Applied Catalysis A: General, Vol.238, No.1, 29-40, 2003
Tuning millisecond chemical reactors for the catalytic partial oxidation of cyclohexane
It is demonstrated that millisecond partial oxidation of cyclohexan-e can be tuned by varying the catalyst and operating conditions to generate product distributions that favor (1) oxygenates, (2) olefins, or (3) syngas (H-2 and CO). High selectivities to parent oxygenates require low conversions using low-temperature catalysts, such as Ag or Co. Olefins are favored by Pt or Pt-Sn and H-2 addition eliminates the production of CO and CO2, thereby increasing olefin selectivities. For syngas, Rh is the catalyst of choice. Finally, a Pt-10% Rh single gauze gives high selectivities to both oxygenates and olefins. Conventional methods for the partial oxidation of cyclohexane are liquid-phase processes that are plagued by poor conversions, high recycle costs, long residence times (minutes to hours), and expensive catalysts. In contrast, with a cyclohexane-oxygen feed at C6H12/O-2 = 2, a Pt-10% Rh single gauze catalyst can give total selectivities exceeding 80% to oxygenates and olefins at 25% cyclohexane conversion and complete oxygen conversion. The products consist of nearly 60% selectivity to the C-6 products, cyclohexene and 5-hexenal. The temperature profile attained in the single-gauze reactor allows the preservation of these highly non-equilibrium products. Alternative catalysts for cyclohexane oxidation to oxygenates and olefins include alpha-alumina monoliths coated with Pt, Rh, Pt-Rh, Pt-Sn, Co, Mo or Ag. The Co, Mo and Ag catalysts give very high selectivities to C-6 oxygenates but are hindered by poor conversions (<5%) of both cyclohexane and oxygen at these millisecond contact times. H-2 addition to cyclohexane oxidation feed mixtures over Pt and Pt-Sn is shown to significantly increase the selectivities to C6 olefins while reducing the formation of CO and CO2. Cyclohexane oxidation in air over Rh monoliths enables the production of high yields (>95%) of syngas. This process could find applications in the automotive industry as the production of hydrogen from liquid fuels becomes important.