Lattice Oxygen Regulation of Perovskites for Chemical Looping Oxidative Dehydrogenation of Ethylbenzene to Styrene

Abstract

The direct dehydrogenation process produces over 90% of global styrene. However, it is hampered by high energy consumption due to equilibrium limitation, a high steam/ethylbenzene feeding ratio, and complicated separation procedures. In this study, we propose the synthesis of a novel perovskitestructured metal oxide as the redox catalyst for chemical looping oxidative dehydrogenation (CL-ODH) of ethylbenzene into styrene. Lower ethylbenzene activation temperature and higher oxygen storage capacity contributing to high ethylbenzene conversion are achieved by Mn doping of the B site in SrFeO 3−δ , and styrene yield is further enhanced by Ba doping of the A site. The optimized Sr 0.8 Ba 0.2 Fe 0.2 Mn 0.8 O 3−δ catalyst exhibits favorable dehydrogenation activity but is deactivated in the first five redox cycles due to the severe carbonation and perovskite structure decomposition. The decarbonization treatment on the catalyst at 950 °C in an O 2 atmosphere restores the perovskite structure and dehydrogenation activity, resulting in 85% ethylbenzene conversion and 89% styrene selectivity at 550 °C. Ethylbenzene on the catalyst undergoes full combustion via adsorbed oxygen, ODH of ethylbenzene into styrene and H 2 O using lattice oxygen, and direct dehydrogenation without available lattice oxygen. The proposed redox catalyst demonstrates efficient conversion of ethylbenzene into styrene, showing great potential for the energy conservation and process intensification of styrene production.

Kinetics of Redox Half-Cycles on Bi2O3 for the Selective Catalytic Combustion of Hydrogen

“…9,10 A novel application of chemical looping, which has gained renewed interest, 11−15 is selective hydrogen combustion (SHC), in which hydrogen is selectively oxidized in a mixture of hydrocarbons. A strategy to surpass thermodynamic limitations in endothermic reactions, such as the catalytic dehydrogenation of ethylbenzene 12,16 or propane, 13 involves coupling of the dehydrogenation reaction with an exothermic SHC step to enable autothermal reactor operation.…”

“…Redox cycles are ubiquitous in catalysis and are commonly encountered in applications such as NO x abatement , and in hydrocarbon partial oxidation. − Chemical looping processes, which involve explicit separation of the reduction and oxidation half-cycles of a redox reaction, have found applications in air separation, the production of chemicals, , and the selective removal of molecules in mixtures. , A novel application of chemical looping, which has gained renewed interest, − is selective hydrogen combustion (SHC), in which hydrogen is selectively oxidized in a mixture of hydrocarbons. A strategy to surpass thermodynamic limitations in endothermic reactions, such as the catalytic dehydrogenation of ethylbenzene , or propane, involves coupling of the dehydrogenation reaction with an exothermic SHC step to enable autothermal reactor operation.…”