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Etherification of 1-hexene with 1-propanol and 1-butanol representative of bioalcohols was performed in a liquid-phase continuous-flow process over a fixed bed of zeolite beta catalyst. Contact time and reaction temperature were optimized to maximize conversion and limit deactivation. The catalyst was stable for at least 14 h on stream. In the conversion of 1-hexene with 1-propanol, zeolite beta catalyst showed over 90 % selectivity for 2-propoxyhexane. In the conversion of 1-hexene and 1-butanol, 2-butoxyhexane was selectively formed. Dialkyl ether from the alcohol and dodecenes and hexanol from 1-hexene were the main side products. As 1-alkenes and terminal alcohols can be synthesized from biomass, this hydroalkoxylation process could be used for grading up green chemicals to high-boiling solvents and renewable ethers for the diesel pool. [ABSTRACT FROM AUTHOR]

1-Hexene was ethoxylated with ethanol and ethanol–water mixtures mimicking bioethanol in a liquid phase, continuous flow process over a fixed bed of zeolite beta catalyst at a reaction temperature of 423 K and a pressure of 6 MPa. The selectivity for ethoxy alkanes on a hexene basis exceeded 90%. GC-MS, 1H & 13C-NMR and 13C DEPT NMR confirmed the main reaction products to be 2-ethoxy hexane and 3-ethoxy hexane in molar ratio 20 : 1. Side products were diethyl ether from ethanol and dodecenes and hexanol from 1-hexene. Under optimized reaction conditions, the catalyst was stable for at least 14 hours on-stream. The 2-ethoxylation activity of 1-alkenes by zeolite beta was confirmed in reactions with 1-octene and 1-decene. 1-Alkenes can be synthesized out of biomass via conversion into synthesis gas and the Fischer–Tropsch process. The here presented ethoxylation process could contribute green chemicals to the diesel pool and presents a pathway for synthesis of high boiling solvents. [ABSTRACT FROM AUTHOR]