WO2014135445A1 - Procédé de réaction chimique à pression partielle constante d'halogénure d'hydrogène - Google Patents
Procédé de réaction chimique à pression partielle constante d'halogénure d'hydrogène Download PDFInfo
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- WO2014135445A1 WO2014135445A1 PCT/EP2014/053889 EP2014053889W WO2014135445A1 WO 2014135445 A1 WO2014135445 A1 WO 2014135445A1 EP 2014053889 W EP2014053889 W EP 2014053889W WO 2014135445 A1 WO2014135445 A1 WO 2014135445A1
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- WIPO (PCT)
- Prior art keywords
- phase
- hydrogen halide
- ionic liquid
- halide
- hydrocarbon
- Prior art date
Links
- 229910000039 hydrogen halide Inorganic materials 0.000 title claims abstract description 83
- 239000012433 hydrogen halide Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 54
- 239000000126 substance Substances 0.000 title abstract description 10
- 239000002608 ionic liquid Substances 0.000 claims abstract description 88
- 239000007789 gas Substances 0.000 claims abstract description 61
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 59
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 56
- 239000007788 liquid Substances 0.000 claims abstract description 47
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 43
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 43
- 239000011541 reaction mixture Substances 0.000 claims abstract description 38
- 229910001507 metal halide Inorganic materials 0.000 claims description 63
- 150000005309 metal halides Chemical class 0.000 claims description 63
- 239000000203 mixture Substances 0.000 claims description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 25
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 21
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 21
- 229910052736 halogen Inorganic materials 0.000 claims description 20
- 150000002367 halogens Chemical class 0.000 claims description 17
- 150000001450 anions Chemical class 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- 238000005191 phase separation Methods 0.000 claims description 14
- 238000005804 alkylation reaction Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 230000029936 alkylation Effects 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 125000005208 trialkylammonium group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- 239000003426 co-catalyst Substances 0.000 claims 1
- 239000012071 phase Substances 0.000 description 126
- 238000007792 addition Methods 0.000 description 48
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 44
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 19
- -1 copper (II) compound Chemical class 0.000 description 17
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 15
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 8
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- QWHNJUXXYKPLQM-UHFFFAOYSA-N 1,1-dimethylcyclopentane Chemical class CC1(C)CCCC1 QWHNJUXXYKPLQM-UHFFFAOYSA-N 0.000 description 6
- 239000011831 acidic ionic liquid Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- YUHZIUAREWNXJT-UHFFFAOYSA-N (2-fluoropyridin-3-yl)boronic acid Chemical class OB(O)C1=CC=CN=C1F YUHZIUAREWNXJT-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000011982 device technology Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910014265 BrCl Inorganic materials 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
-
- 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
- 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 and a hydrogen halide (HX).
- the chemical reaction is carried out in a device (V1), wherein in the device (V1) is a gas phase in direct contact with a liquid reaction mixture.
- the gas phase and the liquid reaction mixture each contain the hydrogen halide, in the liquid reaction mixture additionally at least one hydrocarbon and the ionic liquid are included.
- Gaseous HX is introduced into the device (V1) so that the hydrogen halide partial pressure is kept constant in the gas phase.
- 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
- An analogous process is described in WO 201 1/069957, although the isomerization does not take place in the presence of an olefin, but rather with a copper (II) compound.
- ionic liquids on the one hand and hydrocarbons (organic phases) on the other hand are immiscible or very difficult to mix, forming two separate phases.
- intensive contact must be established between the organic phase and the ionic liquid.
- the two phases are often mixed in stirred tanks with intensive stirring to obtain dispersions.
- 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.
- 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.
- a hydrogen halide carried out so that the hydrogen halide partial pressure is kept constant above the corresponding reaction mixture in a gas phase.
- 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.
- apparatuses for carrying out the corresponding processes comprising a reactor containing an ionic liquid, measuring devices for determining the halogen concentration in the reactor outlet and a control system for controlling the halogen concentration.
- halogen-containing additive is not necessarily fixed to a mold in the process according to US-A 2010/0065476, as gaseous hydrogen chloride or a solid such as sodium chloride can be used as a halogen-containing additive, for example, in dissolved form in the continuous reactor process can be added.
- gaseous halogen-containing additive such as hydrogen chloride
- US-A 2010/0065476 contains no indication that the partial pressure of, for example, hydrogen chloride must be kept constant above the respective reaction mixture in a gas phase.
- the process described in US-A 2010/0065476 involves a continuous sampling and halide analysis of the feed stream for the reaction as a mandatory ingredient. In principle, this costly procedure can be dispensed with 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.
- the ionic liquid used as a catalyst is regenerated by adding hydrogen halide or a haloalkane.
- the hydrogen halide partial pressure is kept constant.
- 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 reaction of at least one hydrocarbon in a device (V1) in the presence of an ionic liquid and a hydrogen halide (HX), characterized in that in the device (V1), a liquid reaction mixture containing at least one Hydrocarbon, the hydrogen halide and the ionic liquid, and a gas phase containing the hydrogen halide, wherein the liquid reaction mixture and the gas phase are in direct contact with each other and wherein in the device (V1) gaseous hydrogen halide is introduced, so that during the chemical reaction the hydrogen halide partial pressure in the gas phase is kept constant.
- HX hydrogen halide
- the method according to the invention can be carried out advantageously of a chemical reaction, in particular an isomerization of hydrocarbons.
- a hydrogen halide (HX) at a constant hydrogen halide partial pressure in the gas phase, the catalytic activity of the corresponding ionic liquid is kept substantially constant.
- the effect can be further enhanced if, in addition to the hydrogen halide, preferably hydrogen chloride, a metal halide, in particular aluminum chloride, is added to the ionic liquid present in the device (V1) or is in constant contact with the metal halide.
- the inventive method can be carried out by the hydrogen halide partial pressure in the device (V1) is kept constant in that the pressure in the device (V1) is controlled such that gaseous hydrogen halide recurring or continuously in the device (V1) is initiated.
- the gaseous hydrogen halide is introduced from a reservoir into the device (V1), wherein a shut-off device, preferably a valve or a tap, is located between the device (V1) and the reservoir.
- the pressure in the gas phase (over the reaction mixture) in the device (V1) can be measured continuously, when falling below a (predetermined) threshold value for the pressure, the obturator, while exceeding the threshold for the Pressure the obturator is closed again.
- the metal halide is not added directly into the device (V1) to the ionic liquid, but if the metal halide initially outside the device (V1) in a device or Apparatus (V2) is premixed with one of the main components located in the device (V1).
- 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).
- the metal halide is added to the feed stream containing the hydrocarbons to be subjected to a chemical reaction, in particular an isomerization, in the apparatus (V1).
- the expenditure on equipment of the metal halide addition is simpler, because the corresponding apparatus (V2), detached from its concrete mode of operation, does not have to be made of corrosion-resistant material, which, when added to the recirculated ionic liquid or added directly into the device (V1 ) is usually necessary because many ionic liquids are highly corrosive.
- 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.
- 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.
- 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.
- 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.
- compounds in the form of mixtures may also be present which are not hydrocarbons themselves.
- 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
- MCP 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.
- Suitable ionic liquids in the context of the present invention are in principle all ionic liquids known to the person skilled in the art. An overview of suitable ionic liquids can be made in the case of isomerization For example, WO 201 1/069929 are taken. 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.
- they may have a dissolving power for another, used in the corresponding reaction catalyst.
- 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.
- 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.
- 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 chloroalumination with the composition Al n Cl (3n + 1) with 1 ⁇ n ⁇ 2.5.
- particularly preferred ionic liquids are trimethylammonium chloroaluminate and triethylammonium chloroaluminate.
- hydrogen halides can be used as hydrogen halide (HX), for example hydrogen fluoride (HF), hydrogen chloride (HCl), hydrogen bromide (HBr) or hydrogen iodide (HI).
- HX hydrogen fluoride
- HCl hydrogen chloride
- HBr hydrogen bromide
- HI hydrogen iodide
- 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 (HX) whose halogen component (X) coincides (at least partially) with the halogen component in the anion of the above-described (acidic) ionic liquid.
- the hydrogen halide (HX) is hydrogen chloride (HCl) or hydrogen bromide (HBr).
- the hydrogen halide (HX) is hydrogen chloride (HCl).
- the hydrogen halide (HX) is dry, in particular it is dry hydrogen chloride.
- the device (V1) is a liquid reaction mixture containing (as components) at least one hydrocarbon containing hydrogen halide (HX) and the ionic liquid.
- the individual components of the liquid reaction mixture according to the above definitions may also contain 2 or more hydrogen halides and / or ionic liquids.
- the liquid reaction mixture is the components which participate in the above-described chemical reaction, preferably in the isomerization, (active).
- the ionic liquid is used as catalyst and the hydrogen halide as cocatalyst in a chemical reaction, preferably in an alkylation or isomerization, in particular in an isomerization.
- the device (V1) is a gas phase containing the hydrogen halide (HX).
- the hydrogen halide in the gas phase and the hydrogen halide in the liquid reaction mixture are the same in chemical definition.
- the liquid reaction mixture and the gas phase are in direct contact with each other.
- the liquid reaction mixture forms one, two or more separate phases, that is, different from the gas phase.
- the liquid reaction mixture and the gas phase can
- the device (V1) is located for example in the lower part of the one or two separate phases existing liquid reaction mixture, wherein the gas phase is again in the upper part of the corresponding device (V1).
- the two "main phases" ie liquid reaction mixture and gas phase.
- the liquid reaction mixture and the gas phase it is also possible for the liquid reaction mixture and the gas phase to be mixed, for example by intensive stirring but the separation in the reaction mixture on the one hand and gas phase on the other hand is maintained.
- At least one hydrogen halide (HX), preferably hydrogen chloride (HCl), is introduced into the device (V1) in gaseous form. Due to the gaseous introduction of the hydrogen halide, the gas phase described above forms in the device (V1). The gaseous introduction of the hydrogen halide is carried out so that during the chemical reaction, in particular during the isomerization, the hydrogen halide partial pressure in the gas phase is kept constant.
- the term "constant hydrogen halide partial pressure" (in the gas phase) is understood as meaning that the hydrogen halide partial pressure is constant (in the gas phase) if it does not exceed 20% during the operating time of the device (V1). , preferably at most 10%, more preferably at most 5%, in particular at most 1%, deviates from the mean value determined over the operating time of the device (V1).
- the hydrogen halide partial pressure (PHX) is defined as follows:
- ⁇ ⁇ ⁇ molar fraction of the hydrogen halide in the gas phase
- Ptotai total pressure of the gas phase over the reaction mixture.
- Ptotai total pressure of the gas phase over the reaction mixture
- the hydrogen halide partial pressure ⁇ ⁇ ⁇ can preferably be determined by taking from the gas phase of the device (V1) a sample of defined amount and the HX mole fraction according to a method known to the skilled person (eg introducing the gas into a defined NaOH solution and then Back titration) is determined and the determined mole fraction according to equation 1 with the total pressure of the gas phase in (V1) is multiplied.
- the hydrogen halide partial pressure ⁇ ⁇ ⁇ can also be estimated according to Equation 2, provided that passenger car is known.
- p K w and p to t a i can be determined by the methods known in the art, in particular measurement of the pressure p to t a i by means of a conventional pressure measuring device and determination of PKW by means of a temperature-vapor pressure correlation (vapor pressure curve), for a given hydrocarbon, or a hydrocarbon mixture is usually known or can be determined by the skilled person known measuring methods.
- the hydrogen halide partial pressure in the gas phase can in principle assume any desired values in the context of the process according to the invention.
- the hydrogen halide partial pressure in the gas phase is between 1, 1 and 5 bara, preferably between 2 and 4 bara.
- the hydrogen halide partial pressure in the gas phase is kept constant by controlling the pressure in the device (V1) by returning or continuously introducing gaseous hydrogen halide into the device (V1).
- a "continuous introduction of gaseous hydrogen halide” is understood to mean that the corresponding addition is maintained over a relatively long period of time, preferably over at least 50%, more preferably over at least 70%, even more preferably over at least 90%, in particular over
- the continuous introduction is carried out so that the corresponding device for gaseous introduction (addition) of the hydrogen halide over the aforementioned periods in operation.
- a "recurring introduction of gaseous hydrogen halide" of the hydrogen halide is understood to mean that the appropriate gaseous introduction (addition) takes place at regular or irregular intervals .
- the time intervals between the individual additions are at least 1 h, preferably at least one day
- the term "recurring” furthermore means at least two, for example 3, 4, 5, 10 or also 100 individual additions.
- the concrete number of individual additions depends on the duration of operation. This ideally goes against infinity.
- a recurring introduction of gaseous hydrogen halide in the context of the present invention is understood to mean the addition of a plurality of partial amounts of metal halide with a time delay.
- the addition of a single subset 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 subset is at least ten times as long as the duration of the addition of the corresponding subset.
- the embodiment of a "recurring addition” with the embodiment of a “continuous addition” may also be combined with one another.
- the gas phase in the device (V1) is connected via a shut-off device to a reservoir, the reservoir containing at least 90 mol%, particularly preferably more than 98 mol%, of the hydrogen halide and a pressure which is greater than the hydrogen halide partial pressure of the gas phase in the device (V1).
- the gaseous hydrogen halide is introduced from a reservoir into the device (V1), wherein a shut-off device, preferably a valve or a tap, is located between the device (V1) and the reservoir.
- a shut-off device preferably a valve or a tap
- the pressure in the gas phase (over the reaction mixture) in the device (V1) recurrently, but preferably continuously measured, when falling below a (predetermined) threshold value for the pressure, the obturator open, while when exceeded the threshold value for the pressure the shut-off valve is closed again.
- the pressure in the device (V1) be kept constant by using a two-point control system acting on a shut-off device to a hydrogen halide reservoir.
- further phases (A and B) are contained, which together form the liquid reaction mixture.
- further phases may also be present in the liquid reaction mixture.
- the 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 .-%.
- 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.
- the hydrogen halide (HX) is contained in both phase (A) and phase (B).
- phase (A) mixtures of two or more ionic liquids may be contained, preferably the phase (A) contains an ionic liquid.
- the phase (A) contains an ionic liquid.
- other components which are miscible with the ionic liquid can also be present in the phase (A).
- phase (A) may also contain cocatalysts used in isomerization reactions using ionic liquids.
- cocatalysts are the hydrogen halides already mentioned above, 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.
- the proportion of ionic liquid is greater than 80 wt .-%.
- 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).
- phase (B) depends on the chosen chemical reaction method. Phase (B) undergoes a change in composition during a chemical reaction process.
- 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 metal halide is added to the device (V1) during the chemical reaction, preferably during the isomerization.
- the addition of the metal halide is thus in addition to the introduction (addition) of the gaseous hydrogen halide (HX).
- the addition of the metal halide in the device (V1) can be carried out in a recurring or continuous manner.
- the anion of the ionic liquid and the metal halide are identical 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 halogen components of ionic liquid, the hydrogen halide (HX) and the metal halide match.
- the ionic liquid used in the device (V1) contains, for example, Al 2 Cl 7 as an anion, it is possible to use AICI 3 as the metal halide.
- AICI 3 As the metal halide.
- mixed-component anions such as, for example, Al 2 BrCl 6 "
- the metal component of the anion is corresponding ionic liquid contains two or more components such as 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 repeated or continuous. In this case, 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 together with the or said component (s) in the device (V1) out (indirect addition of the metal halide according to (V1)).
- the (over) guiding or (over) guiding the metal halide together with the mentioned component (s) from the other device into the device (V1) takes place according to the methods known to the person skilled in the art, for example using pumps.
- 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 one Number of individual additions depends on the operating time. 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 a single 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
- Metal halide thus takes place when the metal halide concentration has fallen below the above limits.
- the periodic addition of the metal halide is such that the aforementioned saturation-related metal halide concentrations in phase (B) are constantly maintained.
- 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 phase (B). Furthermore, it is preferred that the metal halide and the gaseous hydrogen halide (HX), preferably AICI 3 and hydrogen chloride, are added simultaneously to the device (V1).
- the device (V1) contains the following phases: 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 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.
- a stream are discharged, in which the phase (B) and the phase (A) are contained, wherein in the phase (B) at least one hydrocarbon is contained which was produced during the chemical reaction.
- This current in turn is preferably introduced into a 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. Furthermore, it is preferred that the reactor or the stirred tank cascade and optionally the phase separation device are coupled on the gas side.
- 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.
- a first stream comprising at least 70% by weight, preferably at least 90%, of the phase (A) and a second stream containing at least 70%, preferably at least 90%, of the phase (B) are preferably present in the phase separation apparatus. separated from each other.
- 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 crossflow filter.
- a device (V3) for FesW-liquid or liquid / liquid separation apparatus in the contact device (V2) integrated, 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) flows through the recirculated phase (A), which originates from the above-described phase separation device, in particular the phase separator, and (V2) is located between the phase separation device and the device (V1) (V2), if appropriate downstream of a device (V3) for solid / liquid separation or liquid / liquid separation.
- 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
- phase (A) means phase (A), with the corresponding major component of that phase in parentheses (in the present case, ionic liquid presented in device (V1))
- B means phase (B), where "KW1” represents a first hydrocarbon mixture and "KW2" for a second hydrocarbon mixture which is formed in the device (V1) in the context of a chemical reaction, preferably an isomerization, from KW1.
- the reacted at least one hydrocarbon-containing phase B (KW1) is continuously fed into the device (V1), optionally in addition a metal halide (MX) in (V1) is introduced.
- V1 contains, under operating conditions, liquid reaction mixture and a gas phase in contact with it. This is connected via the obturator (AO) with the reservoir (R), which contains a gas which consists of more than 90 mol%, more preferably more than 98 mol%, of the hydrogen halide and a pressure above the pressure of Has gas phase over the reaction mixture.
- AO obturator
- R which contains a gas which consists of more than 90 mol%, more preferably more than 98 mol%, of the hydrogen halide and a pressure above the pressure of Has gas phase over the reaction mixture.
- a pressure measuring device which is connected to a control device. The entirety of pressure measuring device and control device is referred to in Fig. 1 as (PC).
- PC controls the position of the obturator (AO) in such a way that when falling below a threshold value for the pressure, the obturator is opened, on exceeding a threshold value for the pressure, the obturator is closed.
- AO obturator
- Ionic liquid (A) having the composition (CH 3 ) 3 NHAl 2 Cl 7 , a 15 hydrocarbon mixture (B) with the components methylcyclopentane, cyclohexane, n-hexane and isohexane and additionally, for the example according to the invention, gaseous HCl.
- the ionic liquid is hereinafter also referred to as "IL" and the hydrocarbon mixtures B and B1 as "organic” or "organic phase”.
- the ionic liquid (CH 3 ) 3 NHAl 2 Cl 7 is initially charged at 60 ° C. in a 250 ml double-walled stirred reactor (V1).
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (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 et d'un halogénure d'hydrogène (HX). La réaction chimique se déroule dans un dispositif (V1). Dans ce dispositif (V1) se trouve une phase gazeuse en contact direct avec un mélange réactionnel liquide. La phase gazeuse et le mélange réactionnel liquide contiennent respectivement l'halogénure d'hydrogène et le mélange réactionnel liquide contient de plus au moins un hydrocarbure et le liquide ionique. Le HX gazeux est introduit dans le dispositif (V1) afin de maintenir à un niveau constant la pression partielle d'halogénure d'hydrogène dans la phase gazeuse. Au moyen du procédé selon l'invention, il est (entre autres) possible de régénérer du liquide ionique usagé, en particulier pendant une isomérisation.
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CN201480012605.0A CN105189416A (zh) | 2013-03-07 | 2014-02-27 | 在恒定卤化氢分压下的化学转化方法 |
EP14707376.1A EP2964594A1 (fr) | 2013-03-07 | 2014-02-27 | Procédé de réaction chimique à pression partielle constante d'halogénure d'hydrogène |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3946088A (en) * | 1974-10-11 | 1976-03-23 | Exxon Research & Engineering Co. | Hydrocarbon isomerization process |
WO2011069929A1 (fr) * | 2009-12-07 | 2011-06-16 | Basf Se | Procédé d'isomérisation d'un hydrocarbure saturé |
WO2011069957A1 (fr) * | 2009-12-07 | 2011-06-16 | Basf Se | Procédé d'isomérisation d'un hydrocarbure saturé, ramifié et cyclique |
-
2014
- 2014-02-27 WO PCT/EP2014/053889 patent/WO2014135445A1/fr active Application Filing
- 2014-02-27 CN CN201480012605.0A patent/CN105189416A/zh active Pending
- 2014-02-27 EP EP14707376.1A patent/EP2964594A1/fr not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3946088A (en) * | 1974-10-11 | 1976-03-23 | Exxon Research & Engineering Co. | Hydrocarbon isomerization process |
WO2011069929A1 (fr) * | 2009-12-07 | 2011-06-16 | Basf Se | Procédé d'isomérisation d'un hydrocarbure saturé |
WO2011069957A1 (fr) * | 2009-12-07 | 2011-06-16 | Basf Se | Procédé d'isomérisation d'un hydrocarbure saturé, ramifié et cyclique |
Non-Patent Citations (1)
Title |
---|
BERENBLYUM A S ET AL: "The nature of catalytic activity and deactivation of chloroaluminate ionic liquid", APPLIED CATALYSIS A: GENERAL, ELSEVIER SCIENCE, AMSTERDAM, NL, vol. 315, 23 November 2006 (2006-11-23), pages 128 - 134, XP028001951, ISSN: 0926-860X, [retrieved on 20061123], DOI: 10.1016/J.APCATA.2006.09.013 * |
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