Abstract Liquid phase synthesis of one of the important fuel oxygenate, Ethyl tert -butyl ether (ETBE) from ethanol and tert -butyl alcohol (TBA) has been studied in reactive distillation column (RDC) using ion exchange resin catalyst CT-145H. A packed RDC was used to generate experimental data. Effect of different key variables on reactant conversion and product purity in distillate, was investigated to find the optimum operating conditions for ETBE synthesis. The optimum conditions found were; reboiler duty of 375 Watts, molar feed ratio of reactants, 1:1.3 and reflux ratio of seven. Concentration profiles for each component along the length of the column at optimum conditions were also drawn. Index Terms —ETBE synthesis, ion exchange resin catalyst, packed column, reactive distillation 1. INTRODUCTION The ever-increasing numbers of gasoline driven vehicles have necessitated the requirement for an efficient fuel oxygenate as well as octane booster. Due to water solubility problem, MTBE is going to be banned in some parts of U.S; therefore, the alternative ethers are being worked out as fuel additives. Among the alternatives of MTBE, TAME and ETBE are considered next generation fuel oxygenates that fulfill the requirements of being efficient and environment friendly. ETBE has better blending as well as environmental characteristics like high blend octane rating of 111, low blend Ried vapor pressure of 27.8 kPa, low oxygen contents of 15.7 % and low water solubility of 23.7mg/l [1]. Mostly ETBE has been synthesized by exothermic reversible reaction between Isobutylene (IB) and ethanol (EtOH) [2]-[5], but the availability of IB is limited. It is only produced in refinery using catalytic and steam cracking operations. Therefore, alternative routes to synthesize ETBE are under substantial consideration. By far the most important substitute of IB is tert-butyl alcohol (TBA) which is a by-product of propylene oxide Manuscript received July 2, 2008. (Write the date on which you submitted your paper for review.) This work was supported by the Higher Education Commission (HEC) of Pakistan under indigenous scholarship scheme. M. Umar is with the University of Engineering and Technology, Lahore , 54890, Pakistan (corresponding author: phone: +92 345 4641847, fax: +92 42 9250202 e-mail: bazaidumar@ gmail.com). A.R. Saleemi is with Department of Chemical Engineering, University of Engineering and Technology, Lahore , 54890, Pakistan as Professor and head of the Department. (e-mail: darsaleemi@yahoo.com). N. Feroz is with Department of Chemical Engineering, University of Engineering and Technology, Lahore , 54890, Pakistan as Professor. S. Qaiser is with Department of Chemical Engineering, University of Engineering and Technology, Lahore , 54890, Pakistan as PhD student. production in ARCO process. ETBE can be synthesized by direct reaction of TBA and EtOH in the presence of catalyst according to following reactions O H ETBE EtOH TBA 2 (1) This main reaction is also accompanied by two side reactions. O H IB TBA 2 (2) ETBE EtOH IB (3) Major side reaction is dehydration of TBA into IB and water (EQ. 2). As IB exist only in gaseous state at the atmospheric pressure experimental conditions, so backward reaction in equation 2 and reaction in equation 3 can safely be neglected. Reactive distillation (RD) is considered most suitable process for equilibrium limited chemical reactions such as esterification and etherification. There are number of works available for ETBE synthesis via RD using IB and EtOH on various catalysts [4]-[7]. There are fewer works available for ETBE synthesis using TBA and EtOH [3], [8]-[9]. There are even fewer research efforts available in open literature mentioning the ETBE synthesis via RD in packed column and those too emphasize on top and bottom product analysis for effect of different operating variables. Therefore, main objective of this study was to optimize the operating parameters for synthesis of ETBE in packed RD column using ion exchange resin catalyst CT-145H, found most suitable during batch kinetic and residue curve map studies [10]-[11]. Concentration profiles of each component along the length of the column are presented for each condition. 2. EXPERIMENTAL 2.1 Materials Tert -butanol (>99%GLC), ethanol (98±1% GC), iso-propanol (99.8%GC) were purchased from local market manufactured by Merck Germany. ETBE (97% GC) was purchased from Fisher Chemicals UK. Purity of all these chemicals was verified by gas chromatography and after confirmation; these were used without further purification. Ion exchange resin catalyst CT-145H was provided by Purolite ® International Limited and it was used after proper pre-treatment. 2.2 Column and Packing All the reactive distillation experiments were carried out in a packed glass column. QVF ® glass columns of 0.0508 m diameter and 0.3048 m length were assembled to erect the reactive distillation column. Schematic of the reactive distillation column is shown in Figure 1. Total height of the column was 1.22 m, in which stripping and rectification Synthesis of Ethyl tert-Butyl Ether in Packed Reactive Distillation Column Using Macroporous Ion Exchange Resin Catalyst Muhammad Umar, Anwar, R. Saleemi, Nadeem Feroz, Suleman Qaiser Proceedings of the World Congress on Engineering and Computer Science 2008 WCECS 2008, October 22 - 24, 2008, San Francisco, USA ISBN: 978-988-98671-0-2 WCECS 2008