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
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/20—Carbon compounds
  • B01J27/232—Carbonates
• • 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
• • 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
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/06—Halogens; Compounds thereof
  • B01J27/08—Halides
  • B01J27/10—Chlorides
• • 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
  • 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
  • C07C2527/20—Carbon compounds
  • C07C2527/232—Carbonates

Definitions

• the object of the present invention was to provide a process for the side chain alkylation of alkyl aromatics with monoolefins which is distinguished by good space yields and high selectivity.
• Catalysts in which the alkali metal chloride in the inorganic substance is potassium chloride are preferred according to the invention.
• small amounts of other salts, preferably alkali metal salts can be tolerated in the inorganic substance, their content generally not exceeding 5% by weight and in particular 1% by weight.
• at least 95% by weight of the inorganic substance consists of a mixture of potassium chloride and potassium carbonate.
• the inorganic substance particularly preferably consists exclusively of potassium carbonate and potassium chloride, apart from the impurities typically contained in these salts.
• sodium has proven particularly useful as an alkali metal, which may contain up to 5% by weight of other metals, such as are usually found in technical sodium, for example potassium, calcium or strontium.
• technical grade sodium is used, which usually contains less than 1% by weight of the above-mentioned metals as impurities.
• the inorganic substance used to produce the alkali metal catalyst has an average grain size below 1000 ⁇ m, in particular below 200 ⁇ m and particularly preferably in the range from 10 to 100 ⁇ m.
• a carrier material is therefore used which is obtained by grinding the components potassium carbonate and alkali metal chloride. The grinding can be carried out in the equipment customary for this purpose, such as ball mills, Retsch or impact body mills.
• the mixing of alkali metal and inorganic substance is carried out under inert conditions, e.g. B. under an inert gas such as nitrogen or argon or under an inert gas mixture, the inert gas usually containing less than 500 ppm oxygen and less than 100 ppm water.
• inert conditions e.g. B. under an inert gas such as nitrogen or argon or under an inert gas mixture, the inert gas usually containing less than 500 ppm oxygen and less than 100 ppm water.
• Examples of such compounds are mono-, di- and tri -CC-C 3 alkylbenzenes such as toluene, xylenes, methylnaphthalenes, mesitylene, ethylbenzenes and isopropylbenzenes, where the latter two types of compounds can also have one or two further methyl groups.
• Derivatives of benzene or naphthalene in which two alkyl radicals are together with the aromatic ring to which they are attached form an alicyclic ring which may optionally also have an oxygen atom. Examples of such compounds are 1,2,3,4-tetrahydronaphthalene, indane and chroman.
• Suitable monoolefins for the process according to the invention are in particular those having 2 to 10 and particularly preferably those having 2 to 5 carbon atoms. Examples include ethene, propene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene and 3-methyl-1-butene. Particularly preferred monoolefins are ethene and propene.
• the process according to the invention can be used, for example, to react cumene with ethene to give tert-amylbenzene, toluene with ethene to give n-propylbenzene, to convert xylenes with 1- or 2-butene to the corresponding tolylpentanes and particularly preferably to react with toluene Propene to be used isobutylbenzene.
• the reaction of the monoolefin with the alkyl aromatics I according to the invention is generally carried out at elevated temperature, ie. H. at temperatures above room temperature, preferably above 80 ° C and in particular above 100 ° C.
• the reaction temperature in the process according to the invention will not exceed 300 ° C., preferably 250 ° C. and in particular 200 ° C.
• the reaction is particularly preferably carried out below 180 ° C. and very particularly preferably below 160 ° C., for example at 120 ° C. to 140 ° C.
• the process according to the invention can be carried out both in the gas phase and in the liquid phase.
• the monoolefin can also be introduced in gaseous form into the liquid reaction phase which contains the alkali metal catalyst and the alkylaromatic I.
• the reaction is preferably carried out in a liquid reaction phase.
• the liquid reaction phase can also contain a solvent in addition to the starting materials
• Reaction conditions are inert. Examples include aliphatic and alicyclic hydrocarbons such as octane, hexane, cyclo- hexane, cyclooctane and decalin. However, it is preferred to work in bulk, ie the liquid reaction phase contains only the liquid feed components and the alkali metal catalyst.
• the feedstocks generally contain less than 1000 ppm and very particularly preferably less than 100 ppm water.
• the oxygen content of the starting materials is generally below 500 ppm and particularly preferably below
• the reaction can be carried out both under an inert gas atmosphere and under the vapor pressure of the liquid reaction phase.
• the reaction is particularly preferably carried out in a fully
• the monoolefin is preferably used in a molar deficit, based on the alkylaromatic I.
• the molar ratio of monoolefin to alkyl aromatic preferably does not exceed a value of 0.8, in particular 0.6 and particularly preferably 0.5.
• the molver is preferably
• the method according to the invention can be designed as a batch method and as a continuous method.
• the batch method will be carried out in such a way that the alkyl aromatic and the alkali metal catalyst are initially charged and the monoolefin, preferably in, under the reaction conditions liquid form, according to its consumption. In this way, it is achieved that the monoolefin is in a deficit in the reaction mixture, based on the alkylaromatic I.
• the reaction is stopped by cooling the reaction mixture, the alkali metal catalyst is separated off and the mixture is worked up in the usual manner, preferably by distillation.
• the process according to the invention is preferably carried out continuously.
• the feedstocks are passed continuously under reaction conditions through a reaction zone charged with the catalyst.
• the alkali metal catalyst can be in the form of a fixed bed in the reaction zone. However, it is preferably in the form of a suspension in the liquid reaction phase.
• the liquid reaction phase is preferably agitated intensively, turbines, for example, anchor stirrers, impeller or preferably at rotational speeds of> 500 U / min -1 and in particular> 800 U / min -1.
• the starting materials can be fed into the reactor both in one stream and in separate streams.
• the rate at which the feed materials are fed into the reactor naturally depends on the reactivity of the feed materials and the catalyst.
• the feed rate is preferably in the range from 0.05 to 5 kg of starting materials per kg of catalyst mass and hour, in particular in the range from 0.1 to 1 kg / h per kg of catalyst mass.
• a molar ratio of mono-olefin to alkylaromatic I below 1 is preferably chosen, and in particular in the range from 1:10 to 1: 2 and especially in the range from 1: 4 to 2: 3.
• the catalyst will generally be separated from the reaction phase and worked up by distillation. Residues of catalyst that are still in the reaction phase due to incomplete removal of the catalyst are generally deactivated before working up, for example by adding water and / or alkanols such as methanol, ethanol or isopropanol. If the reaction is carried out continuously, the procedure will generally be such that a quantity of liquid reaction phase corresponding to the amount supplied is discharged from the reactor and worked up in the manner described above.
• the liquid reaction phase is preferably discharged with extensive or complete retention of the alkali metal catalyst in the reaction space.
• the catalyst is retained, for example, by means of suitable filters or separators such as cross flow filters, candle filters, membranes or learning sets.
• the liquid reaction phase is separated into the product of value, by-products such as the dimerization product of the monoolefin, optionally solvent and excess alkyl aromatic.
• the excess alkyl aromatic I which may be obtained is preferably returned to the process.
• the process according to the invention provides the desired alkyl aromatics with high selectivity and good space-time yields.
• the process according to the invention shows itself compared to processes which use alkali metal catalysts which
• the catalysts used in the process according to the invention are distinguished by a longer service life than conventional catalysts based on alkali metal / potassium carbonate.
• the disruptive formation of tar-like by-products (deposit formation in the reactor)
• Catalyst A 10.8 g sodium on 70 g potassium carbonate (not according to the invention).
• Catalyst B 10.8 g sodium on a mixture of 35 g potassium chloride and 35 g potassium carbonate (according to the invention).
• Catalyst C 10.8 g sodium on 70 g potassium chloride (not according to the invention).
• the reaction was carried out continuously in a stirred tank reactor with an internal volume of 270 ml, which was equipped with a magnetically coupled stirrer with an impeller turbine.
• the reactor each contained the catalyst suspension and was flooded with the mixture of liquid propene and toluene before the start of the reaction.
• the reactor was heated to 130 ° C. and stirred at speeds in the range from 1,000 to 1,200 rpm. 0.132 mol / h dry liquid propene and 0.316 mol / h dry toluene were fed continuously into the reactor.
• the reaction discharge was drawn off via a 4 ⁇ m filter and analyzed for the content of the products by means of online gas chromatography.
• Tables 1 to 3 below show the results for run times in the range from 10 to 100 hours.
• T toluene
• IBB isobutylbenzene
• nBB n-butylbenzene
• ⁇ indan
• P propene
• Kat catalyst
• GC gas chromatogram
• RZA space-time yield in g (IBB) / (g (Kat) » h) 2 )
• Selectivity calculated from GC peak area% on the basis that the relative peak area corresponds to the percentage by weight.
• T toluene
• IBB isobutylbenzene
• nBB n-butylbenzene
• I indan
• P propene
• Kat catalyst
• GC gas chromatogram
• RZA space-time yield in g (IBB) / (g (Kat) «h) 2 ) Selectivity calculated from GC peak area%, based on the fact that the relative peak area corresponds to the percentage by weight ,

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• 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)

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• 2001
  • 2001-05-08 WO PCT/EP2001/005217 patent/WO2001085652A1/de not_active Application Discontinuation
  • 2001-05-08 CN CN01808822A patent/CN1427810A/zh active Pending
  • 2001-05-08 US US10/258,944 patent/US20030097033A1/en not_active Abandoned
  • 2001-05-08 JP JP2001582254A patent/JP2003532694A/ja not_active Withdrawn
  • 2001-05-08 EP EP01929628A patent/EP1280748A1/de not_active Withdrawn

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