Kinetic studies of upgrading pine pyrolytic oil by hydrotreatment

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Abstract

Pyrolytic oil, produced by the Tech-Air Corporation from Southern Pine sawdust and bark, was hydrotreated in a trickle bed reactor system. Changes in product composition as a function of reaction temperature, hydrogen pressure, space velocity and catalyst type were determined quantitatively by size exclusion chromatography - gas chromatography (SEC-GC) analyses and elemental analyses. The catalysts used in the reactions were Pt/Al2O3/SiO3, and sulfided CoMo/γ-Al2O3, Ni-W/γ-Al2O3 and Ni-Mo/γ-Al2O3. The reaction temperatures ranged from 623 K to 673 K, and the reaction pressures varied from 5,272 kPa (750 psig) to 10,433 kPa (1,500 psig). Weighthourly space velocity was changed from 0.5 to 3.0 h−1.

Two models, one for overall oxygen removal and the other for the compositional changes in hydrotreated oil, were developed. Oxygen removal was not a function of space velocity and was modeled by an empirical function of temperature and pressure. A pseudo first order reaction network was used to relate the kinetics of a five “lump” model.

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    The authors have done two types of studies in two different models, one for the complete deoxygenation and second for the composition of the hydrotreated oil. Similarly, Rupp et al. [214] employed hydroprocessing of fast pyrolysis oil over conventional CoMo, NiMo catalysts. Another attempt was made for analyzing the effect of temperature, hydrogen partial pressure and dwelling time on HDO of pyrolysis oil in micro packed bed reactor over NiMo/Al2O3 catalyst [105].

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