| Summary: | The purpose of the study was the development of water-resistant catalyst and catalytic processes for the conversion of hydrous ethanol to 1-butanol. Water, in hydrous ethanol, strongly inhibits conversion to 1-butanol on solid catalysts. In this study, the nonstoichiometric P-deficient hydroxyapatite containing carbonate anions (C-HAP), Ca<sub>10−x/2</sub>(PO<sub>4</sub>)<sub>6−x</sub>(CO<sub>3</sub>)<sub>x</sub>(OH)<sub>2</sub>, displayed good performance in the Guerbet condensation of hydrated ethanol to 1-butanol, after proper stabilization of reaction conditions. Hydrous ethanol (96 wt%) was converted on C-HAP formed as extrudates with silica binder at 400 °C and weight jour space velocity (WHSV) = 0.5–1.0 h<sup>−1</sup> to yield 21–23% 1-butanol and 73–74% selectivity. It displayed stable operation for up to 170 h on streams conducted in bench and mini-pilot rigs with catalyst loadings of 2 and 50 cm<sup>3</sup>, respectively. The process simulation employed the recycling of ethanol without laboratory verification to reach 68% theoretical yield of 1-butanol. The techno-economic analysis demonstrated the feasibility of this process, showing that it may be profitable depending on the prices of hydrated ethanol and 1-butanol.
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