Byproducts formation in the ethyl tert-butyl ether (ETBE) synthesis reaction on macroreticular acid ion-exchange resins

•Temperature enhances side reactions occurring along with the ETBE synthesis.•Excess of isobutene favors the formation of DEE, ESBE TMP-1 and TMP-2.•High initial molar ratio alcohol/olefin favors the formation of TBA.•At 383K, CT-275 leads to higher productions of ETBE and byproducts than A-35.•ETBE reaction reaches pseudo equilibrium despite simultaneous side reactions. Ethyl tert-butyl ether (ETBE) production is one of the industrial processes of major importance today in Europe. However, the study of side reactions in this synthesis reaction appears scarcely in the open literature. Side reactions take place along with the etherification of C4 olefinic cuts with ethanol, catalyzed by acidic ion-exchange resins. In this work, byproducts formation is studied in a batch reactor. The presence of diethyl ether (DEE), ethyl sec-butyl ether (ESBE), dimers of isobutene (2,4,4-trimethyl-1-pentene (TMP-1) and 2,4,4-trimethyl-2-pentene (TMP-2)) and tert-butyl alcohol (TBA) has been studied in terms of production and selectivity. The effect of temperature, ranging from 323 to 383K, and the influence of initial molar ratio ethanol/isobutene (R°A/O), ranging from 0.5 to 2.0, on byproducts formation have been analyzed. All byproducts formation was favored by high temperatures. A low initial molar ratio ethanol/isobutene favored the formation of DEE, ESBE, TMP-1 and TMP-2, whereas high molar ratios favored TBA formation.