WO2011069957A1 - Procédé d'isomérisation d'un hydrocarbure saturé, ramifié et cyclique - Google Patents

Procédé d'isomérisation d'un hydrocarbure saturé, ramifié et cyclique Download PDF

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WO2011069957A1
WO2011069957A1 PCT/EP2010/068958 EP2010068958W WO2011069957A1 WO 2011069957 A1 WO2011069957 A1 WO 2011069957A1 EP 2010068958 W EP2010068958 W EP 2010068958W WO 2011069957 A1 WO2011069957 A1 WO 2011069957A1
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Prior art keywords
methyl
isomerization
hydrocarbon
ethyl
butyl
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PCT/EP2010/068958
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German (de)
English (en)
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Steffen Tschirschwitz
Stephan Deuerlein
Jochen BÜRKLE
Markus Schmitt
Michael Schreiber
Steffen OEHLENSCHLÄGER
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Basf Se
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Priority to EP10787752.4A priority Critical patent/EP2509935B1/fr
Priority to CN201080055257.7A priority patent/CN102666448B/zh
Publication of WO2011069957A1 publication Critical patent/WO2011069957A1/fr

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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
    • C07C5/29—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
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/72—Copper
    • 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
    • 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

Definitions

  • the invention relates to a process for the isomerization of a saturated, branched and cyclic hydrocarbon, wherein in the isomerization of a tertiary carbon atom of the hydrocarbon is converted into a secondary carbon atom.
  • 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.
  • Branched cyclic hydrocarbons may isomerize under ring expansion to less branched cyclic hydrocarbons;
  • MCP methylcyclopentane
  • 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 provide the process product (a saturated, cyclic hydrocarbon having the same sum formula and lower degree of branching) in high yields, in particular in high space-time yields (RZA), and selectivities.
  • RZA space-time yields
  • a process has been found for the isomerization of a saturated, branched and cyclic hydrocarbon in which a tertiary C atom of the hydrocarbon is converted into a secondary carbon atom in the isomerization, characterized in that the isomerization is carried out in the presence of a supercritical hydrocarbon.
  • acidic ionic liquid comprising an organic cation and an inorganic anion, wherein the anion is a super acidic aluminum trichloride Lewis base adduct, and a copper (II) compound.
  • the inventive method is superior to conventional methods, u. a. because the reaction equilibria are reached much faster.
  • the copper (II) compound is preferably a copper (II) salt.
  • Preferred copper (II) compounds are CuC, CuO, CuS0 4 , CuI 2 , CuBr 2 , Cu (OH) Cl, Cu (HSO 4 ) 2 , Cu (NO 3 ) 2 .
  • the copper (II) compound is particularly preferably CuC, CuO or CuS0 4 .
  • the isomerization process according to the invention is particularly preferably carried out in the presence of a copper (II) compound in the absence of a further compound of another metal, in particular another halide of another metal, the metal being particularly a minor group metal.
  • the isomerization is preferably in the presence of 0.1 to 3 wt .-%, in particular> 0.1 to 2 wt .-%, very particularly 0.5 to 1, 5 wt .-%, of the copper (II) compound , in each case based on the used super acidic ionic liquid.
  • isomerized hydrocarbon is preferably a saturated, branched and cyclic C 4- i8 hydrocarbon, particularly a saturated, branched and cyclic Cs-io hydrocarbon, particularly a saturated, branched and cyclic Cs-s- hydrocarbon.
  • the hydrocarbon to be isomerized is particularly preferably methylcyclopentane (MCP) which is isomerized to the product cyclohexane (CH 2) and / or 1, 2-dimethylcyclopentane, 1, 3-dimethylcyclopentane and / or 1, 1-dimethyl- cyclopentane, which are isomerized to the product methylcyclohexane (MCH).
  • MCP methylcyclopentane
  • a tertiary carbon atom of the hydrocarbon is converted into a secondary carbon atom.
  • the isomerization thus provides a less branched saturated hydrocarbon as a product.
  • a particular example of this is the isomerization of methylcyclopentane (MCP) to cyclohexane (CH).
  • MCP methylcyclopentane
  • CH cyclohexane
  • the hydrocarbon to be isomerized is preferably in a concentration in
  • 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.
  • Ionic liquids in the sense of the present invention are preferred
  • [A 1 ] + [M 4 ] 2+ [Y] n- (I Ij), where n 3 and [A 1 ] + , [A 2 ] + and [A 3 ] + independently of one another for A] + are selected, [Y] n- has the meaning given under (A) and [M 1 ] + , [M 2 ] + , [M 3 ] + monovalent metal cations, [M 4 ] 2+ divalent metal cations and [M 5 ] 3+ are trivalent metal cations.
  • 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 according to the invention are organic compounds, ie at least one cation or an 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. If desired, it is also possible for further heteroatoms such as oxygen, sulfur or phosphorus atoms to be present.
  • 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 C 1 -C 10 -alkyl, particularly preferably C 1 -C 6 -alkyl and very particularly preferably methyl.
  • the alkyl group may be unsubstituted or have one or more identical or different substituents.
  • aromatic heterocycles 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 interrupted by 1 to 5 heteroatoms or functional groups radical having 1 to 20 carbon atoms; and the radicals R 1 to R 9 independently of one another represent 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 9 together also for a divalent, carbon-
  • 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 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 -
  • 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
  • the radicals R 1 to R 9 are independently hydrogen; - halogen; a functional group; optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogens, heteroatoms and / or heterocycles substituted and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino Ci-Cis alkyl; optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogens, heteroatoms and / or heterocycles substituted and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino C2-Cis alkenyl; optionally substituted by functional groups, aryl, alkyl, aryloxy,
  • 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 1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl , 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3 Meth
  • C6-C12-aryl substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is preferably phenyl, tolyl, xylyl, ⁇ -naphthyl, ⁇ -naphthyl, Diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl,
  • aryl, alkyl , Aryloxy, alkyloxy, halogen, heteroa C 5 -C 12 -cycloalkyl which is substituted by tome and / or heterocycles is preferably cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, Dichlorcyclohexyl, dichlorocyclopentyl, CnF2 (Na) - (1 - b) H2a-b with n ⁇ 30, 0 ⁇ a ⁇
  • 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 by functional groups, aryl, alkyl, aryloxy, alkyloxy, Halogen, heteroatoms and / or heterocycles substituted and optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups 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-aza-1, 3-propenylene, 1-C 1 -C 4 -alkyl-1 -aza-1, 3-propenylene, 1, 4-buta-1, 3-dienylene, 1 -za -1,4-buta-1,3-dienylene or 2-aza-1,4-buta
  • the abovementioned 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.
  • the abovementioned radicals contain heteroatoms, then there are generally at least one carbon atom, preferably at least two, between two heteroatoms carbon atoms.
  • radicals R 1 to R 9 are each independently
  • 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 -
  • Glycols, butylene glycols and their oligomers having 1 to 100 units and a hydrogen or a C to Cs-alkyl as an end group, such as R A 0- (CHR B -CH 2 -O) n -CHR B -CH 2 - or 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 preferably hydrogen, methyl or ethyl and n preferably 0 to 3, in particular 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3,6 Dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxa-undecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9,12-tetraoxatetradecyl;
  • 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
  • 2- (methoxycarbonyl) ethyl for 2- (ethoxycarbonyl) ethyl, for 2- (n-butoxycarbonyl) ethyl, for ⁇ , ⁇ -dimethylamino, for ⁇ , ⁇ -diethylamino, for chlorine and for CH30- (CH 2 CH 2 O) n - CH 2 CH 2 - and CH 3 CH 2 O- (CH 2 CH 2 O) n-CH 2 CH 2 - with n being 0 to 3.
  • Very particularly preferred pyridinium ions are those in which one of the radicals R 1 to R 5 is methyl, ethyl or Is chlorine and the remaining radicals R 1 to R 5 are hydrogen; 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 the radicals R 1 to R 5 is methyl or ethyl and the remaining radicals R 1 to R 5 are hydrogen.
  • Very particularly preferred pyridinium ions (IVa) are 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
  • 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.
  • R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are independently hydrogen or methyl; or - R 1 is hydrogen, methyl or ethyl, R 2 and R 4 are methyl and R 3 is hydrogen.
  • Very particularly preferred pyrazinium 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;
  • 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; or R 1 to R 4 are hydrogen.
  • imidazolium ions (IVe) to those in which - 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 independently hydrogen, methyl or ethyl.
  • Very particularly preferred imidazolium ions 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) -3-methyl
  • R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are independently hydrogen or methyl.
  • Very particularly preferred pyrazolium ions (IVh) are those in which
  • 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 to R 3 are independently hydrogen, methyl or ethyl and R 4 to R 6 are independently hydrogen or methyl.
  • R 1 and R 2 are independently hydrogen, methyl, ethyl or phenyl and R 3 is hydrogen, methyl or phenyl.
  • Very particular preference is given to using as 1,3,3-triazolium ions (IVr), (IVr ') or (IVr ") those in which
  • 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 which may be mentioned are 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-butyl Py
  • 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, diiso propylethylamine, 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.
  • 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 and R 3 to R 5 are independently hydrogen, methyl, ethyl, acetyl, - S0 2 OH or - PO (OH) 2 are.
  • 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, 11-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 the Lewis acid aluminum trichloride.
  • 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 different metals are formed, for example, when a first Lewis acid Lewis base adduct of a Lewis acid and a halide ion forms and this then reacts with another, different from the first Lewis acid Lewis acid with adduct formation.
  • all the mead contained in the Lewis acid Lewis base adduct [MetaZb] " are the same, namely Al.
  • 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 of two different Lewis acids releasing Alternatively, they are obtained when Lewis acids 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 Specifically, all the 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 2 " , VCI 6 -, FeCk, FeBr 4 -, Fe 2 Cl 7 -, FesCho " , ZnC “ , ZnBr 3 -, CuC “ , CuBr 2 -, CuCIs " , CuBr 3 -, NbCle “ , SnC “ , SnBr 3 -, SnCIs “ , SnBr 5 - and (CF 3 S0 2 ) 2 N-.
  • Preferred Lewis bases are AICI 4 “ , Al 2 Cl 7 “ , BCI 4 “ , BBr 4 -, TiCl 5 “ , FeCl 4 “ , FeBr 4 -, Fe 2 Cl 7 “ and FesCho “ .
  • the anion of the ionic liquid is, for example, AICI 4 " , 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 BrC “ , AI3CI10 “ , AbBrClg " .
  • anions Y- selected from Al 2 CI 7 “ , AI3CI10 " , especially AI2CI7-.
  • the preparation of such an ionic liquid is carried out 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. Examples
  • the ionic liquid (IL) 150 ml was introduced into the stirred tank and the methylcyclopentane-containing organic mixture (30 ml) to be isomerized was introduced into the feed vessel.
  • the specified amount of a copper (II) salt was added.
  • the entire contents of the feed vessel was transferred within 1 -2 seconds with stirring in the stirred tank with the IL 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.
  • the separated, lighter organic phase was added from the syringe in about 5 ml of 10 wt .-% - aqueous sodium EDTA solution and shaken. Subsequently, the phases were separated. The organic phase was diluted with 2 ml of methylene chloride and, after drying with anhydrous sodium sulfate, analyzed by GC.
  • the following examples relate to the isomerization of methylcyclopentane to cyclohexane.
  • TMA trimethylammonium
  • IL n-butylpyridinium-AbCl.

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  • Organic Chemistry (AREA)
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Abstract

L'invention concerne un procédé d'isomérisation d'un hydrocarbure saturé, ramifié et cyclique. Selon le procédé, lors de l'isomérisation, un atome de C tertiaire de l'hydrocarbure est converti en un atome de C secondaire par mise en oeuvre de cette isomérisation 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 d'un composé du cuivre (II).
PCT/EP2010/068958 2009-12-07 2010-12-06 Procédé d'isomérisation d'un hydrocarbure saturé, ramifié et cyclique WO2011069957A1 (fr)

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WO2014009341A1 (fr) 2012-07-11 2014-01-16 Basf Se Procédé de mise en réaction chimique dans une 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
WO2014009331A1 (fr) 2012-07-11 2014-01-16 Basf Se Procédé d'isomérisation d'hydrocarbures avec recyclage d'halogénures d'hydrogène
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
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
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
WO2014060461A1 (fr) 2012-10-18 2014-04-24 Basf Se Nouveau procédé de production de cyclohexane à partir de méthylcyclopentane et de benzène
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
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
WO2014135444A2 (fr) * 2013-03-07 2014-09-12 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
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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
US9409839B2 (en) 2012-07-11 2016-08-09 Basf Se Removal of ionic liquids by means of a knitted fabric
US9873646B2 (en) 2014-04-22 2018-01-23 Basf Se Process for preparing cyclohexane from benzene and methylcyclopentane with upstream benzene hydrogenation
US10081580B2 (en) 2012-10-18 2018-09-25 Basf Se Process for preparing cyclohexane with starting materials originating from a steamcracking process
US10207201B2 (en) 2012-07-11 2019-02-19 Basf Se Phase separation process by inversion of the direction of dispersion
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US8933262B2 (en) 2011-05-24 2015-01-13 Basf Se Process for preparing polyisocyanates from biomass
US8993819B2 (en) 2011-07-12 2015-03-31 Basf Se Process for preparing cycloheptene
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
WO2014009331A1 (fr) 2012-07-11 2014-01-16 Basf Se Procédé d'isomérisation d'hydrocarbures avec recyclage d'halogénures d'hydrogène
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
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
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
WO2014009341A1 (fr) 2012-07-11 2014-01-16 Basf Se Procédé de mise en réaction chimique dans une dispersion
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
US9409839B2 (en) 2012-07-11 2016-08-09 Basf Se Removal of ionic liquids by means of a knitted fabric
US9095789B2 (en) 2012-07-11 2015-08-04 Basf Se Removal of ionic liquids by means of coalescing filters made from acrylic/phenolic resin
WO2014060461A1 (fr) 2012-10-18 2014-04-24 Basf Se Nouveau procédé de production de cyclohexane à partir de méthylcyclopentane et de benzène
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
WO2014060462A3 (fr) * 2012-10-18 2014-06-26 Basf Se Procédé de conversion d'hydrocarbures en présence d'un liquide ionique acide avec hydrogénation en amont
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
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
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
WO2014135444A2 (fr) * 2013-03-07 2014-09-12 Basf Se Procédé de réaction chimique en ajoutant des halogénures métalliques
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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US8410327B2 (en) 2013-04-02
CN102666448A (zh) 2012-09-12

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