Energy & Fuels, Vol.33, No.9, 9149-9160, 2019
Chemical Looping Hydrogen Generation over Ceria/Zirconia-Enhanced NiO-NiFe2O4 Oxygen Carrier
The objective of this paper is to systematically investigate the influences of different metal modification on the performance of Ni-ferrite as oxygen carrier (OCs) in chemical looping hydrogen (CLH) production. Ni-ferrite OCs were modified with single-metal NiO, bimetallic NiO/ZrO2, and bimetallic NiO/CeO2. The sample was characterized by CO thermogravimetric analysis, X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy, X-ray photoelectron spectroscopy, and Brunauer-Emmett-Teller method. The results showed that NiO could promote the release of oxygen from Ni-ferrite, and the release of oxygen can reach about 99% at 800 degrees C. The addition of ZrO2 and CeO2 could further increase the oxygen release rate of the oxygen carrier, but the oxygen storage amount would decrease. However, the bimetallic modified OCs exhibited higher hydrogen yield, and the hydrogen yields of NiO/ZrO2- and NiO/CeO2-modified Ni-ferrite could reach 9800.0 and 8786.2 mu mol g(oc)(-1), respectively. Furthermore, the bimetallic modified oxygen carrier showed higher structural stability, in which the ZrO2 particles weaken the active particle contact by coating effect, while the CeO2 is mixed into the active particles to form steric hindrance, both of which can inhibit the sintering of the oxygen carrier to maintain structural stability. Finally, the oxygen carrier reaction mechanism is analyzed, and the results show that the oxygen atoms around Ni2+ first migrate through the existing vacancies. And the residual vacancies provided the space for the immigration of other nearby oxygen atoms, which enhanced migration velocity. Moreover, Fe3+ gradually transferred to the adjacent Ni2+ to generate Fe0.64Ni0.36 after its oxygen migration.