Bio-oil
produced from the thermochemical treatment of lignocellulosic
biomass is increasingly recognized as a potentially abundant source
of renewable chemicals and fuels. Single ring phenolics and low molecular
weight carboxylic acids are significant constituent compound groups
found in bio-oil and are important end products or intermediate commodity
chemicals. Fractionation of bio-oil using supercritical fluids (usually
with CO2 as a solvent) is a relatively new process being
investigated worldwide at both laboratory and pilot scales. Solubility
data associated with supercritical carbon dioxide (scCO2) and the many chemical compounds in the complex bio-oil mixture
are required to predict the extraction behavior of different bio-oil
compounds. This article starts with a review of the composition of
bio-oil in terms of the phenolic and low molecular weight carboxylic
acid fractions which are potentially of commercial interest. Binary
solubility data of major compounds in these bio-oil fractions with
supercritical CO2 are summarized and discussed. Results
from previously reported studies in which scCO2 is used
as a solvent to recover bio-oil fractions are reviewed and collated.
Density and temperature-based Chrastil type models are developed using
available data for the solubility in scCO2 of some of the
major bio-oil compounds. Finally, extraction of compounds from the
complex bio-oil mixture is discussed in terms of the trends predicted
by the respective individual binary solubility models.
This study focused
on understanding the relationship between dicarboxylic
acid (DCA) yields derived from lignin and the structural attributes
of their solid residues and corresponding acid-soluble lignin fractions.
It is a continuation of the study by the authors on DCA production
from bagasse lignin via hydrothermal liquefaction. It characterized
the residues derived from the use of H2O2/chalcopyrite
and sodium percarbonate for DCA formation, at temperatures between
60 and 300 °C with a reaction time of 3 h. FTIR, GPC, and 2D
NMR were used to unravel the functional group changes, molecular weight
distribution, and lignin substructures and linkages. The DCA yield
correlated well, in a linear fashion, to the aromatic to aliphatic
functional group ratio (AAFGR) and the degree of aromatic condensation
(DAC). Supporting evidence of lignin depolymerization and repolymerization
to explain the DCA yields was provided by GPC. Interestingly, the
proportion of the α-oxidized substructure S′ was found
to be an indicator of the extent of lignin depolymerization, and its
ratio to the S substructure was found to correlate with DCA yield
at reaction temperatures up to 200 °C.
Supercritical
fluid extraction (SFE) and fractionation of products
from a complex mixture such as bio-oil, where many compounds are present
in low concentrations, is a difficult process to model. This difficulty
arises from the uncertainty associated with those interactions between
mixture components for which fundamental vapor–liquid equilibrium
(VLE) data are not available. In this work a novel extraction and
purification concept is investigated using a predictive model developed
from VLE data of binary solute–solvent systems; solute–solute
interactions in the supercritical carbon dioxide (scCO2) phase are neglected. The predictive component of the work employs
an equation of state (EOS) model to achieve the above task. The results
of pilot plant trials utilizing a biocrude feedstock were shown to
be in good agreement with the model predictions. Aspen Plus process
simulations were developed for the extraction process which comprised
supercritical extraction and subsequent purification steps utilizing
distillation and multistage evaporation. A techno-economic analysis
of different process designs were evaluated for comparison. In particular,
distillation as the primary separation process with and without multistage
evaporation were simulated to compare the economics of supercritical
extraction to distillation. It was found from simulation results that
distillation is a very energy intensive process, and total operating
costs for it are always greater than supercritical extraction counterparts.
Combining multistage evaporation with distillation will bring the
total operating cost slightly lower than supercritical extraction
processes. However, the internal rate of return (IRR) value was similar
for both SFE and distillation combined with multistage evaporation
processes. Solvent/bio-oil (S/B) ratio will have considerable impact
on total profits of SFE process in relation to distillation combined
with multistage evaporation.
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