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Abstract PURPOSE: To obtain a hydrocarbon in high efficiency, by periodically introducing carbon monoxide to a catalyst layer filled with a specific catalyst and carrying out catalytic reaction of the carbon monoxide under specific condition with hydrogen gas introduced into the layer in advance or with hydrogen gas introduced alternately with the carbon monoxide. CONSTITUTION: A >= 5 C liquid hydrocarbon especially decane, hexadecane, etc., is produced in high yield and efficiency by contacting carbon monoxide and hydrogen with a catalyst. In the above process, the catalyst layer is filled with a catalyst produced by supporting cobalt on a carrier containing alumina magnesia spinel and carbon monoxide is intermittently introduced into the catalyst layer maintained at 220-250oC at a period t (sec) satisfying the formula [t is period (sec); T is temperature (deg.C) of the catalyst layer] while introducing hydrogen into the catalyst layer. As an alternative method, carbon monoxide and hydrogen are alternately introduced at the above period into the catalyst layer maintained at the above temperature |