure and / or temperature.
  • the first step and / or the second step and / or the third step of thermal separation are implemented by means of a flash balloon, preferably coupled with a heat exchanger or any other sequence making it possible to partially vaporize an effluent.
  • a wide choice of technology is available for the implementation of any of the thermal separation steps, said technologies are preferably chosen from:
  • the gaseous fraction resulting from the first vaporization stage and / or the gaseous fraction resulting from the second vaporization stage and / or the gaseous fraction resulting from the third vaporization stage are liquefied, upstream of said vaporization.
  • distillation section by reducing the temperature, so as to reach a pressure between 2.0 and 5.0 MPa and preferably to be sent to the distillation section, preferably by means of a pump.
  • this embodiment makes it possible to dispense with the use of a compressor, which makes it possible to limit the costs of implementing the process for treating the effluent resulting from an oligomerization step.
  • the temperature making it possible to liquefy the gas fraction (s) resulting from the vaporization stages is between 0 and 60 ° C, preferably between 10 and 55 ° C, and preferably between 20 and 50 ° C.
  • olefins from the ethylene oligomerization step have a higher molecular weight than unreacted ethylene.
  • unreacted ethylene has a lower boiling point than that of oligomers resulting from the oligomerization step, such as but-1-ene, but-2-enes. , hex-1-ene or oct-1-ene.
  • any separation means known to those skilled in the art making use of these differences in volatility and molecular weight between the products to be separated can be used in the separation step.
  • the separation means used are distillation columns of any type.
  • the method according to the invention optionally comprises a separation step advantageously comprising a distillation section.
  • a separation step advantageously comprising a distillation section.
  • the gas fractions resulting from the thermal separation step comprising in particular the unconverted ethylene, the products formed and the solvent, are sent in mixed gas / liquid form to the section. of distillation.
  • the distillation section advantageously comprises at least three distillation columns, preferably at least four distillation columns. According to a preferred variant of the invention, the distillation section comprises four distillation columns.
  • n-heptane 93 ml of n-heptane are introduced into a reactor, previously dried under vacuum and placed under an ethylene atmosphere, then 6 ml of a solution containing the nickel precursor Ni (2-ethylhexanoate) 2 (noted Ni (2- EH) 2 , 40 pmol and tricyclohexylphosphine (PCy 3 ) (400 pmol).
  • Ni (2- EH) 2 a solution containing the nickel precursor Ni (2- EH) 2 (noted Ni (2- EH) 2 , 40 pmol and tricyclohexylphosphine (PCy 3 ) (400 pmol).
  • PCy 3 tricyclohexylphosphine
  • the reactor is brought to the test pressure (2 MPa). stirring is started, the reaction is carried out under pressure control, the supply of ethylene making it possible to maintain the pressure at the test pressure. After the desired consumption of ethylene, the supply of ethylene is cut off. is sent to the neutralization stage.
  • the gaseous effluents are Ified and qualified by gas chromatography (GC), the liquid fractions are weighed and qualified by GC.
  • the effluent obtained at the end of the oligomerization step is brought into contact with various neutralization systems comprising 2-ethylhexylamine, 2-ethylhexanol, or the mixture (2-ethylhexylamine + 2-ethylhexanol) at a temperature of 50 ° C and at different molar ratios of amine and alcohol relative to ethylaluminum dichloride (noted Al).
  • Al ethylaluminum dichloride
  • the neutralization system according to the invention makes it possible to ensure the neutralization of the mixture without isomerizing the olefins and therefore while retaining the selectivity for the desired olefins resulting from the oligomerization step and by preventing the corrosion problems associated with the presence of chlorine.
  • Example 2 Corrosion resistance test.
  • Example 3 thermal separation step with 2 vaporization steps in series (according to the invention)
  • the effluent neutralized according to Example 1 inlet 7 of Table 1 is compressed to a pressure of 3.25 MPa and then partially vaporized by heating in a heat exchanger to a temperature of 115 ° C.
  • the gas fraction is then separated from the liquid fraction in a flask.
  • the gas fraction is sent to a distillation section and the liquid fraction is sent to a second flash.
  • the liquid fraction resulting from the first flash is expanded to a pressure of 1.35 MPa.
  • Said expanded liquid fraction is then partially vaporized by heating in a heat exchanger to a temperature of 117 ° C.
  • the gas fraction is then separated from the liquid fraction in a flask.
  • the gas fraction is sent to the distillation section and the liquid fraction comprising the neutralized catalyst and the neutralization system is sent to an incinerator.
  • Table 2 below shows the conditions at the various stages as well as the composition of each fraction.
  • the last liquid effluent from the second flash comprises the hetero-elements from the catalytic system and from the inhibitor (s) (Ni, P, Al, Cl, O, N etc.) as well as their associated organic part.
  • s inhibitor
  • Table 2 shows the conditions at the various stages as well as the composition of each fraction.
  • the last liquid effluent from the second flash comprises the hetero-elements from the catalytic system and from the inhibitor (s) (Ni, P, Al, Cl, O, N etc.) as well as their associated organic part.
  • the effluent according to Example 1 neutralized under the conditions according to entry 7 of Table 1, is compressed to a pressure of 3.25 MPa and then partially vaporized by heating in a heat exchanger to a temperature of 115 ° C.
  • the vapor fraction is then separated from the liquid fraction in a flask.
  • the vapor fraction is sent to a distillation section and the liquid fraction is sent to a second flash.
  • the liquid fraction resulting from the first flash is expanded to a pressure of 1.3 MPa. Said expanded liquid fraction is then partially vaporized by heating in a heat exchanger to a temperature of 107 ° C. The vapor fraction is then separated from the liquid fraction in a flask. The vapor fraction is sent to the distillation section and the liquid fraction is sent to a third flash.
  • the liquid fraction resulting from the second flash is expanded to a pressure of 0.5 MPa. Said expanded liquid fraction is then vaporized by heating in a heat exchanger to a temperature of 98 ° C.
  • Table 3 below shows the conditions at the different stages as well as the average composition of each stream.
  • the last liquid effluent from the third flash comprises the hetero-elements from the catalytic system and from the inhibitor (s) (Ni, P, Al, Cl, O, N, etc.) as well as their associated organic part.
  • s inhibitor
  • no isomerization of the desired olefins is observed, which makes it possible to maximize the recovery of the products of interest.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/EP2020/082322 2019-11-26 2020-11-17 Procede de neutralisation d'une composition catalytique contenu dans un effluent issu d'une etape d'oligomerisation WO2021104925A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1913244A FR3103486A1 (fr) 2019-11-26 2019-11-26 Procede de neutralisation d’une composition catalytique contenu dans un effluent issu d’une etape d’oligomerisation
FRFR1913244 2019-11-26

Publications (1)

Publication Number Publication Date
WO2021104925A1 true WO2021104925A1 (fr) 2021-06-03

Family

ID=69572218

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2020/082322 WO2021104925A1 (fr) 2019-11-26 2020-11-17 Procede de neutralisation d'une composition catalytique contenu dans un effluent issu d'une etape d'oligomerisation

Country Status (3)

Country Link
FR (1) FR3103486A1 (zh)
TW (1) TW202128601A (zh)
WO (1) WO2021104925A1 (zh)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1410430A (fr) 1963-08-10 1965-09-10 Studiengesellschaft Kohle Mbh Procédé pour l'oligomérisation et la polymérisation d'oléfines et catalyseurs pour ces opérations
US3321546A (en) 1962-11-30 1967-05-23 Shell Oil Co Olefin dimerization using aluminum alkyl halide-nickel complex catalyst
US3485881A (en) 1967-10-09 1969-12-23 Phillips Petroleum Co Dimerization of olefins
FR2114114A5 (en) 1970-11-10 1972-06-30 Inst Francais Du Petrole Olefin dimerisation catalyst - contg halogen deactivated by ammonia or amine
US5910618A (en) * 1993-03-04 1999-06-08 Sumitomo Chemical Company, Limited Process for preparing 2,3-dimethyl-2-butene
WO2001047839A1 (en) * 1999-12-29 2001-07-05 Phillips Petroleum Company Processes for preventing generation of hydrogen halides in an oligomerization product recovery system
FR2979836B1 (fr) 2011-09-08 2014-08-08 IFP Energies Nouvelles Nouvelle composition catalytique a base de nickel et procede d'oligomerisation des olefines utilisant ladite composition
FR3061034A1 (fr) * 2016-12-22 2018-06-29 IFP Energies Nouvelles Procede d'oligomerisation d'olefines mettant en œuvre un dispositif de nettoyage
FR3061175A1 (fr) 2016-12-22 2018-06-29 IFP Energies Nouvelles Procede de neutralisation d'un systeme catalytique de dimerisation d'olefines contenant au moins un derive halogene.

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3321546A (en) 1962-11-30 1967-05-23 Shell Oil Co Olefin dimerization using aluminum alkyl halide-nickel complex catalyst
FR1410430A (fr) 1963-08-10 1965-09-10 Studiengesellschaft Kohle Mbh Procédé pour l'oligomérisation et la polymérisation d'oléfines et catalyseurs pour ces opérations
US3485881A (en) 1967-10-09 1969-12-23 Phillips Petroleum Co Dimerization of olefins
FR2114114A5 (en) 1970-11-10 1972-06-30 Inst Francais Du Petrole Olefin dimerisation catalyst - contg halogen deactivated by ammonia or amine
US5910618A (en) * 1993-03-04 1999-06-08 Sumitomo Chemical Company, Limited Process for preparing 2,3-dimethyl-2-butene
WO2001047839A1 (en) * 1999-12-29 2001-07-05 Phillips Petroleum Company Processes for preventing generation of hydrogen halides in an oligomerization product recovery system
FR2979836B1 (fr) 2011-09-08 2014-08-08 IFP Energies Nouvelles Nouvelle composition catalytique a base de nickel et procede d'oligomerisation des olefines utilisant ladite composition
FR3061034A1 (fr) * 2016-12-22 2018-06-29 IFP Energies Nouvelles Procede d'oligomerisation d'olefines mettant en œuvre un dispositif de nettoyage
FR3061175A1 (fr) 2016-12-22 2018-06-29 IFP Energies Nouvelles Procede de neutralisation d'un systeme catalytique de dimerisation d'olefines contenant au moins un derive halogene.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
REVUE DE L'INSTITUT FRANÇAIS DU PÉTROLE, vol. 37, no. 5, September 1982 (1982-09-01), pages 639

Also Published As

Publication number Publication date
FR3103486A1 (fr) 2021-05-28
TW202128601A (zh) 2021-08-01

Similar Documents

Publication Publication Date Title
CA3007314C (fr) Composition catalytique a base de nickel et de ligand de type phosphine et d'une base de lewis et son utilisation dans un procede d'oligomerisation des olefines
EP2567752B1 (fr) Nouvelle composition catalytique à base de nickel et procédé d'oligomérisation des oléfines utilisant ladite composition
EP2572782B1 (fr) Procédé de séparation du butène-2 d'une coupe C4 contenant du butène-2 et du butène-1 par oligomérisation sélective du butène-1
FR2804622A1 (fr) Composition catalytique pour la dimerisation, la codimerisation et l'oligomerisation des olefines
FR2735399A1 (fr) Nouvelle composition catalytique a base de complexes de metaux de transition et procede pour l'hydrogenation des composes insatures
EP2939742A1 (fr) Nouvelle composition catalytique à base de nickel et son utilisation dans un procédé d'oligomérisation des oléfines
FR3083129A1 (fr) Procede d'oligomerisation d'ethylene avec enchainement reacteur agite gaz/liquide et reacteur piston
FR2806644A1 (fr) Composition catalytique et procede pour la catalyse de dimerisation, de codimerisation et d'oligomerisation des olefines
EP3328542B1 (fr) Procédé de dimerisation de l'éthylène
WO2021104925A1 (fr) Procede de neutralisation d'une composition catalytique contenu dans un effluent issu d'une etape d'oligomerisation
WO2021104924A1 (fr) Procede de separation d'un effluent issu d'une etape d'oligomerisation
EP2572783A1 (fr) Procédé de séparation du pentène-2 d'une ocupe C5 contenant du pentène-2 et du pentène-1 par oligomérisation sélective du pentène-1
EP1519787B1 (fr) Procede d hydrogenation selective de composes polyinsatures en composes monoinsatures utilisant un catalyseur homogene
CA3158083A1 (fr) Reacteur gaz/liquide d'oligomerisation a zones successives de diametre variable
FR3074065A1 (fr) Nouvelle composition catalytique a base de nickel, d’un phosphonium et son utilisation pour l’oligomerisation des olefines
FR3121439A1 (fr) Procede d'oligomerisation comprenant une etape de recyclage d'un solvant prealablement refroidi
FR3109741A1 (fr) Nouvelle composition catalytique a base de nickel, d’un complexe cationique d’yttrium et son utilisation pour l’oligomerisation des olefines
FR3116739A1 (fr) Nouvelle composition catalytique a base de chrome comprenant un additif hydrocarbure aromatique et procede associe pour l’oligomerisation de l’ethylene en octene-1
EP4347542A1 (fr) Procede d'oligomerisation dans un reacteur a zones de diametres variables comprenant une etape de recyclage d'un solvant prealablement refroidi
FR3074064A1 (fr) Nouvelle composition catalytique a base de nickel, d'un compose phosphoree et d'un acide sulfonique et son utilisation pour l'oligomerisation des olefines
WO2022023028A1 (fr) Procede d'oligomerisation d'ethylene comprenant la preparation in situ de la composition catalytique
FR3105018A1 (fr) Reacteur gaz/liquide d’oligomerisation comprenant des internes transversaux
FR3086552A1 (fr) Composition catalytique a base de nickel (i)
FR3087773A1 (fr) Nouveau compose a base d’aluminium
FR3051683A1 (fr) Composition catalytique a base de chrome et d'un ligand a base de phosphine et son utilisation dans un procede de procuction d'octenes

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20804301

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20804301

Country of ref document: EP

Kind code of ref document: A1