Classifications

• • 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
  • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
  • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
  • C07C2521/04—Alumina
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
  • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • C07C2521/08—Silica
• • 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
  • C07C2529/00—Catalysts comprising molecular sieves
  • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
  • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2529/00—Catalysts comprising molecular sieves
  • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
  • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y

Definitions

• the invention concerns a preparation process for 1- (2-methylbutyl)-4-methyl- benzene, in which p-xylene is alkylated with l-butene using a basic catalyst.
• the invention is especially focusing on the use of some special catalysts.
• 1- (2-methylbutyl)-4-methylbenzene can be used as a raw-material in chemical synthesis. For instance in the petrochemical industry it can be used as a raw- material for the preparation of 2,6-dimethyl-naphthalene.
• One possibility for preparing 1- (2-methylbutyl)-4-methylbenzene or l-(p-toluyl)-2- methylbenzene is to alkylate one of the methyl groups in p-xylene with l-butene.
• basic catalysts especially alkali metals, are the most suitable ones.
• the catalyst is supported on a solid carrier.
• Especially potassium carbonate has been used as a carrier.
• a common catalyst system has been solid sodium dispersed on the surface of potassium carbonate.
• the problem has been a rather poor selectivity. Different alkylbenzenes are obtained and they are difficult to separate from each other. Furthermore, l-butene easily dimerizes.
• alkali metal catalyst systems have been proposed in order to improve the selectivity of the alkyiation of p-xylene.
• the alkali metals for instance Na, K, their combinations
• the metal compounds for instance elementary, oxide, hydr ⁇ oxide
• the carriers for instance K2CO3, AI2O3, silica
• the selectivity can be improved by different types of promotors (for instance organo- metal compounds).
• promotors for instance organo- metal compounds.
• a selective heterogeneous catalyst is used, which catalyst is a zeolite impregnated with an alkali metal like sodium, a supported hydrotalcite or a supported CsOH.
• the process can be continuous, and a solid bed catalyst can be used.
• the selectivity of the process is good.
• the zeolite which is impregnated with an alkali metal can for instance be X or Y faujasite.
• the support for hydrotalcite or CsOH can be for instance Si ⁇ 2, AI2O3 or a zeolite.
• the reaction can take place for instance at a temperature of 100-350°C and a pressure of 1-3 bar.
• the temperature can preferably be 150-350°C and the pressure is preferably 1-3 bar.
• the catalyst is hydrotalcite or CsOH the temperature can preferably be 100-300°C.
• a zeolite which has been impregnated with an alkali metal can preferably be prepared so that
• the zeolite is impregnated with an alkali metal azide after which it is heated to about 450°C
• the zeolite is impregnated with the vapour of an alkali metal or
• the zeolite is impregnated with an alkali metal solution like a solution with ammo ⁇ nia or a solution with tetrahydrofurane which contains naphthalene.
• an intermediate product usually a carbanion, is obtained in the alkyl chain and in this way the side chain is alkylated.
• a selective heterogeneous alkylating catalyst is used which catalyst is a zeolite that has been impregnated with alkali metal, hydrotalsite or CsOH.
• zeolite active alkali metal clusters can be created for instance in the following ways:
• metal clusters can already be seen from the change in colour, and this observation can be confirmed by using ESR-spectroscopy.
• the form and position of the clusters in the zeolite structure can be studied by using diffractometric techniques.
• Alkali metal clusters on the surface of a zeolite can be considered as Br ⁇ nstedt- bases, and they act as active centers in base catalyzed reactions of hydrocarbons.
• a most useful preparation process for a zeolite catalyst is azide impregnation and thermal decomposition. It has been observed that both steps are rather complicated. Part of the azide is enclosed into the pores of the zeolite and obtains a significant thermal stability. As a result a system with many different kinds of chemical compounds is obtained.
• a 30% solution was made by dissolving 0.384 mol NaN3 in water. 100 g LZ-Y52 zeolite powder was added under efficient agitation. The water was evaporated at 80°C and the solid material obtained was stored in the vessel.
• a 13 X zeolite powder made in Hungary was saturated with a NaN3 solution so that materials were obtained which contained 4 or 10% NaN3/zeolite-g.
• the saturation was carried out in a water solution.
• 35.49 g granulated 13 zeolite (UC) was ion exchanged according to Example 4 using 700 and 600 ml 0.1 mol 1 CsCl solution. CsOH was precipitated onto the ion exchanged material according to Example 4.
• Hydrotalcite was made by co-precipitating Al and Mg hydroxide.
• Mg-Al-C ⁇ 3 In order to synthesize 3.1 [Mg-Al-C ⁇ 3] one prepared two solutions: 14.07 g A1(N03) 3*9H2 ⁇ and 28.85 g Mg(N03) 2*6H2 ⁇ was dissolved in 250 ml distilled water (solution A) and 10.59 g Na2C ⁇ 3 and 13.5g NaOH was dissolved in 250 ml distilled water (solution B).
• Solutions A and B were combined by dropping at a speed of 100 ml/min under continuous agitation. At the same time pH was controlled to 8.5+0.05. The agitation was continued for 48 h after which the gel was treated under hydrothermal conditions at 180°C. The crystalline material obtained was filtrated and washed. From the water containing material obtained a suspension with a solids content of 50% was made, and 100 g of a silica gel with large pores was added to this suspension. The water was evaporated and the solid material was dried.
• Absolute tetrahydrofurane was made by drying with NaA zeolite and distilling it from sodium in an argon phase. Finally the tetrahydrofurane treated in this way was distilled from ketene in an argon phase and the product was used immediately.
• the reaction between p-xylene and l-butene was performed in a medium pressure continuous reactor at a temperature of 100-350°C and a pressure of 1-10 bar, most preferably 3-8 bar.
• the volume flow rates of the reactants were between 1500- 4000h " 1 , most preferably 1000-2000h " ] , for l-butene and 3000-3500h _ 1 for p- xylene.
• l-butene and p-xylene were fed at a rate of 2000 and 3000h " .
• the results are presented as a summary in the table below.
• the reaction between p-xylene and 1 -butene was performed in a Berty-type reactor, in which a longer contact time can be used.
• the volume flow rate of l-butene was 100-300h " most preferably 200-250h " and the volume flow rate of p-xylene was 300-500h " , most preferably 450-500h " .
• the pressure was kept between 1-3 bar. The results are presented in the table below.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Cited By (1)

Citations (1)

• 1995
  • 1995-12-29 FI FI956325A patent/FI956325A0/fi not_active Application Discontinuation
• 1996
  • 1996-12-27 WO PCT/FI1996/000699 patent/WO1997024305A1/en active IP Right Grant
  • 1996-12-27 JP JP9524048A patent/JP2000502692A/ja active Pending
  • 1996-12-27 EP EP96943148A patent/EP1019343A1/en not_active Withdrawn
  • 1996-12-27 AU AU12702/97A patent/AU1270297A/en not_active Abandoned
  • 1996-12-27 KR KR1019980705037A patent/KR100516491B1/ko not_active IP Right Cessation

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