EP1373168A2 - Procede d'alkylation ou d'alkenylation de chaine laterale - Google Patents

Procede d'alkylation ou d'alkenylation de chaine laterale

Info

Publication number
EP1373168A2
EP1373168A2 EP01980242A EP01980242A EP1373168A2 EP 1373168 A2 EP1373168 A2 EP 1373168A2 EP 01980242 A EP01980242 A EP 01980242A EP 01980242 A EP01980242 A EP 01980242A EP 1373168 A2 EP1373168 A2 EP 1373168A2
Authority
EP
European Patent Office
Prior art keywords
catalyst
reaction
side chain
alkali metal
distillation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01980242A
Other languages
German (de)
English (en)
Inventor
Ulrich Steinbrenner
Ralf Böhling
Peter Zehner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1373168A2 publication Critical patent/EP1373168A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J23/04—Alkali metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/72—Addition to a non-aromatic carbon atom of hydrocarbons containing a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C07C2523/04—Alkali metals
    • 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
    • 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
    • C07C2527/20—Carbon compounds
    • C07C2527/232—Carbonates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/949—Miscellaneous considerations
    • Y10S585/95—Prevention or removal of corrosion or solid deposits

Definitions

  • the invention relates to a process for reducing the formation of polymers in the case of side chain alkylation or side chain alkenylation of alkylaromatic compounds.
  • No. 2,448,641 describes a ner driving in particular for the side chain alkylation of toluene.
  • 0.1 to 20% of an alkali metal, based on toluene, is used as the catalyst. It is described that the catalyst can be separated from the reaction product by filtration, whereupon the product is purified by fractional distillation. Sodium is used as the preferred catalyst.
  • No. 3,291,847 describes in particular the potassium-catalyzed alkylation of toluene with propene.
  • Potassium, sodium or a sodium-potassium alloy together with graphite on sodium carbonate are used as the catalyst.
  • the catalyst is formed in situ in particular in the reactor. It is described that the combination of the alkali metal with graphite and the support in the reactor does not form a brown tar-like polymer, which is the case without the use of a catalyst support. It is described that the catalyst can be removed from the reaction mixture after the reaction by filtration.
  • the catalyst can also be inactivated or reacted with a polar compound such as an alcohol. Unreacted starting materials can be recovered and returned to the implementation. According to the examples, the catalyst in the reaction mixture is deactivated by quenching with an alcohol.
  • No. 4,914,250 relates to a process, in particular for the alkenylation of toluene with propene in the presence of a supported potassium or potassium alloy catalyst using sodium hydroxide or potassium hydroxide as co-catalyst.
  • suitable carrier materials are diatomaceous earth, activated carbon, carbon, silicon dioxide, aluminum oxide etc. After the reaction, the catalyst is deactivated by reaction with methanol.
  • the object of the present invention is to provide a process for reducing the formation of polymers in the case of side chain alkylation or side chain alkenylation of alkylaromatic compounds.
  • the object is achieved according to the invention by a process for reducing the formation of polymers in the side chain alkylation or side chain alkenylation of alkylaromatic compounds by reaction with olefins or diolefins in the presence of an alkali metal catalyst and subsequent distillation to obtain the alkylated or alkenylated compound, the alkali metal in the catalyst is present on an inorganic support and the catalyst is mechanically separated from the reaction mixture after the reaction and before the distillation. This means that only the organic phase mechanically separated from the catalyst is fed to the distillation without the catalyst having been protolysed.
  • (spent) mechanically separated catalyst can be protolysed, an organic phase formed during the protolysis not being returned to the distillation. It has also been found that the use of alkali metal carbonates, alkali metal halides or mixtures thereof as catalyst supports allows the alkali metal catalyst to be completely separated from the reaction mixture by simple filtration.
  • the mechanical separation of the catalyst is preferably carried out using a mixer-settler, settier, filter or cross-flow filter, depending on the particular design of the reaction apparatus.
  • the alkali metal catalyst can thus be completely removed from the reaction mixture before the reaction mixture is distilled. This largely, preferably completely, prevents the formation of tar-like polymers in the distillation apparatus.
  • the catalyst support is particularly preferably selected from K CO 3 , K 2 CO 3 / KCl and K 2 CO 3 / NaCl.
  • the alkali metal applied to the carrier is preferably sodium, potassium or a NaK alloy. Sodium is preferably used on the carrier.
  • the preparation of the supported catalyst is known and can be carried out, for example, as described in DE-A-197 15 203.
  • the catalyst preferably has 0.5 to 20, in particular 1 to 15,% by weight of metallic sodium and / or potassium, based on the total catalyst.
  • the catalyst is prepared from alkali metal and support at temperatures above 100 ° C. before being used in the reaction. It can also be formed with hydrogen and / or alkyl aromatic compounds at temperatures above 100 ° C.
  • the reaction can be carried out batchwise or preferably continuously.
  • Suitable apparatus are stirred tank reactors, stirred tank cascades, stirred columns, loop reactors, cascades of loop reactors or similar devices.
  • the catalyst can be used as a suspension or moving bed (fluidized bed), preferably as a suspension. As described above, the catalyst is preferably retained by a mixer settler, a settier, a filter, a crossflow filter or a similar process engineering unit. Filter devices are particularly preferably used.
  • the residence time of the catalyst in the reaction stage is significantly longer compared to the organic phase, that is, the catalyst is retained and used until loss of activity.
  • the product mixture is separated by distillation. Unreacted starting materials can be returned to the reaction.
  • the alkylated or alkenylated product can then be further purified by further processes, for example by fractional distillation, fractional crystallization, extraction, etc.
  • the reaction is preferably carried out continuously in the suspension mode, the catalyst being retained in the reactor.
  • the reaction is preferably carried out with vigorous stirring.
  • the reaction is generally carried out at a temperature of -50 to 400 ° C., preferably at a temperature of -20 to 300 ° C., particularly preferably 80 to 250 ° C., in particular 100 to 200 ° C. and a pressure of preferably 0, 1 to 200, particularly preferably 1 to 150, in particular 1 to 100 bar, preferably in the liquid phase without a gas phase.
  • alkyl aromatics can be used as alkyl aromatic compounds. They can have, for example, a benzene or naphthalene nucleus as the aromatic nucleus.
  • Alkylalicyclic compounds in which the cyclic nucleus can be a cyclic alkyl, alkenyl or alkynyl radical are also suitable. Residues in which several of the ring restrictions are linked can also be used.
  • the link structures have an acidic hydrogen atom in the ⁇ -position of the side chain. They preferably have at least one alkyl radical which is bonded to the cyclic structure.
  • the alkyl radicals can have any length and can be substituted by further substituents.
  • alkylaromatic Verbindunden benzenes o- by 1 to 6, preferably 1 to 3, in particular 1 to 2 C ⁇ - 2, preferably 3 -Al C ⁇ - yl radicals are substituted naphthalenes substituted by 1 to 10, preferably 1 to 5 , particularly preferably 1 to 2 C ⁇ . 2 o-, preferably C ⁇ . 3 alkyl radicals are substituted, and the alkylalicyclic compounds employed cyclopentenes or cyclohexenes by 1 to 5, preferably 1 or 2, or 1 to 6, preferably 1 to 3, especially 1 or 2 C 1 - 20 -, preferably C ⁇ . 3 alkyl radicals are substituted.
  • the olefins preferably have 2 to 20, particularly preferably 2 to 10, in particular 2 to 5, carbon atoms. Ethene, propene, 1-butene, 2-butene, iosbutene, 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene and / or 3-methyl-1-butene are preferably used , Ethene and propene are particularly preferred.
  • the diolefms preferably have 4 to 20, particularly preferably 4 to 10, in particular 4 to 6, carbon atoms. Butadiene and / or isoprene are particularly preferably used.
  • reaction of toluene with ethene or propene to give propylbenzene or isobutylbenzene, the reaction of cumene with ethene to give tert-amylbenzene and the reaction of xylenes with butadiene to give 5-tolylpentenes are particularly preferred.
  • Used catalyst can be removed from the reactor, protolysed and then disposed of.
  • the addition of salt to the alkali metal in conjunction with a filter can prevent alkali metal from escaping from the reactor into the work-up stage, where it would lead to major technical and safety-related problems.
  • the invention also relates to the use of alkali metal catalysts supported on an inorganic support in the side chain alkylation or side chain alkenylation of alkylaromatic compounds by reaction with olefins or diolefins and subsequent distillation to reduce the formation of polymers during distillation.
  • reaction discharge 75 ml of the reaction discharge were mixed with 15 ml of 30% aqueous NaOH and heated to 250 ° C. in a glass pressure autoclave with stirring for 72 h.
  • the organic phase turned slightly yellow and there were no visible deposits either.
  • EtOH / H 2 O was added to the contents of the steel autoclave under argon and the organic phase (88 g, composition see table 1) was heated to 250 ° C. in a glass pressure autoclave with stirring for 72 h.
  • the solution turned deep brown and black, sticky, tar-like deposits formed.
  • Table 1 Composition of the organic phases according to GC analysis

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé destiné à réduire la formation de polymérisats lors de l'alkylation de chaîne latérale ou de l'alkénylation de chaîne latérale de composés alkylaromatiques par transformation d'oléfines ou de dioléfines en présence d'un catalyseur à métal alcalin, et distillation consécutive pour la production des composés alkylés ou alkénylés. Selon l'invention, le métal alcalin du catalyseur est situé sur un support minéral, et le catalyseur est séparé mécaniquement du mélange de réaction après transformation et avant distillation.
EP01980242A 2000-08-17 2001-08-10 Procede d'alkylation ou d'alkenylation de chaine laterale Withdrawn EP1373168A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10040184 2000-08-17
DE10040184A DE10040184A1 (de) 2000-08-17 2000-08-17 Verfahren zur Seitenkettenalkylierung oder -alkenylierung
PCT/EP2001/009296 WO2002014241A2 (fr) 2000-08-17 2001-08-10 Procede d'alkylation ou d'alkenylation de chaine laterale

Publications (1)

Publication Number Publication Date
EP1373168A2 true EP1373168A2 (fr) 2004-01-02

Family

ID=7652726

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01980242A Withdrawn EP1373168A2 (fr) 2000-08-17 2001-08-10 Procede d'alkylation ou d'alkenylation de chaine laterale

Country Status (6)

Country Link
US (1) US6984766B2 (fr)
EP (1) EP1373168A2 (fr)
JP (1) JP2004529846A (fr)
CN (1) CN1454193A (fr)
DE (1) DE10040184A1 (fr)
WO (1) WO2002014241A2 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004009549B4 (de) * 2004-02-24 2005-12-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Durchführung von basisch katalysierten Reaktionen
CN114950400A (zh) * 2022-06-02 2022-08-30 青岛科技大学 一种碱金属复合材料及其制备方法和应用

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2448641A (en) * 1946-02-27 1948-09-07 Du Pont Alkylation of cyclic unsaturated hydrocarbons using alkali metal catalyst
US3291847A (en) * 1964-01-02 1966-12-13 Phillips Petroleum Co Catalytic alkylation of alkyl-substituted aromatics with monoolefins
GB1269280A (en) * 1969-08-05 1972-04-06 Bp Chem Int Ltd Process for the production of alkyl aromatic hydrocarbons
US4914250A (en) * 1988-06-17 1990-04-03 Ethyl Corporation Coupling process
US5329058A (en) * 1990-04-25 1994-07-12 Teijin Limied Process for producing alkenylbenzene
US5104843A (en) * 1990-11-13 1992-04-14 Ethyl Corporation Catalyst composition for coupling process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0214241A2 *

Also Published As

Publication number Publication date
WO2002014241A3 (fr) 2002-06-27
CN1454193A (zh) 2003-11-05
WO2002014241A2 (fr) 2002-02-21
JP2004529846A (ja) 2004-09-30
US6984766B2 (en) 2006-01-10
US20040106834A1 (en) 2004-06-03
DE10040184A1 (de) 2002-02-28

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