A novel multifunctional reactor concept has been developed for the production of ultrapure H2
(<10 ppm CO) from light hydrocarbons such as CH4, for online use in downstream polymer
electrolyte membrane fuel cells for small-scale applications (typically 1−50 kW). A high degree
of process intensification is achieved by integrating permselective Pd metallic membranes for
H2 removal (500−600 °C operating temperature) inside a fluidized-bed reactor along with
selective O2 addition through dense perovskite membranes (900−1000 °C operating temperature).
Incorporation of both types of membranes within a single reactor has the clear advantage of
producing ultrapure H2 and pure CO2, circumventing expensive CO2 sequestration. The
membrane-assisted fluidized-bed reactor consists of a partial oxidation bottom section and a
steam reforming/water gas shift top section. Using thermodynamic equilibrium calculations and
more detailed fluidized-bed membrane reactor modeling, it is demonstrated that autothermal
operation with high CH4 conversions and H2 yields can be achieved with a relatively small
catalyst inventory. Moreover, by tuning the feed ratios to the bottom and top sections, the
temperatures in both sections can be effectively controlled for optimal membrane performance.
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