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WO2011069929A1 - Procédé d'isomérisation d'un hydrocarbure saturé - Google Patents

Procédé d'isomérisation d'un hydrocarbure saturé Download PDF

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Publication number
WO2011069929A1
WO2011069929A1 PCT/EP2010/068902 EP2010068902W WO2011069929A1 WO 2011069929 A1 WO2011069929 A1 WO 2011069929A1 EP 2010068902 W EP2010068902 W EP 2010068902W WO 2011069929 A1 WO2011069929 A1 WO 2011069929A1
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Prior art keywords
methyl
olefin
isomerization
butyl
ethyl
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German (de)
English (en)
Inventor
Steffen Tschirschwitz
Stephan Deuerlein
Jochen BÜRKLE
Markus Schmitt
Steffen OEHLENSCHLÄGER
Kathrin Wissel-Stoll
Veronika Wloka
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2767—Changing the number of side-chains
    • C07C5/277—Catalytic processes
    • C07C5/2778—Catalytic processes with inorganic acids; with salts or anhydrides of acids
    • C07C5/2786—Acids of halogen; Salts thereof
    • C07C5/2789—Metal halides; Complexes thereof with organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/29—Rearrangement of carbon atoms in the hydrocarbon skeleton changing the number of carbon atoms in a ring while maintaining the number of rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/125—Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
    • C07C2527/126—Aluminium chloride

Definitions

  • the invention relates to a process for the isomerization of a saturated hydrocarbon.
  • the isomerization of saturated hydrocarbons (paraffins) to the corresponding branched isomers is an important process to produce e.g. For example, to increase the research octane (RON) of gasoline to improve its combustion properties.
  • RON research octane
  • Branched cyclic hydrocarbons may isomerize under ring expansion to less branched cyclic hydrocarbons;
  • One example is the rearrangement of methylcyclopentane (MCP) to cyclohexane. These reactions are catalyzed by strong Lewis acids or strong Br ⁇ nsted acids.
  • Cyclic hydrocarbons having a tertiary carbon atom as additives such as methylcyclohexane and dimethylcyclopentane, according to EP 1 403 236 A1 (Haldor Topsoe A / S) increase the selectivity with regard to the formation of more branched hydrocarbons from less or unbranched hydrocarbons.
  • Ionic liquids consisting of n-butylpyridinium chloride and aluminum chloride can be used to isomerize methylcyclopentane and cyclohexane: V.A. Ksenofontov, T.V. Vasina, Y.E. Zubarev, L.M. Kustov, React. Kinet. Catal. Lett. 2003, Vol. 80 (2), pages 329-335.
  • the present invention was based on the object, overcoming
  • the preparation process should be particularly simple and economical and should yield the process product (a saturated hydrocarbon having the same empirical formula) in high yields, in particular in high space-time yields (RZA).
  • RZA space-time yields
  • a process has been found for the isomerization of a saturated hydrocarbon characterized by carrying out the isomerization in the presence of a superacidic ionic liquid comprising an organic cation and an inorganic anion, the anion being a super acidic aluminum trichloride Lewis base.
  • Adduct is, and an olefin performs.
  • the isomerization of a saturated hydrocarbon can be greatly accelerated if the isomerization is carried out in the presence of a super-acidic ionic liquid containing aluminum chloride and in the presence of an olefin as a catalyst.
  • the inventive method is superior to conventional methods, because the reaction equilibria are reached much faster.
  • the olefin is preferably a linear or branched and / or cyclic C 2-14 -olefin, in particular a linear or branched and / or cyclic C 2-10 -olefin, in particular a linear or branched and / or cyclic C2-7 olefin.
  • Preferred olefins are ethene, propene, 1-butene, cis-butene-2, trans-butene-2, isobutene, 3-methyl-1-butene, 1-pentene, 2-methyl-1-butene, trans-pentene-2, cis-pentene-2, 2-methyl-2-butene, cyclopentene, 4-methyl-1-pentene, 3-methyl-1-pentene, methylpentadiene, 2-methyl-1-pentene, trans-hexene-2, cis- Hexene-2, 2-methyl-2-pentene, 3-methylcyclopentene, 3-methyl-cis-pentene-2, cis-hexene-2, 3-methyl-trans-pentene-2, 4,4-dimethyl-trans- pentene-2, 1-methylcyclopentene, cyclohexene and trans-heptene-3, in particular 3-methyl-1-butene, 1-pentene, 2-methyl-1-butene, trans
  • the olefin is preferably a monoolefin.
  • the olefin is ethene, 2-methyl-1-butene, 2-methyl-2-butene or 1-methylcyclopentene.
  • the isomerization is preferably in the presence of 0.01 to 5 wt .-%, particularly 0.1 to 3 wt .-%, in particular> 0.1 to 2 wt .-%, more particularly 0.5 to 1, 5 wt .-%, of the olefin, in each case based on the saturated hydrocarbon used, performs.
  • the hydrocarbon to be isomerized is preferably a linear or branched and / or cyclic C 4-18 hydrocarbon, especially a linear or branched and / or cyclic C 1-10 -hydrocarbon, more particularly a linear or branched one and / or cyclic Cs-8 carbon hydrogen.
  • Examples of a linear isomerizing hydrocarbon and possible isomerization products are n-pentane (2-methylbutane, 1,1-dimethylpropane), n-hexane (2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, 3-ethylpentane), n-heptane (2-methylhexane, 3-methylhexane, 2,3-dimethylpentane), n-octane (isooctanes).
  • Examples of a branched (non-cyclic) hydrocarbon to be isomerized and possible isomerization products are 1-methylbutane (2-methylbutane), 1-methylpentane (2-methylpentane), 1-methylhexane (2-methylhexane).
  • cyclic hydrocarbon to be isomerized and possible isomerization products are cyclohexane (methylcyclopentane), cycloheptane (methylcyclohexane, MCH).
  • Examples of a branched and cyclic hydrocarbon to be isomerized and possible isomerization products are methylcyclopentane (cyclohexane); 1, 2-dimethylcyclopentane, 1, 1-dimethylcyclopentane, 1, 3-dimethylcyclopentane (methylcyclohexane).
  • MCP methylcyclopentane
  • CH cyclohexane
  • the hydrocarbon to be isomerized is preferably used in a concentration in the range from 1 to 90% by weight, in particular from 5 to 20% by weight, in each case based on the ionic liquid.
  • the isomerization is preferably carried out at a temperature in the range of -20 to 150 ° C, especially 40 to 100 ° C, performed.
  • the isomerization is preferably carried out at an absolute pressure in the range of 1 to 10 bar, especially 1 to 6 bar.
  • [A] + is a quaternary ammonium cation, an oxonium cation, a sulfonium cation or a phosphonium cation, and [Y ] n- represents a mono-, di-, tri- or tetravalent anion;
  • the ionic liquids have a melting point of less than 180 ° C. Further preferably, the melting point is in a range of -50 ° C to 150 ° C, more preferably in the range of -20 ° C to 120 ° C, and further more preferably, less than 100 ° C.
  • the ionic liquids of the invention are organic compounds, d. H. in that at least one cation or anion of the ionic liquid contains an organic radical.
  • Compounds suitable for forming the cation [A] + of ionic liquids are e.g. B. from DE 102 02 838 A1.
  • such compounds may contain oxygen, phosphorus, sulfur or in particular nitrogen atoms, for example at least one nitrogen atom, preferably 1-10 nitrogen atoms, particularly preferably 1-5, very particularly preferably 1-3 and in particular 1-2 nitrogen atoms.
  • other heteroatoms such as oxygen, sulfur or phosphorus atoms may be included.
  • the nitrogen atom is a suitable carrier of the positive charge in the cation of the ionic liquid from which, in equilibrium, a proton or an alkyl radical can then be transferred to the anion to produce an electrically neutral molecule.
  • a cation can first be generated by quaternization on the nitrogen atom of, for example, an amine or nitrogen heterocycle.
  • the quaternization can be carried out by protonation or alkylation of the nitrogen atom.
  • salts with different anions are obtained.
  • this can be done in a further synthesis step.
  • the halide can be reacted with a Lewis acid to form a complex anion from halide and Lewis acid.
  • halide ion replacement of a halide ion with the desired anion is possible. This can be done by adding a metal salt with precipitation of the resulting Metallha- logenids, via an ion exchanger or by displacement of the halide ion by a strong acid (to release the hydrohalic acid). Suitable methods are, for example, in Angew. Chem. 2000, 12, pp. 3926-3945 and the literature cited therein.
  • Suitable alkyl radicals with which the nitrogen atom in the amines or nitrogen heterocycles can be quaternized are C 1 -C 6 -alkyl, preferably Cio-alkyl, particularly preferably Ci-C6-alkyl and most preferably methyl.
  • the alkyl group may be unsubstituted or have one or more identical or different substituents.
  • those compounds which contain at least one five- to six-membered heterocycle in particular a five-membered heterocycle, which has at least one nitrogen atom and optionally an oxygen or sulfur atom
  • aromatic heterocycles are particularly preferred.
  • Particularly preferred compounds are those which have a molecular weight below 1000 g / mol, very particularly preferably below 500 g / mol.
  • the radical R is hydrogen, a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or by 1 to 5 heteroatoms or functional Groups are interrupted or substituted radicals having from 1 to 20 carbon atoms; and the radicals R 1 to R 9 independently of one another are hydrogen, a sulfo group or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups or substituted radical having 1 to 20 carbon atoms, wherein the radicals R 1 to R 9 , which in the abovementioned formulas (IV) are bonded to a carbon atom (and not to a heteroatom), may additionally also stand for halogen or a functional group ; or two adjacent radicals from the series R 1 to R
  • the carbon-containing group contains heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferable.
  • the radicals R 1 to R 9 are, in the cases in which those in the above formulas (IV) to a carbon atom (and not to a heteroatom) bound also be bound directly via the heteroatom.
  • Fractional groups and heteroatoms can also be directly adjacent, so that combinations of several adjacent atoms, such as -O- (ether), -S- (thioether), -COO- (ester), -CONH- (secondary amide) or -CONR'- (tertiary amide), are included, for example, di- (Ci-C4-alkyl) -amino, C1-C4-alkyloxycarbonyl or Ci-C4-alkyloxy.
  • the radicals R ' are the remaining part of the carbon-containing radical.
  • Halogens are fluorine, chlorine, bromine and iodine.
  • the radical R is unbranched or branched, unsubstituted or monosubstituted to polysubstituted by hydroxyl, halogen, phenyl, cyano, Ci-C6-alkoxycarbonyl and / or SO3H Ci-Ci8-alkyl having a total of 1 to 20 carbon atoms, such as methyl, Ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2 Pentyl, 3-pentyl, 2-methyl-1-butyl,
  • R A 0- (CH 2 CH 2 CH 2 CH 2 O) n-CH 2 CH 2 CH 2 CH 2 O- with R A and R B is preferably hydrogen, methyl or ethyl and n is preferably 0 to 3, in particular 3-oxabutyl,
  • N, N-di-C 1 -C 6 -alkyl-amino such as ⁇ , ⁇ -dimethylamino and N, N-diethylamino.
  • the radical R particularly preferably represents unbranched and unsubstituted C 1 -C 18 -alkyl, such as, for example, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, 1-decyl, 1 -dodecyl, 1-tetradecyl, 1 -hexadecyl, 1-octadecyl, especially for methyl, ethyl, 1-butyl and 1-octyl and for CH 3 0- (CH 2 CH 2 O) n -CH 2 CH 2 - and
  • radicals R 1 to R 9 are preferably each independently
  • Ci-cis-alkyl is preferably methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3 -Methyl-
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is preferably phenyl, tolyl, xylyl, a-naphthyl, ß-naphthyl, 4-diphenylyl, Chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl,
  • An optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted five- to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle is preferably furyl, thiophenyl, pyrryl, Pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxo, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl or difluoropyridyl.
  • Two adjacent radicals together form an unsaturated, saturated or aromatic, optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and optionally substituted by one or more oxygen and / or sulfur atoms and / or one or more several substituted or unsubstituted imino groups interrupted ring, it is preferably 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 2-oxa-1, 3-propylene, 1 -Oxa-1, 3-propylene, 2-oxa-1, 3-propylene, 1-oxa-1, 3-propenylene, 3-oxa-1, 5-pentylene, 1 -za-1, 3-propenylene, 1-Ci-C4- Alkyl 1 -aza-1, 3-propenylene, 1,4-buta-1,3-dienylene, 1-az-1, 4-buta-1,3-dienylene or 2-aza-1,4-butane
  • radicals contain oxygen and / or sulfur atoms and / or substituted or unsubstituted imino groups
  • the number of oxygen and / or sulfur atoms and / or imino groups is not restricted. As a rule, it is not more than 5 in the radical, preferably not more than 4, and very particularly preferably not more than 3.
  • radicals contain heteroatoms, then between two heteroatoms there are generally at least one carbon atom, preferably at least two carbon atoms.
  • radicals R 1 to R 9 independently of one another are hydrogen; - unbranched or branched, unsubstituted or one to several times with
  • C 1 -C 20 -alkyl having in total 1 to 20 carbon atoms such as, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2 Butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3 -Methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1 -
  • N, N-di-C 1 -C 6 -alkyl-amino such as ⁇ , ⁇ -dimethylamino and N, N-diethylamino.
  • the radicals R 1 to R 9 are independently hydrogen or Ci-Ci8-alkyl, such as methyl, ethyl, 1-butyl, 1-pentyl, 1 - hexyl, 1 -heptyl, 1-octyl, phenyl , for 2-hydroxyethyl, for 2-cyanoethyl, for
  • R 3 is dimethylamino and the remaining radicals R 1 , R 2 , R 4 and R 5 are hydrogen; - All radicals R 1 to R 5 are hydrogen; R 2 is carboxy or carboxamide and the remaining radicals R 1 , R 2 , R 4 and R 5 are hydrogen; or
  • R 1 and R 2 or R 2 and R 3 is 1, 4-buta-1, 3-dienylene and the remaining R 1 , R 2 , R 4 and R 5 are hydrogen; and in particular those in which
  • R 1 to R 5 are hydrogen; or one of R 1 to R 5 is methyl or ethyl and the remaining R 1 to R 5 are hydrogen.
  • pyridinium ions (IVa) there may be mentioned 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) -pyridinium, 1 (1-Hexyl) -pyridinium, 1- (1-octyl) -pyridinium, 1- (1-dodecyl) -pyridinium, 1- (1-tetradecyl) -pyridinium, 1- (1-hexadecyl) -pyridinium, 1, 2-dimethylpyridinium, 1-ethyl-2-methylpyridinium, 1- (1-butyl) -2-methylpyridinium, 1- (1-hexyl) -2-methylpyridinium, 1- (1-octyl) -2-methylpyridinium, 1 - (1-dodecyl) -2-methylpyridinium, 1
  • R 1 to R 4 are hydrogen; or one of the radicals R 1 to R 4 is methyl or ethyl and the remaining radicals R 1 to R 4 are hydrogen.
  • Very particularly preferred pyrimidinium ions are those in which - R 1 is hydrogen, methyl or ethyl and R 2 to R 4, independently of one another, are hydrogen or methyl; or R 1 is hydrogen, methyl or ethyl, R 2 and R 4 are methyl and R 3 is hydrogen.
  • R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are independently hydrogen or methyl;
  • R 1 is hydrogen, methyl or ethyl, R 2 and R 4 are methyl and R 3 is hydrogen;
  • R 1 to R 4 are methyl
  • R 1 to R 4 are hydrogen.
  • R 1 is hydrogen, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-octyl, 2-hydroxyethyl or 2-cyanoethyl and R 2 to R 4 are each independently hydrogen, methyl or ethyl are.
  • imidazolium ions which may be mentioned are 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1- (1-Tetradecyl) -imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1 Butyl) -3-ethylimidazolium, 1- (1-hexyl) -3-methylimidazolium, 1- (1-hexyl) -3-ethylimidazolium, 1- (1-hexyl) -3-butylimidazolium, 1- (1-octyl)
  • R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are independently hydrogen or methyl.
  • R 1 to R 4 are independently hydrogen or methyl.
  • R 1 is hydrogen, methyl, ethyl or phenyl and R 2 to R 6 are independently of one another hydrogen or methyl.
  • Imidazoliniumionen are those in which
  • R 1 and R 2 are independently hydrogen, methyl, ethyl, 1-butyl or phenyl, R 3 and R 4 are independently hydrogen, methyl or ethyl, and R 5 and R 6 are independently hydrogen or methyl.
  • IVm imidazolinium ions
  • IVm ' imidazolinium ions
  • R 1 and R 2 are independently hydrogen, methyl or ethyl and R 3 to R 6 are independently hydrogen or methyl.
  • R 1 is hydrogen, methyl, ethyl or phenyl and R 2 and R 3 are independently hydrogen or methyl.
  • Very particular preference is given to using 1, 2,4-triazolium ions (IVq), (IVq ') or (IVq ") those in which
  • R 1 and R 2 are independently hydrogen, methyl, ethyl or phenyl and R 3 is hydrogen, methyl or phenyl.
  • R 1 is hydrogen, methyl or ethyl and R 2 and R 3 are independently hydrogen or methyl, or R 2 and R 3 together are 1, 4-buta-1,3-dienylene.
  • R 1 is hydrogen, methyl, ethyl or phenyl and R 2 to R 9 are independently hydrogen or methyl.
  • R 1 and R 4 are independently hydrogen, methyl, ethyl or phenyl and R 2 and R 3 and R 5 to R 8 are independently hydrogen or methyl.
  • R 1 to R 3 are independently C 1 to C 18 alkyl; or - R 1 and R 2 together are 1, 5-pentylene or 3-oxa-1, 5-pentylene and R 3 is C 1 -C 18 alkyl, 2-hydroxyethyl or 2-cyanoethyl.
  • ammonium ions IVu may be mentioned trimethylammonium, triethylammonium, dimethylethylammonium, diethylmethylammonium, tetramethylammonium.
  • Examples of the tertiary amines from which the quaternary ammonium ions of the general formula (IVu) are derived by quaternization with the abovementioned radicals R are trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, diethylmethylamine, dimethylethylamine, triisopropylamine, Isopropyldiethylamine, diisopropylethylamine, diethyl-n-butylamine, diethyl-tert-butylamine, diethyl-n-pentylamine, diethyl-hexylamine, diethyloctylamine, diethyl (2-ethylhexyl) -amine, di-n-propylbutylamine, di-n-propylamine.
  • n-pentylamine di-n-propylhexylamine, di-n-propyloctylamine, di-n-propyl- (2-ethyl-hexyl) -amine, diisopropylethylamine, di-iso-propyl-n-propylamine, di-isopropyl butylamine, diisopropylpentylamine, di-iso-propylhexylamine, di-isopropyloctylamine, di-iso-propyl- (2-ethylhexyl) -amine, di-n-butylethylamine, di-n-butyl-n-propylamine, di-n- butyl-n-pentylamine, di-n-butylhexylamine, di-n-butyloctylamine, di-n-butyl (2-ethylhexyl) amine, Nn-butylpyr
  • Preferred quaternary ammonium salts of the general formula (IVu) are those which can be derived from the following tertiary amines by quaternization with the abovementioned radicals R, such as dimethylamine, trimethylamine, diethylamine, triethylamine, dimethylethylamine, diethyl-tert-butylamine, diisopropylethylamine , Tripropylamine, tributylamine.
  • Particularly preferred tertiary amines are trimethylamine and triethylamine.
  • R 1 to R 5 are methyl.
  • guanidinium ion may be mentioned N, N, N ', N', N ", N" - hexamethylguanidinium.
  • cholinium ions those in which R 1 and R 2 are independently methyl, ethyl, 1-butyl or 1-octyl and R 3 is hydrogen, methyl, ethyl, acetyl, -SO 2 OH or -PO (OH) 2 ;
  • R 1 is methyl, ethyl, 1-butyl or 1-octyl
  • R 2 is a -CH 2 -CH 2 -OR 4 group and R 3 and R 4 independently of one another are hydrogen, methyl, ethyl, acetyl, -SO 2 OH or PO (OH) 2 are; or
  • R 1 is a -CH 2 -CH 2 -OR 4 group
  • R 2 is a -CH 2 -CH 2 -OR 5 group
  • R 3 to R 5 are independently hydrogen, methyl, ethyl, acetyl, -SO 2 OH or - PO (OH) 2 .
  • Particularly preferred cholinium ions are those in which R 3 is selected from hydrogen, methyl, ethyl, acetyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxo-octyl, 1 1 -methoxy 3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 1-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxa-pentadecyl, 9- Methoxy-5-oxa-nonyl, 14-methoxy-5,10-oxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 1-ethoxy-3,6 , 9-trioxa undecyl, 7-ethoxy-4-
  • R 1 to R 3 independently of one another are C 1 -C 6 -alkyl, in particular butyl, isobutyl, 1-hexyl or 1-octyl.
  • the pyridinium ions, pyrazolinium, pyrazolium ions and imidazolinium and imidazolium ions are preferable. Furthermore, ammonium ions are preferred.
  • [M 4 ] 2+ and [M 5 ] 3+ are generally metal cations of the 1, 2, 6, 7, 8, 9, 10, 1 1, 12, and 13 Group of the periodic table. Suitable metal cations are, for example, Li + , Na + , K + , Cs + , Mg 2+ , Ca 2+ , Ba 2+ , Cr 3+ , Fe 2+ , Fe 3+ , Co 2+ , Ni 2+ , Cu 2 + , Ag + , Zn 2+ and Al 3+ .
  • the organic cation is particularly preferably an ammonium ion, optionally C 1-4 -alkyl-substituted pyridinium ion or optionally C 1-4 -alkyl-substituted imidazolium ion.
  • the organic cation is a trimethylammonium ion, triethylammonium ion, unsubstituted pyridinium ion or 1-ethyl-3-methylimidazolium ion.
  • the anion of the ionic liquids used in the invention is selected from super acidic aluminum trichloride Lewis base adducts.
  • Aluminum trichloride (AlC) is a Lewis acid.
  • the term "superacid trichloride-Lewisbase aluminum adducts" such aluminum trichloride Lewis base adducts which have a pK s value in protonated form, which is less than or equal to a strong acid pK s value of a very strong acid.
  • the superacid aluminum trichloride Lewis base adducts used according to the invention in protonated form preferably have a pK s value ⁇ -7, ie a pK s value which is smaller than HCl.
  • aluminum trichloride Lewis base adduct refers to complex anions formed by the addition of an anion, especially a chloride or bromide to which Lewis acid aluminum trichloride is formed.
  • the addition products may also form adducts with one or two further (identical or different) Lewis acid molecules.
  • a is 2 or 3.
  • the metals or semimetals Met contained in the Lewis acid-Lewis base adduct may be the same or different.
  • Lewis acid Lewis base adducts with various metals are formed, for example, when a Lewis acid Lewis base adduct of a Lewis acid and a halide ion first forms and this then reacts with another, different from the first Lewis acid Lewis acid with adduct formation.
  • a Lewis acid Lewis base adduct of a Lewis acid and a halide ion first forms and this then reacts with another, different from the first Lewis acid Lewis acid with adduct formation.
  • the Lewis acid-Lewis base adduct of the formula [Met a Zb]" Z may be the same or different.
  • Lewis acid Lewis base adducts with mixed Z are obtained, for example, when, as described above, the Lewis acid Lewis base adduct is formed from two different Lewis acids. Alternatively, they are obtained when Lewis acid with mixed halogen atoms are used or when the halide ion, which acts as a Lewis base, is different from the halogen atom of the Lewis acid.
  • all Z contained in the Lewis acid Lewis base adduct of formula [Met a Zb] " are the same, in particular Z is chlorine or bromine.
  • Lewis bases Ch, Br, AICk, AIBrC “ , Al 2 Cl 7 “ , Al 2 BrCl 6 “ , Al 3 Cho “ , A BrClg “ , BCI 4 “ , BBr 4 “ , TiCl 5 “ , VCI 6 " , FeCk, FeBr 4 -, Fe 2 Cl 7 -, FesCho “ , ZnC, ZnBr 3 -,
  • Preferred Lewis bases are AICI 4 , Al 2 Cl 7 “ , BCI 4 -, BBr 4 -, TiCl 5 " , FeCk, FeBr 4 -, Fe 2 Cl 7 “ and FesC 0 " .
  • the anion of the ionic liquid is, for example, AlCk, AIBrCIs “ , Al 2 Cl 7, Al 2 BrCl 6 -, A Cho " , AbBrClg " or (CF 3 S0 2 ) 2 NaCl 3 -.
  • Preferred anions Y- are selected from AIBrC “ , AI2CI7 “ , A BrCk, Al3CI10 “ , AbBrClg “ .
  • the preparation of such an ionic liquid is effected in particular by adding the appropriate amount of aluminum chloride to the ionic liquid or to an ammonium chloride.
  • the molar ratio of aluminum trichloride to Lewis base is preferably> 1, 0, especially> 1, 5, further especially> 2.0.
  • the Hamm function Ho is preferably in the range of -16 to -20, especially in the range of -17 to -19.
  • the ionic liquid (IL) 150 ml was placed in the stirred tank and filled to be isomerized methylcyclopentane-containing organic mixture (30 ml) in the feed vessel. After tempering of all educts to 60 ° C, the entire contents of the feed vessel was transferred with stirring within 1 - 2 seconds in the stirred tank with the IL with stirring by opening the Teflon tap. In each case 5 ml of sample were taken at predetermined time intervals by means of 30 cm cannula and syringe via the sampling nozzle with septum.
  • TMA trimethylammonium
  • IL TMA-AI2CI7
  • Organics 39% by weight of MCP, 12% by weight of CH, 49% by weight of n-hexane, 0.3% by weight of 2-methyl-1-pentene
  • Example 1 1 (according to the invention):

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé d'isomérisation d'un hydrocarbure saturé, dans lequel l'isomérisation est réalisée en présence d'un liquide ionique super-acide, comprenant un cation organique et un anion inorganique, l'anion étant un produit d'addition super-acide trichlorure d'aluminium-base de Lewis, et une oléfine.
PCT/EP2010/068902 2009-12-07 2010-12-06 Procédé d'isomérisation d'un hydrocarbure saturé Ceased WO2011069929A1 (fr)

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WO2014009343A1 (fr) 2012-07-11 2014-01-16 Basf Se Procédé de traitement d'un déversement d'une conversion d'hydrocarbures par lavage à l'aide d'un agent aqueux
WO2014009353A1 (fr) 2012-07-11 2014-01-16 Basf Se Isolement de liquides ioniques à l'aide d'un filtre de coalescence en résine acrylo- phénolique
WO2014009332A1 (fr) 2012-07-11 2014-01-16 Basf Se Procédé de séparation de phases par basculement de la direction de dispersion
WO2014009347A1 (fr) 2012-07-11 2014-01-16 Basf Se Procédé pour traiter une matière obtenue après une conversion d'hydrocarbures avec séparation des halogénures d'hydrogène et lavage subséquent
WO2014009341A1 (fr) 2012-07-11 2014-01-16 Basf Se Procédé de mise en réaction chimique dans une dispersion
WO2014009331A1 (fr) 2012-07-11 2014-01-16 Basf Se Procédé d'isomérisation d'hydrocarbures avec recyclage d'halogénures d'hydrogène
WO2014009351A1 (fr) 2012-07-11 2014-01-16 Basf Se Procédé pour séparer des halogénures d'hydrogène dans une colonne de rectification comportant un condenseur partiel
WO2014009350A1 (fr) 2012-07-11 2014-01-16 Basf Se Réalisation d'une conversion d'hydrocarbures ou traitement d'une conversion d'hydrocarbures dans des dispositifs aux surfaces en matériaux non métalliques
WO2014009335A1 (fr) 2012-07-11 2014-01-16 Basf Se Isolement de liquides ioniques à l'aide d'un tricot
WO2014060460A2 (fr) 2012-10-18 2014-04-24 Basf Se Procédé de production de cyclohexane en utilisant des matériaux de départ issus d'un procédé de vapocraquage
WO2014060461A1 (fr) 2012-10-18 2014-04-24 Basf Se Nouveau procédé de production de cyclohexane à partir de méthylcyclopentane et de benzène
WO2014060462A2 (fr) 2012-10-18 2014-04-24 Basf Se Procédé de conversion d'hydrocarbures en présence d'un liquide ionique acide avec hydrogénation en amont
WO2014135445A1 (fr) * 2013-03-07 2014-09-12 Basf Se Procédé de réaction chimique à pression partielle constante d'halogénure d'hydrogène
WO2014135444A3 (fr) * 2013-03-07 2014-10-30 Basf Se Procédé de réaction chimique en ajoutant des halogénures métalliques
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US10207201B2 (en) 2012-07-11 2019-02-19 Basf Se Phase separation process by inversion of the direction of dispersion
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US9126881B2 (en) 2013-06-28 2015-09-08 Uop Llc Catalytic isomerization of pentane using ionic liquids
US9096482B2 (en) 2013-06-28 2015-08-04 Uop Llc Catalytic reverse disproportionation of paraffins using ionic liquids
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US9095789B2 (en) 2012-07-11 2015-08-04 Basf Se Removal of ionic liquids by means of coalescing filters made from acrylic/phenolic resin
WO2014009335A1 (fr) 2012-07-11 2014-01-16 Basf Se Isolement de liquides ioniques à l'aide d'un tricot
WO2014009347A1 (fr) 2012-07-11 2014-01-16 Basf Se Procédé pour traiter une matière obtenue après une conversion d'hydrocarbures avec séparation des halogénures d'hydrogène et lavage subséquent
WO2014009341A1 (fr) 2012-07-11 2014-01-16 Basf Se Procédé de mise en réaction chimique dans une dispersion
WO2014009331A1 (fr) 2012-07-11 2014-01-16 Basf Se Procédé d'isomérisation d'hydrocarbures avec recyclage d'halogénures d'hydrogène
WO2014009351A1 (fr) 2012-07-11 2014-01-16 Basf Se Procédé pour séparer des halogénures d'hydrogène dans une colonne de rectification comportant un condenseur partiel
WO2014009350A1 (fr) 2012-07-11 2014-01-16 Basf Se Réalisation d'une conversion d'hydrocarbures ou traitement d'une conversion d'hydrocarbures dans des dispositifs aux surfaces en matériaux non métalliques
WO2014009353A1 (fr) 2012-07-11 2014-01-16 Basf Se Isolement de liquides ioniques à l'aide d'un filtre de coalescence en résine acrylo- phénolique
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US10815168B2 (en) 2012-07-11 2020-10-27 Basf Se Chemical conversion process in a dispersion
US10207201B2 (en) 2012-07-11 2019-02-19 Basf Se Phase separation process by inversion of the direction of dispersion
CN104411664B (zh) * 2012-07-11 2016-08-24 巴斯夫欧洲公司 通过反转分散方向的相分离方法
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WO2014009343A1 (fr) 2012-07-11 2014-01-16 Basf Se Procédé de traitement d'un déversement d'une conversion d'hydrocarbures par lavage à l'aide d'un agent aqueux
WO2014009332A1 (fr) 2012-07-11 2014-01-16 Basf Se Procédé de séparation de phases par basculement de la direction de dispersion
CN104411664A (zh) * 2012-07-11 2015-03-11 巴斯夫欧洲公司 通过反转分散方向的相分离方法
WO2014060460A2 (fr) 2012-10-18 2014-04-24 Basf Se Procédé de production de cyclohexane en utilisant des matériaux de départ issus d'un procédé de vapocraquage
CN104736502A (zh) * 2012-10-18 2015-06-24 巴斯夫欧洲公司 使用源自蒸汽裂化方法的原料制备环己烷的方法
CN104755447A (zh) * 2012-10-18 2015-07-01 巴斯夫欧洲公司 具有在先氢化的在酸性离子液体存在下的烃转化方法
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WO2014060460A3 (fr) * 2012-10-18 2014-06-26 Basf Se Procédé de production de cyclohexane en utilisant des matériaux de départ issus d'un procédé de vapocraquage
CN104736502B (zh) * 2012-10-18 2017-11-10 巴斯夫欧洲公司 使用源自蒸汽裂化方法的原料制备环己烷的方法
US10081580B2 (en) 2012-10-18 2018-09-25 Basf Se Process for preparing cyclohexane with starting materials originating from a steamcracking process
WO2014060462A2 (fr) 2012-10-18 2014-04-24 Basf Se Procédé de conversion d'hydrocarbures en présence d'un liquide ionique acide avec hydrogénation en amont
WO2014060461A1 (fr) 2012-10-18 2014-04-24 Basf Se Nouveau procédé de production de cyclohexane à partir de méthylcyclopentane et de benzène
WO2014135444A3 (fr) * 2013-03-07 2014-10-30 Basf Se Procédé de réaction chimique en ajoutant des halogénures métalliques
WO2014135445A1 (fr) * 2013-03-07 2014-09-12 Basf Se Procédé de réaction chimique à pression partielle constante d'halogénure d'hydrogène
US10137386B2 (en) 2013-12-02 2018-11-27 Basf Se Separation of ionic liquids in coalescing devices
US9873646B2 (en) 2014-04-22 2018-01-23 Basf Se Process for preparing cyclohexane from benzene and methylcyclopentane with upstream benzene hydrogenation

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