期刊
FUEL
卷 321, 期 -, 页码 -出版社
ELSEVIER SCI LTD
DOI: 10.1016/j.fuel.2022.124009
关键词
Hydrogen; Steam reforming; Bio-oil; Oxygenates reforming; Coke deposition; Catalyst deactivation
资金
- Ministry of Science and Innovation of the Spanish Government - MCIN/AEI [RTI2018-100771-B-I00]
- Ministry of Science and Innovation of the Spanish Government - ERDF A way of making Europe
- European Commission [823745]
- Department of Education, Universities and Investigation of the Basque Government [IT1645-22, IT1218-19, PRE_2021_2_0147]
This study investigates the influence of oxygenate composition in bio-oil on catalyst deactivation due to coke deposition. The results show that the morphology, structure, and location of coke have a greater impact on catalyst stability than its content. Pyrolytic and amorphous coke deposition leads to rapid deactivation in the steam reforming of guaiacol, while the presence of carbon nanotubes in the steam reforming of aliphatic oxygenates only causes slight deactivation. Increasing the temperature significantly reduces coke deposition but has minimal impact on deactivation.
The catalyst stability, mainly affected by coke deposition, remains being a challenge for the development of a sustainable process for hydrogen production by steam reforming (SR) of bio-oil. In this work, the influence of oxygenates composition in bio-oil on the deactivation by coke of a NiAl2O4 spinel derived catalyst has been approached by studying the SR of a wide range of model oxygenates with different functionalities, including acetic acid, acetone, ethanol, acetaldehyde, acetol, catechol, guaiacol and levoglucosan. A fluidized bed reactor was used in the following conditions: 600 and 700 degrees C; steam/carbon ratio, 3 (6 for levoglucosan); space-time, 0.034 gcatalyst h/gbio-oil (low enough to favor the rapid catalyst deactivation), and; time on stream, 5 h. The spent catalysts were analyzed with several techniques, including Temperature Programed Oxidation (TPO), X-ray Diffraction (XRD), N2 adsorption-desorption, Scanning and Transmission Electron Microscopy (SEM, TEM) and Raman Spectroscopy. The main factors affecting the catalyst stability are the morphology, structure and location of coke, rather than its content, that depend on the nature of the oxygenate feed. The deposition of pyrolytic and amorphous coke that blocks the Ni sites inhibiting the formation of filamentous carbon causes a rapid deactivation in the guaiacol SR. Conversely, the large amount of carbon nanotubes (CNTs) giving rise to a filamentous coke deposited in the SR of aliphatic oxygenates only causes a slight deactivation. The increase in the temperature significantly reduces coke deposition, but has low impact on deactivation.
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