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n-Butanol is an important industrial chemical usually produced by the oxo process, an expensive, energyconsuming set of reactions over metal catalysts, using petrochemical raw materials at high pressure. We developed nonstoichiometric hydroxyapatite (HAP), a highly active calcium phosphate compound and found it catalyzed selective conversion of ethanol to n-butanol in a single reaction at atmospheric pressure and low temperature, with maximum selectivity of 76%. Higher alcohols were also formed. We postulate that ethanol is adsorbed and activated on HAP as CH 3 CH 2 OH(a) and that a C-C bond was formed between β-C in the CH 3 CH 2 OH(a) and R-C in n-C n H 2n+1 OH to produce n-C n H 2n+1 CH 2 CH 2 OH. We further postulate that, by successive propagation, part of this n-C n H 2n+1 CH 2 CH 2 OH is then adsorbed and activated on HAP as n-C n H 2n+1 CH 2 CH 2 OH(a) and that C-C bond was formed between β-C in the n-C n H 2n+1 CHCH 2 OH(a) and R-C in n-alcohol to produce branched alcohols. Reaction simulation supported this hypothesis, suggesting that efficient, environmentally friendly production of n-butanol might be possible in future using bioethanol as raw material.

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Plant-derived, dehydrated ethanol was effectively converted to biogasoline in a one-step process on a highly active nonstoichiometric hydroxyapatite (HAP) catalyst. The biogasoline had a research octane number of 99 and comprised chiefly hydrocarbons from C6 to C10 as well as oxygenates not generated in the methanol-to-gasoline (MTG) process using zeolite. To confirm a proposed scheme for the synthesis of gasoline from ethanol over HAP, alcohol conversions were carried out using paired combinations of five different alcohols with ethanol. Results indicated that:  (1) normal and branched alcohols were obtained by the Guerbet reaction from normal alcohols, (2) dienes were synthesized by the Lebedev reaction, and (3) aldehydes and olefins were mainly synthesized by dehydrogenation and dehydration of branched alcohols respectively.