EP2909156A2 - Procédé de conversion d'hydrocarbures en présence d'un liquide ionique acide avec hydrogénation en amont - Google Patents

Procédé de conversion d'hydrocarbures en présence d'un liquide ionique acide avec hydrogénation en amont

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Publication number
EP2909156A2
EP2909156A2 EP13777060.8A EP13777060A EP2909156A2 EP 2909156 A2 EP2909156 A2 EP 2909156A2 EP 13777060 A EP13777060 A EP 13777060A EP 2909156 A2 EP2909156 A2 EP 2909156A2
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EP
European Patent Office
Prior art keywords
hydrocarbon
isomerization
cyclohexane
hydrocarbon conversion
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP13777060.8A
Other languages
German (de)
English (en)
Inventor
Roman Prochazka
Martin Bock
Steffen Tschirschwitz
Gauthier Luc Maurice Averlant
Joni JONI
Markus Schmitt
Katharina SPUHL
Jochen BÜRKLE
Alois Kindler
Daniela Malkowsky
Stefan Bitterlich
Michael HÜBNER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP13777060.8A priority Critical patent/EP2909156A2/fr
Publication of EP2909156A2 publication Critical patent/EP2909156A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • 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
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium
    • 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
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to a process for hydrocarbon conversion in the presence of an acidic ionic liquid.
  • the hydrocarbon conversion is preferably an isomerization, in particular an isomerization of methylcyclopentane (MCP) to cyclohexane.
  • MCP methylcyclopentane
  • a hydrogenation is carried out, preferably benzene is hydrogenated to cyclohexane.
  • the resulting in the hydrogenation and / or isomerization cyclohexane is preferably isolated from the process.
  • low boilers in particular C 5 -C 6 -alkanes such as cyclopentane or iso-hexanes, are separated by distillation from the hydrocarbon mixture used for the hydrocarbon conversion.
  • Ionic liquids can be used in various hydrocarbon conversion processes, in particular they are suitable as catalysts for the isomerization of hydrocarbons.
  • a corresponding use of an ionic liquid is disclosed for example in WO 201 1/069929, where a special selection of ionic liquids in the presence of an olefin is used for the isomerization of saturated hydrocarbons, in particular for the isomerization of methylcyclopentane (MCP) to cyclohexane.
  • MCP methylcyclopentane
  • An analogous process is described in WO 201 1/069957, although the isomerization is not carried out in the presence of an olefin there, but with a copper (I I) compound.
  • US-A 2003/0109767 discloses a process for the isomerization of C 5 -C 8 paraffin hydrocarbons (paraffins) in the presence of an ionic liquid as a catalyst.
  • the ionic liquid comprises as cations nitrogen-containing heterocycles or nitrogen-containing aliphatics, the corresponding anions are derived from metal halides.
  • the paraffins to be isomerized are linear alkanes such as n-hexane or n-octane and monosubstituted alkanes such as 3-methylhexane or mixtures thereof.
  • cyclohexane has a lower degree of branching than MCP.
  • US-A 2003/0109767 does not contain any information to the effect that aromatics possibly contained in the starting mixture are hydrogenated before the isomerization.
  • a higher degree of branching should likewise be obtained in the paraffins (hydrocarbons) to be isomerized in the presence of an ionic liquid.
  • the isomerization process is also carried out in the presence of cyclic hydrocarbons as additives and in a reaction medium, wherein the cyclic hydrocarbons contain a tertiary carbon atom as a structural unit or are converted by the reaction medium into a corresponding compound having such a structural unit.
  • cyclic hydrocarbons Preferably, methylcyclohexane or dimethylcyclopentane are used as such cyclic hydrocarbon additives.
  • the paraffins to be isomerized are linear alkanes, such as n-butane or n-octane, and monomethyl-substituted alkanes, such as 2-methylhexane.
  • the ionic liquids are preferably based on nitrogen-containing heterocycles or nitrogen-containing aliphatics as cations and on inorganic anions such as aluminum halides.
  • inorganic anions such as aluminum halides.
  • US-A 2005/0082201 discloses a process for the preparation of gasoline with a low benzene content, wherein first in a first process step, a hydrocarbon mixture containing benzene, olefins and sulfur-containing compounds such as thiophenes, is fed to a distillation column from the overhead the low-boiling Compounds, a side draw a benzene-containing fraction and from the bottom of the column, the high boilers are separated. In a second stage of the process, the fraction recovered from the side draw is hydrogenated in the presence of a hydrogenation catalyst to convert benzene to cyclohexane and the thiophenes to hydrogen sulfide.
  • the obtained in the second process stage cyclohexane-containing mixture is suitable for the production of gasoline with a low benzene content.
  • An isolation of the cyclohexane contained therein or an isomerization of MCP to cyclohexane are not disclosed in US-A 2005/0082201.
  • WO 2010/027987 relates to another process for reducing the concentration of benzene in a hydrocarbon-containing mixture.
  • a benzene-containing fraction comprising benzene and other C 6 hydrocarbons is separated from a high boiler fraction comprising carbons of seven and more carbon atoms.
  • the benzene-containing fraction is then hydrogenated to give a hydrocarbon fraction having a reduced benzene content.
  • cyclohexane is formed.
  • WO 2010/027987 also contains no information that cyclohexane can be isolated from the mixture obtained in the hydrogenation; on the contrary, this process product should also be used for gasoline production.
  • US Pat. No. 3,311,1667 relates to a process for the removal of benzene from a mixture which is subsequently fed into an isomerization of MCP to cyclohexane.
  • benzene is hydrogenated with hydrogen to cyclohexane in the presence of a suitable catalyst, for example a metal catalyst on kieselguhr.
  • the isomerization of MCP to cyclohexane is carried out in the presence of metal halides such as acid-reinforced aluminum halide.
  • a suitable catalyst for example a metal catalyst on kieselguhr.
  • metal halides such as acid-reinforced aluminum halide.
  • US Pat. No. 3,311,1667 does not describe that an acidic ionic liquid can also be used for isomerization. Consequently, this document also contains no information that a hydrocarbon conversion, in particular an isomerization, with acidic ionic liquids in the presence of aromatics, especially of benzene, is problematic.
  • EP-A 1 995 297 discloses a process and related apparatus for the hydrogenation and decyclization of benzene and the isomerization of C 5 -C 6 paraffins contained in a mixture containing at most 1% by weight of benzene.
  • Metal-containing catalysts can be used for the hydrogenation of benzene, the elements of the platinum group, tin or cobalt and molybdenum being suitable as the metal.
  • zeolites are used as catalyst.
  • EP-A 1 995 297 the parameters are set in the isomerization in such a way that an opening of the cyclohexane rings obtained in the hydrogenation of benzene to isoalkanes is achieved.
  • this process is not primarily concerned with the production of cyclohexane but with the production of alkanes with a high degree of branching.
  • EP-A 1 995 297 contains no information that an acidic ionic liquid can also be used for isomerization or that the separation of aromatics, in particular of benzene, before isomerization is advantageous.
  • a method analogous to EP-A 1 995 297 is described in EP-A 1 992 673.
  • the object underlying the present invention is to provide a novel process for carrying out a hydrocarbon conversion in the presence of an acidic ionic liquid.
  • the object is achieved by a process for hydrocarbon conversion comprising the following steps: a) hydrogenation of a hydrocarbon mixture (KG1) comprising at least one aromatic and at least one non-aromatic hydrocarbon to obtain a hydrocarbon mixture (KG2) which has a reduced amount of (KG1) at least having an aromatic, b) Hydrocarbon conversion of at least one non-aromatic hydrocarbon contained in (KG2) in the presence of an acidic ionic liquid.
  • the removal of the aromatics, in particular of benzene, has the additional advantage that optionally subsequently carried out distillation work-up steps are facilitated because it avoids the otherwise occurring formation of azeotropes of aromatics such as benzene with saturated C 6 -C 7 alkanes.
  • MCP and benzene-containing hydrocarbon mixture (KG1) are hydrogenated in a first step and subsequently passed into a distillation column (D1) to remove a low-boiler stream (LS) Departure of the low boiler current (LS) remaining current (KG2- (LS)) is passed into the isomerization, where at least partial isomerization of the MCP to cyclohexane occurs.
  • the target product of the process is cyclohexane and the compound to be hydrogenated is benzene
  • another advantage of the process according to the invention is that the amount of product obtained is increased by the cyclohexane obtained in the hydrogenation of the benzene.
  • step a the hydrogenation of a hydrocarbon mixture (KG1) comprising at least one aromatic and at least one non-aromatic hydrocarbon is carried out in step a) to obtain a hydrocarbon mixture (KG2) which has a reduced amount of at least one aromatic compound compared to (KG1).
  • step a) the aromatics contained in the hydrocarbon mixture (KG1) are hydrogenated to give the corresponding non-aromatic hydrocarbons, preferably the fully saturated hydrocarbons resulting in the formation of all carbon-carbon bonds.
  • hydrocarbon mixture (KG1) preferably contains benzene as the aromatic and / or the hydrocarbon mixture (KG2) has an increased amount of cyclohexane compared to (KG1).
  • any hydrocarbons can be used as hydrocarbon mixture (KG1), provided that i) at least one of the hydrocarbons used is an aromatic which is hydrogenated in step a) and ii) at least one of the hydrocarbons used is a non-aromatic one Hydrocarbon which, according to (described below) step b) in the presence of an acidic ionic liquid of a hydrocarbon conversion, in particular an isomerization, can be subjected.
  • an acidic ionic liquid of a hydrocarbon conversion in particular an isomerization
  • hydrocarbon mixture (KG1) can be used from two, three or even more hydrocarbons, but it can also be used only a mixture of a single aromatic, for example benzene, and a single non-aromatic hydrocarbon, such as MCP.
  • hydrocarbon mixtures (KG1) which, apart from the two abovementioned components (hydrogenatable aromatic and convertible, preferably isomerizable, nonaromatic hydrocarbon), comprise further components, for example hydrocarbons which are not hydrogenatable and also no hydrocarbon conversion, in particular no isomerization , can be subjected. If appropriate, compounds which are themselves non-hydrocarbon but miscible with them can also be present in such mixtures.
  • the individual components of the hydrocarbon mixture (KG1) can be present in any desired concentrations / ratios.
  • the hydrocarbon mixture (KG1) to at least 90 wt .-%, preferably at least 95 wt .-% hydrocarbons having 5 to 8 carbon atoms, provided that i) at least one of the hydrocarbons used a hydrogenatable aromatic and ii) at least one of used hydrocarbons is a convertible non-aromatic hydrocarbon.
  • the hydrocarbons may otherwise be saturated or unsaturated and / or cyclic, linear or branched.
  • the hydrocarbon mixture (KG1) contains between 10% by weight and 60% by weight, more preferably between 20% by weight and 50% by weight, MCP and / or between 1% by weight and 30% by weight, more preferably between 4% and 20% by weight of benzene.
  • the hydrocarbon mixture (KG1) contains benzene, methylcyclopentane (MCP) and at least one further compound selected from cyclohexane, cyclopentane, olefins or non-cyclic C 5 -C 8 -alkanes.
  • the further compounds preferably also comprise at least one low-boiling component selected from linear or branched C 5 -alkanes, cyclopentane or linear or branched C 6 -alkanes.
  • olefin In addition to linear, monounsaturated olefins such as pentene or hexene, the term “olefin” also includes cyclic olefins, in particular cyclohexene, and also dienes and cyclic dienes .. In the group of C 5 -C 8 -alkanes, compounds with a normal boiling point> 78 ° can also be used C, hereinafter also referred to as "high boiler" may be included.
  • the hydrocarbon mixture (KG1) particularly preferably contains benzene, methylcyclopentane (MCP) and at least one further hydrocarbon selected from cyclohexane, n-hexane, isohexanes, n-heptane, iso-heptanes, methylcyclohexane or dimethylcyclopentanes.
  • MCP methylcyclopentane
  • the hydrocarbon mixture (KG1) and high boilers with a normal boiling point> 78 ° C, in particular dimethylpentane (DMP) are included, these high boilers, especially DMP, preferably before the implementation of the inventive step a) separated from the hydrocarbon mixture (KG1).
  • the high boiler removal is therefore preferably upstream of the hydrogenation.
  • the high boiler separation is usually carried out in a distillation apparatus, which is preferably a rectification column, preferably from the bottom of the corresponding distillation apparatus.
  • the separation of the high boiler with a normal boiling point> 78 ° C from the hydrocarbon mixture (KG1) is complete or almost complete (up to 2% based on the amount of all high boilers contained in the starting mixture, in particular all DMP isomers).
  • the above-mentioned embodiment of the present invention which is also referred to as heavy boiling pre-separation, has an important advantage, especially if the high boilers with a normal boiling point> 78 ° C contain DMP and if in the hydrogenation and / or preferably in the hydrocarbon conversion in the form of an isomerization Cyclohexane is produced. This is due to the fact that prior to the actual cyclohexane production process, the extremely complex separation, in particular distillation, of DMP from the process product cyclohexane can be avoided.
  • the hydrogenation of the hydrocarbon mixture (KG1) takes place in the context of the present invention in a device (V) suitable for this, which preferably comprises at least one hydrogenation reactor (HR).
  • Benzene is preferably hydrogenated in the device (V) to cyclohexane, wherein the hydrogenation is preferably carried out using hydrogen. Furthermore, it is preferred that the hydrogenation takes place in the liquid phase.
  • the hydrogenation of at least one aromatic compound in step a), preferably from benzene to cyclohexane, is generally carried out in the presence of a suitable catalyst.
  • Suitable catalysts are in principle all known to those skilled in the catalysts, such as a metal catalyst on diatomaceous earth according to US-A 3,311 1, 667 or metal-containing catalysts according to EP A 1 995 297, where as the metal elements of the platinum group, tin or cobalt and Molybdenum preferably be used.
  • the hydrogenation is carried out in the presence of a catalyst containing as active metal (also referred to as metal component or active component) at least one element of the 8th to 10th group of the Periodic Table of the Elements (PSE), for example iron, cobalt, nickel or ruthenium (corresponds to Subgroup VIIIB of the CAS version of the PSE), in particular nickel or ruthenium.
  • active metal also referred to as metal component or active component
  • the active metal is applied to a carrier material (carrier).
  • carrier material carrier
  • Suitable carriers are in principle all carriers known to the person skilled in the art, for example SiO 2 -containing, zirconium oxide-containing or aluminum oxide-containing carriers. Particular preference is given to using a catalyst which contains nickel as active metal on an alumina-containing support.
  • the hydrogenation as such is carried out and operated in a manner known per se to the person skilled in the art, preferably a combination of an optionally cooled one Circulation-operated main reactor (recycling a portion of the effluent from the reactor mixture in the reactor inflowing mixture, where appropriate, the cooling is placed before or after said feed) and a subsequent in a single pass, that is operated without recirculation downstream reactor.
  • the device (V) thus comprises two hydrogenation reactors (HR).
  • the hydrogenation reactors (H R) are preferably designed as fixed bed reactors without internal cooling.
  • the hydrogenation is preferably operated so that the temperature difference between incoming and exiting mixture is monitored continuously and when this value falls below a certain setpoint, the inlet temperature is raised.
  • the hydrogenation reactors are operated in trickle mode.
  • the hydrogenation is followed by an apparatus in which is expanded to a pressure below that set in the post-reactor pressure. In this case, a gas stream is produced which contains hydrogen previously dissolved in the hydrocarbon mixture and in any case is compressed and returned to at least one of the hydrogenation reactors (HR).
  • the hydrogenation is preferably carried out at a temperature between 50 and 200 ° C, more preferably between 100 and 180 ° C and / or a pressure between 10 and 300 bar abs., Particularly preferably between 30 and 200 bar abs. carried out.
  • the total conversion of the aromatics, in particular of the benzene (and optionally other unsaturated compounds present in the hydrocarbon mixture (KG1)) is at least 90%, more preferably 99% and / or the residual content of the aromatics, in particular of the benzene (and optionally other unsaturated compounds contained in the hydrocarbon mixture (KG1) in the hydrocarbon mixture (KG2) 1 wt .-%, preferably at most 0, 1 wt .-%, particularly preferably at most 0.01 wt .-% is.
  • the hydrocarbon mixture (KG2) is obtained in step a) of the invention, which differs in its composition from the hydrocarbon mixture (KG1) superficially with respect to the hydrogenated compounds.
  • the hydrocarbon mixture (KG2) thus contains at least one hydrocarbon formed by hydrogenation of an aromatic and at least one non-aromatic hydrocarbon which has already been present in (KG1).
  • the hydrocarbon mixture (KG2) contains all other components according to the hydrocarbon mixture (KG1), which are not chemically changed in the hydrogenation, and optionally by hydrogenation of olefins or serve formed hydrocarbons. If benzene is present as aromatic in hydrocarbon mixture (KG1), the hydrocarbon mixture (KG2) contains cyclohexane accordingly.
  • the hydrocarbon mixture (KG2) preferably contains cyclohexane, MCP, at most 0.1% by weight of aromatics and optionally at least one further compound selected from olefins or non-cyclic C 5 -C 8 -alkanes.
  • the hydrocarbon mixture (KG2) particularly preferably contains cyclohexane, methylcyclopentane (MCP) and at least one further hydrocarbon selected from cyclohexane, n-hexane, isohexanes, n-heptane, iso-heptanes, methylcyclohexane or dimethylcyclopentanes.
  • step b) of the process according to the invention a hydrocarbon conversion of at least one non-aromatic hydrocarbon, which is contained in (KG2), takes place in the presence of an acidic ionic liquid.
  • Hydrocarbon conversions as such are known to those skilled in the art.
  • the hydrocarbon conversion is selected from alkylation, polymerization, dimerization, oligomerization, acylation, metathesis, polymerization or copolymerization, isomerization, carbonylation, or combinations thereof.
  • Alkylations, isomerizations, polymerizations, etc. are known in the art.
  • the hydrocarbon conversion is an isomerization.
  • the hydrocarbon conversion is preferably carried out in the presence of an acidic ionic liquid having the composition K1Al n X (3n + 1) , wherein K1 is a monovalent cation, X is halogen and 1 ⁇ n ⁇ 2.5.
  • Such acidic ionic liquids are known to the person skilled in the art, they are disclosed (in addition to other ionic liquids), for example in WO 201 1/069929.
  • mixtures of two or more acidic ionic liquids can be used, preferably an acidic ionic liquid is used.
  • K1 is preferably an unsubstituted or at least partially alkylated ammonium ion or a heterocyclic (monovalent) cation, in particular a pyridinium ion, an imidazolium ion, a pyridazinium ion, a pyrazolium ion, an imidazolinium ion, a thiazolium ion, a triazolium ion, a pyrrolidinium ion, an imidazolidinium ion or a phosphonium ion.
  • X is preferably chlorine or bromine.
  • the acidic ionic liquid contains as cation at least a partially alkylated ammonium ion or a heterocyclic cation and / or as an anion a chloroaluminum having the composition Al n Cl (3n + 1) with 1 ⁇ n ⁇ 2.5.
  • the at least partially alkylated ammonium ion contains one, two or three alkyl radicals having (each) 1 to 10 carbon atoms. If two or three alkyl substituents with the corresponding ammonium ions are present, the respective chain length can be selected independently of one another, preferably all alkyl substituents have the same chain length. Particularly preferred are trialkylated ammonium ions having a chain length of 1 to 3 carbon atoms.
  • the heterocyclic cation is preferably an imidazolium ion or a pyridinium ion.
  • the acidic ionic liquid contains as cation an at least partially alkylated ammonium ion and as anion a chloroalumination with the composition Al n Cl (3n + 1) with 1 ⁇ n ⁇ 2.5.
  • Such particularly preferred acidic ionic liquids are trimethylammonium chloroaluminate and triethylammonium chloroaluminate.
  • the acidic ionic liquid used in the present invention is preferably used as a catalyst in hydrocarbon conversion, especially as an isomerization catalyst.
  • a hydrogen halide may also be used as cocatalyst.
  • hydrogen halide for example hydrogen fluoride (HF), hydrogen chloride (HCl), hydrogen bromide (HBr) or hydrogen iodide (HI).
  • the hydrogen halides can also be used as a mixture, but preferably only one hydrogen halide is used in the context of the present invention.
  • the hydrogen halide is used, the halide part of which is also contained in the above-described acidic ionic liquid (at least partially) in the corresponding anion.
  • the hydrogen halide (HX) is hydrogen chloride (HCl) or hydrogen bromide (HBr).
  • the hydrogen halide (HX) is hydrogen chloride (HCl).
  • the hydrocarbon conversion can be carried out in principle in all the skilled person for such a purpose known devices.
  • the corresponding device is preferably a stirred tank or a stirred tank cascade.
  • R.kesselkaskade means that two or more, for example, three or four, stirred tanks are connected in series (in series).
  • the hydrocarbon conversion preferably as isomerization, is carried out in a dispersion (D1), in which dispersion (D1) the phase (B) is dispersed in the phase (A), the volume ratio the phase (A) to phase (B) in the range of 2.5 to 4 to 1 [vol / vol], the phase (A) contains> 50 wt .-% at least one acidic ionic liquid and the phase (B) to> 50 wt .-% at least one non-aromatic hydrocarbon ,
  • the dispersion (D1) additionally contains HCl and / or gaseous HCl is introduced into the dispersion (D1).
  • hydrocarbons obtained in the hydrocarbon conversion are contained in a hydrocarbon mixture (KG2b).
  • the mixture (KG2b) thus differs in terms of the (chemical) composition and / or amount of the hydrocarbons contained therein from the corresponding hydrocarbon mixture (KG2), which is present before the hydrocarbon conversion, in particular before the isomerization.
  • the hydrocarbon mixture (KG2) has already been defined above in connection with step a).
  • the hydrocarbon conversion is preferably an isomerization in which methylcyclopentane (MCP) is isomerized to cyclohexane.
  • MCP methylcyclopentane
  • the isomerization is preferably carried out as follows. Carrying out an isomerization of hydrocarbons in the presence of a ionic liquid as a catalyst and optionally a hydrogen halide as cocatalyst is known in the art.
  • the hydrocarbons and the ionic liquid each form a separate phase in the isomerization, wherein subsets of the ionic liquid may be contained in the 5 hydrocarbon phase and subsets of the hydrocarbons in the ionic liquid phase.
  • the hydrogen halide especially hydrogen chloride, is preferably introduced in gaseous form into the apparatus for carrying out the isomerization (if present).
  • the hydrogen halide may be present, at least in part, in the two above-mentioned liquid phases as well as in one, preferably additionally present, gaseous phase.
  • the isomerization is preferably carried out at a temperature between 0 ° C and 100 ° C, more preferably at a temperature between 30 ° C and 60 ° C. Furthermore, it is preferred that the pressure in the isomerization between 1 and 15 20 bar abs. (absolute), preferably between 2 and 10 bar abs., Is.
  • the isomerization is carried out in the apparatus so that there are two liquid phases and one gas phase in a stirred tank or a stirred tank cascade.
  • the first liquid phase contains at least 90 wt .-% of the
  • the second liquid phase contains at least 90 wt .-% of the hydrocarbons.
  • the gas phase contains at least 90% by weight of at least one hydrogen halide, preferably hydrogen chloride.
  • the pressure and composition of the gas phase are adjusted so that the partial pressure of the gaseous hydrogen halide, in particular of HCl gas, in the gas phase between 0.5 and 20 bar abs. (absolute), preferably between 1 and 10 bar abs. is.
  • cyclohexane is isolated from the mixture obtained in the hydrocarbon conversion, in particular when the hydrocarbon conversion is an isomerization.
  • cyclohexane in a purity of at least
  • the isolation of the cyclohexane can be carried out by methods known to the person skilled in the art, for example using one or more distillation columns, into which the discharge of the device is introduced, in which the hydrocarbon conversion, in particular the isomerization, is carried out
  • cyclohexane which was produced in the step a) according to the invention, already after the hydrogenation and before the Hydrocarbon conversion can be isolated from the hydrocarbon mixture (KG2).
  • purification steps are carried out with the discharge of the hydrocarbon conversion, preferably the isomerization.
  • These purification steps may be, for example, a neutral and / or alkaline wash, which may be carried out in one or more stages.
  • special devices such as distillation or rectification devices, may be used to separate, for example, any existing hydrogen halide from the hydrocarbons.
  • Such devices also include devices for single-stage evaporation, in particular for flash evaporation.
  • phase separation units preferably phase separators
  • phase separation units can also be connected upstream of the abovementioned special devices, in particular in order to separate off the acidic ionic liquid from the hydrocarbons.
  • FIG. 1 the method according to the invention is again clarified in accordance with a preferred embodiment of steps a) and b).
  • CH is cyclohexane
  • B is benzene and the terms in parenthesis indicate the most relevant and / or major components of the particular stream for the process.
  • first the hydrocarbon mixture (KG1) is hydrogenated in at least one hydrogenation reactor (HR) using hydrogen.
  • the hydrocarbon mixture (KG1) contains benzene as aromatics and MCP as non-aromatic hydrocarbon, optionally (as described above in connection with (KG1)) also contain other hydrocarbons in the hydrocarbon mixture (KG1).
  • step a) the benzene is converted completely or almost completely (to give the hydrocarbon mixture (KG2)) in cyclohexane.
  • the hydrocarbon conversion is in the embodiment of Figure 1 isomerization.
  • the isomerization of the hydrocarbon mixture (KG2), in which MCP is isomerized to cyclohexane in the presence of an acidic ionic liquid, is carried out in an isomerization apparatus (IV) suitable for this purpose.
  • the isomerization is carried out in a stirred tank or a stirred tank cascade. From the Isomenstechnikstechnik then cyclohexane is isolated, for example using one or more distillation columns, in which the discharge of the isomerization (IV) is initiated.
  • low boilers especially C 5 -C 6 alkanes such as cyclopentane or iso-hexanes, from the hydrocarbon conversion used hydrocarbon mixture (KG2) separated.
  • the separation is carried out by means of distillation.
  • This (preferably distillative) separation is hereinafter also referred to as "low boiler separation", which can be carried out in devices known in the art, in particular using a distillation column (D1).
  • low boilers are preferably removed by distillation from the hydrocarbon mixture (KG2) which has a reduced amount of at least one aromatic compound compared to the hydrocarbon mixture (KG1) and moreover contains at least one nonaromatic hydrocarbon.
  • the hydrocarbon mixture (KG2) depleted of the low boilers is then fed to the hydrocarbon conversion, in particular the isomerization, according to step b) of the present invention.
  • the hydrocarbon mixture (KG2) depleted of the low-boiling components is preferably separated off from the bottom of the corresponding distillation column.
  • the low boiler removal is carried out so that at least one compound selected from linear or branched C 5 alkanes, cyclopentane or linear or branched C 6 alkanes is removed by distillation before the hydrocarbon conversion according to step b) from the hydrocarbon mixture (KG2). Isohexanes are particularly preferably separated by distillation from the hydrocarbon (KG2).
  • the low boiler removal is carried out from the top of the corresponding distillation column.
  • LS means low-boiling components, preferably the low-boiling components are linear or branched C 5 -alkanes, cyclopentane and / or linear or branched C 6 -alkanes, in particular iso-hexanes.
  • D1 the low boilers from the hydrocarbon mixture (KG2) are separated as stream (LS), wherein the stream (LS) boils lower than (KG2).
  • the current (LS) is preferably enriched for isohexanes and / or cyclopentane over (KG2) and depleted in MCP.
  • the stream (KG2 - (LS)) is opposite (KG2
  • the low boiler removal is carried out and operated such that the stream (LS) contains less than 5% by weight, particularly preferably less than 2.5% by weight, of MCP and the stream (KG2 - (LS)) contains less than 10% by weight, particularly preferably less than 5% by weight, of isohexanes
  • the stream (LS) can be introduced, for example, into a steam cracker as so-called cocrack feed, while the stream (optionally, as part of the low boiler removal, a further stream can be withdrawn, which is depleted of isohexanes compared to the stream (LS) and to
  • hydrocarbon mixture (KG2) the following composition is chosen:
  • Feed or organic means the corresponding hydrocarbon mixture (KG1) or (KG2).
  • the test arrangement represents a continuous driving style ("contingent system").
  • the hydrocarbon mixture (KG1) is used instead of the hydrocarbon mixture (KG2) as follows: After the 1000 h operation of (KG2) (KG2) initially 30 ppm benzene (to obtain (KG1)) is added and over a longer period in the Kontistrom hazards. No effect on reaction conversion can be observed and the measured absolute cyclohexane (CH) content remains constant. Even when the benzene content is increased to 50, 80, 150 or 200 ppm of benzene, no changes in the reaction conversion can be observed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de conversion d'hydrocarbures en présence d'un liquide ionique acide. La conversion d'hydrocarbures est, de préférence, une isomérisation, notamment une isomérisation de méthylcyclopentane (MPC) en cyclohexane. Avant la conversion d'hydrocarbures, une hydrogénation est effectuée, de préférence du benzène étant hydrogéné pour obtenir du cyclohexane. Le cyclohexane résultant de l'hydrogénation et/ou de l'isomérisation est de référence isolé du procédé. Dans un mode de réalisation préféré de la présente invention, après l'hydrogénation et avant la conversion d'hydrocarbures, notamment avant l'isomérisation, des composés volatils légers, notamment des alcanes en C5-C6 comme le cyclopentane ou les iso-hexanes, issus du mélange d'hydrocarbures utilisé pour la conversion d'hydrocarbures, sont séparés par distillation.
EP13777060.8A 2012-10-18 2013-10-16 Procédé de conversion d'hydrocarbures en présence d'un liquide ionique acide avec hydrogénation en amont Withdrawn EP2909156A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP13777060.8A EP2909156A2 (fr) 2012-10-18 2013-10-16 Procédé de conversion d'hydrocarbures en présence d'un liquide ionique acide avec hydrogénation en amont

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP12188954 2012-10-18
EP13777060.8A EP2909156A2 (fr) 2012-10-18 2013-10-16 Procédé de conversion d'hydrocarbures en présence d'un liquide ionique acide avec hydrogénation en amont
PCT/EP2013/071604 WO2014060462A2 (fr) 2012-10-18 2013-10-16 Procédé de conversion d'hydrocarbures en présence d'un liquide ionique acide avec hydrogénation en amont

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EP2909156A2 true EP2909156A2 (fr) 2015-08-26

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Family Cites Families (9)

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Publication number Priority date Publication date Assignee Title
US3311667A (en) * 1963-05-06 1967-03-28 Phillips Petroleum Co Process for the preparation of cyclohexane
RU2001130402A (ru) * 2001-11-13 2003-08-20 Хальдор Топсеэ А/С (DK) Способ изомеризации С5-С8 парафинового углеводородного сырья
US6855853B2 (en) 2002-09-18 2005-02-15 Catalytic Distillation Technologies Process for the production of low benzene gasoline
EP1403236A1 (fr) 2002-09-25 2004-03-31 Haldor Topsoe A/S Procédé d'isomérisation d'hydrocarbures paraffiniques catalysé par un liquide ionique en présence d'un hydrocarbure cyclique comme additif
CA2628361C (fr) 2007-05-18 2012-08-07 Uop Llc Isomerisation de charges d'alimentation contenant du benzene
CA2625905C (fr) 2007-05-18 2012-06-12 Uop Llc Isomerisation de charges d'alimentation contenant du benzene
US9315741B2 (en) 2008-09-08 2016-04-19 Catalytic Distillation Technologies Process for ultra low benzene reformate using catalytic distillation
WO2011069957A1 (fr) 2009-12-07 2011-06-16 Basf Se Procédé d'isomérisation d'un hydrocarbure saturé, ramifié et cyclique
WO2011069929A1 (fr) 2009-12-07 2011-06-16 Basf Se Procédé d'isomérisation d'un hydrocarbure saturé

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2014060462A2 *

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WO2014060462A2 (fr) 2014-04-24
CN104755447A (zh) 2015-07-01

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