Pore engineered ZSM-5 zeolite in extrudate form was prepared and used as shape-selective catalyst for vapor phase ethylation of ethylbenzene to selectively form para-diethylbenzene. The physico-chemical properties of the catalyst were established by XRD; N-2 sorption, FTIR, FESEM, NH3-TPD and P-31 MAS NMR. Alkylation of ethylbenzene with ethanol was carried out in a continuous, down-flow, tubular reactor, at atmospheric pressure and H-2 as a carrier gas in vapor phase. Effect of silica to alumina ratio (SAR), crystal size, acidity of phosphate modified ZSM-5, stepwise phosphate modification and reaction conditions were studied in detail. ZSM-5 with SAR 187 was found to contain optimum acidity for phosphate modification to achieve good conversion and high selectivity for p-diethylbenzene. Under optimized reaction conditions, viz. temperature = 380 degrees C, ethylbenzene:ethanol mole ratio = 4:1, WHSV = 3 h(-1), H-2/reactants = 2, 5PZSM-5 W catalyst gave 22.8% of ethylbenzene conversion with similar to 98% selectivity for para-diethylbenzene. (C) 2014 Elsevier B.V. All rights reserved.