Abstract
Catalysts prepared from nickel oxide deposited on kieselguhr, silica, silicaalumina, and alumina were reduced and studied for the conversion of primary alcohols. The alcohols studied were n-propanol, n-butanol, 2-methylbutanol, and 2,2-dimethylbutanol (neopentyl alcohol). The exepriments were made in a pulse reactor in the presence of a flow of hydrogen, at atmospheric pressure and at about 190 °. Three main reactions occur in the presence of a nickel-kieselguhr catalyst: (1) reductive dehydroxymethylation, (2) reductive dehydroxylation, and (3) ether formation. The last two reactions are related to the intrinsic acidic sites of the catalyst. Nickel-kieselguhr catalyst containing 6–10% of nickel gave in the case of n-butanol 73% conversion, with 72 mole % of di- n-butyl ether in the product. The presence of Na + in the catalyst inhibits the formation of ethers, while the dehydroxymethylation reaction increases. A continuous flow reaction at 190 ° demonstrated that nickel-kieselguhr catalyst containing 6% of nickel shows no deterioration after 16 hr of use. At 170 °, with a hydrogen to alcohol ratio of 10 and LHSV of 2, n-butanol reacted to the extent of 89%, with 91% yield of di- n-butyl ether.
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