Fuel Processing Technology,
Journal Year:
2023,
Volume and Issue:
249, P. 107860 - 107860
Published: June 2, 2023
Biofuels
upgrading
gathering
momentum
in
view
of
the
gradual
depletion
fossil
fuels
and
pursuit
renewable
energy
sources
to
mitigate
global
warming.
Hydrodeoxygenation
(HDO)
is
a
key
reaction
bio-oil
produce
hydrocarbon
or
high-value
chemicals.
Oxygen
removal
increases
its
calorific
value,
improve
thermal
chemical
stability,
reduce
corrosiveness,
etc.,
making
upgraded
suitable
as
fuel
blending
fuel.
However,
dependence
on
high-pressure
hydrogen
serious
disadvantage,
it
an
expensive
resource
whose
use
also
poses
safety
concerns.
In
this
scenario,
we
propose
pioneering
route
for
model
biomass
compounds
via
H2-free
HDO.
Herein
have
developed
multifunctional
catalysts
based
Ru
ceria
supported
carbon
able
conduct
hydrodeoxygenation
using
water
source.
We
found
that
cerium
oxide
improves
ruthenium
metallic
dispersion
overall
redox
properties
multicomponent
system
leading
enhanced
catalytic
performance.
Along
with
successful
formulation
identify
300
°C
optimal
temperature
validating
HDO
bio-compounds
upgrading.
Energy & Fuels,
Journal Year:
2023,
Volume and Issue:
37(21), P. 16612 - 16628
Published: Oct. 11, 2023
One
of
the
few
similarities
between
petroleum
and
bio-oils
derived
from
biomass
pyrolysis
is
that
they
are
both
complex
organic
mixtures
composed
thousands
distinct
elemental
compositions,
but
oils
uniquely
contain
ultrahigh
oxygen
content
a
more
diverse
collection
chemical
functionalities.
Thus,
their
chemistry
different
fossil
fuels,
advanced
upgrading
strategies
for
coprocessing
such
unique
materials
along
with
conventional
refinery
feeds
will
benefit
comprehensive
knowledge
molecular
composition,
known
as
petroleomics.
The
work
presented
herein
focuses
on
characterization
nonvolatile
species
loblolly
pine
bio-oil
its
hydrotreated
effluents
by
soft
ionization
methods
coupled
to
high-field
Fourier
transform
ion
cyclotron
resonance
mass
spectrometry
(FT-ICR
MS).
Electrospray
(ESI)
facilitates
analysis
polar
oxygen-containing
molecules,
whereas
atmospheric
pressure
(APCI)
enables
access
hydrocarbons.
data
revealed
time-dependent
compositional
changes,
visualized
in
van
Krevelen
diagrams,
highlighted
optimal
catalyst
performance
impacts
fouling
or
deactivation.
Furthermore,
elucidation
features
abundance-weighted
H/C,
O/C,
weight,
aromaticity
facilitated
interpretation
suggested
value-added
likely
produced
upon
concurrent
decrease
content,
aromaticity,
weight
marked
increase
H/C.
temporal
changes
specific
hydrotreatment
reaction
pathways,
including
deoxygenation
hydrogenation,
transalkylation,
cracking
highly
aromatic
lignin-like
oligomers.
detailed
provided
FT-ICR
MS
common
formulas
(those
detected
before
after
upgrading).
Common
hypothetically
recalcitrant
compounds,
which
feature
nature
(low
H/C)
alkyl
deficiency.
Understanding
remaining
species,
critical
future
advances
upgrading.
Energy & Fuels,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 7, 2025
The
highly
complex
nature
of
wood
pyrolysis
bio-oils,
which
contain
thousands
distinct
molecular
species
with
varying
ionization
efficiencies,
poses
a
significant
challenge
for
characterization
by
direct-infusion
high-resolution
mass
spectrometry.
This
study
presents
novel
method
combining
high-performance
liquid
chromatography
(HPLC)
21
Tesla
Fourier
transform
ion
cyclotron
resonance
spectrometry
(21T
FT-ICR
MS)
detailed
bio-oils
within
the
scope
negative-ion
ESI.
HPLC
is
optimized
to
separate
polyfunctional
oxygen-containing
molecules
using
polymeric
stationary
phase
dimethylaminopropyl
functionalities,
and
methanol–water
eluent
dimethylamine.
acidic
compounds
in
equilibrate
between
DEA-containing
mobile
phase,
facilitating
efficient
gradient
elution
oxygen-rich
species.
Coupling
online
21T
MS
revealed
∼3,000
additional
monoisotopic
Ox
formulas
compared
MS.
Newly
detected
exhibited
higher
H/C
ratios
wider
range
oxygen
content,
characteristic
low-molecular-weight
carbohydrates
composition
that
resembles
biomass.
enabled
detection
carbohydrate-like
(O/C
≈
1,
2)
aromatic
(H/C
<
0.6,
O/C
0.3)
were
undetectable
via
direct
infusion.
Early
eluting,
methanol-soluble
showed
(∼1.5
2.0)
content
consistent
lignin
oligomers,
while
later-eluting
increased
aromaticity,
compositions
typical
condensed
Advanced
data
processing
Python-based,
PyC2MC,
software
package
further
compositional
trends
aligned
solubility
bio-oils.
Despite
overlap
LC–MS
infusion
MS,
single
chromatograms
patterns
identical
formulas,
providing
insights
into
potential
isomeric
diversity
are
not
accessible
through
analyses.
These
findings
demonstrate
enhanced
molecular-level
achieved
HPLC-FT-ICR
key
intricate
their
energy
applications.
proposed
approach
provides
unique
perspective
on
distribution
functional
groups,
laying
groundwork
understanding
basis
reactivity
upgrading
As
developed
targets
separation
species,
it
can
also
be
applied
dissolved/natural
organic
matter,
photo-oxidation
products,
emerging
contaminants,
e.g.,
water-soluble
leaching
from
materials
like
asphalt
petroleum-based
road
sealants.
