WO2014009347A1 - Procédé pour traiter une matière obtenue après une conversion d'hydrocarbures avec séparation des halogénures d'hydrogène et lavage subséquent - Google Patents

Procédé pour traiter une matière obtenue après une conversion d'hydrocarbures avec séparation des halogénures d'hydrogène et lavage subséquent Download PDF

Info

Publication number
WO2014009347A1
WO2014009347A1 PCT/EP2013/064449 EP2013064449W WO2014009347A1 WO 2014009347 A1 WO2014009347 A1 WO 2014009347A1 EP 2013064449 W EP2013064449 W EP 2013064449W WO 2014009347 A1 WO2014009347 A1 WO 2014009347A1
Authority
WO
WIPO (PCT)
Prior art keywords
mixture
hydrocarbon
hydrogen halide
hydrocarbon conversion
isomerization
Prior art date
Application number
PCT/EP2013/064449
Other languages
German (de)
English (en)
Inventor
Katharina SPUHL
Markus Schmitt
Jochen BÜRKLE
Joni JONI
Steffen Tschirschwitz
Daniel Pfeiffer
Stefan Bitterlich
Michael HÜBNER
Pawel CZAJKA
Original Assignee
Basf Se
Basf Schweiz Ag
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, Basf Schweiz Ag filed Critical Basf Se
Publication of WO2014009347A1 publication Critical patent/WO2014009347A1/fr

Links

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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/0208—Separation of non-miscible liquids by sedimentation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/06—Flash distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/005—Processes comprising at least two steps in series
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • 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
    • 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
    • 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 the treatment of a hydrocarbon conversion effluent wherein the hydrocarbon conversion is carried out in the presence of an acidic ionic liquid.
  • the hydrocarbon conversion is preferably an isomerization.
  • the hydrogen halide is first withdrawn in a device, whereupon the hydrogen halide depleted mixture is subjected to a wash.
  • 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 but with a copper (II) compound.
  • Hydrocarbon conversion processes especially in Isomer Deutschens Sammlungen, also hydrogen halides, preferably as cocatalysts are used. Frequently, the hydrogen halides are used in gaseous form.
  • a partial pressure of 1-10 bar of hydrogen halide, in particular hydrogen chloride is generally set above the reaction mixture by carrying out the isomerization.
  • the hydrogen halide used is dissolved to some extent in the hydrocarbons and thus discharged from the isomerization reaction. This portion of hydrogen halide dissolved in the hydrocarbons must be removed from the hydrocarbons following isomerization, particularly due to the corrosive nature of the hydrogen halide, which is often associated with problems in practice.
  • US-A 201 1/0155632 discloses a process for the preparation of products with a low hydrogen halide content, wherein in at least two separation steps by stripping or distillation from a mixture which originates from a reactor and contains an ionic liquid as a catalyst, the content of hydrogen halides is reduced.
  • the ionic liquid used as a catalyst is recycled to an alkylation reactor from a downstream phase separator, from a first distillation column downstream of the phase separator is hydrogen chloride and from a further downstream second distillation column is a Isobutane-containing stream is returned to the alkylation reactor.
  • 3,271,467 discloses a method and an associated apparatus for maintaining the hydrogen halide concentration in a hydrocarbon conversion, using as catalyst a metal halide and the hydrogen halide as promoter.
  • Suitable metal halides are, for example, aluminum chloride, aluminum bromide, boron trifluoride or halides of zinc, tin, antimony or zirconium, but such compounds are not ionic liquids.
  • the hydrocarbon conversion may, for example, be an isomerization of methylcyclopentane (MCP) to cyclohexane. From the hydrocarbon-containing outlet of the hydrocarbon conversion, a stream rich in gaseous hydrogen halide is separated in a (first) stripping device and discharged from the arrangement.
  • MCP methylcyclopentane
  • a second stream, enriched in hydrogen halide, is passed from the stripping apparatus to an absorber to selectively separate, on a solid absorber, the hydrogen halide contained in that stream.
  • the thus separated hydrogen halide is removed from the solid absorber again and returned to the system.
  • WO 2010/075038 discloses a process for reducing the content of organic halides in a reaction product formed as a result of a hydrocarbon conversion process in the presence of a halogen-containing acidic ionic liquid-based catalyst.
  • the hydrocarbon conversion process is in particular an alkylation, but this process may also be an isomerization be performed.
  • the organic halides are removed from the reaction product by washing with an aqueous alkaline solution.
  • hydrogen halide as cocatalyst of ionic liquids in hydrocarbon conversions such as isomerization processes and the associated removal of hydrogen halide from the isomerization product is not disclosed in WO 2010/075038.
  • the object underlying the present invention is to provide a novel process for the separation of hydrogen halide from a mixture obtained in a hydrocarbon conversion, in particular in an isomerization, of at least one hydrocarbon in the presence of an acidic ionic liquid.
  • the object is achieved by a process for the treatment of a discharge of a hydrocarbon conversion, wherein the hydrocarbon conversion in the presence of an acidic ionic liquid having the composition K1Al n X (3n + 1) is performed, wherein K1 is a monovalent cation, X is halogen and 1 ⁇ n ⁇ 2.5, the discharge comprises a mixture (G1) and the mixture (G1) contains at least one hydrocarbon and at least one hydrogen halide (HX), characterized in that the process comprises the following steps:
  • hydrogen halide which is contained / dissolved in the corresponding product (hydrocarbons) following a hydrocarbon conversion, in particular to an isomerization, can be removed from this product, in particular from an isomerization product, in an advantageous manner. Due to the optional feasible, at least partial return of the hydrogen halide, this can also be used in the process again.
  • a flash device or another simple evaporation is used as the device (V1) in the context of the method according to the invention, this is associated with the following advantages.
  • the use of a flash device or other simple evaporation in step a) is initially less expensive and simpler in terms of apparatus, in particular compared with the use of a rectification column (due to the corrosivity of the hydrogen halide, which has a particularly disadvantageous effect on the complex geometries given in a column).
  • the use of a flash device as device (V1) is particularly advantageous because the separation effect in the flash device is achieved only by a pressure reduction compared to the pressure selected for the hydrocarbon conversion, in particular for the isomerization.
  • a phase separation unit in particular a phase separator, precedes the device (V1), in particular a flash device.
  • the process according to the invention for the treatment of a discharge of a hydrocarbon conversion wherein the hydrocarbon conversion is carried out in the presence of an acidic ionic liquid, is defined in more detail.
  • 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. Particularly preferred in the context of the present invention, the hydrocarbon conversion is an isomerization.
  • the hydrocarbon conversion takes place in the presence of an acidic ionic liquid having the composition K1 Al n X (3n + 1) , where K1 is a monovalent cation, X is halogen and 1 ⁇ n ⁇ 2.5.
  • acidic ionic liquids are known to those 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.
  • 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.
  • 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. Furthermore, in the context of the present invention, the hydrocarbon conversion is also carried out in the presence of a hydrogen halide (HX), preferably the hydrogen halide (HX) is used as cocatalyst.
  • HX hydrogen halide
  • hydrogen halides can be used as hydrogen halide (HX), 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).
  • any hydrocarbons may be used in the context of the present invention, with the proviso that at least one of the hydrocarbons used in the presence of the above-described acidic ionic liquids of a hydrocarbon conversion, in particular an isomerization, can be subjected.
  • the person skilled in the art on the basis of his general knowledge, knows which hydrocarbons can be subjected to a hydrocarbon conversion by acidic ionic liquids, in particular which hydrocarbons are isomerizable. For example, mixtures of two or more hydrocarbons can be used, but it can also be used only one hydrocarbon.
  • a hydrocarbon conversion in particular isomerized.
  • compounds which are themselves non-hydrocarbon but miscible with them can also be present in such mixtures.
  • MCP methylcyclopentane
  • 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 hydrocarbons obtained in the hydrocarbon conversion are contained in a mixture (G1).
  • the mixture (G1) thus differs in terms of the (chemical) composition and / or amount of hydrocarbons contained therein from the corresponding hydrocarbon composition, which is present before the hydrocarbon conversion, in particular before the isomerization. Since in such hydrocarbon conversions, especially in Isomer Deutschensvon, the hydrocarbon conversion to be carried out often does not run to 100% (ie completely), is in the product usually also the hydrocarbon with which the hydrocarbon conversion was carried out (in lesser amount than before the isomerization) contain. If, for example, MCP is to be isomerized to cyclohexane, the isomerization product frequently contains a mixture of cyclohexane and MCP (in less amount than prior to isomerization).
  • the mixture (G1) contains at least one hydrogen halide (HX) and optionally further components.
  • the hydrogen halide (HX) contained in the mixture (G1) is usually the same hydrogen halide as that used in the hydrocarbon conversion (preferably as cocatalyst) because the hydrogen halide normally does not change in its chemical structure due to the hydrocarbon conversion however, partial replacement of the anion portion of the hydrogen halide used with other halide ions in the process may occur.
  • As another Component in the mixture (G1) is preferably the ionic liquid described above.
  • the mixture (G1) contains between 10 and 99 wt .-%, preferably between 50 and 95 wt .-% acidic ionic liquid (the amounts are based on the total weight of hydrocarbons and hydrogen halide in the mixture (G1)).
  • the mixture contains (G1) as a hydrocarbon -so as a product of the hydrocarbon conversion- cyclohexane. More preferably, the mixture (G1) contains as cyclohexane cyclohexane or a mixture of cyclohexane with at least one further hydrocarbon selected from methylcyclopentane (MCP), n-hexane, iso-hexanes, n-heptane, iso-heptanes, methylcyclohexane or dimethylcyclopentanes.
  • MCP methylcyclopentane
  • the mixture (G1) particularly preferably contains as hydrocarbon a mixture of cyclohexane, MCP and at least one further hydrocarbon.
  • the further hydrocarbon is selected from n-hexane, iso-hexanes, n-heptane, iso-heptanes, methylcyclohexane or dimethylcyclopentanes. If the hydrocarbon conversion is carried out as isomerization, the proportion of branched hydrocarbons in the mixture (G1) is preferably less than 10% by weight (based on the sum of all the hydrocarbons present in the mixture (G1)).
  • the mixture (G1) i) contains as hydrocarbon a mixture of cyclohexane with at least one further hydrocarbon selected from methylcyclopentane (MCP), n-hexane, iso-hexanes, n-heptane, iso-heptanes, Methylcyclohexane or dimethylcyclopentanes, ii) hydrogen chloride (HCl) and iii) an acidic ionic liquid containing as cation an at least partially alkylated ammonium ion and as the anion a chloroaluminum having the composition Al n Cl (3n + 1) with 1 ⁇ n ⁇ 2.5 having.
  • MCP methylcyclopentane
  • HCl hydrogen chloride
  • iii) an acidic ionic liquid containing as cation an at least partially alkylated ammonium ion and as the anion a chloroaluminum having the composition Al n Cl (3n + 1) with 1 ⁇ n
  • the hydrocarbons present in the mixture (G1) have at least 80% by weight of at least 5 carbon atoms per molecule. These hydrocarbons particularly preferably have at least 6 carbon atoms per molecule.
  • the mixture (G1) is initially in the apparatus in which the hydrocarbon conversion is carried out.
  • the mixture (G1) is discharged from this device as a discharge.
  • the discharge comprises the mixture (G1) and the discharge or mixture (G1) after it has been the device for Carrying out the hydrocarbon conversion has been subjected to the inventive steps (a) to c) (defined below in the text).
  • the isomerization is preferably carried out as follows.
  • Carrying out an isomerization of hydrocarbons in the presence of an ionic liquid as catalyst and a hydrogen halide as cocatalyst is known to the person skilled in the art.
  • the hydrocarbons and the ionic liquid each form a separate phase in the isomerization, wherein subsets of the ionic liquid in the hydrocarbon phase and subsets of the hydrocarbons may be contained in the ionic liquid phase.
  • the hydrogen halide in particular hydrogen chloride, is preferably introduced in gaseous form into the device for carrying out the isomerization.
  • the hydrogen halide may, at least in part, be contained in the two aforementioned liquid phases, preferably the hydrogen halide forms a separate 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 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% by weight of the acidic ionic liquid and the second liquid phase contains at least 90% by weight 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 1 and 20 bar abs., Preferably between 2 and 10 bar abs. is.
  • the mixture (G1) is fed into a device (V1), a mixture (Gi b) containing at least 50% by weight of the hydrogen halide (HX) contained in (G1) being selected from ( V1) is subtracted.
  • the mixture (Gi b) is withdrawn from the device (V1) partially or completely gaseous, particularly preferably completely gaseous.
  • At least 50%, more preferably at least 70% of the hydrogen halide introduced with the mixture (G1) are preferably removed with mixture (Gi b).
  • a partial or complete return of the mixture (Gi b) takes place in the apparatus for carrying out the hydrocarbon conversion, optionally with pressure increase by means of a suitable device such as a jet, piston, turbo or screw compressor.
  • the mixture (Gi b) is completely recycled to the apparatus for carrying out the hydrocarbon conversion. If no complete return of the mixture (Gi b) is carried out, the excess amounts of mixture (Gi b) are carried out from the process according to the invention and discarded or fed to a further process step.
  • V1 for carrying out the gaseous removal (separation) of the hydrogen halide (HX) from the mixture (G1) it is possible in principle to use all devices known to the person skilled in the art for such a purpose, preferably an evaporation device, a rectification column, a device for flash evaporation (Flash device) or a stripping device. More preferably, V1 is a flash device.
  • the device (V1) should be carried out in the context of the inventive method, preferably a separation of the hydrogen halides of the hydrocarbons.
  • step a) is to be understood such that when using a flash device as the device (V1), a corresponding flash process (flashing) is carried out with the mixture (G1).
  • flashing a flash process
  • evaporation which is carried out in a corresponding evaporation apparatus, the following understood:
  • evaporation is characteristic that evaporated from the liquid mixture to be separated under heat, a part, and condensed after separation from the residual liquid mixture
  • a vapor phase is generated for the original liquid phase in which the lower-boiling mixture components accumulate.
  • rectification which is carried out in a corresponding rectification column (rectification apparatus), also called a rectification column or rectification apparatus, is understood as follows: In the rectification, the steam produced by distillation is passed in a rectification column in countercurrent to a In this way, more volatile components in the overhead and heavier volatile in the bottom product of the rectification are enriched.
  • flashing which is carried out in a corresponding flash device and can also be referred to as flash evaporation, means the following:
  • a liquid mixture is introduced into a suitable device (flash device) ), for example, in a vapor-liquid separation vessel (ie, on a suitable device such as a valve, a reduction of the pressure takes place, which is sufficient to spontaneously evaporate a portion of the liquid mixture)
  • flash device a suitable device
  • the liquid mixture can, for example, operated at a higher pressure reaction stage
  • it may also be preheated in a preheater, for example at boiling temperature, wherein the pressure in the preheater must be higher than the pressure in the downstream precipitation vessel higher proportion of lower-boiling components.
  • the flash evaporation thus provides for a partial separation of the incoming mixture, wherein the separator can act as a single theoretical separation stage.
  • the flashing can also be combined with a heat input into the liquid mixture remaining during the flash process, for example by means of a circulation evaporator connected to the separation vessel.
  • the term "stripping", which is carried out in a corresponding stripping apparatus means the following: during stripping, the depletion of one or more lower-boiling components takes place from a liquid, this being carried out, preferably in a countercurrent column, is contacted with gases such as nitrogen, air or water vapor, so that as a result of the gas caused by the reduction of the partial pressure of the lower-boiling components in the gas phase, their solubility in the liquid decreases.
  • step b) of the process according to the invention the discharge of a mixture (G2) from the device (V1), wherein the mixture (G2) at least one hydrocarbon and compared to the mixture (G1) to the mixture (Gi b) reduced amount of at least a hydrogen halide (HX).
  • the mixture (G2) may contain at least 50% reduced amount of at least one hydrogen halide (HX).
  • Preferred is in Mixture (G2) containing an over the mixture (G1) by at least 70% reduced amount of at least one hydrogen halide (HX) included.
  • step c) of the process according to the invention the mixture (G2) is washed with an aqueous medium to obtain a mixture (G3) containing at least one hydrocarbon and not more than 100 ppm by weight, preferably not more than 10 ppm by weight of hydrogen halide (HX ) (based on the total weight of (G3)).
  • HX hydrogen halide
  • the term "broad agreement” is to be understood as meaning that at least 90% by weight, preferably at least 95% by weight, in particular at least 99% by weight, of the hydrocarbons contained in the mixture (G1)
  • the mixture (G3) particularly preferably contains no further components apart from at least one hydrocarbon and not more than 100 ppm by weight, preferably not more than 10 ppm by weight of hydrogen halide.
  • the method step c) is preferably carried out such that the laundry according to step c) comprises at least two washing steps, wherein c1) in a first washing step the aqueous medium used has a pH> 9, preferably> 12, c2) in a second washing step used aqueous medium has a pH between 5 and 9, preferably between 6 and 8, having.
  • the aqueous medium according to the first washing step contains an alkali metal hydroxide, more preferably NaOH.
  • the aqueous medium according to the second washing step is water, more preferably demineralized water. If appropriate, method step c) can be carried out such that step c2) can be carried out before step c1).
  • washing is first carried out with an aqueous medium having a lower pH, followed by washing with an aqueous medium having a higher pH.
  • the washing step c) is carried out in two stages, with step c1) first, followed by step c2).
  • step c1) first, followed by step c2).
  • step c2) only a one-step washing step c) is carried out, wherein the aqueous medium has a pH of 5 to 9, preferably between 6 and 8, and is particularly preferably demineralized water.
  • washing step c) is preferably carried out in a countercurrent extraction column or mixer-settler arrangement.
  • step c) is carried out using at least one dispersing and phase separation unit or at least one extraction column per wash step.
  • the dispersing and phase separation unit is a mixer-settler apparatus (combination of a stirred tank with a subsequent phase separator), a combination static mixer with phase separator or a combination of mixing pump with phase separator.
  • the mixture (G2) is conducted in countercurrent to the aqueous medium.
  • the mixture (G2) discharged from the device (V1) is particularly preferably washed without intermediate steps with the aqueous medium (according to step c)).
  • the washing step c) is carried out in a, preferably in countercurrent, multistage mixer-settler apparatus or it is extracted in a countercurrent extraction column with water.
  • the mixer-settler apparatus or extraction column in the direction of flow of the mixture (G 2) (containing the hydrocarbons), this is preferably followed by a further washing stage, which is fed with fresh water.
  • a further washing stage In its aqueous outlet there is a device for the continuous measurement of the pH or the electrical conductivity so as to monitor the complete removal of the non-hydrocarbon components, in particular HCl.
  • the steps a) and b) according to the invention are carried out according to at least one, more preferably according to all three variants i) to iii) listed below, wherein i) the mixture (G2) discharged from the device (V1) is at least 95% by weight liquid (in step b)), the mixture (Gi b) withdrawn from the device (V1) amounts to at least 95% by weight is gaseous (in step a)), the discharged mixture (G2) by at most 150 K, preferably at most 100 K, is warmer than the withdrawn mixture (Gi b) (in step b)).
  • a one-stage evaporation takes place in the device (V1) and the mixture (G2) discharged from the device (V1) is washed with the aqueous medium without intermediate steps.
  • the inventive method is illustrated again according to a preferred embodiment.
  • an at least partial return of the in step a), preferably gaseous, separated mixture (Gi b) is performed.
  • R1 represents the device in which the hydrocarbon conversion, in particular an isomerization, is carried out. This is preferably a stirred tank or a stirred tank cascade.
  • the device (V1) is preferably an evaporator, in particular a flash device.
  • the washing step c) according to FIG. 1 can be one-stage or multi-stage as described above, preferably a multi-stage, in particular two-stage washing of the mixture (G2) in countercurrent to aqueous medium is carried out and / or a dispersing and phase separation unit, in particular a mixer-settler apparatus, is used.
  • the mixture (G1) as discharge from the device in which the hydrocarbon conversion is carried out discharged, passed through a phase separation unit, in particular in a phase separator, and then fed into the device (V1).
  • an intermediate step is carried out.
  • the acidic ionic liquid contained in the mixture (G1) is preferably completely or at least partially separated from the mixture (G1), whereupon the mixture (G1) depleted of acidic ionic liquid is fed into the device (V1).
  • At least 90%, preferably at least 99%, of the acidic ionic liquid is separated from the mixture (G1) in the phase separation unit and, if appropriate, recycled to the apparatus in which the hydrocarbon conversion is carried out.
  • the acidic ionic liquid separated from the mixture (G1) in the phase separation unit is completely or partially returned to the device for carrying out the hydrocarbon conversion, in particular for carrying out an isomerization.
  • FIG. 2 The further preferred embodiment of the present invention described above is additionally illustrated in FIG.
  • the abbreviations, arrows and other symbols have a meaning corresponding to that stated above for FIG. 1;
  • PT means phase separation unit,
  • IL means acidic ionic liquid.
  • cyclohexane is preferably isolated in the context of the present invention. Methods and apparatus for the separation of cyclohexane from the mixture (G3) are known in the art.
  • ionic liquid IL
  • TMA-I L trimethylammonium heptachlorodialuminate
  • (A) and (B) are mixed so that the resulting mixture after phase separation G1 (-I L) has an HCl content of 1.5% by weight.
  • Example 1 with HCI separation or recirculation via flash device (V1) and subsequent washing with an aqueous medium
  • Example 1 is carried out according to the embodiment schematically illustrated in FIG.
  • a device R1 is an isomerization of a hydrocarbon mixture (A) in the presence of an ionic liquid (trimethylammonium heptachlorodialuminate - TMA-I L), which serves as a catalyst, instead.
  • This isomerization preferably refers to the reaction of methylcyclopentane to cyclohexane.
  • the volume ratio of ionic liquid to organic phase is 5.
  • an operating pressure of 3.5 bar (abs) and a temperature of 50 ° C are assumed.
  • the resulting mixture G1 is passed into a phase separation device PT.
  • the organic phase G1 (-I L) is passed into the flash device V1, where it is expanded to an operating pressure of 1 bar (abs).
  • the resulting gas fraction Gi b is returned to the device R1.
  • the liquid mixture G2 is discharged from V1 and the organic stream G2 is further depleted in a subsequent step W by washing (multi-stage) with an aqueous medium of hydrogen chloride.
  • Comparative Example 2 is shown schematically in FIG. In contrast to example 1, however, no washing step c) is carried out, but instead a distillation column (K1) is used instead of the device (V1).
  • a distillation column (K1) is used instead of the device (V1).
  • isomerization of a hydrocarbon mixture (A) takes place in the presence of an ionic liquid (trimethylammonium chloroaluminate - TMA-IL), which serves as a catalyst.
  • This isomerization preferably refers to the reaction of methylcyclopentane to cyclohexane.
  • the volume ratio of ionic liquid to organic phase is 5 l / l.
  • hydrogen chloride gas (B) is supplied to stabilize the IL.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention concerne un procédé pour traiter une matière obtenue après une conversion d'hydrocarbures, cette conversion d'hydrocarbures étant effectuée en présence d'un liquide ionique acide. Cette conversion est de préférence une isomérisation. Ce procédé consiste à retirer tout d'abord, dans un dispositif, l'halogénure d'hydrogène d'un mélange provenant de la conversion d'hydrocarbures, contenant au moins un hydrocarbure et au moins un halogénure d'hydrogène, puis à soumettre ce mélange appauvri en halogénure d'hydrogène à un lavage.
PCT/EP2013/064449 2012-07-11 2013-07-09 Procédé pour traiter une matière obtenue après une conversion d'hydrocarbures avec séparation des halogénures d'hydrogène et lavage subséquent WO2014009347A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP12175852 2012-07-11
EP12175852.8 2012-07-11

Publications (1)

Publication Number Publication Date
WO2014009347A1 true WO2014009347A1 (fr) 2014-01-16

Family

ID=48771432

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2013/064449 WO2014009347A1 (fr) 2012-07-11 2013-07-09 Procédé pour traiter une matière obtenue après une conversion d'hydrocarbures avec séparation des halogénures d'hydrogène et lavage subséquent

Country Status (1)

Country Link
WO (1) WO2014009347A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3271467A (en) 1963-08-29 1966-09-06 Phillips Petroleum Co Maintaining hydrogen halide concentration in the conversion of hydrocarbons employing metal halide catalysts and hydrogen halide promoter
WO2010075038A2 (fr) 2008-12-16 2010-07-01 Chevron U.S.A. Inc. Réduction de la contamination par un halogénure organique dans des produits hydrocarbures
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
US20110155632A1 (en) 2009-12-31 2011-06-30 Chevron U.S.A., Inc. Process for making products with low hydrogen halide.
US20110155640A1 (en) 2009-12-31 2011-06-30 Chevron U.S.A., Inc. Process for recycling hydrogen halide to a reactor comprising an ionic liquid

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3271467A (en) 1963-08-29 1966-09-06 Phillips Petroleum Co Maintaining hydrogen halide concentration in the conversion of hydrocarbons employing metal halide catalysts and hydrogen halide promoter
WO2010075038A2 (fr) 2008-12-16 2010-07-01 Chevron U.S.A. Inc. Réduction de la contamination par un halogénure organique dans des produits hydrocarbures
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
US20110155632A1 (en) 2009-12-31 2011-06-30 Chevron U.S.A., Inc. Process for making products with low hydrogen halide.
US20110155640A1 (en) 2009-12-31 2011-06-30 Chevron U.S.A., Inc. Process for recycling hydrogen halide to a reactor comprising an ionic liquid

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
R.H.PERRY; D.W.GREEN: "Perry's Chemical Engineers' Handbook", 1997, MCGRAW- HILL
SATTLER: "Thermische Trennverfahren", 1988, VCH

Similar Documents

Publication Publication Date Title
DE112010005065T5 (de) Verfahren zum Herstellen von Produkten mit wenig Wasserstoffhalogenid
WO2003070667A1 (fr) Procede de separation de substances par extraction ou lavage par des liquides ioniques
EP1718585A1 (fr) Procede pour recuperer du 1,3-butadiene brut
DE2742148C2 (de) Verfahren zur Abtrennung und Gewinnung von Butadien aus Kohlenwasserstoffmischungen
EP3134376B1 (fr) Procédé de fabrication de cyclohexane à partir de benzène et méthylcyclopentane par hydrogénation du benzène en aval
DE112009004586T5 (de) Verfahren zur umwandlung von kohlenwasserstoffen unter verwendung eines säurekatalysators und verfahren zu dessen herstellung und zusammensetzungen davon
EP0017118B1 (fr) Procédé pour obtenir une dioléfine conjuguée à partir d'un mélange d'hydrocarbures C 4 ou C 5
EP2872470A1 (fr) Procédé d'isomérisation d'hydrocarbures avec recyclage d'halogénures d'hydrogène
WO2014060461A1 (fr) Nouveau procédé de production de cyclohexane à partir de méthylcyclopentane et de benzène
WO2014009347A1 (fr) Procédé pour traiter une matière obtenue après une conversion d'hydrocarbures avec séparation des halogénures d'hydrogène et lavage subséquent
DE2521965C3 (de) Verfahren zur Abtrennung von Butadien aus einem Strom von C4 -Kohlenwasserstoffen
EP2909159B1 (fr) Procédé de production de cyclohexane en utilisant des matériaux de départ issus d'un procédé de vapocraquage
WO2014009351A1 (fr) Procédé pour séparer des halogénures d'hydrogène dans une colonne de rectification comportant un condenseur partiel
WO2014009343A1 (fr) Procédé de traitement d'un déversement d'une conversion d'hydrocarbures par lavage à l'aide d'un agent aqueux
DE888618C (de) Verfahren zur Entfernung des Katalysators und des Beschleunigers von olefinpolymerenProdukten
DE2249212C3 (de) Verfahren zum Isomerisieren von aliphatischen oder naphtenischen Kohlenwasserstoffen
DE60003775T2 (de) Verfahren und Vorrichtung zur Alkylierung von Isobutan mittels leichten Olefinen
DE1954707B2 (de) Verfahren zur Wiedergewinnung von Metallkatalysatoren
EP2872471B1 (fr) Procédé de mise en réaction chimique dans une dispersion
DE1520783B1 (de) Verfahren zum Aufarbeiten von Olefin-Polymerisatsuspensionen
DE1443794C3 (fr)
DE1645140B2 (de) Verfahren zur Polymerisation eines ungesättigten Kohlenwasserstoffs
EP2909156A2 (fr) Procédé de conversion d'hydrocarbures en présence d'un liquide ionique acide avec hydrogénation en amont
DE3049213A1 (de) Verfahren zur gemeinsamen herstellung von alkyl-tert.-butylether und gewinnung von butadien
WO2014135444A2 (fr) Procédé de réaction chimique en ajoutant des halogénures métalliques

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13735015

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13735015

Country of ref document: EP

Kind code of ref document: A1