The catalytic transformation over a HZSM-5 zeolite of key components of the liquid product obtained by the flash pyrolysis of biomass, namely, acetaldehyde, ketones (acetone and butanone), and acetic acid, has been studied, and great differences in reactivity and degradation to coke have been found. Acetaldehyde has a low reactivity to hydrocarbons, with a noticeable deactivation caused by coke deposition, which can be attributed to its capacity for oligomerization with the trimer trimethyltrioxane obtained as an intermediate product. The transformation of ketones [less reactive than the alcohols studied in part I of this work (see the preceding paper in this issue)] and of acetic acid (which gives rise to acetone as the primary product) mainly occurs through decarboxylation and, to a lesser degree, dehydration. Above 400 °C, this transformation gives olefins and aromatics according to a reaction scheme similar to that better known for the reaction of alcohols. The generation of coke (attenuated by the presence of water in the reaction medium) is more significant than in the corresponding process for alcohols, and it limits the formation of aromatics and increases the formation of olefins (intermediate products of the reaction scheme).

The effects of temperature and space time on the transformation over a HZSM-5 zeolite catalyst of several model components of the liquid product obtained by the flash pyrolysis of vegetable biomass (1-propanol, 2-propanol, 1-butanol, 2-butanol, phenol, and 2-methoxyphenol) have been studied. The transformation of alcohols follows a route similar to that of methanol and ethanol toward the formation of hydrocarbon constituents of the lumps of gasoline and light olefins. Phenol and 2-methoxyphenol have a low reactivities to hydrocarbons, and the deposition of coke of thermal origin caused by the condensation of 2-methoxyphenol is noticeable. The generation of catalytic coke and the deactivation by this cause attenuate as the space time and water content in the feed are increased. To avoid the irreversible deactivation of the HZSM-5 zeolite, operations must be carried out at a temperature below 400°C. Above this temperature, the increase in product aromaticity is also significant.

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The transformation of crude bio-oil to hydrocarbons has been studied in an online thermal catalytic process that is comprised of two steps: the thermal treatment reactor, followed by the catalytic reactor. The deposition of pyrolytic lignin formed by the polymerization of biomass-derived products is enhanced in the thermal step. Volatiles are processed in a fluidized-bed reactor with a catalyst that is hydrothermally stable and selective for aromatic production, which is based on a HZSM-5 zeolite modified by the incorporation of 1 wt % of nickel. The effect of operating conditions (temperature, space time, and time-on-stream), as well as feedstock ratio, on bio-oil conversion, product lump yields, and the selectivity of aromatics has been studied. These conditions also have a significant effect on deactivation, which is attributed to coke deposit on the catalyst. The temperature-programmed oxidation (TPO) curves of coke combustion allow the identification of two fractions: one of thermal origin (pyrolytic lignin) and the other of catalytic origin, whose formation is dependent on the concentration of oxygenates in the reaction medium. A feed with 60 wt % methanol, at 450 °C, with a space time of 0.371 (g of catalyst) h (g of oxygenates)−1 allows one to obtain 90 wt % conversion of the bio-oil in the feed in the catalytic transformation step, with a selectivity of aromatics of 0.4 (benzene, toluene, xylenes (BTX) selectivity of 0.25). These results remain almost constant in the first hour of reaction. The yields of CO and CO2 are low, because their formation is attenuated by co-feeding methanol.

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The effect of the operating conditions (temperature, space time, and time-on-stream) has been studied in the catalytic transformation of the aqueous fraction of the biomass pyrolysis oil obtained in a conical spouted bed reactor under atmospheric pressure. The results show that (i) the deactivation by coke (reversible) of the HZSM-5 zeolite catalyst is similar to the deactivation of the same catalyst in the transformation of light oxygenates (such as methanol and ethanol) and (ii) the deactivation attenuates as space time is increased. The results of product distribution are in agreement with those obtained in the transformation of the pure oxygenates contained in the pyrolysis oil. In experiments conducted following reaction-regeneration (by coke combustion) cycles, it has been proven that (i) at the reaction temperature of 450 °C, deactivation by dealumination of the zeolite in the reaction stage is important and (ii) this deactivation is due to the high water content in the reaction medium. This dealumination causes an irreversible deterioration of the total acidity, although the acid strength of the remaining sites is hardly modified.

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