高圧接触還元による高級アルコール製造時に生成する炭化水素について

抄録

Authors investigated the hydrocarbons which were generated in the process of catalytic reduction of fatty ester to obtain higher alcohol under high pressure H₂.
Methyl palmitate, cetyl alcohol and cetyl acetate were treated under high pressure H₂ (initial pressure 100200atm.) in the existence of various kinds of catalysts, such as Cu-Cr-O, Zn-Al-O, Zn-Cr-O, Fe-Al-O, Fe-Cu-Al-O, Fe₂O₃, reduced Fe, ZnO, Al₂O₃, CuO, Cr₂O₃ and Raney Ni (W-7).
The amount and the constituent of generated hydrocarbon depended on catalyst used and reaction temperature. In the case of reduced Fe and metal oxides, the generation of hydrocarbon having 16 carbons, considered to be produced by dehydration of the alcohol, was preferential to the generation of hydrocarbon having 15 carbons, considered to be produced by elimination of methylol group from alcohol.
The order of its priority was as follows, Fe-Cu-Al-O>ZnO, CuO, reduced Fe, Al₂O₃>Zn-Cr-O, Fe-Al-O>Cr₂O₃, Fe₂O₃>Cu-Cr-O.
In the case of Cu-Cr-O catalyst, there was no appreciable difference in the amount of both hydrocarbons generated.
On the other hand, in the case of Raney Ni the generation of C₁₅ hydrocarbon was predominant, and the generation of C₁₆ hydrocarbon was almost the same as those of C₁₄ and less carbon number hydrocarbons.
In spite of the presence of high pressure H₂, the content of olefin in hydrocarbon formed increased in such order as Fe-Al-O<Zn-Al-O<Zn-Cr-O<Cr₂O₃<ZnO<Al₂O₃<Fe₂O₃.
At the same reaction temperature, about 300°C, the ease of generation of hydrocarbon was as follows,
Raney Ni>Cu-Cr-O>Fe-Cu-Al-O>reduced Fe>Fe-Al-O>Zn-Al-O, ZnO>Cr₂O₃>CuO>Fe₂O₃, Zn-Cr-O, Al₂O₃.
The optimum reaction temperature to produce higher alcohol was different by each of the catalyst and the amount of hydrocarbon formed increased in such order as Fe-Al-O>Zn-Al-O>Zn-Cr-O>Cu-Cr-O.