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| Naji, M. |
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| Motta, Antonella |
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| Aletan, Dirar |
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| Mohamed, Tarek |
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| Ertürk, Emre |
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| Taccardi, Nicola |
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| Kononenko, Denys |
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| Petrov, R. H. | Madrid |
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| Alshaaer, Mazen | Brussels |
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| Bih, L. |
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| Casati, R. |
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| Muller, Hermance |
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| Kočí, Jan | Prague |
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| Šuljagić, Marija |
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| Kalteremidou, Kalliopi-Artemi | Brussels |
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| Azam, Siraj |
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| Ospanova, Alyiya |
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| Blanpain, Bart |
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| Ali, M. A. |
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| Popa, V. |
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| Rančić, M. |
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| Ollier, Nadège |
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| Azevedo, Nuno Monteiro |
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| Landes, Michael |
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| Rignanese, Gian-Marco |
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Gardini, Diego
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Publications (4/4 displayed)
- 2014Intermetallic compounds of Ni and Ga as catalysts for the synthesis of methanolcitations
- 2014Intermetallic compounds of Ni and Ga as catalysts for the synthesis of methanolcitations
- 2014Electron microscopy study of the deactivation of nickel based catalysts for bio oil hydrodeoxygenation
- 2012Origin of low temperature deactivation of Ni5Ga3 nanoparticles as catalyst for methanol synthesis
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document
Electron microscopy study of the deactivation of nickel based catalysts for bio oil hydrodeoxygenation
Abstract
Hydrodeoxygenation (HDO) is proposed as an efficient way to remove oxygen in bio-oil, improving its quality as a more sustainable alternative to conventional fuels in terms of CO2 neutrality and relative short production cycle [1].<br/>Ni and Ni-MoS2 nanoparticles supported on ZrO2 show potential as high-pressure (100 bar) catalysts for purification of bio-oil by HDO. However, the catalysts deactivate in presence of sulfur, chlorine and potassium species, which are all naturally occurring in real bio-oil.<br/>The deactivation mechanisms of the Ni/ZrO2 have been investigated through scanning transmission electron microscopy (STEM), energy dispersive X-ray spectroscopy (EDX), scanning electron microscopy (SEM) and X-ray diffraction (XRD). Catalytic testing has been performed using guaiacol in 1-octanol acting as a model compound for bio-oil.<br/>Addition of sulphur (0.3 vol% octanethiol) in the feed resulted in permanent deactivation of the catalyst by formation of a catalytically inactive Ni-S phase, as suggested by the very similar spatial distribution of nickel and sulphur signals in STEM-EDX elemental maps (Figure 1) and confirmed by XRD and X-ray absorption spectroscopy (XAS) techniques.<br/>Deactivation by chlorine (0.3 vol% chlorooctane) co-feeding was found to be reversible, as the catalyst could regain close to its initial deoxygenation activity upon restoration of a clean feed. SEM-EDX investigations excluded the presence of chlorine species; however, XRD analysis revealed sintering of nickel nanoparticles (Figure 2).<br/>Impregnating KCl and KNO3 on two different batches of catalysts decreased permanently their deoxygenation activity, suggesting the adsorption of potassium at low coordinated nickel sites [2]. The high mobility of potassium under the electron beam [3] prevented the spatial distribution study of this element through STEM-EDX. Moreover, nickel sintering was observed in the KCl poisoned sample and was ascribed once again to the formation of mobile Ni-Cl species upon reaction of HCl with surface oxides [4].<br/>Furthermore, environmental transmission electron microscopy (ETEM) has been used in order to investigate the oxidation of Ni-MoS2/ZrO2 catalyst active phase as a function of different HDO reaction conditions and using methanol as a model molecule for bio-oil.