AbstractThis paper compared the performance of β‐zeolite and Amberlyst‐15 catalysts on a liquid phase synthesis of ethyl tert‐butyl ether (ETBE) from ethanol (EtOH) and tert‐butyl alcohol (TBA) β‐Zeolite was synthesized and deposited on monolith support. Its structure was confirmed by an XRD measurement and its composition was analyzed by an XRF measurement. It was found that even though the catalytic activity of β‐zeolite was lower than that of Amberlyst‐15, the selectivity of ETBE was much higher than that of Amberlyst‐15, resulting in almost the same level of ETBE yield. The dehydration of TBA to isobutene (IB) was the major side reaction. The kinetic study of the reaction catalyzed by β‐zeolite supported on monolith was carried out by using a semibatch reactor. The effect of external mass transfer was investigated by varying stirring speeds. The activity‐based rate expressions were developed taking into account of water inhibition. Three temperature levels of 323, 333, and 343 K were performed in the study to obtain the parameters in the Arrhenius's equation and the Van't Hoff's equation. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 292–299, 2002