Performance and Stability of Metal (Co, Mn, Cu)-Promoted La2O2SO4 Oxygen Carrier for Chemical Looping Combustion of Methane

Abstract

Oxygen carrier materials based on La₂O₂SO₄ and promoted by small amounts (1% wt.) of transition metals, namely Co, Mn and Cu, have been synthesized and characterized by means of X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), Temperature-programmed reduction/oxidation (TPR/TPO) and thermogravimetry-mass-Fourier transform infrared spectrometry (TG-MS-FTIR) experiments under alternating feeds in order to investigate their potential use for the Chemical Looping Combustion process using either hydrogen or methane as the fuel. The chemical looping reactivity is based on the reversible redox cycle of sulfur from S⁶⁺ in La₂O₂SO₄ to S²⁻ in La₂O₂S and entails a large oxygen storage capacity, but it generally requires high temperatures to proceed, challenging material stability and durability. Herein we demonstrate a remarkable improvement of lattice oxygen availability and activity during the reduction step obtained by cost-effective metal doping in the order Co > Mn > Cu. Notably, the addition of Co or Mn has shown a significant beneficial effect to prevent the decomposition of the oxysulfate releasing SO₂, which is identified as the main cause of progressive deactivation for the unpromoted La₂O₂SO₄.