energies

Article

Catalytic Pyrolysis of Wild Reed over a Zeolite-Based

Waste Catalyst
Myung Lang Yoo 1 , Yong Ho Park 1 , Young-Kwon Park 2 and Sung Hoon Park 1, *
1
2

Department of Environmental Engineering, Sunchon National University, 255 Jungang-ro, Suncheon,

Jeonnam 57922, Korea; yml1052@naver.com (M.L.Y.); mik900804@naver.com (Y.H.P.)
School of Environmental Engineering, University of Seoul, Seoul 02504, Korea; catalica@uos.ac.kr
Correspondence: shpark@sunchon.ac.kr; Tel.: +82-61-750-3816; Fax: +82-61-750-3810

Academic Editors: Jang-Ho Lee and Animesh Dutta

Received: 30 December 2015; Accepted: 8 March 2016; Published: 15 March 2016

Abstract: Fast catalytic pyrolysis of wild reed was carried out at 500 C. Waste fluidized catalytic cracking
(FCC) catalyst disposed from a petroleum refinery process was activated through acetone-washing and
calcination and used as catalyst for pyrolysis. In order to evaluate the catalytic activity of waste FCC
catalyst, commercial HY zeolite catalyst with a SiO2 /Al2 O3 ratio of 5.1 was also used. The bio-oil
produced from pyrolysis was analyzed using gas chromatography/mass spectrometry (GC/MS).
When the biomass-to-catalyst ratio was 1:1, the production of phenolics and aromatics was promoted
considerably by catalysis, whereas the content of oxygenates was affected little. Significant conversion
of oxygenates to furans and aromatics was observed when the biomass-to-catalyst ratio of 1:10 was
used. Activated waste FCC catalyst showed comparable catalytic activity for biomass pyrolysis to HY
in terms of the promotion of valuable chemicals, such as furans, phenolics and aromatics. The results
of this study imply that waste FCC catalyst can be an important economical resource for producing
high-value-added chemicals from biomass.
Keywords: waste fluidized catalytic cracking (FCC) catalyst; fast pyrolysis; bio-oil; wild reed

1. Introduction
As rapid development and population increase have caused global environmental problems
and depletion of fossil fuels, extensive efforts are devoted to renewable energy technologies to
develop alternative energy resources and counteract global warming. Biomass has several strengths as
an energy resource. Firstly, the net carbon emission from biomass is, at least theoretically, zero, i.e., it is
carbon-neutral, because the carbon included in biomass originated from atmospheric CO2 as a result of
photosynthesis of plants. Secondly, its sulfur content is very low compared to fossil fuels and hence it
causes less air pollution upon combustion. Thirdly, it is renewable resource in that it is produced using
solar energy. Due to these strengths, biomass is regarded as one of the most important future energy
resources and the technologies for energy production from biomass have received large attention from
all over the world [1,2].
Being a potential energy-producing biomass, reed is a C3 perennial grass with rich contents of
lignin and cellulose. Wild reed that grows at Suncheon Bay Ecological Park (SBEP) is cut regularly to
maintain the ecological equilibrium. Although some cut reed is recycled as construction materials,
most of it is incinerated or landfilled. Therefore, finding an energy production method using SBEP
wild reed is important in terms of both waste reduction and developing a new regional renewable
energy resource.
Pyrolysis is a process in which organic matter is thermally converted to solid, liquid and gas
products under a high-temperature oxygen-free atmosphere [3]. In particular, fast pyrolysis was

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devised to maximize the liquid pyrolysis product, called bio-oil. In order to obtain high bio-oil yield
from pyrolysis, short gas residence time in reactor and high temperature rise rate are required [1].
Catalytic pyrolysis of biomass over acidic catalysts has attracted significant attention as a method
of promoting the production of aliphatic and aromatic hydrocarbons [4,5]. Zeolite is an aluminosilicate
material containing micropores. Having acid sites in its pores, zeolite is widely used in catalytic
pyrolysis of biomass [6,7]. In a couple of previous studies, we reported the results of non-catalytic
and catalytic fast pyrolysis of SBEP wild reed [8,9]. HZSM-5 zeolite catalysts were used for catalytic
pyrolysis. Compared to non-catalytic pyrolysis, catalytic pyrolysis reduced the quantity of oxygenates
in bio-oil considerably, while increasing the contents of furans and aromatics. This was attributed to
the conversion of oxygenates to furans and aromatics on the Brnsted acid sites. A shortcoming of
catalytic pyrolysis is the high price of the catalysts. Application of waste catalyst can reduce the cost of
catalytic pyrolysis.
Fluidized catalytic cracking (FCC) catalyst, which is used in petrochemical refinery processes to
reduce the molecular mass of oil species, is composed mostly of synthetic silica-alumina, containing
520 wt % of zeolite. In order to increase the hydrothermal stability of the catalyst, ultrastable Y (USY)
zeolite, in which alkali metal ions of zeolite are ion-exchanged with H+ or rare-earth metal cations,
is usually used as the framework of FCC catalysts [10]. After use, the waste FCC catalyst consisting
mostly of Si and Al is usually used as raw material for cement production with low value-added.
In a previous study [11], waste FCC catalyst was applied for the pyrolysis of polypropylene. The main
species of the bio-oil obtained were found to be hydrocarbons in diesel range. Jang, et al. [12] activated
waste FCC catalyst using HCl and NaOH solutions and used it for liquid-phase decomposition reaction
of waste agricultural film. They reported that waste FCC catalyst can be an economical resource for
recycling waste agricultural film although its catalytic activity was lower than commercial USY zeolite
catalyst. These previous studies demonstrated the potential of waste FCC catalyst as a catalyst for
biomass pyrolysis. To the best of our knowledge, however, the application of waste FCC catalyst for
the pyrolysis of natural biomass has never been reported.
In this study, waste FCC catalyst was applied for the catalytic pyrolysis of wild reed. A zeolite
catalyst HY was also used for comparison.
2. Experimental
2.1. Materials
Zeolite-based waste FCC catalyst and commercial HY zeolite catalyst were used in this study.
HY with a SiO2 /Al2 O3 ratio of 5.1 was purchased from Zeolyst International. Waste FCC catalyst
disposed from a petrochemical refinery process was soaked in acetone with a mass ratio of 1:10 and
the mixture was stirred for 24 h, aimed at washing out residual organic materials (physical activation).
After the acetone washing, it was dried for an hour in a 60 C dryer. As another method of activation
of waste FCC catalyst, the dried catalyst was calcined for 3 h in air using a 550 C quartz tube reactor
(chemical activation). All catalysts were pelletized into uniform size (1.52.5 mm) prior to use.
Thermo-gravimetric analysis (TGA) was performed using a pyris1 thermo-gravimetric analyzer
(Perkin Elmer, Waltham, MA, USA) to evaluate the effects of physical and chemical activation treatments.
During the analysis, temperature was increased at a rate of 30 C/min from 30 C to 700 C. The specific
surface area of catalysts was measured using Brunauer-Emmett-Teller (BET) method. After pre-treating
catalyst samples in vacuum at 200 C, the adsorption and desorption of nitrogen by the samples were
measured at 77 K using a BELSORP-MINI system (BEL Japan Inc., Osaka, Japan) to create the sorption
isotherms. The specific surface area was determined from the isotherms based on the BET method.
The crystalline structure of the catalysts was examined using a high-power X-ray diffractometer (XRD).
Wild reed of SBEP was collected for the experiments of this study. Dried wild reed sample was
pulverized and sieved into uniform diameter of 2 mm on average (13 mm). The sample particles were
then dried in an oven at 105 5 C for 24 h.

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2.2. Experiment and Analysis

The batch-type reactor used in the previous studies [8,9] was used for catalytic pyrolysis in
this study. The reactor was a U-tube quartz reactor, with an internal volume of 50 mL. The furnace
temperature was controlled using a proportional-integral-derivative controller with an uncertainty of
5 C. The reactor temperature was increased to the pyrolysis temperature instantly by inserting the
reactor into pre-heated furnace.
The reactor was filled with a mixture of 1 g of reed sample and 1 or 10 g of catalyst. Pyrolysis was
allowed to proceed at 500 C with a nitrogen gas flowrate of 50 mL/min controlled at room temperature.
Taking the volume expansion of carrier gas at 500 C and the reactor volume reduction due to biomass
and catalyst into account, the residence time in the reactor was 20 s and 14 s with the catalyst mass of
1 g and 10 g, respectively. The reactor was purged with nitrogen gas for 5 min before the pyrolysis
experiment to make the reactor atmosphere oxygen-free. All the experiments were conducted in
triplicate to obtain the average and standard deviation of bio-oil yield.
The vapor-phase pyrolysis product was quenched using a condenser (RW1025G, JEIO TECH).
The condensed liquid product (bio-oil) was analyzed using gas chromatography/mass spectrometry
(GC/MS) (QP2010, Shimadzu, Japan) equipped with an HP-5 MS (30 m 0.25 mm 0.25 m)
capillary column. Bio-oil was dissolved in HPLC-grade acetone with a 1:10 mass ratio prior to analysis.
After being stabilized for 5 min at 40 C, temperature was increased to 200 C at a rate of 5 C/min and
then to 300 C at a rate of 20 C/min. Then 300 C was maintained for 10 min. The peaks appearing in
the mass spectra obtained were interpreted using the NIST05 library.
The gas product that was not condensed in the condenser was collected in a Teflon bag for 20 min
and was analyzed later using gas chromatography (ACME 6000, Young Lin Instrument, Co., Ltd.,
Anyang, Korea) equipped with a thermal conductivity detector (TCD) and a flame ionization detector
(FID). CO and CO2 were analyzed using TCD with a Carboxen 1000 (15 ft 1/8 in) column, whereas
FID with HP-plot Al2 O3 /KCl (50 m 0.322 mm 8.0 m) column was used for the analysis of
C1 C10 hydrocarbons.
3. Results and Discussion
The TGA analysis results of the catalysts are shown in Figure 1. The weight reduction is explained
by the decomposition of carbonaceous material deposited on the surface of the waste catalyst. The mass
of non-treated waste FCC catalyst (FCC) and the acetone-treated waste FCC catalyst (FCC-acetone)
kept decreasing until the end of the analysis. FCC-acetone showed an even higher mass reduction
than non-treated FCC during the TGA analysis, indicating that the physical activation was not very
effective in removing the carbon deposit and that it rather caused the adsorption of acetone, leading
to an increase of organic residue on the catalyst surface. On the other hand, the mass of chemically
activated waste FCC catalyst (FCC-calcined) stopped decreasing at 550 C, indicating that calcination
was effective in removing organic deposit on the catalyst surface to a considerable extent. The derivative
thermogravimetry (DTG) curves are shown in Figure 2. Although all the three curves showed similar
trend, FCC-calcined showed the highest maximum mass reduction rate around 100 C.
The BET surface area, pore size, and pore volume of the catalysts were summarized in Table 1.
The specific surface area was increased significantly by both activation treatments but the effect of
calcination was larger than that of acetone washing. Pore size and pore volume did not show large
difference among the catalysts. Based on the TGA analysis and BET surface area measurement results,
chemical activation was more effective in removing carbon deposit and organic residues on the catalyst
surface. The XRD analysis showed that the waste FCC catalyst had the same basic structure as HY
zeolite and that physical and chemical activations did not alter the crystalline structure of the catalyst.

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100.0
FCC
FCC acetone
FCC calcined

100.0

FCC
FCC acetone
FCC calcined

99.5

Weight fraction(wt.%)

Weight fraction(wt.%)

99.5

99.0
99.0

98.5
98.5

98.0
98.0

100
100

200
200

300

400

300
400 ()
Temperature

500
500

600
600

700
700

Temperature ()

Figure 1. Thermo-gravimetric analysis (TGA) curves of catalysts.

Figure
1. Thermo-gravimetric
(TGA)curves
curves
catalysts.
Figure
1. Thermo-gravimetric analysis
analysis (TGA)
of of
catalysts.
0.010
0.010

FCC
FCC acetone
FCC
FCCacetone
calcined
FCC
FCC calcined

0.008

0.006

DTG (dX/dT)

DTG (dX/dT)

0.008

0.006

0.004

0.004

0.002

0.002

0.000
0.000
100
100

200
200

300
300

400
400

500
500

600
600

700
700

Temperature
()
Temperature ()

Figure
Derivativethermogravimetry
thermogravimetry (DTG)
Figure
2.2.Derivative
(DTG) curves
curvesofofcatalysts.
catalysts.
Figure 2. Derivative thermogravimetry (DTG) curves of catalysts.
Table
Brunauer-Emmett-Teller(BET)
(BET) surface
surface area,
area, pore
pore size
Table
1. 1.
Brunauer-Emmett-Teller
size and
and pore
porevolume
volumeofofthe
thecatalysts.
catalysts.
TableFluidized
1. Brunauer-Emmett-Teller
(BET) surface area, pore size and pore volume of the catalysts.
catalytic
cracking:
FCC.
Fluidized catalytic cracking: FCC.
Fluidized catalytic cracking: FCC.
2/g)
Catalysts
BETSurface
SurfaceArea
Area(m
(m22/g)
/g)
Pore
Pore
(cm
2/g)
Catalysts
BET
Pore Size
Size(nm)
(nm)
PoreVolume
Volume
(cm
FCC
136
6.67
0.1574
2
2
FCC
136
6.67
0.1574
Catalysts
Pore Size
(nm)
BET Surface146
Area (m /g)
Pore Volume
FCC-acetone
6.96
0.1402(cm /g)
FCC-acetone
146
6.96
0.1402
FCC-calcined
159
6.65
0.1404
FCC
136
6.67
0.1574
FCC-calcined
159
6.65
0.1404
FCC-acetone
146
6.96
0.1402
FCC-calcined
159 obtained from the pyrolysis
6.65
0.1404
Figure
3 shows the bio-oil yields
of reed conducted
under different
Figure 3 shows the bio-oil yields obtained from the pyrolysis of reed conducted under different
catalytic conditions. The error bar indicates the standard deviation obtained from the triplicate
catalytic conditions. The error bar indicates the standard deviation obtained from the triplicate
experiments. In the non-catalytic pyrolysis, the yields of oil, solid residue and gas were 50.7%, 22.0%,
Figure 3 shows
bio-oil yields
obtained yields
from the
pyrolysis
of reed
conducted
under 22.0%,
different
experiments.
thethe
non-catalytic
pyrolysis,
of oil,
solid residue
gas
50.7%,
and 27.3%, In
respectively.
Catalytic
pyrolysisthe
with a biomass-to-catalyst
massand
ratio
ofwere
1:1 led
to a lower
catalytic
conditions.
TheCatalytic
error
bar
indicates
standardpyrolysis
deviation
obtained
andoil27.3%,
respectively.
pyrolysis
with
a biomass-to-catalyst
mass
ratio
1:1
ledthe
to atriplicate
lower
yield
(and a higher
gas
yield)
compared
to the
non-catalytic
mainly
due of
tofrom
decomposition
experiments.
In
the
non-catalytic
pyrolysis,
the
yields
of
oil,
solid
residue
and
gas
were
50.7%,
22.0%,
oil of
yield
(and
a
higher
gas
yield)
compared
to
non-catalytic
pyrolysis
mainly
due
to
decomposition
oil species into gaseous species (with lower molecular mass). However, when the catalyst dosage
of 27.3%,
oil
species
into
gaseous
species
(with
lower
molecular
mass).
However,
when
the
catalyst
dosage
and
respectively.
Catalytic
pyrolysis
with
a
biomass-to-catalyst
mass
ratio
of
1:1
led
to
a
was increased further (to a biomass-to-catalyst mass ratio of 1:10), the oil yield increased because thelower
was
increased
furthergas
(to yield)
a biomass-to-catalyst
mass
ratio ofpyrolysis
1:10), the mainly
oil yielddue
increased
because the of
oil yield
(and
a residue)
higher
compared
to non-catalytic
to decomposition
coke
(solid
formation
was suppressed
by catalysts.
(solid
residue)
formation
wasofsuppressed
by catalysts.
The
GC-MS
chromatogram
the bio-oil
produced
in this
study showed
than 100dosage
peaks. was
oilcoke
species
into
gaseous
species (with
lower
molecular
mass).
However,
whenmore
the catalyst
Thefurther
GC-MS
chromatogram
the bio-oil
produced
in this
study
showed
more
than
100acids,
peaks.
Therefore,
all (to
the
speciesofdetected
in this
study
were
grouped
into increased
seven
categories:
increased
abio-oil
biomass-to-catalyst
mass
ratio
of 1:10),
the
oil yield
because
the coke
oxygenates,
phenolics,
aliphatic
hydrocarbons
(aliphatics
hereafter),
monocyclic
aromatic
hydrocarbons
Therefore,
all
the
bio-oil
species
detected
in
this
study
were
grouped
into
seven
categories:
acids,
(solid residue) formation was suppressed by catalysts.
(aromaticsphenolics,
hereafter),
polycyclic
aromatic hydrocarbons
(PAHs), monocyclic
and nitrogen-containing
species
oxygenates,
aliphatic
hydrocarbons
(aliphatics
hereafter),
aromatic
hydrocarbons
The GC-MS chromatogram of the bio-oil produced in this study showed more than 100 peaks.
(N compounds hereafter).
Figure 4 compares
the bio-oil compositions
(expressed
in area %) obtained
(aromatics
polycyclic
(PAHs),
nitrogen-containing
species
Therefore, allhereafter),
the bio-oil
speciesaromatic
detectedhydrocarbons
in this study
were and
grouped
into seven categories:
using
different
catalysts:
acetone-washed
waste
FCC
catalyst
(FCC-acetone),
waste
FCC
catalyst
(N compounds hereafter). Figure 4 compares the bio-oil compositions (expressed in area %) obtained
acids,calcined
oxygenates,
phenolics,
aliphatic(FCC-calcined),
hydrocarbons
(aliphatics
hereafter),
monocyclic
aromatic
for 3 hcatalysts:
after
acetone-washing
commercial
HY. The results
obtained
with
using different
acetone-washed
waste FCCand
catalyst
(FCC-acetone),
waste
FCC catalyst
hydrocarbons
(aromatics
hereafter),
polycyclic
aromatic
hydrocarbons
(PAHs),
and
nitrogen-containing
two different
biomass-to-catalyst
ratios
1:1 and 1:10 are
shown
separately.
calcined
for 3 h after
acetone-washing
(FCC-calcined),
and
commercial
HY. The results obtained with

species (N compounds hereafter). Figure 4 compares the bio-oil compositions (expressed in area %)
two different biomass-to-catalyst ratios 1:1 and 1:10 are shown separately.
obtained using different catalysts: acetone-washed waste FCC catalyst (FCC-acetone), waste FCC
catalyst calcined for 3 h after acetone-washing (FCC-calcined), and commercial HY. The results obtained
with two different biomass-to-catalyst ratios 1:1 and 1:10 are shown separately.

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Figure 3. Yields of solid, liquid, and gas products of pyrolysis obtained under different catalytic conditions.
Figure3.3.Yields
Yieldsofofsolid,
solid,liquid,
liquid,and
andgas
gasproducts
products of
of pyrolysis
pyrolysis obtained
Figure
obtained under
under different
differentcatalytic
catalyticconditions.
conditions.

(a)
(b)
(a)
(b)
Figure 4. Pyrolysis product distribution obtained under different catalytic conditions at 500 C:
Figure
4. Pyrolysis =product
distribution
obtained= 1:10.
under different catalytic conditions at 500 C:
(a) biomass:catalyst
1:1; anddistribution
(b) biomass:catalyst
Figure
4. Pyrolysis product
obtained under different catalytic conditions at 500 C:
(a) biomass:catalyst = 1:1; and (b) biomass:catalyst = 1:10.
(a) biomass:catalyst = 1:1; and (b) biomass:catalyst = 1:10.

When the biomass-to-catalyst ratio was 1:1, phenolics (FCC-acetone, FCC-calcined, and HY) and
When
the biomass-to-catalyst
ratio was
1:1, phenolics
(FCC-acetone,
FCC-calcined,
and HY)
aromatics (FCC-calcined
and HY) were
increased
significantly
by catalysis,
while the contents
ofand
the
When the
biomass-to-catalyst
ratio
was
1:1, phenolics
(FCC-acetone,
FCC-calcined,
and HY)
and
aromatics
(FCC-calcined
and
HY)
were
increased
significantly
by
catalysis,
while
the
contents
of
the
other species were little affected by catalysis. When the biomass-to-catalyst ratio was 1:10, the content
aromatics
(FCC-calcined
and
HY)
were
increased
significantly
by
catalysis,
while
the
contents
of
the
other
species were
affected
by catalysis. When
ratio and
was 1:10,
the content
of oxygenates
waslittle
reduced
considerably,
while the
thebiomass-to-catalyst
contents of phenolics
aromatics
were
other
species werewas
littlereduced
affectedconsiderably,
by catalysis. When
biomass-to-catalyst
ratio
wasaromatics
1:10, the content
of
oxygenates
whileN the
contents of
phenolics
and
were
increased
significantly
for all catalysts. The
compounds
also
decreased
by all catalysts.
of oxygenates
was reducedfor
considerably,
while
theNcontents
of phenolics
and aromatics
were
increased
increased
significantly
all
catalysts.
The
compounds
also
decreased
by
all
catalysts.
Considerable increase in PAHs content was obtained only for HY. The conversion of oxygenates to
significantly
for increase
allacid
catalysts.
N compounds
alsoisdecreased
by all
catalysts.
Considerable
increase
Considerable
in PAHs
content
was
obtained
for HY.
The
conversion
of oxygenates
aromatics over
sites
ofThe
zeolite-based
catalysts
aonly
well-known
phenomenon;
xylan,
which
istoa
over
acid
sites
of
zeolite-based
catalysts
is
a
well-known
phenomenon;
xylan,
which
is
a
in aromatics
PAHs
content
was
obtained
only
for
HY.
The
conversion
of
oxygenates
to
aromatics
over
acid
sites
thermally unstable fibrin linking cellulose and lignin, is easily decomposed on the acid sites and
unstable
fibrin
linking
cellulose
and
lignin,
is
easily
decomposed
on
the
acid
sites
and
of thermally
zeolite-based
catalysts
is
a
well-known
phenomenon;
xylan,
which
is
a
thermally
unstable
fibrin
converted to aromatics through decarbonylation and aromatization [13,14].
converted
to
aromatics
through
decarbonylation
and
aromatization
[13,14].
linking
cellulose
and
lignin,
is easily
decomposed
the
acid
converted
to aromatics
through
Acids
were
mostly
acetic
acid.
The content on
of acids
didsites
not and
change
significantly
as a result
of
Acids
were
mostly
acetic
acid.
The
content
of
acids
did
not
change
as acorrosion
result of
decarbonylation
and aromatization
catalysis regardless
of the catalyst [13,14].
dosage. Acetic acid contained in liquidsignificantly
fuels can cause
catalysis
regardless
of while
the
catalyst
Acetic
acid
contained
liquid fuels
can cleansing
causeascorrosion
wereengines,
mostly
acetic
The
content
of
acids
did
notinchange
significantly
a result
of Acids
pipes and
itacid.
candosage.
be
used
for producing
bulk-chemical,
vinegar,
agent, of
of
pipes
and
engines,
while
it
can
be
used
for
producing
bulk-chemical,
vinegar,
cleansing
agent,
catalysis
regardless
the catalyst
dosage.
Acetic
contained
liquid acetate)
fuels can
cause
corrosion
vinyl acetate,
aceticofanhydride,
esters,
solvent,
andacid
road
deicer (asin
calcium
if it
is separated
acetic
anhydride,
esters,
solvent,
and
road deicer
(as
calcium
acetate)
it is separated
properly
[15].
Therefore,
it must
bebe
separated
bio-oil
before
using
the oil.
of vinyl
pipesacetate,
and
engines,
while
it can
used
forfrom
producing
bulk-chemical,
vinegar,if cleansing
agent,
properly
[15]. Therefore,
it must
be separated
from bio-oil
before using
the oil. as a high-value-added
The main
species
among
PAHs
was
naphthalene.
Naphthalene
regarded
vinyl acetate,
acetic
anhydride,
esters,
solvent,
and road
deicer (asiscalcium
acetate) if it is separated
The main
species
among
PAHs was
naphthalene.
Naphthalene
is regardedaasnumber
a high-value-added
chemical
because
it can
widely
used
as from
a rawbio-oil
material
for using
producing
of chemical
properly
[15].
Therefore,
it be
must
be separated
before
the oil.
chemical
because
it
can
be
widely
used
as
a
raw
material
for
producing
a
number
of
chemical
products,
such
as synthetic
and dye [7].
PAHs were is
notregarded
produced
non-catalytic
The main
species
amongresin,
PAHspesticide
was naphthalene.
Naphthalene
asfrom
a high-value-added
products,
such
as
synthetic
resin,
pesticide
and
dye
[7].
PAHs
were
not
produced
from
non-catalytic
pyrolysis
and from
pyrolysis
thematerial
biomass-to-catalyst
ratio
of 1:1. On
the otherproducts,
hand,
chemical
because
it cancatalytic
be widely
used aswith
a raw
for producing
a number
of chemical
pyrolysis
and
from catalytic pyrolysis
with
the
biomass-to-catalyst
ratio of
of PAHs
1:1. On
the detected
other hand,
when
the
biomass-to-catalyst
ratio
was
1:10,
significant
quantity
(9.01%)
were
for
such
as synthetic
resin, pesticide
andwas
dye1:10,
[7]. significant
PAHs were
not produced
from non-catalytic pyrolysis
when
thePAHs
biomass-to-catalyst
ratio
quantity
(9.01%) of PAHs were detected for
HY.
The
content
obtained
from
waste
FCC
catalyst
was
marginal.
and
from
catalytic
pyrolysis
withfrom
the biomass-to-catalyst
ratio
of 1:1. On the other hand, when the
HY.
The
PAHs
content
waste
FCC catalyst
was
marginal.
Figure
5 shows
theobtained
detailed species
distribution
of oxygenates
obtained under different catalytic
biomass-to-catalyst
ratio
was
1:10, species
significant
quantityof
(9.01%)
of PAHs
were detected
for HY.catalytic
The PAHs
Figure
5
shows
the
detailed
distribution
oxygenates
obtained
underfrom
different
conditions. While considerable quantity of levoglucosan (5.92%) was produced
non-catalytic
content
obtained
from
waste
FCC
catalyst
was
marginal.
conditions.
While considerable
of levoglucosan
produced
from non-catalytic
pyrolysis, pyrolysis
with the quantity
biomass-to-catalyst
ratio(5.92%)
of 1:1 was
reduced
it dramatically:
0.78%
Figure 5 pyrolysis
shows thewith
detailed
species
distribution of
oxygenates
obtaineditunder
different catalytic
pyrolysis,
the
biomass-to-catalyst
ratio
of
1:1
reduced
dramatically:
(FCC-acetone), 0.75% (FCC-calcined), and 2.08% (HY). Further, when the biomass-to-catalyst0.78%
ratio
conditions.
While0.75%
considerable
quantity
of2.08%
levoglucosan
(5.92%)
wasthe
produced
from non-catalytic
(FCC-acetone),
(FCC-calcined),
and
(HY). Further,
when
biomass-to-catalyst
ratio

Energies 2016, 9, 201

6 of 9

was 1:10, virtually no levoglucosan remained. The conversion of levoglucosan on the acid sites of
catalysts
to9,furans
and aromatics has been reported repeatedly in previous studies [6,16,17].
Energies
2016,
201
6 of 9
Furans are widely used in the petrochemical industry for producing furan resin, fuel additives,
and medicines. Furans are known to be produced from the dehydration reaction of carbohydrate
pyrolysis,
pyrolysis with
the acid
biomass-to-catalyst
ratio
of 1:1
it dramatically:
0.78%due
(FCC-acetone),
(e.g., levoglucosan)
on the
sites of catalysts
[16].
Thereduced
increase
in furans content
to catalysis
0.75%
(FCC-calcined),
and
2.08%
(HY).
Further,
when
the
biomass-to-catalyst
ratio
was
1:10, virtually
was smaller than the reduction in levoglucosan content (Figure 5). This was attributed
to the
no
levoglucosan
remained. The
conversionand
of levoglucosan
on the
acid
sites of catalysts to[17]
furans
conversion
of levoglucosan
to furanones
cyclocompounds
due
to dehydrogenation
andand
the
aromatics
has
been
reported
repeatedly
in
previous
studies
[6,16,17].
production of aromatics due to aromatization reaction [16].

(a)

(b)

Figure 5. Detailed species distributions of oxygenates obtained from non-catalytic and catalytic
Figure 5. Detailed species distributions of oxygenates obtained from non-catalytic and catalytic
pyrolyses of wild reed: (a) biomass:catalyst = 1:1; and (b) biomass:catalyst = 1:10.
pyrolyses of wild reed: (a) biomass:catalyst = 1:1; and (b) biomass:catalyst = 1:10.

Phenolics are another high-value-added products of pyrolysis of biomass. They are produced
are widely used
in thecontained
petrochemical
industry
for producing
fuel additives,
fromFurans
the decomposition
of lignin
in biomass.
Figures
6 and 7 furan
show resin,
the detailed
species
and
medicines.
Furans
are
known
to
be
produced
from
the
dehydration
reaction
of
carbohydrate
(e.g.,
distribution of phenolics obtained from different catalytic conditions. In both figures, low-molecularlevoglucosan)
on
the
acid
sites
of
catalysts
[16].
The
increase
in
furans
content
due
to
catalysis
mass phenolics (a) and high-molecular-mass phenolics (b) are shown separately. Pyrolysis withwas
the
smaller
than
the
reduction
in
levoglucosan
content
(Figure
5).
This
was
attributed
to
the
conversion
of
biomass-to-catalyst ratio of 1:1 (Figure 6) promoted the production of low-molecular-mass phenolics
levoglucosan
to furanones
and cyclocompounds
due to dehydrogenation
and the depending
production on
of
to a large extent,
while high-molecular-mass
phenolics
were increased or[17]
decreased
aromatics
due
to
aromatization
reaction
[16].
the species. This result is attributed to promoted decomposition of lignin to phenolics and of
Phenolics are another
high-value-added
products of pyrolysis
of biomass.
are produced
high-molecular-mass
phenolics
to low-molecular-mass
phenolics
or They
aromatics
owingfrom
to
the
decomposition
of
lignin
contained
in
biomass.
Figures
6
and
7
show
the
detailed
species
distribution
deoxygenation (dehydration, decarbonylation, and decarboxylation) and cracking occurring on the
of
phenolics
from different
catalytic
In bothwas
figures,
low-molecular-mass
phenolics
acid
sites ofobtained
the catalysts
[7,18]. When
theconditions.
catalyst dosage
increased
further (Figure
7), the
(a)
and
high-molecular-mass
phenolics
(b)
are
shown
separately.
Pyrolysis
with
the
biomass-to-catalyst
conversion of high-molecular-mass phenolics to low-molecular-mass phenolics was more evident.
ratio
of 1:1
(Figure 6) promotedphenolics
the production
low-molecular-mass phenolics
to a large extent,
All the
high-molecular-mass
exceptof2,6-dimethoxy-phenol,
whose molecular
mass while
is the
high-molecular-mass
phenolics
were
increased
or
decreased
depending
on
the
species.
This
result
is
smallest among them, were decreased by pyrolysis. In particular, 2-methoxy-4-(1-propenyl)-phenol
attributed
to promoted decomposition
of lignin
to phenolics
and of high-molecular-mass
phenolics
to
and 2-methoxy-4-vinylphenol,
which were
removed
or considerably
decreased by pyrolysis
with the
low-molecular-mass
phenolics
or
aromatics
owing
to
deoxygenation
(dehydration,
decarbonylation,
biomass-to-catalyst ratio of 1:10, are unsaturated compounds containing C=C bonds that are not
and
decarboxylation)
and cracking
occurring
on the acid
sites the
of the
catalysts
[7,18].
When the
inside
benzene rings. Since
they can cause
the instability
of fuels,
removal
of these
compounds
is
catalyst
dosage
was
increased
further
(Figure
7),
the
conversion
of
high-molecular-mass
phenolics
advantageous in terms of the oil quality improvement.
to low-molecular-mass
phenolics
was more
evident.
All thearomatic
high-molecular-mass
Figure 8 shows the
most valuable
four
monocyclic
compounds phenolics
produced except
under
2,6-dimethoxy-phenol,
whose
molecular
mass
is
the
smallest
among
them,
were
decreased
by
pyrolysis.
different catalytic conditions: benzene, toluene, ethylbenzene, and xylene (often called BTEX). It is
In
particular,
2-methoxy-4-(1-propenyl)-phenol
and 2-methoxy-4-vinylphenol,
which
were
removed
shown
that most
aromatics produced in this study
were benzene; a little toluene
and
xylene
were
or
considerably
decreased
by
pyrolysis
with
the
biomass-to-catalyst
ratio
of
1:10,
are
unsaturated
produced only by using HY with the biomass-to-catalyst ratio of 1:10. The production of aromatics
compounds
containing
C=C bonds
thateffect
are not
benzene
rings. Since
theythe
cancatalyst
cause the
instability
was promoted
by catalysis
and the
of inside
catalysis
was stronger
when
dosage
was
of
fuels,
the
removal
of
these
compounds
is
advantageous
in
terms
of
the
oil
quality
improvement.
higher. This result is in good agreement with the reports of previous studies that acid sites are
Figure
shows the
most valuable
monocyclic
aromatic
compounds
different
required
to 8produce
aromatics
duringfour
biomass
pyrolysis
[4,5,7,9,16].
BTEXproduced
are very under
important
raw
catalytic
conditions:
benzene,
toluene,
ethylbenzene,
and
xylene
(often
called
BTEX).
It
is
shown
materials in the petrochemical industry. Therefore, the production of BTEX using waste biomass that
and
most
produced
this
study
were
benzene;
a littlefor
toluene
and xylene
werethat
produced
only
wastearomatics
catalyst achieved
inin
this
study
has
deep
implications
developing
resources
can replace
by
using
HY with the biomass-to-catalyst ratio of 1:10. The production of aromatics was promoted by
fossil
fuels.
catalysis and the effect of catalysis was stronger when the catalyst dosage was higher. This result is in
good agreement with the reports of previous studies that acid sites are required to produce aromatics
during biomass pyrolysis [4,5,7,9,16]. BTEX are very important raw materials in the petrochemical

Energies 2016, 9, 201

7 of 9

industry. Therefore, the production of BTEX using waste biomass and waste catalyst achieved in this
study
has2016,
deep
implications for developing resources that can replace fossil fuels.
Energies
9, 201
7 of 9
Energies 2016, 9, 201
Energies 2016, 9, 201

7 of 9
7 of 9

(a)

(b)

Figure 6. Detailed phenolic

distributions obtained from non-catalytic(b)
and catalytic pyrolyses
(b)
(a) species
Figure 6. Detailed (a)
phenolic
species distributions obtained from non-catalytic
and catalytic
with biomass:catalyst = 1:1: (a) small-molecular-mass phenolics; and (b) large-molecular-mass phenolics.
pyrolyses
with
biomass:catalyst
=
1:1:
(a)
small-molecular-mass
phenolics;
and (b)
Figure
6. Detailed
phenolic
species
andcatalytic
catalyticpyrolyses
pyrolyses
Figure
6. Detailed
phenolic
speciesdistributions
distributionsobtained
obtained from
from non-catalytic
non-catalytic and
large-molecular-mass
phenolics.
with
biomass:catalyst
= 1:1:
(a)(a)
small-molecular-mass
large-molecular-massphenolics.
phenolics.
with
biomass:catalyst
= 1:1:
small-molecular-massphenolics;
phenolics; and
and (b) large-molecular-mass

(a)

(b)

Figure 7. Detailed phenolic

species distributions obtained from non-catalytic(b)
and catalytic pyrolyses
(a)
(a)= 1:10: (a) small-molecular-mass phenolics; and (b) large-molecular-mass
(b)
with biomass:catalyst
phenolics.
Figure 7. Detailed phenolic species distributions obtained from non-catalytic and catalytic pyrolyses
Figure 7.
7. Detailed
Detailed phenolic
species distributions
obtained
from
non-catalytic
andand
catalytic
pyrolyses
with
Figure
phenolic
distributions
obtained
from
non-catalytic
catalytic
pyrolyses
with biomass:catalyst
= 1:10:species
(a) small-molecular-mass
phenolics;
and
(b) large-molecular-mass
phenolics.
biomass:catalyst
=
1:10:
(a)
small-molecular-mass
phenolics;
and
(b)
large-molecular-mass
phenolics.
with biomass:catalyst = 1:10: (a) small-molecular-mass phenolics; and (b) large-molecular-mass phenolics.

Figure 8. Comparison of the benzene, toluene, ethylbenzene, and xylene (BTEX) fractions obtained
from non-catalytic and catalytic pyrolyses of wild reed.
Figure 8. Comparison of the benzene, toluene, ethylbenzene, and xylene (BTEX) fractions obtained
fromgas
non-catalytic
catalytic
pyrolyses
of wild reed.
The
products and
obtained
over
FCC-calcined
with the biomass-to-catalyst ratio of 1:1 and 1:10
Figure
8.
Comparison
of
the
benzene,
toluene,
ethylbenzene,
and xylene
(BTEX)
fractions
Figure
8.
Comparison
of
the
benzene,
toluene,
ethylbenzene,
xylene
(BTEX)Catalysis
fractions obtained
obtained
are shown in Figure 9. The results obtained without
catalyst areand
shown
together.
apparently
from
non-catalytic
and
catalytic
pyrolyses
of
wild
reed.
from
non-catalytic
andobtained
catalytic over
pyrolyses
of wild reed.
The
gas products
FCC-calcined
with the biomass-to-catalyst ratio of 1:1 and 1:10

increased the production of C1C4 hydrocarbon, CO, and CO2. C5C6 components were not detected,
are shown that
in Figure
The results
obtained
without Enhanced
catalyst areproduction
shown together.
Catalysis
apparently
indicating
the 9.
condenser
worked
properly.
of CO
and CO
2 can be
The
gas
products
obtained
over
FCC-calcined
with
the
biomass-to-catalyst
ratio
of
1:1 and 1:10
increased
the
production
of
C
1C4 hydrocarbon, CO, and CO2. C5C6 components were not detected,
attributed to the catalytic deoxygenation (decarbonylation and decarboxylation) of oxygenates in
are indicating
shown in Figure
9. The
results obtained
without catalyst
are production
shown together.
Catalysis
that the
condenser
worked
properly.
Enhanced
of CO
and
COapparently
2 can be
bio-oil. Catalytic
cracking
of bio-oil
components
converted
large-molecular-mass
compounds
into
increased
the
production
of
C
1
C
4
hydrocarbon,
CO,
and
CO
2
.
C
5
C
6
components
were
not detected,
attributed to the catalytic deoxygenation (decarbonylation and decarboxylation) of oxygenates
in
indicating
that the cracking
condenser
worked
properly. converted
Enhancedlarge-molecular-mass
production of CO compounds
and CO2 can
bio-oil. Catalytic
of bio-oil
components
intobe

attributed to the catalytic deoxygenation (decarbonylation and decarboxylation) of oxygenates in

Energies 2016, 9, 201

8 of 9

The gas products obtained over FCC-calcined with the biomass-to-catalyst ratio of 1:1 and 1:10
are shown in Figure 9. The results obtained without catalyst are shown together. Catalysis apparently
increased the production of C1 C4 hydrocarbon, CO, and CO2 . C5 C6 components were not detected,
indicating that the condenser worked properly. Enhanced production of CO and CO2 can be
attributed to the catalytic deoxygenation (decarbonylation and decarboxylation) of oxygenates in
Energies 2016, 9, 201
8 of 9
bio-oil. Catalytic cracking of bio-oil components converted large-molecular-mass compounds into
C
hydrocarbons. A
A high
high correlation
C11C
C44 hydrocarbons.
correlation between
between the
the enhanced
enhanced CO
CO production
production due
due to
to catalytically
catalytically
promoted
decarbonylation
and
decarboxylation
and
increased
production
of
aromatic
hydrocarbons
promoted decarbonylation and decarboxylation and increased production of aromatic hydrocarbons
has
which
is in
agreement
with with
the result
of thisof
study.
in the catalyst
hasbeen
beenreported
reported[19],
[19],
which
is good
in good
agreement
the result
this Increase
study. Increase
in the
dosage
(change
of
the
biomass-to-catalyst
ratio
from
1:1
to
1:10)
resulted
in
reduced
CO
production,
catalyst dosage (change of the biomass-to-catalyst ratio from 1:1 to 1:10) resulted in 2reduced
CO2
while
the
production
of
C
C
hydrocarbons
was
enhanced.
This
can
be
attributed
to
enhanced
1
4
production, while the production of C1C4 hydrocarbons was enhanced. This can be attributed to
catalytic
and demethoxylation
of lignin-derived
phenolic compounds,
resulting in
enhanceddemethylation
catalytic demethylation
and demethoxylation
of lignin-derived
phenolic compounds,
reduced
content
of
phenolics
with
methoxy
functional
groups
in
bio-oil
[20].
resulting in reduced content of phenolics with methoxy functional groups in bio-oil [20].
30
CO
CO2
25

C1~C4

Yield (wt%)

20

15

10

0
t
lys
ata

c
ut
tho

Wi

1:1
ed
lcin

ca
CFC

:10
d1
ine

lc
ca
CFC

Figure 9. Detailed species distributions of gas obtained from non-catalytic and catalytic pyrolyses of
Figure 9. Detailed species distributions of gas obtained from non-catalytic and catalytic pyrolyses of
wild reed.
wild reed.

4. Conclusions
4. Conclusions
Wild reed of SBEP was pyrolyzed over waste FCC catalyst and HY zeolite catalyst. Catalysis
Wild reed of SBEP was pyrolyzed over waste FCC catalyst and HY zeolite catalyst. Catalysis reduced
reduced the yield of bio-oil because of enhanced decomposition of oil species into gaseous species.
the yield of bio-oil because of enhanced decomposition of oil species into gaseous species. However, the
However, the use of excess catalyst rather increased the bio-oil yield resulting from suppressed
use of excess catalyst rather increased the bio-oil yield resulting from suppressed coke formation.
coke formation.
The production of phenolics and aromatics were promoted considerably by catalysis.
The production of phenolics and aromatics were promoted considerably by catalysis.
Oxygenates were reduced significantly when catalyst dosage was very high. In particular, most
Oxygenates were reduced significantly when catalyst dosage was very high. In particular, most
levoglucosan was removed by catalysis, converting to other compounds such as furans and aromatics
levoglucosan was removed by catalysis, converting to other compounds such as furans and aromatics
on the acid sites of the catalysts.
on the acid sites of the catalysts.
Waste FCC catalyst activated through acetone-washing and calcination for 3 h exhibited considerable
Waste FCC catalyst activated through acetone-washing and calcination for 3 h exhibited
catalytic activity which was comparable to that of HY zeolite catalyst. The results of this study imply that
considerable catalytic activity which was comparable to that of HY zeolite catalyst. The results of this
waste FCC catalyst can be an important economical resource to produce high-value-added chemicals
study imply that waste FCC catalyst can be an important economical resource to produce high-valuefrom biomass.
added chemicals from biomass.
Acknowledgments: This research was supported by Basic Science Research Program through the National
Acknowledgments:
This
research
supported
by Basic
Research
through(grant
the National
Research
Foundation of
Korea
(NRF) was
funded
by the Ministry
of Science
Education,
ScienceProgram
and Technology
number
2013R1A1A4A01005840).
Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology
(grant number
2013R1A1A4A01005840).
Author
Contributions:
Young-Kwon Park and Sung Hoon Park conceived and designed the experiments;
Myung Lang Yoo and Yong Ho Park performed the experiments; Myung Lang Yoo and Sung Hoon Park analyzed
Author Contributions: Young-Kwon Park and Sung Hoon Park conceived and designed the experiments;
the data; Young-Kwon Park contributed reagents/materials/analysis tools; Myung Lang Yoo and Sung Hoon Park
Myung
Yoo and Yong Ho Park performed the experiments; Myung Lang Yoo and Sung Hoon Park
wrote
theLang
paper.
analyzed the data; Young-Kwon Park contributed reagents/materials/analysis tools; Myung Lang Yoo and
Conflicts of Interest: The authors declare no conflict of interest.
Sung Hoon Park wrote the paper.

Conflicts of Interest: The authors declare no conflict of interest.

References
1.
2.

Demirbas, A. Biomass resources for energy and chemical industry. Energy Educ. Sci. Technol. 2000, 5, 2145.
Subramanian, P. A review on gasification of biomass. Renew. Sustain. Energy Rev. 2009, 13, 179186.

Energies 2016, 9, 201

9 of 9

References
1.
2.
3.
4.

5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.

Demirbas, A. Biomass resources for energy and chemical industry. Energy Educ. Sci. Technol. 2000, 5, 2145.
Subramanian, P. A review on gasification of biomass. Renew. Sustain. Energy Rev. 2009, 13, 179186.
Mohan, D. Pyrolysis of wood/biomass for bio-oil: A critical review. Energy Fuels 2006, 20, 848889. [CrossRef]
Park, H.J.; Heo, H.S.; Jeon, J.K.; Kim, J.; Ryoo, R.; Jeong, K.E.; Park, Y.K. Highly valuable chemicals production
from catalytic upgrading of radiata pine sawdust-derived pyrolytic vapors over mesoporous MFI zeolites.
Appl. Catal. B Environ. 2010, 95, 365373. [CrossRef]
Heo, H.S.; Kim, S.G.; Jeong, K.E.; Jeon, J.K.; Park, S.H.; Kim, J.M.; Kim, S.S.; Park, Y.K. Catalytic upgrading of
oil fractions separated from food waste leachate. Bioresour. Technol. 2011, 102, 39523957. [CrossRef] [PubMed]
Choi, S.J.; Park, S.H.; Jeon, J.-K.; Lee, I.G.; Ryu, C.; Suh, D.J.; Park, Y.K. Catalytic conversion of particle board
over microporous catalysts. Renew. Energy 2013, 54, 105110. [CrossRef]
Kim, J.W.; Park, S.H.; Jung, J.; Jeon, J.K.; Ko, C.H.; Jeong, K.-E.; Park, Y.-K. Catalytic pyrolysis of mandarin
residue from the mandarin juice processing industry. Bioresour. Technol. 2013, 136, 431436. [CrossRef] [PubMed]
Park, Y.-K.; Yoo, M.L.; Heo, H.S.; Lee, H.W.; Park, S.H.; Jung, S.-C.; Park, S.-S.; Seo, S.-G. Wild reed of
Suncheon Bay: Potential bio-energy source. Renew. Energy 2012, 42, 168172. [CrossRef]
Park, Y.-K.; Yoo, M.L.; Jin, S.H.; Jung, S.-C.; Park, S.-S.; Park, S.H. Pyrolysis of Suncheon-Bay wild reed over
zeolite catalysts. J. Renew. Sustain. Energy 2014, 6. [CrossRef]
Jeon, S.K.; Yang, J.G.; Kim, J.H.; Lee, S.S. Separation and Recovery of Ce, Nd and V from Spent FCC Catalyst.
J. Korean Ind. Eng. Chem. 1997, 8, 679684.
Bak, Y.C.; Choi, J.H.; Oh, S.H. The Effects of Zeolite-Type Catalysts on the Pyrolysis Reaction of PP to Produce
Fuel-oil. J. Korea Chem. Eng. Res. 2012, 50, 442448. [CrossRef]
Jang, N.P.; Park, J.W.; Seo, G. Liquid-Phase Degradation of Waste Agricultural Film over Used-FCC Catalysts.
Korea Chem. Eng. Res. 2003, 41, 694699.
Gutierrez, A.; Kaila, R.K.; Honkela, M.L.; Slioor, R.; Krause, A.O.I. Hydrodeoxygenation of guaiacol on noble
metal catalysts. Catal. Today 2009, 147, 239246. [CrossRef]
Sitthisa, S.; Resasco, D.E. Hydrodeoxygenation of Furfural over Supported Metal Catalysts: A Comparative
Study of Cu, Pd and Ni. Catal. Lett. 2011, 141, 784791. [CrossRef]
De Wild, P.; Reith, H.; Heeres, E. Biomass pyrolysis for chemicals. Biofuels 2011, 2, 185208. [CrossRef]
Lee, I.G.; Jun, B.R.; Kang, H.K.; Park, S.H.; Jung, S.C.; Jeon, J.K.; Ko, C.H.; Park, Y.K. Catalytic Pyrolysis of
Cellulose over SAPO-11 Using Py-GC/MS. Bull. Korean Chem. Soc. 2013, 34, 23992402. [CrossRef]
Shen, D.K.; Gu, S. The mechanism for thermal decomposition of cellulose and its main products. Bioresour. Technol.
2009, 100, 64966504. [CrossRef] [PubMed]
Carlson, R.T.; Tompsett, A.G.; Conner, C.W.; Huber, W.G. Aromatic Production from Catalytic Fast Pyrolysis
of Biomass-Derived Feedstocks. Top. Catal. 2009, 52, 241252. [CrossRef]
Wang, K.; Kim, K.H.; Brown, R.C. Catalytic pyrolysis of individual compounds of lignocellulosic biomass.
Green Chem. 2014, 16, 727735. [CrossRef]
Jin, S.H.; Lee, H.W.; Ryu, C.; Jeon, J.-K.; Park, Y.-K. Catalytic fast pyrolysis of Geodae-Uksae 1 over zeolites.
Energy 2015, 81, 4146. [CrossRef]
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