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WO2016005769A1 - Procédé d'oligomérisation - Google Patents

Procédé d'oligomérisation Download PDF

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WO2016005769A1
WO2016005769A1 PCT/GB2015/052007 GB2015052007W WO2016005769A1 WO 2016005769 A1 WO2016005769 A1 WO 2016005769A1 GB 2015052007 W GB2015052007 W GB 2015052007W WO 2016005769 A1 WO2016005769 A1 WO 2016005769A1
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alpha
olefins
process according
ionic liquid
olefinic feedstock
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Inventor
Fergal COLEMAN
Sesime COFFIE
Martin Philip Atkins
James Hogg
Albert Ferrer UGALDE
Malgorzata SWADZBA-KWASNY
Gabriela FEDOR
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Queens University of Belfast
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    • 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
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/10—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
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    • C07C2527/06—Halogens; Compounds thereof
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    • C07C2527/125—Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
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    • C07C2527/128—Compounds comprising a halogen and an iron group metal or a platinum group metal
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    • C07C2527/14—Phosphorus; Compounds thereof
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    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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    • 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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material

Definitions

  • This invention relates to an oligomerisation process for forming base oils for lubricating compositions.
  • the present invention provides a process for the selective oligomerisation of Cs to C20 alpha-olefins to produce polyalphaolefin oligomers, preferably with a molecular weight distribution that is suitable for use in lubricant base oils.
  • Lubricant compositions generally comprise a base oil of lubricating viscosity together with one or more additives to deliver properties such as reduced friction and wear, improved viscosity index, detergency, and resistance to oxidation and corrosion.
  • a lubricant base oil may comprise one or more sources of lubricating oil, referred to as base stocks.
  • Lubricant base stocks useful in automotive engine lubricants may be obtained as higher boiling fractions from the refining as crude oil or via synthetic routes, and are classified as Group I, I I, I II, IV and V base stocks according to API standard 1509, "ENGINE OIL LICENSING AND CERTIFICATION SYSTEM", April 2007 version 16th edition Appendix E.
  • Group IV refers to polyalphaolefin (PAO) base stocks, which are typically synthesised by oligomerisation of 1-decene.
  • PAO polyalphaolefin
  • the principal component of these base stocks is decene trimer, although the dimer, tetramer and pentamer are typically also present in the various base stock blends.
  • Ziegler-Natta catalysts are a class of catalysts that comprise titanium compounds in combination with an organoaluminium compound.
  • Ziegler-Natta catalysts used commercially for the polymerisation of alpha-olefins comprise a titanium complex (such as TiCU) together with an organoaluminium compound (such as triethylaluminium) on a magnesium chloride support.
  • Metallocene complexes (such as dicyclopentadienylzirconium dichloride, Cp2ZrCl2) have also been used as catalysts for the oligomerisation of alpha-olefins in combination with a methylaluminoxane activator. It is also known that Lewis acids such as BF3, AlC and EtAIC can be used as catalysts for cationic polymerisation of alpha-olefins in conjunction with an alkyl halide (for instance feri-butyl chloride), alcohol or Bransted acid.
  • Cp2ZrCl2 dicyclopentadienylzirconium dichloride
  • ionic liquids as catalysts for the cationic polymerisation of alpha-olefins.
  • Ionic liquids are a class of compounds that have been developed over the last few decades.
  • the term "ionic liquid” as used herein refers to a liquid that can be obtained by melting a salt, and which is composed entirely of ions.
  • the term "ionic liquid” by standard definition includes salts melting below 100 °C. Ionic liquids having melting points below around 30 °C are commonly referred to as "room temperature ionic liquids" and are often derived from organic salts having nitrogen- containing heterocyclic cations, such as imidazolium and pyridinium-based cations.
  • the ionic liquid catalysts disclosed in US 7,572,944 comprise pyridinium or imidazolium cations together with acidic chloroaluminate anions, such as [AI 2 CI 7 ] " .
  • the use of ionic liquids as polymerisation catalysts is known to provide certain advantages over conventional catalysts.
  • ionic liquids are generally immiscible with hydrocarbons and thus can be separated from polyalphaolefin products by phase separation and recycled.
  • conventional Lewis acid catalysts are generally quenched during the isolation of products.
  • a disadvantage of known ionic liquid systems is that the organic cations are spectator ions which play no part in the catalytic reaction, other than to moderate the melting point of the ionic liquid reaction medium.
  • the cation also represents an expensive component of the ionic liquid.
  • a further disadvantage of known ionic liquid systems, in common with other Lewis acid catalysts, is that the catalysts can be extremely active, particularly those ionic liquids comprising acidic chloroaluminate anions, such as [AI 2 CI 7 ] ⁇ High catalytic activity tends to result in the formation of undesired highly oligomerised products, thereby wasting resources.
  • the present invention is based on the discovery that a certain class of Lewis acidic ionic liquids has been found to give unexpected selectivity when used as a catalyst for the production of polyalphaolefin oligomers. More specifically, the class of ionic liquids comprises a tricoordinate borenium(ll l) cation. This cation is a Lewis acidic species, and therefore not merely a spectator cation, as in known Lewis acid ionic liquid systems.
  • boron(ll l) cations may be classified into three distinct structural classes based on the coordination number at boron.
  • the three different classes, borinium (a), borenium (b) and boronium (c), are illustrated below:
  • Neutral tricoordinate boron group species such as BF 3
  • the corresponding tricoordinate borenium (b) cationic species illustrated above has been postulated to be an even stronger Lewis acid as a result of its increased electron deficiency (Angew. Chem. I nt. Ed. 2005, 44, 5016 to 5036).
  • Dicoordinate borinium (a) cations are speculated to be extremely strong Lewis acids, but are so reactive that they only exist transiently.
  • tetracoordinate boronium (c) cations have received most attention historically, as they are inherently more stable as a result of a filled octet and a complete coordination sphere, but for the same reasons their Lewis acidity is compromised.
  • the present inventors have prepared ionic liquids comprising a borenium cation together with conventional anions, such as [AICI 4 ] “ or [NTf 2 ] “ , including Lewis acidic chloroaluminates, such as [AI 2 CI 7 ] ⁇ , thereby forming a class of ionic liquids comprising two Lewis acidic centres, having overall Lewis acidities far exceeding those of conventional Lewis acidic ionic liquid systems.
  • conventional anions such as [AICI 4 ] " or [NTf 2 ] "
  • Lewis acidic chloroaluminates such as [AI 2 CI 7 ] ⁇
  • the Gutmann Acceptor Number (AN) value for Lewis acidity of the borenium cation alone is over 160
  • the AN value for the chloroaluminate(lll) anion is approximately 100.
  • the present invention provides a process for the preparation of alpha-olefin oligomers, comprising contacting an olefinic feedstock comprising Cs to C20 alpha-olefins with an ionic liquid comprising:
  • each X is independently selected from fluorine and chlorine. In more preferred embodiments, X is either fluorine or chlorine. In even more preferred embodiments, X is chlorine.
  • the Lewis basic donor ligand is preferably selected from small molecule donor ligands having a molecular weight of 500 or less, preferably a molecular weight of 400 or less, more preferably a molecular weight of 300 or less, still more preferably a molecular weight of 200 or less, and most preferably a molecular weight of 100 or less.
  • the Lewis basic donor ligand is selected from ligands containing a donor atom selected from oxygen, sulphur, selenium, nitrogen and phosphorus, more preferably from oxygen, nitrogen and phosphorus, still more preferably from nitrogen and phosphorus. Most preferably, the Lewis basic donor ligand is selected from ligands containing a nitrogen donor atom.
  • the Lewis basic donor ligand is selected from the group of compounds consisting of ketones, sulfoxides, phosphine-oxides, ureas, esters, amides, ethers, thioketones, thioureas, thioamides, thioethers, amines, nitriles and phosphines. More preferably, the Lewis basic donor ligand is selected from the group of compounds consisting of amines, amides and phosphines. Still more preferably, the Lewis basic donor ligand is selected from the group of compounds consisting of amines and amides. Most preferably, the Lewis basic donor ligand is an amine.
  • the Lewis basic donor ligand is selected from a heterocyclic group, which is an aromatic or non-aromatic cyclic, fused bi- or tri-cyclic, substituted or unsubstituted hydrocarbon group comprising one or more of O, N, NH and S in the ring.
  • Preferred heterocyclic groups for use as the Lewis basic donor ligand in accordance with the present invention are selected from imidazolyl, pyridyl and pyrrolyl, more preferably selected from imidazolyl and pyridyl.
  • Heterocyclic group Lewis basic donor ligands for use in the present invention may be unsubstituted or substituted.
  • suitable substituents include Ci to Ci 0 , preferably Ci to C 6 , straight chain or branched alkyl, Ci to C 6 alkoxy, C 2 to C 12 alkoxyalkoxy, C 3 to C 8 cycloalkyl, C 3 to C 8 heterocyclic, C 6 to Ci 0 aryl, C 7 to Cio alkaryl, C 7 to Cio aralkyl, -CN, -OH, -SH, -N0 2 , -C0 2 R x , -OC(0)R x , -C(0)R x , -C(S)R X , -CS.
  • Preferred substituents include Ci to Cio, preferably Ci to C 6 , straight chain or branched alkyl, Ci to C 6 alkoxy, C 2 to C 8 alkoxyalkoxy, C 3 to C 8 cycloalkyl, -OH or -NR y R z , wherein R y and R z are independently selected from hydrogen or d to C 6 straight chain or branched alkyl group.
  • Suitable d to Cio alkyl groups include methyl, ethyl, propyl, isopropyl, n- butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, trifluoromethyl and pentafluoroethyl.
  • Preferred alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl. More preferred alkyl groups include methyl, ethyl, propyl, and isopropyl. Most preferably, the alkyl group is methyl.
  • particularly preferred heterocyclic compounds for use as Lewis basic donor ligands in accordance with the present invention are selected from picoline, lutidine, pyridine, collidine, dimethylaminopyridine (DMAP), 1-alkylimidazole, for example 1- methylimidazole (mim).
  • the Lewis basic donor ligand is selected from compounds having a formula selected from R 1 -C(0)-R 1 , R 1 -S(0)-R ⁇ R 2 NH-C(0)-NHR 2 , R 2 NH-C(S)-NHR 2 R 1 -C(0)-N(R 2 ) 2 , R 1 -C(0)-OR 1 , (R 3 ) 3 P, (R 3 ) 3 P(0) and R 1 -CN wherein: each R 1 independently represents a Ci to Ci 0 straight chain or branched alkyl group, preferably a Ci to C 6 alkyl group, more preferably a Ci to C 3 alkyl group and most preferably a methyl group;
  • R 2 is selected from hydrogen or a Ci to Cio straight chain or branched alkyl group, more preferably from hydrogen or a Ci to C 6 alkyl group, still more preferably from hydrogen or a Ci to C 3 alkyl group, and most preferably from hydrogen or a methyl group; and
  • R 3 represents a C 4 to Cio straight chain or branched alkyl group
  • R 1 , R 2 and R 3 may optionally be substituted by one or more fluorine atoms.
  • Ci to Cio alkyl groups examples include methyl, ethyl, propyl, isopropyl, n- butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, trifluoromethyl and pentafluoroethyl.
  • Preferred alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl. More preferred alkyl groups include methyl, ethyl, propyl, and isopropyl. Most preferably, the alkyl group is methyl.
  • the Lewis basic donor ligand is selected from compounds having a formula selected from R 1 -S(0)-R 1 , R 2 NH-C(0)-NHR 2 , R 2 NH-C(S)-NHR 2 R 1 -C(0)-NR 2 2 , (R 3 ) 3 P and (R 3 ) 3 P(0); more preferably, the Lewis basic donor ligand is selected from compounds having a formula selected from R 2 NH-C(0)-NHR 2 and R 1 -C(0)-N(R 2 ) 2 ; and most preferably the Lewis basic donor ligand is a compound having the formula R 2 NH-C(0)-NHR 2 , wherein R 1 and R 2 are as defined above.
  • Lewis basic donor ligands examples include urea, ⁇ /, ⁇ -dimethylurea, ⁇ , ⁇ /'-dimethylthiourea, acetamide, dimethylacetamide, acetone, ethyl acetate dimethylsulfoxide, trioctylphosphine oxide, and trioctylphosphine.
  • the Lewis basic donor ligand may comprise a mixture of two or more Lewis basic donor ligands as described herein.
  • non-coordinating anion used herein, which is common in the field of olefin oligomerisation, is intended to mean an anion that does not coordinate with the metal cation, or does so only weakly.
  • non-coordinating anions typically have their charge dispersed over several atoms in the molecule which significantly limits their coordinating capacity.
  • Preferred non-coordinating anions are selected from a) halometallate anions of the formula [MX 4 ] “ or [M2X7] " , where M is Al or Ga, preferably Al, and X is independently CI or Br, preferably CI; b) bis(triflamide) ([NTf 2 ] “ ) or triflate ([OTf] “ ); c) bis(perfluoroalkylsulphonyl)imides (preferably methyl, ethyl, butyl and nonyl) d) tetrafluoroborate ([BF 4 ] " ) or tetrachloroborate ([BCI 4 ] " ); e) hexafluorophosphate ([PF 6 ] " ); f) [SnX 3 ] “ or [Sn 2 X 5 ] " , where X is independently CI or Br g) dichlorocuprate ([CuCI 2 ] " ); h) hex
  • More preferred non-coordinating anions are selected from a) halometallate anions of the formula [MX 4 ] “ or [M 2 X 7 ] " , where M is Al or Ga, preferably Al, and X is independently CI or Br, preferably CI; b) bis(triflamide) ([NTf 2 " ]); c) bis(perfluoroalkylsulphonyl)imides (preferably methyl, ethyl, butyl or nonyl); d) tetrafluoroborate ([BF 4 ] " ); e) hexafluorophosphate ([PF 6 ] “ ); and f) [SnX 3 ] “ or [Sn 2 X 5 ] " where and X is independently CI or Br.
  • non-coordinating anions are selected from a) halometallate anions of the formula [MX 4 ] “ or [M 2 X 7 ] " , where M is Al or Ga and X is independently CI or Br.
  • Still more preferred non-coordinating anions are those selected from the preferred non- coordinating anions mentioned above which are also Lewis acidic, for example, [M 2 X 7 ] " , where M is Al or Ga, preferably Al, and X is independently CI or Br, preferably CI.
  • Non- coordinating anions which are also Lewis acidic (as opposed to Lewis neutral) are particularly advantageous for use in the present invention, for example [AI 2 CI 7 ]-, Most preferably, the non-coordinating anion is Lewis
  • Particularly preferred ionic liquids for use in the present invention include [BCI 2 (4pic)][AI 2 CI 7 ], [BCI 2 (4pic)][AICI 4 ], [BCI 2 (4pic)][Ga 2 CI 7 ], [BCI 2 (4pic)][GaCI 4 ], [BCI 2 (mim)][AI 2 CI 7 ], [BCI 2 (mim)][AICI 4 ], [BCI 2 (mim)][GaCI 4 ], [BCI 2 (mim)][Ga 2 CI 7 ], [BCI 2 (P 888 0)][AICI 4 ], [BCI 2 (P 888 0)][AI 2 CI 7 ], [BCI 2 (P 888 0)][GaCI 4 ], [BCI 2 (P 888 0)][GaCI 4 ], [BCI 2 (P 888 0)][GaCI 4 ], [BCI 2 (P 888 0)][GaCI
  • Most preferred ionic liquids for use in the present invention are those having a Lewis acidic, non-coordinating anion, for example: [BCI 2 (4pic)][AI 2 CI 7 ], [BCI 2 (4pic)][Ga 2 CI 7 ], [BCI 2 (mim)][AI 2 CI 7 ], [BCI 2 (mim)][Ga 2 CI 7 ], [BCI 2 (P 888 0)][AI 2 CI 7 ], [BCI 2 (P 888 0)][Ga 2 CI 7 ], [BCI 2 (SUr)][AI 2 CI 7 ], [BCI 2 (SUr)][Ga 2 CI 7 ], [BCI 2 (DMA)][AI 2 CI 7 ], and [BCI 2 (DMA)][Ga 2 CI 7 ].
  • a Lewis acidic, non-coordinating anion for example: [BCI 2 (4pic)][AI 2 CI 7 ], [BCI 2 (4pic)][Ga
  • the borenium ionic liquid comprising (i) at least one borenium cation of the formula [BX 2 L] + and ii) at least one non-coordinating anion
  • this also covers the option of the ionic liquid consisting of only components (i) and (ii).
  • the borenium ionic liquid may consist solely of components (i) and (ii) defined hereinbefore.
  • the step of contacting the olefinic feedstock with the ionic liquid includes embodiments where the olefinic feedstock is contacted with the borenium ionic liquid described hereinbefore in the absence of a solvent and/or a carrier material.
  • the present inventors have surprisingly found that the use of borenium ionic liquids as defined above as catalysts for the oligomerisation of C 5 to C 20 alpha-olefins provides an oligomerised product with a molecular weight distribution that is particularly suitable for use as a lubricant base stock, i.e. consisting predominantly of dimers, trimers, tetramers and pentamers, and with only low levels of undesired highly oligomerised products, such nonamers and decamers.
  • the ionic liquids are also immiscible with the oligomeric product and thus can readily be separated from the product by phase separation. Furthermore, the separated ionic liquids can be readily recycled to the oligomerisation reaction.
  • a further advantage of the ionic liquid systems of the present invention is that cheap, widely available Lewis donor ligands such as urea, thiourea, acetamide and dimethylsulfoxide may be used to prepare the borenium ionic liquids. This is in contrast to conventional ionic liquids systems used in oligomerisation, such as chloroaluminates(l ll), where the halide salt of the spectator cation has to be typically pre- prepared in an expensive quaternisation step.
  • Lewis donor ligands such as urea, thiourea, acetamide and dimethylsulfoxide
  • oligomerisation reaction Many mechanisms have been suggested for the catalysis of oligomerisation reactions.
  • One suggested mechanism for oligomerisation of olefins is a carbocationic mechanism.
  • catalysis proceeds following the formation of acidic protons, formed by the presence of protic promoter ⁇ e.g. alcohol) or water (residual traces of moisture in the reaction system being sufficient).
  • protic promoter e.g. alcohol
  • water residual traces of moisture in the reaction system being sufficient
  • the oligomerisation reaction is performed in the presence of trace amounts of moisture (for example, between 50 and 500 ppm, preferably 50 to 150 ppm of water).
  • protons may be generated as illustrated in Equation 1 below.
  • the acidity of these protons depends on the strongest base in the system, which in this case will be the anions of the ionic liquids. Consequently, the weaker the basicity of the anion, the weaker will be its association with the proton, hence the stronger will be the acidity of the protons.
  • the ionic liquid catalyst is used in the presence of a Bnzsnsted acid.
  • a Bransted acid may act as a source of an acidic proton in addition to or in place of residual traces of moisture.
  • the superior Lewis acid strength of the ionic liquids described herein is believed to lead to the formation of superacidic protons upon reaction with a Bnzsnsted acid, which may further enhance the catalytic activity of the ionic liquids described herein.
  • Suitable Bransted acids include, for example, H 2 S0 4 , HF, HCI, HBr, HI and H 3 P0 4 .
  • Other protic promotors, such as alcohols may also be used in place of, or in combination with, Bransted acids.
  • the borenium ionic liquids used in the present invention may be prepared by methods known to the skilled person, and which are described in Ryschkewitsch et ai, J. Am. Chem Soc, 92:6, 1790-1791 (1970).
  • a suitable method for preparing borenium ionic liquids comprises B-X bond heterolysis, as illustrated below in example reactions (i) to (iv):
  • a notable advantage in the preparation of the borenium ionic liquid catalysts used in the process of the present invention is that they may be made by recycling a boron based compound which may have previously been used as a catalyst, such as a Lewis acid catalyst.
  • a boron trihalide which has wide catalytic applications, may be converted into a borenium ionic liquid as illustrated above and in the Examples hereinbelow. This may make preparation of a borenium ionic liquid even more economical.
  • existing systems utilising boron trihalides for catalysing oligomerisation reactions can be readily adapted so that the boron trihalide catalyst may be converted into a borenium ionic liquid oligomeristation catalyst as described herein.
  • the borenium ionic liquid used in the process of the invention is prepared from the recycle of a boron trihalide which has previously been used as a catalyst. Furthermore, by selecting a Lewis donor ligand from cheap, widely available donor ligands such as urea, thiourea, acetamide and dimethylsulfoxide, preparation of the borenium ionic liquid catalyst may be prepared at even lower cost.
  • olefinic feedstock comprising C 5 to C 20 alpha-olefins preferably refers to a hydrocarbonaceous feedstock that comprises at least one C 5 to C 2 o alpha-olefin hydrocarbon.
  • the olefinic feedstock comprises at least 50 wt% of one or more C 5 to C 2 o alpha-olefins, more preferably at least 60 wt% of one or more C 5 to C 2 o alpha-olefins, more preferably at least 70 wt% of one or more C 5 to C 2 o alpha-olefins, more preferably at least 80 wt% of one or more C 5 to C 20 alpha-olefins, more preferably at least 90 wt% of one or more C 5 to C 20 alpha-olefins, and most preferably at least 95 wt% of one or more C 5 to C 20 alpha-olefins.
  • the olefinic feedstock may comprise at least 98 wt% of one or more C 5 to C 20 alpha- olefins, or at least 99 wt% of one or more C 5 to C 20 alpha-olefins.
  • the remainder of the olefinic feedstock may suitably be composed of other olefins, paraffins, or a mixture thereof.
  • the olefinic feedstock comprises at least 50 wt% C 6 to Ci 8 alpha-olefins, more preferably at least 60 wt% C 6 to C 18 alpha-olefins, more preferably at least 70 wt% C6 to C18 alpha-olefins, still more preferably at least 80 wt% C 6 to Ci 8 alphaolefins, and most preferably at least 90 wt% C 6 to Ci 8 alpha-olefins.
  • the olefinic feedstock 5 may comprise at least 95 wt% C 6 to Ci 8 alpha-olefins, at least 98 wt% C 6 to C18 alpha-olefins or at least 99 wt% C 6 to Ci 8 alpha-olefins.
  • the olefinic feedstock comprises at least 30 wt% C 8 to C 14 alphaolefins, more preferably at least 50 wt% C 8 to Ci 4 alpha-olefins, more preferably at least 70 wt% C 8 to Ci 4 alpha-olefins, still more preferably at least 80 wt% C 8 to d 4 alpha olefins, and most preferably at least 90 wt% C 8 to Ci 4 alpha-olefins.
  • the olefinic feedstock may comprise at least 95 wt% C 8 to Ci alpha-olefins, at least 98 wt% C 8 to Ci 4 alpha-olefins or at least 99 wt% C 8 to CM alpha-olefins.
  • the olefinic feedstock comprises at least 30 wt% C10 to Ci 4 alphaolefins, more preferably at least 50 wt% C 10 to C 14 alpha-olefins, more preferably at least 70 wt% C 10 to C 14 alpha-olefins, still more preferably at least 80 wt% C 8 to C 14 alpha olefins, and most preferably at least 90 wt% Ci 0 to Ci 4 alpha-olefins.
  • the olefinic feedstock may comprise at least 95 wt% Ci 0 to Ci 4 alpha-olefins, at least 98 wt% Cio to C 14 alpha-olefins or at least 99 wt% Ci 0 to Ci alpha-olefins.
  • the olefinic feedstock comprises at least 30 wt% Ci 0 to C 12 alpha-olefins, more preferably at least 50 wt% C 10 to C 12 alpha-olefins, more preferably at least 70 wt% Cio to C12 alpha-olefins, still more preferably at least 80 wt% Cio to Ci2 alpha-olefins, and most preferably at least 90 wt% Ci 0 to C12 alpha-olefins.
  • the olefinic feedstock may comprise at least 95 wt% Cio to Ci 2 alphaolefins, at least 98 wt% Cio to C 12 alpha-olefins or at least 99 wt% Cio to C 12 alphaolefins.
  • the olefinic feedstock preferably comprises at least 30 wt% 1- decene, more preferably at least 50 wt% 1 -decene, more preferably at least 70 wt% 1 - decene, still more preferably at least 80 wt% 1 -decene, and most preferably at least 90 wt% 1 -decene.
  • the olefinic feedstock may comprise at least 95 wt% 1- decene, at least 98 wt% 1 -decene or at least 99 wt% 1 -decene.
  • the olefinic feedstock preferably comprises at least 30 wt% 1 - dodecene, more preferably at least 50 wt% 1 -dodecene, more preferably at least 70 wt% 1 -dodecene, still more preferably at least 80 wt% 1 -dodecene and most preferably at least 90 wt% 1-dodecene.
  • the olefinic feedstock may comprise at least 95 wt% 1 -dodecene, at least 98 wt% 1 -dodecene or at least 99 wt% 1 -dodecene.
  • the olefinic feedstock may comprise at least 30 wt% Ci 6 to Ci 8 alpha-olefins, more preferably at least 50 wt% C 16 to C 18 alpha-olefins, more preferably at least 70 wt% Ci 6 to Ci 8 alpha-olefins, still more preferably at least 80 wt% Ci 6 to Ci 8 alpha-olefins, and most preferably at least 90 wt% Ci 6 to Ci 8 alpha-olefins.
  • the olefinic feedstock may comprise at least 95 wt% Ci 6 to Ci 8 alpha-olefins, at least 98 wt% Ci 6 to Cis alpha-olefins or at least 99 wt% Ci 6 to Ci 8 alpha-olefins.
  • the olefinic feedstock preferably comprises at least 30 wt% 1- hexadecene, more preferably at least 50 wt% 1-hexadecene, more preferably at least 70 wt% 1-hexadecene, still more preferably at least 80 wt% 1 -hexadecene, and most preferably at least 90 wt% 1 -hexadecene.
  • the olefinic feedstock may comprise at least 95 wt% 1 -hexadecene, at least 98 wt% 1 -hexadecene or at least 99 wt% 1 -hexadecene.
  • the olefinic feedstock preferably comprises at least 30 wt% 1 - octadecene, more preferably at least 50 wt% 1-octadecene, more preferably at least 70 15 wt% 1 -octadecene, still more preferably at least 80 wt% 1 -octadecene and most preferably at least 90 wt% 1 -octadecene.
  • the olefinic feedstock may comprise at least 95 wt% 1 -octadecene, at least 98 wt% 1 -octadecene or at least 99 wt% 1 -octadecene.
  • the olefinic feedstock may also comprise paraffins.
  • the olefinic feedstock comprises a minor amount of paraffins.
  • the olefinic feedstock may optionally comprise up to 20 wt% paraffins, for instance up to 10 wt% paraffins, or up to 5 wt% paraffins.
  • olefinic feedstocks comprising larger amounts of paraffins are also suitable as feedstocks for the present invention.
  • olefinic feedstocks comprising up to 60 wt%, 70 wt%, 80 wt% or 90 wt% paraffins are found to be suitable feedstocks for the process of the present invention.
  • Suitable paraffins include C 5 to C 2 o paraffins, such as C 10 to C 12 paraffins.
  • the olefinic feedstock may suitably be contacted with the borenium ionic liquid catalyst at a temperature of from 0 °C up to the boiling point of the alpha-olefins at the reaction pressure.
  • the olefinic feedstock is contacted with the ionic liquid at a temperature of from 0 to 160 °C, more preferably 40 to 140 °C, more preferably 80 to 140 °C, still more preferably 100 to 140 °C, and most preferably about 120 °C.
  • the formation of oligomers in accordance with the present invention is exothermic, and thus cooling system may be used so as to maintain the desired reaction temperature.
  • the olefinic feedstock may suitably be contacted with the borenium ionic liquid catalyst at a pressure of from 10 to 1000 kPa, preferably from 20 to 500 kPa, more preferably from 50 to 200 kPa, for instance from 80 to 120 kPa.
  • the olefinic feedstock is contacted with the ionic liquid at ambient pressure, i.e. around 100 kPa.
  • the olefinic feedstock may suitably be contacted with the borenium ionic liquid catalyst for a 10 period of from 1 minute to 10 hours, for example from 10 minutes to 1 hour.
  • the reaction is preferably carried out under an inert atmosphere and substantially in the absence of moisture, defined as less than 500 ppm by weight water based on the total weight of ionic liquid and olefinic feedstock.
  • the process of the present invention may suitably be carried out by contacting the olefinic feedstock with at least 0.01 wt% of the ionic liquid catalyst, more preferably at least 0.05 wt% of the borenium ionic liquid catalyst, still more preferably at least 0.1 wt% of the borenium ionic liquid catalyst, and most preferably at least 0.2 wt% of the borenium ionic liquid catalyst, based on the total weight of the borenium ionic liquid catalyst and olefinic feedstock.
  • the olefinic feedstock may suitably be contacted with from 0.01 to 5 wt% of 20 the borenium ionic liquid catalyst, preferably from 0.05 to 2 wt% of the borenium ionic liquid catalyst, still more preferably from 0.1 to 1 wt% of the borenium ionic liquid catalyst, and still more preferably from 0.2 to 0.8 wt% of the borenium ionic liquid catalyst, based on the total weight of the borenium ionic liquid catalyst and olefinic feedstock.
  • the olefinic feedstock is contacted with about 0.5 wt% of the borenium ionic liquid catalyst, based on the total weight of the borenium ionic liquid catalyst and olefinic feedstock.
  • the oligomer product obtained by the present invention may be separated from the ionic liquid catalyst by any suitable means, for instance by gravity separation and decantation or by centrifugation. In this way, the ionic liquid catalyst may also be recycled. Alternatively, the reaction may be quenched by the addition of water, optionally containing a mild base, and the organic and aqueous phases may be separated, for instance by gravity separation and decantation or by centrifugation. Quenching the reaction in this way may be preferred where recycling of the ionic liquid catalyst is not practical or economical.
  • the oligomerised product obtained by the process of the present invention typically contains minor amounts of highly oligomerised products (defined herein as hexamers and higher oligomers) as well as unreacted starting material.
  • the process of the invention may further comprise distillation of the oligomerised product to separate starting material and/or highly oligomerised products from the desired lower oligomers (defined herein as dimers, trimers, tetramers and pentamers).
  • the catalytic oligomerisation of alpha-olefins generally provides oligomerised products that contain one remaining double bond.
  • the presence of double bonds generally reduces the oxidative stability of a lubricating oil base stock.
  • the process of the present invention further comprises a step in which the remaining olefinic double bonds in the oligomerised product are reduced to carbon- carbon single bonds so as to improve the oxidation stability of the product.
  • the reduction of olefinic double bonds may be carried out by hydrogenation in the presence of a suitable hydrogenation catalyst, for instance a Group VIII metal such as platinum, palladium, nickel, rhodium or iridium on a solid support.
  • the process may further comprise a step in which the remaining olefinic double bonds in the oligomerised product are alkylated.
  • the process of the present invention is selective for the preparation of dimers, trimers and tetramers. In further preferred embodiments, the process of the present invention is selective for the preparation of dimers and trimers. As noted above, the formation of higher oligomers may be further suppressed, if required, by the inclusion of paraffins in the olefinic feedstock.
  • the oligomerised products produced according to the process of the present invention have a range of desirable properties.
  • the oligomerised products produced according to the process of the present invention have a Kv40 of from 5 to 60 cSt, preferably from 10 to 40 cSt.
  • the oligomerised products produced according to the process of the present invention have a Kv100 of from 1 to 15 cSt, preferably from 1.5 to 10 cSt, 5 more preferably from 1.5 to 8.5 cSt (such as 2, 4, 5, 6, 7 or 8), still more preferably from 3.5 to 8.5 cSt (such as 4, 5, 6, 7 or 8), and most preferably from 3.5 to 6.5 cSt (such as 4, 5 or 6).
  • the oligomerised products produced according to the process of the present invention have a pour point of -40 °C or less, preferably of -60 °C or less (in accordance with ASTM D97-1 1).
  • the oligomerised products produced according to the process of the present invention have a viscosity index (VI) of 100 or greater, more preferably from 120 to 160 (according to ASTM D2270).
  • VI viscosity index
  • the borenium ionic liquids described hereinbefore will also exhibit selectivity in other reactions comprising a carbocation mechanism, including Friedel- Crafts alkylation and alkane isomerisation reactions.
  • the present invention provides a use of the borenium ionic liquids described hereinbefore as a selective Lewis acid catalyst in Friedel-Crafts alkylation and alkane isomerisation reactions.
  • FIGURE 1 shows the SimDist GC chromatograph for the products of oligomerisation of 1 -decene in the presence of [BCI 2 (4pic)][AI 2 CI 7 ];
  • FIGURE 2 shows the SimDist analysis of the product distribution obtained by oligomerising 1 -decene in the presence of [C 2 mim][AI 2 CI 7 ] (not of the invention) and [BCI 2 (4pic)][AI 2 CI 7 ] (according to the invention);
  • FIGURE 3 shows the SimDist GC chromatograph for the products of oligomerisation of 1 -hexadecene in the presence of [BCI 2 (4pic)][AI 2 CI 7 ]; and
  • FIGURE 4 shows the SimDist analysis of the product distribution obtained by oligomerising 1-hexadecene in the presence of [BCI 2 (4pic)][AI 2 CI 7 ] and [BCI 2 (4pic)][AI 2 CI 7 ].HCI.
  • alkyl triflate was added slowly using a dry gas-tight syringe or a dry pressure-equalising dropping funnel to a vigorously stirred solution of the [BX 3 (base)] complex in dichloromethane under argon, at 0 °C.
  • Alkyl chloride gas was evolved before the removal of solvent under reduced pressure, affording the dry ionic liquid.
  • the apparatus for HCI generation comprised of a dropping funnel containing sulfuric acid, mounted on top of a two-necked round-bottomed flask containing sodium chloride. Drop-wise addition of the acid to the salt resulted in generation of HCI, following the reaction:
  • H 2 S0 4 + NaCI ⁇ Na[HS0 4 ] + HCI The second neck of the two-necked flask was connected (via bubbler with H 2 S0 4 ) to a dry Schlenk flask, containing vigorously stirred borenium ionic liquid (e.g. [BCI 2 (4pic)][AI 2 CI 7 ]). Excess of HCI gas was captured in a bubbler filled with a basic solution, placed after the Schlenk flask with the ionic liquid. The ionic liquid was stirred under flow of HCI gas for 30 min. The resulting liquid was more viscous that the starting ionic liquid, the mass balance indicated absorption of nearly equimolar amount of HCI.
  • borenium ionic liquid e.g. [BCI 2 (4pic)][AI 2 CI 7 ]
  • olefin 40 cm 3 was placed in a dry, glass reactor (AutoMATE H.E.L. Reactor system), equipped with an overhead stirrer (Hastelloy®), a thermocouple, a heating coil, a cooling mantle, argon inlet and a septum inlet.
  • the reactor was purged with argon, and maintained under positive pressure of argon throughout the experiment.
  • the olefin was stirred vigorously (1000 rpm) and equilibrated at the temperature of reaction (120 °C).
  • Ionic liquid (1 .0 wt %) was added drop-wise to the vigorously stirred olefin, via a gas- tight syringe through the septum of the reactor, which resulted in a strong exotherm. After the addition, the mixture was allowed to react (30 min, 120 °C). Afterwards, stirring and heating was stopped, and the reaction was quenched with deionised water. A sample from the top (hydrocarbon) layer was dissolved in toluene, dried over magnesium sulfate, and analysed using gas chromatography (SimDist).
  • the borenium cation is thus an active Lewis acidic species which confers favourable selectivity in an oligomerisation reaction, whilst also mitigating against a lack of selectivity associated with the Lewis acidic anion, when present.
  • This is especially advantageous since it means that a catalytic system comprising two Lewis acidic centres having particularly high activity can be used whilst retaining favourable selectivity, which has not previously been realised.
  • Oligomerisation of 1 -hexadecene was carried out according to the general procedure described above. Catalysis was conducted with borenium ionic liquids in accordance with the present invention, [BCI 2 (4pic)][AI 2 CI 7 ] (Entry 14) and [BCI 2 (4pic)][AI 2 CI 7 ] HCI (Entry 15). [BCI 2 (4pic)][AI 2 CI 7 ] HCI was prepared in accordance with the procedure described above. Results of the oligomerisation reactions are provided in Table 2 below.
  • Oligomerisation of a 1 : 1 weight ratio mixture of 1 -hexadecene/1 -octadecene was carried out according to the general procedure described above. Catalysis was conducted with borenium ionic liquids in accordance with the present invention, [BCI 2 (P 888 0)][AI 2 CI 7 ] (Entry 16) and [BCI 2 (P 888 )][AI 2 CI 7 ] (Entry 17). Results of the oligomerisation reactions are provided in Table 3 below. Product distribution for oligomerisation of 1 -hexadecene/1-octadecene

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Abstract

L'invention concerne un procédé d'oligomérisation pour la production d'huiles de base pour des compositions de lubrification, et en particulier, un procédé pour l'oligomérisation sélective d'alpha-oléfines C5 à C20 pour produire des oligomères de polyalphaoléfine, de préférence avec une répartition des poids moléculaires qui est appropriée pour une utilisation dans des huiles de base de lubrifiant, selon lequel la charge oléfinique est mise en contact avec un liquide ionique comprenant (i) au moins un cation de borénium de formule [BX2L]+, dans laquelle L représente un ligand donneur de base de Lewis et chaque X est choisi indépendamment parmi le fluor, le chlore et le brome ; et (ii) au moins un anion de non-coordination.
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US10144904B2 (en) 2015-12-04 2018-12-04 Evonik Degussa Gmbh Process for extraction of aroma chemicals from fat-containing and/or aqueous liquid phases
US10150933B2 (en) 2015-05-27 2018-12-11 Evonik Degussa Gmbh Process for removing metal from a metal-containing glyceride oil comprising a basic quaternary ammonium salt treatment
US10221374B2 (en) 2015-05-27 2019-03-05 Evonik Degussa Gmbh Process for refining glyceride oil comprising a basic quaternary ammonium salt treatment
US10301572B1 (en) 2017-11-10 2019-05-28 Evonik Degussa Gmbh Process for extracting fatty acids from triglyceride oils
US10316268B2 (en) 2015-05-27 2019-06-11 The Queen's University Of Belfast Process for removing chloropropanols and/or glycidol, or their fatty acid esters, from glyceride oil, and an improved glyceride oil refining process comprising the same
US10493400B2 (en) 2016-06-14 2019-12-03 Evonik Degussa Gmbh Process for dehumidifying moist gas mixtures
US10500540B2 (en) 2015-07-08 2019-12-10 Evonik Degussa Gmbh Method for dehumidifying humid gas mixtures using ionic liquids
US10512881B2 (en) 2016-06-14 2019-12-24 Evonik Degussa Gmbh Process for dehumidifying moist gas mixtures
US10512883B2 (en) 2016-06-14 2019-12-24 Evonik Degussa Gmbh Process for dehumidifying moist gas mixtures

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10150933B2 (en) 2015-05-27 2018-12-11 Evonik Degussa Gmbh Process for removing metal from a metal-containing glyceride oil comprising a basic quaternary ammonium salt treatment
US10221374B2 (en) 2015-05-27 2019-03-05 Evonik Degussa Gmbh Process for refining glyceride oil comprising a basic quaternary ammonium salt treatment
US10316268B2 (en) 2015-05-27 2019-06-11 The Queen's University Of Belfast Process for removing chloropropanols and/or glycidol, or their fatty acid esters, from glyceride oil, and an improved glyceride oil refining process comprising the same
US10500540B2 (en) 2015-07-08 2019-12-10 Evonik Degussa Gmbh Method for dehumidifying humid gas mixtures using ionic liquids
US10144904B2 (en) 2015-12-04 2018-12-04 Evonik Degussa Gmbh Process for extraction of aroma chemicals from fat-containing and/or aqueous liquid phases
US10493400B2 (en) 2016-06-14 2019-12-03 Evonik Degussa Gmbh Process for dehumidifying moist gas mixtures
US10512881B2 (en) 2016-06-14 2019-12-24 Evonik Degussa Gmbh Process for dehumidifying moist gas mixtures
US10512883B2 (en) 2016-06-14 2019-12-24 Evonik Degussa Gmbh Process for dehumidifying moist gas mixtures
US10301572B1 (en) 2017-11-10 2019-05-28 Evonik Degussa Gmbh Process for extracting fatty acids from triglyceride oils

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