The valorization of lignin that derives as by product in various biomass conversion processes has become a major research and technological objective. The potential of the production of valuable mono-aromatics (BTX and others) and (alkyl)phenols by catalytic fast pyrolysis of lignin is investigated in this work by the use of ZSM-5 zeolites with different acidic and porosity characteristics. More specifically, conventional microporous ZSM-5 (Si/Al = 11.5, 25, 40), nano-sized (≤20 nm, by direct synthesis) and mesoporous (9 nm, by mild alkaline treatment) ZSM-5 zeolites were tested in the fast pyrolysis of a softwood kraft lignin at 400–600°C on a Py/GC-MS system and a fixed-bed reactor unit. The composition of lignin (FT-IR, 2D HSQC NMR) was correlated with the composition of the thermal (non-catalytic) pyrolysis oil, while the effect of pyrolysis temperature and catalyst-to-lignin (C/L) ratio, as well as of the Si/Al ratio, acidity, micro/mesoporosity and nano-size of ZSM-5, on bio-oil composition was thoroughly investigated. It was shown that the conventional microporous ZSM-5 zeolites are more selective toward mono-aromatics while the nano-sized and mesoporous ZSM-5 exhibited also high selectivity for (alkyl)phenols. However, the nano-sized ZSM-5 zeolite exhibited the lowest yield of organic bio-oil and highest production of water, coke and non-condensable gases compared to the conventional microporous and mesoporous ZSM-5 zeolites.

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Ultrasmall ceria (CeO2) and metal-doped CeO2 nanoparticles in the sub-3 nm size regime were synthesized via a facile, single-step, liquid-phase thermal decomposition reaction in a monosurfactant medium, which plays the role of a solvent and coordination molecule. The nanoparticles were characterized by a combination of techniques including powder X-Ray diffraction, Raman spectroscopy, and high-resolution transmission electron microscopy, and their catalytic activity was tested for the CO oxidation reaction. The results show that all the materials are highly crystalline in the as-synthesized form and monodispersed with a near-spherical shape. N2 sorption studies and porosity analysis confirm that the prepared materials after thermal treatment at 450 °C possess a very high specific surface area, up to 240 m2 g–1, and additionally a hierarchical mesoporous structure. The CeO2 and doped-CeO2 particles demonstrate superior catalytic activity for the low-temperature CO oxidation. Among the different kinds of doping, the Cu–Co co-doped CeO2 nanoparticles are the most active for the CO oxidation (T 50 ≈ 54 °C and E a = 39.5 kJ mol–1) followed by the Cu and Sm-doped CeO2 ones.

Lignin, one of the three main structural biopolymers of lignocellulosic biomass, is the most abundant natural source of aromatics with a great valorization potential towards the production of fuels, chemicals, and polymers. Although kraft lignin and lignosulphonates, as byproducts of the pulp/paper industry, are available in vast amounts, other types of lignins, such as the organosolv or the hydrolysis lignin, are becoming increasingly important, as they are side-streams of new biorefinery processes aiming at the (bio)catalytic valorization of biomass sugars. Within this context, in this work, we studied the thermal (non-catalytic) and catalytic fast pyrolysis of softwood (spruce) and hardwood (birch) lignins, isolated by a hybrid organosolv–steam explosion biomass pretreatment method in order to investigate the effect of lignin origin/composition on product yields and lignin bio-oil composition. The catalysts studied were conventional microporous ZSM-5 (Zeolite Socony Mobil–5) zeolites and hierarchical ZSM-5 zeolites with intracrystal mesopores (i.e., 9 and 45 nm) or nano-sized ZSM-5 with a high external surface. All ZSM-5 zeolites were active in converting the initially produced via thermal pyrolysis alkoxy-phenols (i.e., of guaiacyl and syringyl/guaiacyl type for spruce and birch lignin, respectively) towards BTX (benzene, toluene, xylene) aromatics, alkyl-phenols and polycyclic aromatic hydrocarbons (PAHs, mainly naphthalenes), with the mesoporous ZSM-5 exhibiting higher dealkoxylation reactivity and being significantly more selective towards mono-aromatics compared to the conventional ZSM-5, for both spruce and birch lignin.

Ultra fine cerium oxide and copper doped cerium oxide nanoparticles are prepared in a one-step reaction by thermal decomposition of Ce acetate in commercial oleylamine. The products are highly crystalline and were characterized by XRD, Raman spectroscopy, XPS, TEM and BET. The TEM images show that the CeO2 particles prepared are uniformly nanosized. The size of the nanoparticles can be controlled in the sub-10 nm range by the presence of other capping agent in the reaction mixture such as tri-octylphosphine oxide and oleic acid. The copper doped cerium oxide nanoparticles show high specific surface area (up to 299 m2/gr) and high catalytic activity for the low temperature CO oxidation even at low copper loading such as 9 at.%.

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