The main objective of the present work was the evaluation of commercial ZSM-5 catalysts (diluted with a silica–alumina matrix) in the in situ upgrading of lignocellulosic biomass pyrolysis vapours and the validation of their bench-scale reactor performance in a pilot scale circulating fluidized bed (CFB) pyrolysis reactor. The ZSM-5 based catalysts were tested both fresh and at the equilibrium state, and were further promoted with cobalt (Co, 5% wt%) using conventional wet impregnation techniques. All the tested catalysts had a significant effect on product yields and bio-oil composition, both at bench-scale and pilot scale experiments, producing less bio-oil but of better quality. Incorporation of Co exhibited no additional effect on water or coke production induced by ZSM-5, compared to non-catalytic fast pyrolysis. On the other hand, Co addition significantly increased the formation of CO₂ compared to the CO increase which was favored by the use of ZSM-5 alone. These changes in CO₂/CO yields are indicative of the different decarbonylation/decarboxylation mechanism that applies for Co₃O₄ compared to ZSM-5 zeolite, due to the differences in their acidic properties (mainly type of acid sites). Co-promoted ZSM-5 catalysts simultaneously enhanced the production of aromatics and phenols with a more pronounced performance in the pilot-scale experiments resulting in the formation of a three phase bio-oil, rather than the usual two phase catalytic pyrolysis oil (aqueous and organic phases). The third phase produced is even lighter than the aqueous phase and consists mainly of aromatic hydrocarbons and phenolic compounds. Addition of Co in ZSM-5 is thus suggested to strongly enhance aromatization reactions that result in selectivity increase towards aromatics in the bio-oil produced. Possible routes of catalyst deactivation in the pilot plant's continuous operation process have been suggested and are related to pore blocking and masking of acid sites by formed coke (reversible deactivation), partial framework dealumination of the fresh zeolitic catalyst, and accumulative ash deposition on the catalyst that depends on the nature of biomass (content of ash).

Mesopore-modified mordenite zeolitic materials with different Si/Al ratios have been prepared and tested in the biomass pyrolysis and catalytic cracking of vacuum gasoil. Alkaline treatment was carried out to generate mesoporosity. Severity of alkaline treatment was found to be of paramount importance to tune the generated mesoporosity, while it significantly affected the crystallinity of treated mordenites. It was moreover observed that the alkaline treatment selectively extracted Si decreasing the Si/Al ratio of treated samples. Catalytic activity of parent and alkaline treated mordenites was studied in the pyrolysis of biomass. All zeolitic based materials produced less amounts of bio-oil but of better quality (lowering the oxygen content from ∼40% to as much as 21%) as compared to the non-catalytic pyrolysis experiments. On the other hand, it was found that the combination of mesopore formation and high surface area after alkaline treatment of the mordenite with a high Si/Al ratio resulted in the enhancement of its catalytic activity, despite the reduction of its acidity. The increment of the decarboxylation and dehydration reactions, combined with a reduction of carbon deposition on the catalyst, resulted in a remarkable decrease in the oxygen content in the organic fraction and therefore, resulted in a superior quality liquid product. Alkaline treated mordenites were additionally acid treated targeting dealumination and removal of the extra framework debris, thus generating mesopore-modified mordenite samples with stronger acid sites and higher total acidity, as candidate catalysts for catalytic cracking of vacuum gasoil. Desilicated and especially desilicated and dealuminated mordenites exhibited the highest activity and selectivity towards LCO with the best olefinicity in gases and higher bottoms conversion. Therefore, an optimized desilicated–dealuminated mordenite additive could be an interesting candidate as a component of the FCC catalyst for a high LCO yield.

Transition metal oxides have recently attracted considerable attention as candidate catalysts for the complete oxidation of methane, the main component of the natural gas, used in various industrial processes or as a fuel in turbines and vehicles. A series of novel Co-Ce mixed oxide catalysts were synthesized as an effort to enhance synergistic effects that could improve their redox behavior, oxygen storage ability and, thus, their activity in methane oxidation. The effect of synthesis method (hydrothermal or precipitation) and Co loading (0, 2, 5, and 15 wt.%) on the catalytic efficiency and stability of the derived materials was investigated. Use of hydrothermal synthesis results in the most efficient Co/CeO₂ catalysts, a fact related with their improved physicochemical properties, as compared with the materials prepared via precipitation. In particular, a CeO₂ support of smaller crystallite size and larger surface area seems to enhance the reducibility of the Co₃O₄/CeO₂ materials, as evidenced by the blue shift of the corresponding reduction peaks (H₂-TPR, H₂-Temperature Programmed Reduction). The limited methane oxidation activity over pure CeO₂ samples is significantly enhanced by Co incorporation and further improved by higher Co loadings. The optimum performance was observed over a 15 wt% Co/CeO₂ catalyst, which also presented sufficient tolerance to water presence.