(78d) Hydrogen and Chemicals in Millisecond Reactors

Autothermal reactors have great promise for hydrogen and chemicals production because they have reactor residence times of 10-3 seconds and require very simple reactors. We describe the production of hydrogen and olefins from fossil fuels from methane to diesel and from renewable fuels such as ethanol and biodiesel in millisecond reactors. For successful vaporization and mixing of heavy fuels the use of fuel injectors for rapid vaporization and mixing is essential to suppress flames and carbon formation. For ethanol to hydrogen we obtain 80% selectivity to hydrogen at nearly 100% conversion of ethanol and oxygen for an ethanol-air feed. By adding water we obtain 110% (H2 from ethanol and water) in a single stage reactor and 130% H2 selectivity in a staged reactor where a cooler section undergoes the water gas shift reaction. For biodiesel (the methyl ester of C18 fatty acids from soy oil), we can obtain 80% H2 selectivity at C/O=0.8 and 80% selectivity to olefins at C/O=1.5. At higher C/O ratios the ester linkage also survives to produce olefinic esters. Modeling with detailed surface and homogeneous chemistry is used to simulate and understand these processes.