Exceeding equilibrium conversion with a catalytic membrane reactor for the dehydrogenation of methylcyclohexane

https://doi.org/10.1016/0009-2509(94)E0035-OGet rights and content

Abstract

A catalytic membrane reactor containing a tubular palladium—silver (PdAg) membrane sealed in the centre to separate in situ the hydrogen produced, was used to exceed equilibrium limitations in the dehydrogenation of methylcyclohexane. A sulphided, monometallic, noble metal catalyst produced higher than equilibrium yields of toluene and hydrogen from methylcyclohexane at economically viable throughputs. Experiments in the membrane reactor in the temperature range of 573–673 K, pressure range of 0.5–2.0 MPa and liquid hourly space velocity range of 2–12 volume feed/h/reactor volume showed conversions up to 4 times higher than equilibrium values after 300 h onstream and repeated temperature cycling. Exceeding equilibrium was due to the selective permeation of one of the reaction products, i.e. hydrogen, through the membrane. Reactor axial temperature profiles for the reaction with and without a membrane showed that the total amount of catalyst is more efficiently utilized in the membrane reactor.

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    Therefore, there has been substantial interest in using organic hydride as an energy carrier, whose volumetric energy density is higher than high-pressure hydrogen, and it can be transported in a liquid form under normal conditions of temperature and pressure [7–10]. The organic chemical hydride method for hydrogen storage using hydrogenation and dehydrogenation chemical reactions has been developing recently [11–16]. However, methylcyclohexane and toluene, which are used as organic hydrides, However, methylcyclohexane and toluene, which are used as organic hydrides, have potential toxic effects on humans, and the health effects on residents near a refueling station are unclear.

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Paul Scherrer Institute, CH-5232 Villigen-PSI, Switzerland.

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