Transformation of Oxygenate Components of Biomass Pyrolysis Oil on a HZSM-5 Zeolite. I. Alcohols and Phenols

Abstract

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.

Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering

“…228 Phenol has a low reactivity on HZSM-5 and only produces small amounts of propylene and butanes. 2-Methoxyphenol also has a low reactivity to hydrocarbons and thermally decomposes generating coke.…”

Synergies between Bio‐ and Oil Refineries for the Production of Fuels from Biomass

“…[50,56,57] These feeds have higher H/C eff ratios than would be present in most bio-oils. Nevertheless, these experiments do teach us some of the chemistry involved, as these molecules would be important intermediates in the conversion of biomass-derived molecules into olefins and aromatics.…”

“…Alcohols convert into olefins at temperatures around 200 8C, then into higher olefins at 250 8C, and into paraffins and a small proportion of aromatics at 350 8C. [50,56,57] Phenol has a low reactivity on ZSM-5 and only produces small amounts of propylene and butanes. Both 2-methoxyphenol and acetaldehyde have a low reactivity on ZSM-5 catalysts and undergo thermal decomposition to generate coke.…”

“…Both 2-methoxyphenol and acetaldehyde have a low reactivity on ZSM-5 catalysts and undergo thermal decomposition to generate coke. [56] Acetone, which is less reactive than alcohols, is first dehydrated and then undergoes disproportionation to isobutene at 250 8C and then converts into C 5+ olefins at temperatures above 350 8C. These olefins are then converted into C 5+ paraffins, aromatics, and light alkenes.…”

FCC testing at bench scale: New units, new processes, new feeds

“…Yet the coke yield remained high, and the liquid cracked product, although lower in oxygen, was still considered of low quality with high concentration of aromatics and phenolics [66]. The different component classes found in pyrolysis oil have exhibited very different reactivity and selectivity on ZSM5 catalyst [67][68]. Alcohols will dehydrate rapidly under catalytic cracking operating conditions, giving small olefins.…”