In several countries forest-based biofuels are being
developed
and to some extent also deployed. Fast pyrolysis bio-oil produced
from, for example, sawdust, has now been coprocessed in fluid catalytic
cracking refinery units in a number of commercial trials. However,
this application is limited to about 10% of the total feed, and coprocessing
in conventional fixed bed hydrotreaters is necessary to reach the
high potential with this feedstock. Feeding and upgrading of fast
pyrolysis bio-oil in a fixed bed reactor configuration is still problematic
due to the inherent bio-oil properties. Stabilization of reactive
compounds in fast pyrolysis bio-oil and mild hydrotreatment in a separate
refining unit prior to refinery integration has therefore been developed
the past decade. Another approach, presented here, involves complete
dewatering of fast pyrolysis bio-oil by azeotropic distillation using
mesityl oxide as the solvent, followed by conversion of the abundant
hydroxyl compounds via mixed anhydride esterification methodology
using an external source of mixed carboxylic acids of different chain
lengths originating from renewable tall oil fatty acids, providing
a lipophilic feed component. Dewatering and derivatizing were carried
out in reactors up to 50 dm3 with a mass ratio of fast
pyrolysis bio-oil to tall oil fatty acid of 10:13. The produced lipophilic
oils were miscible with a petroleum light gas oil fraction and exhibited
superior stability even after accelerated aging at elevated temperature
(80 °C). The derivatized oils were thus mixed with light gas
oil, with a proportion of 30 wt % derivatized oil in final blends
and hydrotreated continuously in pilot fixed bed reactors for 14 days
at 4 operating conditions without plugging or excessive exotherms.
The test conditions were varied; the reactor pressure was either 55
or 80 bar, temperature 380 or 400 °C, and liquid hourly space
velocity either 1 or 2 h–1 during the hydrotreatment.
Successful hydrodeoxygenation and desulfurization were accomplished,
whereas an increasing nitrogen concentration could be observed in
the liquid products with the particular catalyst and reaction conditions
employed. The observed hydrogen consumption (15–20 g/kg feed)
was compared with the stoichiometric consumption for direct deoxygenation
and with typical consumptions for industrial hydrotreated vegetable
oil processing. The measured biogenic carbon content in hydrotreated
liquid products (26.7%) agreed extremely well with the calculated
biogenic carbon content in the hydrotreating feed (26.6%) that consisted
of the blend of derivatized oil and petroleum light gas oil. The overall
results are very promising since simple unit operations can be used
to produce derivatized fast pyrolysis bio-oils that do not need additional
standalone hydrotreating units but can be coprocessed in existing
ones.
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