novel phthalocyanine pigments, plasticizers, photographic materials and other valuable products.
-Butylated xylenes are usually manufactured by reacting xylenes in the presence of liquid acid catalysts, with pure isobutylene or C
fraction from naphthacrackers containing isobutylene, giving wide product distribution. These processes suffer from problems associated with the use of highly corrosive liquid acids and also the sourceof isobutylene. The development of a technologically efficient, highly productive andenvironmentally safe method for the synthesis of dimethyl-
-butylbenzene (DMTBB)is challenging. There is a tremendous scope for devising a new catalytic process for thesynthesis of
-butylated xylenes to replace conventional homogenously catalyzed,highly polluting processes. Besides, due to the problems associated with unavailability,transportation and handling of isobutylene, particularly for usage in low-tonnage fine andspeciality chemical industry (typically 10-100 TPA production), it is advantageous togenerate isobutylene
. Dehydration of
-butanol is an attractive source for thesame. Further,
-butanol is available as a by-product in the ARCO process for propylene oxide which could be used effectively for this purpose. We have successfullycarried out
-butylation of several aromatic compounds by using
-butyl ether (MTBE) and isobutene as alkylating agents using ecofriendly solid acidcatalysts.
The only problem which needs to be considered was activity and stability of solid acid catalysts in the presence of water, which is evolved during the reaction.For the past few years, our laboratory is engaged vociferously in the synthesis,characterization and application of selective, ecofriendly and active catalysts such asUDCaT series catalysts, sulfated zirconia, heteropolyacids and their modified versionssupported on clays. In particular, sulfated zirconia has been extensively studied in anumber of reactions
and it should be modified to bring in shape selectivity,mesoporosity and better acidity. Recently we prepared novel mesoporous superacidsnamed as UDCaT-4, UDCaT-5 and UDCaT-6, which are modified versions of zirconiaand have found a great potential for industrially important reactions.
We havereported, for the first time, that a sulfated zirconia, with sulfur content as high as 9% w/w,was produced with preservation of tetragonal phase by using chlorosulfonic acid as a newsource for sulfate ion. It was designated as UDCaT-5. The acronym “UDCaT” symbolizesour research institute, formerly called
), which is now renamed as
). The work summarizes the investigation of activity and selectivity of these new breed of catalyticmaterials in alkylation of xylenes with
-butanol, including reaction kinetics. Thecatalyst can be used as the basis for a high performance and environmentally safe methodfor the synthesis of DMTBB. The model studies were done with
-xylene and thenextended to other xylene isomers.
Experimental SectionChemicals and Catalysts
Pure xylene isomers,
-butanol, zirconium oxychloride, aluminum nitrate,ammonium persulfate and aqueous ammonia solution were procured from Aldrich, USA.Hexadecyl amine and chlorosulfonic acid was purchased from Spectrochem Ltd.Mumbai, India. Tetraethyl orthosilicate (TEOS) was procured from Fluka, Germany. Allchemicals were of analytical reagent (A.R.) grade. These were used as received withoutany further purification.
Preparation of Catalysts