EP2964595A2 - Procédé de réaction chimique en ajoutant des halogénures métalliques - Google Patents

Procédé de réaction chimique en ajoutant des halogénures métalliques

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Publication number
EP2964595A2
EP2964595A2 EP14711698.2A EP14711698A EP2964595A2 EP 2964595 A2 EP2964595 A2 EP 2964595A2 EP 14711698 A EP14711698 A EP 14711698A EP 2964595 A2 EP2964595 A2 EP 2964595A2
Authority
EP
European Patent Office
Prior art keywords
phase
liquid
metal halide
ionic liquid
separation
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.)
Withdrawn
Application number
EP14711698.2A
Other languages
German (de)
English (en)
Inventor
Steffen Tschirschwitz
Stefan Bitterlich
Nicole HOLUB
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP14711698.2A priority Critical patent/EP2964595A2/fr
Publication of EP2964595A2 publication Critical patent/EP2964595A2/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Withdrawn legal-status Critical Current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
    • 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
    • C07C2527/08—Halides
    • C07C2527/10—Chlorides
    • C07C2527/11—Hydrogen chloride
    • 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
    • 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
    • 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 chemical conversion process, preferably an isomerization process, of at least one hydrocarbon in the presence of an ionic liquid.
  • the chemical reaction is carried out in a device (V1), in which device (V1) is added, either continuously or continuously, at least one metal halide, preferably aluminum halide.
  • the anion of the ionic liquid used comprises at least one metal component and at least one halogen component.
  • the anion of the ionic liquid and the metal halide added to the device (V1) are the same with respect to the respective halogen component and the metal component.
  • Ionic liquids in particular acidic ionic liquids, are suitable, inter alia, 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
  • the dispersion may be present either as a dispersion of an ionic liquid in the organic phase or it may be a dispersion of the organic phase in the ionic liquid.
  • a continuous procedure is in a chemical reaction process, especially in an isomerization, over the organic phase, a subset and / or constituents of the ionic liquid used, in particular the anion portion, in the form of metal halides such as aluminum chloride and / or hydrogen halides such as HCl, carried out, whereby a reduction in the activity of the chemical reaction method, preferably used as a catalyst, ionic liquid is observed.
  • EP-A 2 455 358 relates to processes for the regeneration and activity maintenance of an ionic liquid used as catalyst, in particular in connection with the preparation of alkylates by alkylation reactions.
  • hydrogen halide or halogenated hydrocarbons are added to the catalyst (acidic ionic liquid) in the feed stream during the alkylation reaction.
  • the addition of the hydrogen halide or halogenated hydrocarbon may also be continuous.
  • EP-A 2 455 358 discloses an analogous process for the preparation of alkylates by alkylation reaction using isobutene and C4-alkenes as a feed stream and acidic ionic liquids as a catalyst.
  • EP-A-2 455 358 is a metal halide added to the acidic ionic liquid used.
  • US-A 2010/0065476 discloses methods for measuring and adjusting the flow of a halogen-containing additive in a continuous reactor process, for example in alkylations of olefins or aromatics or in dehydrogenation processes.
  • the halogen-containing additives may be Bronsted acids such as hydrogen chloride, hydrogen bromide or fluorinated alkanesulfonic acids and metal halides such as sodium chloride or copper chloride.
  • the ionic liquids which can be used for the process according to US-A 2010/0065476 are not subject to any restrictions since, in principle, all known anions such as Cl “ , NOy, PF 6 " or also AICI 4 " can be used in the anion portion of the ionic liquids
  • an ionic liquid is used in an alkylation process which comprises Al as the metal component and Cl as the halogen component, whereas the halogen-containing additive used is not a metal halide but hydrogen chloride
  • US-A 2010/0065476 a continuous sampling and halide analysis of the feed stream for the reaction as a mandatory constituent is described in. This complicated procedure can be dispensed with in principle in the present invention.
  • US-A-2007/0249485 discloses a process for regenerating spent acidic ionic liquids used as a catalyst wherein the corresponding ionic liquid is contacted with at least one metal in a regeneration zone in the absence of hydrogen.
  • the ionic liquid is preferably used for catalysis of Friedel-Crafts reactions.
  • a similar method is disclosed in US-A 2007/0142217, wherein there the regeneration is carried out additionally in the presence of a Brönsted acid such as hydrogen chloride.
  • WO 201/006848 discloses a process for converting an alkylation unit for HF or sulfonic acid and an alkylation unit for ionic liquids. In this process, among other things, the ionic liquid used as a catalyst is regenerated by adding hydrogen halide or a haloalkane. The use of metal halide, however, is not disclosed.
  • the object underlying the present invention is to provide a novel process for the chemical reaction of at least one hydrocarbon in the presence of an ionic liquid, in particular for the isomerization of at least one hydrocarbon in the presence of an ionic liquid.
  • the object is achieved by a chemical conversion process of at least one hydrocarbon in a device (V1) in the presence of an ionic liquid in which the anion comprises at least one metal component and at least one halogen component, characterized in that in the device (V1) recurring or continuous at least one metal halide is added and the anion of the ionic liquid and the metal halide match with respect to the respective halogen component and the metal component.
  • the method according to the invention can be carried out advantageously of a chemical reaction, in particular an isomerization of hydrocarbons. Due to the recurring or continuous addition of at least one metal halide to the ionic liquid present in the device (V1), the catalytic activity of the corresponding ionic liquid is kept substantially constant.
  • the effect can be further enhanced if, in addition to the metal halide, preferably aluminum chloride, a hydrogen halide, in particular hydrogen chloride, is added to the ionic liquid present in the device (V1) or is constantly in contact with a preferably gaseous phase containing the hydrogen halide , Furthermore, it is advantageous if the metal halide is not added directly to the device (V1) to the ionic liquid, but if the metal halide is initially outside the device (V1) in a device (V2) with one in the device ( V1) is premixed.
  • a hydrogen halide in particular hydrogen chloride
  • This may initially be the ionic liquid itself, which originates from the reaction effluent of the device (V1) and is separated from the reaction effluent with a phase separation unit, preferably a phase separator, and returned to the device (V1) (see also the following FIG. 1).
  • a phase separation unit preferably a phase separator
  • the equipment cost of the metal halide addition is easier, because the corresponding apparatus (V2), detached from their concrete operation, must not be made of corrosion-resistant material, resulting in an addition to the recirculated ionic liquid or an addition directly into the device (V1) is usually necessary because many ionic liquids have a strong corrosive effect.
  • the metal halide is added to the hydrocarbonaceous stream, it is also not necessary for the corresponding apparatus to be designed for high reaction pressures.
  • the chemical conversion process according to the invention of at least one hydrocarbon in the presence of an ionic liquid with the addition of metal halide is defined in more detail below.
  • chemical reaction process or “chemical reaction” is understood in principle to mean any chemical reaction or chemical reaction known to the person skilled in the art in which at least one hydrocarbon is chemically reacted, modified or changed in any other way with respect to its composition or structure becomes.
  • the chemical reaction method 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 chemical reaction process is an isomerization.
  • Suitable ionic liquids in the context of the present invention are in principle all ionic liquids known to the person skilled in the art, in which the anion comprises at least one metal component and at least one halogen component. In addition, they can themselves catalyze the particular reaction carried out or have a solvent power for each catalyst used.
  • An overview of suitable ionic liquids can be found in the case of isomerization, for example WO 201 1/069929.
  • Preferred within the scope of the present invention is an acidic ionic liquid.
  • the ionic liquid is preferably used as a catalyst in a chemical reaction, preferably in the alkylation or isomerization, in particular in an isomerization.
  • the metal component is preferably selected from Al, B, Ga, In, Fe, Zn and Ti and / or the halogen component selected from F, Cl, Br or I, in particular from Cl or Br.
  • Al n X (3n + 1) with 1 ⁇ n ⁇ 2.5
  • all cations known to those skilled in the art are suitable as cations.
  • Examples of these are an unsubstituted or at least partially alkylated ammonium ion or an optionally alkyl-side chain 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.
  • 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
  • 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 ionic liquid comprises as cation an ammonium ion, more preferably trialkylammonium, and / or as anion a chloroalumination of the composition Al x Cl 3x + 1 with 1 ⁇ x ⁇ 2.5.
  • the ionic liquid in particular the acidic ionic liquid, contains as cation at least partially alkylated ammonium ion and as anion a chloroaluminum with the composition Al n Cl (3n + 1) with 1 ⁇ n ⁇ 2.5.
  • particularly preferred ionic liquids are trimethylammonium chloroaluminate and triethylammonium chloroaluminate.
  • any hydrocarbons may be present in the device (V1) in the process according to the invention.
  • the person skilled in the art on the basis of his general knowledge, knows for which specific chemical reaction processes which hydrocarbons and in which compositions are most suitable.
  • it may also contain (in the form of mixtures) compounds which themselves are not hydrocarbons.
  • the composition of the hydrocarbons contained in the device (V1) is illustrated by the preferred as a chemical reaction in the context of the present invention isomerization.
  • MCP hydrocarbon methylcyclopentane
  • MCP mixture of methylcyclopentane
  • MCP methylcyclopentane
  • methylcyclopentane is particularly preferably isomerized to cyclohexane.
  • cyclohexane or a mixture of cyclohexane with at least one further hydrocarbon selected from methylcyclopentane (MCP), n-hexane, iso-hexane, n-heptane, iso Heptane, methylcyclohexane or dimethylcyclopentane.
  • MCP methylcyclopentane
  • a mixture of cyclohexane, MCP and at least one further hydrocarbon is obtained.
  • the further hydrocarbon is selected from n-hexane, iso-hexane, n-heptane, iso-heptane, methylcyclohexane or dimethylcyclopentane.
  • a lower proportion of MCP and open-chain linear hydrocarbons is present compared to the corresponding composition of hydrocarbons or the phase (B) before the isomerization.
  • the chemical reaction preferably the isomerization, is carried out in a device (V1) which is known to the person skilled in the art.
  • Suitable devices (V1) are for example reactors, other reactors, stirred tank or a stirred tank cascade.
  • the device (V1) is preferably a reactor or a stirred tank cascade.
  • at least one metal halide is added to the device (V1) repeatedly or continuously.
  • the anion of the ionic liquid and the metal halide coincide with respect to the respective halogen component and the metal component.
  • all metal halides known to those skilled in the art which fulfill this criterion are suitable.
  • the metal halide is AICI 3 .
  • the ionic liquid used in the device (V1) contains, for example, Al 2 Cl 7 " as anion, it is possible to use as metal halide corresponding to AICI 3.
  • metal halide corresponding to AICI 3 In the case of mixed-component anions such as Al 2 BrCl 6 " , for example, a corresponding mixture of AICI 3 and AIBr 3 are used.
  • the metal component of the anion of the corresponding ionic liquid contains two or more components, for example Al or Cu, with regard to the selection of the corresponding metal component of the metal halide used.
  • the addition of at least one metal halide into the device (V1) can be carried out either continuously or continuously as stated above.
  • the metal halide can be added in liquid or solid form.
  • the metal halide need not be added directly into the device (V1), but the metal halide can first be added in another device, for example in a contact device (V2), one or more of the components involved in the chemical reaction process , From this other device, the metal halide is fed into the device (V1) (indirect addition of the metal halide according to (V1)).
  • the (over) guiding or (over) guiding the metal halide from the other device into the device (V1) is carried out according to the methods known to the person skilled in the art, for example using pumps.
  • Preferred for the addition of the metal halide are the two embodiments which are defined in more detail in the following text in conjunction with Figures 1 and 2. Both embodiments are such an indirect addition, wherein the metal halide is first added to the system via the contact device (V2), from where it enters the device (V1).
  • a “continuous addition” of the metal halide is understood to mean that the corresponding addition over a relatively long period, preferably over at least 50%, more preferably over at least 70%, even more preferably over at least 90%, in particular over the entire
  • the continuous addition is carried out so that the corresponding device for introducing (adding) the metal halide (eg a rotary valve) is in operation for the aforementioned periods.
  • a "recurring addition" of the metal halide is understood as meaning that the corresponding addition takes place at regular or irregular intervals
  • Phase (B) The time intervals between the individual additions are at least 1 h, preferably at least one day
  • the term "recurring” furthermore includes at least two, for example 3, 4, 5, 10 or even 100 individual Additions understood.
  • the concrete number of individual additions depends on the duration of operation. This ideally goes against infinity.
  • a recurring addition of the metal halide in the context of the present invention is understood to mean the time-limited addition of a plurality of charges of metal halide.
  • the addition of a single batch can take from several seconds to several minutes, possibly even slightly longer periods are conceivable.
  • the time interval between the respective addition of a single batch is at least ten times as long as the duration of the addition of the corresponding batch.
  • the embodiment of a "recurring addition” with the embodiment of a "continuous addition” may also be combined with one another.
  • the addition of the metal halide is particularly preferably carried out in such a way that in the device (V1) a concentration of
  • the respectively next addition is carried out in such a way that a concentration of
  • the next addition of metal halide thus takes place when the metal halide concentration has fallen below the above limits.
  • the recurring occurs Adding the metal halide so as to constantly maintain the aforementioned saturation-related metal halide concentrations in the phase (B).
  • the next addition of metal halide thus takes place before the metal halide concentration has fallen below the above limits.
  • the continuous addition of the metal halide is such that in the device (V1) a concentration of> 70%, preferably> 90% of the saturation concentration of the metal halide is maintained continuously. In particular, this is maintained in the phase (B) (described below).
  • phase (A) contains at least one ionic liquid according to the above description, wherein the proportion of ionic liquid in the phase (A) is greater than 50 wt .-%.
  • the phase (A) is preferably a phase containing ionic liquids which is immiscible or only very difficult to mix with hydrocarbons and / or which contains at most 10% by weight of hydrocarbons.
  • phase (A) mixtures of two or more ionic liquids may be contained, preferably the phase (A) contains an ionic liquid.
  • ionic liquid in addition to the ionic liquid, other components which are miscible with the ionic liquid can also be present in the phase (A). These may be hydrocarbons from phase (B) described below, which typically have limited solubility in ionic liquids.
  • phase (A) may also contain cocatalysts used in isomerization reactions using ionic liquids. A preferred example of such cocatalysts are hydrogen halides, in particular hydrogen chloride.
  • phase (A) may also contain constituents or decomposition products of the ionic liquids, which may arise, for example, during the isomerization process.
  • phase (A) the proportion of ionic liquid is greater than 80 wt .-%.
  • the phase (B) is characterized in the context of the present invention in that it contains at least one hydrocarbon, wherein the content of hydrocarbon in the phase (B) is greater than 50 wt .-%.
  • Phase (B) is preferably a hydrocarbon-containing phase which is immiscible or only very difficult to mix with ionic liquids and / or which contains at most 1% by weight of ionic liquids (based on the total weight of the phase).
  • the concrete composition of phase (B) depends on the chosen chemical reaction method. Phase (B) undergoes a change in composition during a chemical reaction process.
  • the specific hydrocarbons which may be present in phase (B) before and after the chemical reaction, in particular the isomerization, are described below.
  • the ionic liquid to greater than 50 wt .-% in a phase (A) is contained, which has a higher viscosity than a phase (B), in which greater than 50 wt. -% at least one hydrocarbon is contained, and the phases (A) and (B) are in direct contact with each other, for example by forming together a heterogeneous mixture.
  • the chemical reaction in particular the isomerization, takes place in a dispersion (D1) in which the phase (B) is dispersed in the phase (A).
  • the direction of dispersion (that is, the information as to which phase is in disperse form in the other phase) can be determined by examining a sample under transmitted light under a light microscope, optionally after adding a dye which selectively dyes the phase.
  • the phases (A) and (B) have the above definitions.
  • the dispersion (D1) can be prepared by methods known to those skilled in the art, for example, such a dispersion can be produced by intensive stirring of the phases.
  • the volume ratio of the phase (A) to phase (B) is in the range of 2.5 to 4 to 1 [vol / vol], preferably in the range of 2.5 to 3 to 1 [vol / vol].
  • At least one hydrogen halide (HX), preferably hydrogen chloride (HCl), is added to the device (V1), preferably the hydrogen halide addition is repeated or continuous.
  • HX hydrogen halide
  • HCl hydrogen chloride
  • the recurrent or continuous addition of the hydrogen halide is carried out analogously to the above-described recurrent or continuous addition of the metal halide.
  • the hydrogen halide (HX) is added in gaseous form to the device (V1), preferably by setting a constant HX partial pressure over the ionic liquid, preferably at a constant HX partial pressure of 0.5 to 10 bara, more preferably 1 to 5 bara , If gaseous hydrogen halide (HX) is introduced into the device (V1), in one embodiment of the present invention, a mixture containing the following phases can be obtained: i) the phase (A) containing the ionic liquid,
  • phase (C) containing solid metal halide preferably solid AIX 3
  • solid AIX 3 preferably solid AIX 3
  • phase (D) containing gaseous HX iv
  • the process according to the invention in particular the isomerization, is preferably carried out continuously.
  • the compounds (products) formed during the chemical reaction, in particular during the isomerization, can be removed from the device (V1) by methods known to the person skilled in the art.
  • phase separation device phase separation unit
  • phase separation devices as such are known to the person skilled in the art.
  • This phase separation device is preferably a phase separator.
  • the device (V1) is a reactor or a stirred tank cascade, and downstream of the device (V1) is a phase separator, preferably a phase separator.
  • the phase (A) containing the ionic liquid is separated from the phase (B) containing at least one hydrocarbon, preferably the phase (A) is returned to the device (V1) , is returned in particular to the reactor or to the starting point of the stirred tank cascade.
  • the phase separation device preferably a first stream containing at least 70 wt .-%, preferably at least 90% of the phase (A), and a second stream containing at least 70%, preferably at least 90% of the phase (B), from each other separated.
  • the above figures in% refer to the corresponding amounts contained in the stream, which is introduced into the phase separator.
  • the device (V1) it is preferred in the context of the present invention for the device (V1) to be preceded by a contact device (V2), which is preferably a fluidized bed, a fluidized bed or a stirred vessel, the metal halide initially being added to the contact device (V2) and being supplied by there in the device (V1) is performed.
  • the metal halide may be added in solid or liquid, more preferably in solid form.
  • the contact device (V2) can in turn be followed by a device (V3) for liquid or liquid / liquid separation, which is preferably a phase separator, a gravity separator, a hydrocyclone, a dead-end filter or a cross-flow filter.
  • the device (V3) for FesW liquid or liquid / liquid separation is apparatus integrated into the contact device (V2), for example such that (V2) is a stirred tank having a stirring zone and a rest zone arranged above this, in which a through Gravity caused separation of solid and liquid takes place.
  • a solids-enriched stream separated in the device (V3) for FesW liquid or liquid / liquid separation is returned to the contact device (V2).
  • the liquid flows through the contact device (V2), which contains the substances to be converted in the device (V1) and / or which is supplied to the device (V1).
  • the presence of a second, in particular solid, phase in the contact device (V2) is constantly monitored optically or by means of another suitable device or method, preferably by means of a turbidity measurement, and when the second phase disappears by means of a device for Dosing or promotion of solid metal halide registered in the contact device (V2).
  • the contact device (V2) is derived from the recirculated phase (A), which is derived from the above-described phase separation device, in particular the phase separator. flows through and (V2) is located between the phase separation device and device (V1), wherein (V2) optionally downstream of a device (V3) for solid / liquid separation or liquid / liquid T separation.
  • V3 a device for solid / liquid separation or liquid / liquid T separation.
  • IL means ionic liquid
  • VDF means means for metering or conveying solid
  • A means phase (A), wherein the corresponding main component of this phase is enclosed in parentheses (ionic liquid in the present case).
  • B means phase (B), where "KW1” represents a first hydrocarbon mixture and “KW2” represents a second hydrocarbon mixture formed in the device (V1) in the context of a chemical reaction, preferably an isomerization, of KW1.
  • the phase separation unit (PT) is preferably a phase separator
  • the device (V1) is preferably a reactor or a stirred tank or a stirred tank cascade.
  • FIG. 1 also shows a device (V3) for solid-liquid separation or liquid / liquid separation from which a stream enriched in solids (ie MX) is returned to the contact device (V2).
  • the embodiment according to FIG. 1 can also be carried out without the device (V3) and the corresponding return line into the device (V2).
  • a complete separation of solid (MX S ) is performed in the device (V3) a complete separation of solid (MX S ) is performed.
  • phase (A) recycled from the phase separation unit (PT) preferably also contains, in addition to the ionic liquid, HX and MX (in dissolved form) in a lower concentration than the current introduced into the phase separation unit (PT).
  • hydrogen halide preferably hydrogen chloride
  • aluminum chloride is used as the metal halide.
  • the contact device (V2) is flowed through by a liquid containing the phase (B), particularly preferably the feed mixture for the reaction to be carried out, and (V2) is connected upstream of the device (V1), wherein (V2) if appropriate, a device (V3) for solid / liquid separation or liquid / liquid separation is connected downstream.
  • phase separation unit preferably a phase separator
  • cyclohexane From the discharge of the device (V1), in particular from the hydrocarbon-containing discharge of a device downstream of the device (V1) phase separation unit, preferably a phase separator, is preferably isolated in the present invention, cyclohexane.
  • Methods and apparatus for the separation of cyclohexane from such a discharge or stream, in particular when it is a hydrocarbon mixture are known in the art.
  • further purification steps for example washing with an aqueous and / or alkaline phase
  • further purification steps for example washing with an aqueous and / or alkaline phase
  • the experimental setup is shown in FIG.
  • the hydrocarbon mixture B is introduced into a stirred tank (V1) in which a defined amount of ionic liquid is present. Depending on the experiment, this can be saturated with solid AICI 3 .
  • V1 stirred tank
  • the isomerized hydrocarbon mixture is referred to as B1.
  • the level of (V1) is regulated by setting the variable overflow between V1 and PT.
  • the dispersion of A in B is passed into the phase separator (PT), in which the two phases separate.
  • the ionic liquid as heavier phase (A) falls as the lower phase and is transported by a pump back into the container V1.
  • the upper organic Phase is subtracted and analyzed by gas chromatography for their composition.
  • an overpressure of 2 bar is set in the system with gaseous HCl.
  • the IL (ionic liquid) is introduced into the reactor and 10 g of AICI 3 are suspended therein.
  • a hydrocarbon mixture containing about 20 wt .-% MCP (cyclohexane 50 wt .-%, n-hexane 28 wt .-% and iso-hexane 2 wt .-%), is driven continuously into the reactor (V1) and separated again in a phase separator. Over time, AICI 3 is discharged from the reactor by solution in the hydrocarbon mixture. If AICI 3 is no longer suspended in the IL, 10 g AICI 3 are added each time (approximately every 500 hours).
  • the constant addition of AICI 3 can achieve a constant MCP turnover over a long period of time. Due to the lower initial concentration of MCP in the feed, the conversion is thus lower compared to the starting conversion in the comparative example.
  • MCP turnover drops below 20% within 700 hours.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de réaction chimique, de préférence un procédé d'isomérisation, d'au moins un hydrocarbure en présence d'un liquide ionique. La réaction chimique est réalisée dans un dispositif (V1). Dans ce dispositif (V1), on ajoute de manière répétée ou continue au moins un halogénure métallique, de préférence un halogénure d'aluminium. L'anion du liquide ionique utilisé comprend au moins un composant métallique et au moins un composant halogéné. L'anion du liquide ionique et l'halogénure métallique ajouté dans le dispositif (V1) correspondent du point de vue du composant halogéné respectif et du composant métallique. Par le procédé selon l'invention, il est possible (entre autres) de régénérer le liquide ionique utilisé lors de la réaction chimique respective, en particulier lors d'une isomérisation.
EP14711698.2A 2013-03-07 2014-02-27 Procédé de réaction chimique en ajoutant des halogénures métalliques Withdrawn EP2964595A2 (fr)

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