On the Activity and Selectivity of CoAl and CoAlCe Mixed Oxides in Formaldehyde Production from Pulp Mill Emissions

Contaminated methanol has very good potential for being utilized in formaldehyde production instead of its destructive abatement. The activities, selectivities and stabilities of cobalt-alumina and cobalt-alumina-ceria catalysts prepared by the hydrotalcite-method were investigated in formaldehyde production from emissions of methanol and methanethiol. Catalysts were thoroughly characterized and the relationships between the characterization results and the catalytic performances were drawn. The preparation method used led to the formation of spinel-type structures in the form of Co2AlO4 based on x-ray diffraction (XRD) and Raman spectroscopy. Ceria seems to be present as CeO2, even though interaction with alumina is possible in the fresh catalyst. The same structure is maintained after pelletizing the cobalt-alumina-ceria catalyst. The cobalt-alumina-ceria catalyst was slightly better in formaldehyde production, probably due to lower redox temperatures and higher amounts of acidity and basicity. Methanol conversion is negatively affected by the presence of methanethiol; however, formaldehyde yields are improved. The stability of the pelletized catalyst was promising based on a 16 h experiment. During the experiment, cobalt was oxidized (Co2+ -> Co3+), cerium was reduced (Ce4+ -> Ce3+) and sulfates were formed, especially on the outer surface of the pellet. These changes affected the low temperature performance of the catalyst; however, the formaldehyde yield was unchanged.