Fuel Processing Technology 91 (2010) 2532

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Fuel Processing Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / f u p r o c

Catalytic pyrolysis of biomass for biofuels production

Richard French, Stefan Czernik
National Bioenergy Center, National Renewable Energy Laboratory, 1617 Cole Blvd., Golden, CO 80401, United States

a r t i c l e

i n f o

Article history:
Received 3 February 2009
Received in revised form 10 July 2009
Accepted 17 August 2009
Keywords:
Biomass
Pyrolysis
Catalytic cracking
Zeolites
Mass spectroscopy

a b s t r a c t
Fast pyrolysis bio-oils currently produced in demonstration and semi-commercial plants have potential as a
fuel for stationary power production using boilers or turbines but they require signicant modication to
become an acceptable transportation fuel. Catalytic upgrading of pyrolysis vapors using zeolites is a
potentially promising method for removing oxygen from organic compounds and converting them to
hydrocarbons. This work evaluated a set of commercial and laboratory-synthesized catalysts for their
hydrocarbon production performance via the pyrolysis/catalytic cracking route. Three types of biomass
feedstocks; cellulose, lignin, and wood were pyrolyzed (batch experiments) in quartz boats in physical
contact with the catalysts at temperature ranging from 400 C to 600 C and catalyst-to-biomass ratios of 5
10 by weight. Molecular-beam mass spectrometry (MBMS) was used to analyze the product vapor and gas
composition. The highest yield of hydrocarbons (approximately 16 wt.%, including 3.5 wt.% of toluene) was
achieved using nickel, cobalt, iron, and gallium-substituted ZSM-5. Tests performed using a semi-continuous
ow reactor allowed us to observe the change in the composition of the volatiles produced by the pyrolysis/
catalytic vapor cracking reactions as a function of the catalyst time-on-stream. The deoxygenation activity
decreased with time because of coke deposits formed on the catalyst.
2009 Elsevier B.V. All rights reserved.

1. Introduction
In recent years biofuels have attracted considerable attention
mainly because of high crude oil prices, national security concerns,
and potential climate change consequences. In addition to the
commercial production of biodiesel and corn-based ethanol, research
is increasingly being focused on developing processes for producing
liquid fuels from lignocellulosic biomass. One of the emerging
technologies is fast pyrolysis that produces high yields of a liquid
product, called bio-oil, which contains up to 70% of the energy of the
biomass feed [1]. However, certain bio-oil properties such as its low
heating value, incomplete volatility, acidity, instability, and incompatibility with standard petroleum fuels signicantly restrict its
application [2]. The undesirable properties of pyrolysis oil result
from the chemical composition of bio-oil that mostly consists of
different classes of oxygenated organic compounds. The elimination
of oxygen is thus necessary to transform bio-oil into a liquid fuel that
would be broadly accepted and economically attractive. Two types of
processes that have been used to reject oxygen from organic
molecules are hydrotreating and catalytic cracking. The former uses
hydrogen to remove oxygen in the form of water while the latter
accomplishes the removal of oxygen in the form of water and carbon
oxides using shape-selective catalysts like zeolites. Recent reviews on

Corresponding author. Tel.: +1 303 384 7703; fax: +1 303 384 6363.
E-mail address: Stefan_Czernik@nrel.go (S. Czernik).
0378-3820/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2009.08.011

hydrotreating [3] and on catalytic cracking [4] describe the principles

of these processes and provide numerous references to original
studies in those areas. The research described in this paper focuses on
catalytic reforming using zeolite catalysts. This approach offers
several potential advantages over hydrotreating such as no or low
need for hydrogen, atmospheric pressure processing, and a possibility
of close coupling with pyrolysis that could make the process
logistically and economically attractive.

2. Catalytic cracking of oxygenated organic compounds

Catalytic cracking accomplishes deoxygenation through simultaneous dehydration, decarboxylation, and decarbonylation reactions
occurring in the presence of zeolite catalysts. In the late 1970s,
synthetic zeolites such as ZSM-5 were successfully used to convert
oxygenated organic compounds into hydrocarbons [5,6]. ZSM-5
proved to be particularly effective for the conversion of methanol to
gasoline range hydrocarbons [7], which led to the commercialization
of the methanol-to-gasoline process by Mobil. This discovery also
stimulated research focused on the production of hydrocarbons from
biomass-derived pyrolysis oil and pyrolysis vapors [810]. Because of
the complexity of bio-oil, most of the research was conducted using
model compounds representing different chemical classes of bio-oil
components. Extensive research in this area has been conducted in
several centers, especially at Laval University [911], University of
Saskatchewan [1215], University of The Basque Country [16,17] and
most recently at University of Massachusetts [18]. In the temperature

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R. French, S. Czernik / Fuel Processing Technology 91 (2010) 2532

range of 350450 C oxygenated organic compounds in contact with

zeolite catalysts have been found to undergo a suite of chemical
reactions including dehydration, decarboxylation, cracking, aromatization, alkylation, condensation, and polymerization. The product was
always a two-phase liquid (aqueous and organic) and gas, while coke
deposits formed on the catalyst surface. The conversion and the
product composition varied depending on the class of compounds
tested. Using a xed bed of ZSM-5 catalyst, high conversions (N90%)
were obtained for alcohols, aldehydes, ketones, acids, and esters while
phenols and ethers remained mostly unchanged. Alcohols and
ketones reacted to produce high yields of aromatic hydrocarbons
while acids and esters were mostly converted to gas, water, and coke
with low yield of hydrocarbons. For example, initially complete acetic
acid conversion declined to 60% after 3 h on stream with the total
hydrocarbon yield below 10%. The high production of coke resulting in
a rapid catalyst deactivation was observed especially for the
compounds having low (b1) effective hydrogen index dened by
Chen [10] as:
H =Ceff = H2O = C
where H, C, and O represent the number of moles of hydrogen,
carbon, and oxygen in the feedstock. This coke is mostly produced by
dehydration of oxygenated organic compounds containing high
amount of oxygen; dehydration of low-oxygen-content compounds
produces mostly hydrocarbons. Chen [10] demonstrated that a
signicant improvement in the production of hydrocarbons from
low effective-hydrogen-index compounds such as acetic acid can be
obtained by co-processing with methanol, which has a hydrogen
index equal to 2. When zeolites were applied for deoxygenation of
biomass pyrolysis oils and its fractions [9,12,19] hydrocarbon yields of
1215% were reported but also high coke production and rapid
catalyst deactivation were observed due to hydrogen deciency
(effective hydrogen index b0.3) of biomass pyrolysis oils.
Diebold and Scahill of the National Renewable Energy Laboratory
[20,21] proposed an integrated fast pyrolysis/catalytic cracking
process concept in which vapors from the pyrolyzer were not
condensed and collected as bio-oil but directly fed to a catalytic
reactor and converted to aromatic and olen hydrocarbons. Using a
pilot plant vortex reactor followed by a xed-bed catalytic cracker
(450 C, commercial Mobil MCSG-2 catalyst), they achieved 12.7% of
total hydrocarbon yield based on wood feedstock. The IEA Biomass
Liquefaction Task technoeconomic evaluation [22] of the process
based on this data estimated the production cost of gasoline at $0.97/
gal (1992 dollars) for a biomass cost of $30/ton, which was not
attractive at that time. Comparable yields of hydrocarbons were also
reported by Evans and Milne [23] who used a packed-bed microreactor coupled with a molecular-beam mass-spectrometer (MBMS)
and obtained 11% total hydrocarbons, with 36% single-ring aromatics
and similar amounts of alkenes and heavier aromatics. This was only a
third of the theoretical yield estimated based on the assumption that
oxygen would be rejected mostly as carbon oxides with the excess as
water [20]. In the experiments of Evans and Milne, excessive coking
was also noted and was hypothesized to be due to the high acidity of
the HZSM-5 catalyst that enhanced dehydration reactions. In an effort
to improve the process performance a series of modied ZSM-5
catalysts was produced at the University of Utah and at NREL with
varying silica-to-alumina ratio and metal substitutions. We hoped
that the presence of transition metals would affect the mode of
oxygen rejection by producing more carbon oxides and less water
making that way more hydrogen available for incorporation into
hydrocarbons. The present work is an attempt to verify that modied
zeolite catalysts of reduced acidity can produce higher yields of
hydrocarbons and less coke than commercial ZSM-5 catalysts tested
before.

3. Experimental
The catalytic pyrolysis tests were performed using a tubular quartz
micro-reactor coupled with the MBMS. About 10 mg of biomass
sample contained in a quartz boat was covered with a layer of catalyst
(50100 mg) then inserted into owing, preheated carrier gas. Such a
high catalyst-to-biomass ratio in those exploratory tests was chosen
arbitrarily only to show the potential for producing hydrocarbons
from biomass; it will have to be optimized in later stages of the
process development. The carrier gases (helium) at a ow rate of 10 L/
min and 10 cm3/min of argon (used as a tracer gas) were introduced
through the end of the reactor that consisted of a 22 mm inner
diameter quartz tube. The reactor was electrically heated to the
desired temperature (400600 C) and coupled to the MBMS for
product detection. The experimental sequence consisted of: 1)
biomass pyrolysis in the bottom of the boat, 2) pyrolysis vapor
reaction in the catalyst bed, and 3) movement of the catalytically
upgraded vapors through the sampling orice of the MBMS to form a
molecular beam, which provided rapid sample quenching and
inhibited condensation and aerosol formation. Using an ionization
energy of 22.5 eV, the MBMS detected volatile products within a mass
range of 15350 amu. A detailed description of the experimental unit
and the MBMS techniques is provided elsewhere [24].
The three biomass feedstocks used in the pyrolysis/catalytic
cracking tests were ground aspen wood, Avicel PH-105 cellulose,
and straw lignin (provided by a biotechnology company Granit). The
elemental composition of these materials is shown in Table 1.
Forty catalysts were tested representing four groups: 10 commercial zeolites (including ZSM-5, Y, and SAPO types), 22 laboratoryprepared ZSM-5 catalysts modied by substituting Al or hydrogen
with different metals (Co, Fe, Ni, Ce, Ga, Cu, Na), four laboratory X and
Y zeolites, and four different silica and alumina materials. The list of
catalysts is provided in Table 2. The laboratory catalysts were
prepared using gel precipitation method followed by drying and
calcinations similar to that described in the Mobil patent [7].
Laboratory ZSM-5 catalysts had silica-to-alumina ratio of 75, which
varied for the transition metal-substituted catalysts. The catalysts
were not fully characterized yet and the degree of substitution is not
known at this time. For each catalyst two samples were tested usually
at varying catalyst-to-wood ratios. At least one sample of aspen wood
was pyrolyzed without catalyst each day when the experiments were
conducted to measure the pyrolysis products for comparison with
previous data to assess variability, which was on the order of
experimental error. Initial pyrolysis/catalytic cracking tests were
carried out for all three feeds at 400 C and catalyst-to-feed ratios of
approximately 5 and 10. Following the results of the preliminary tests,
the nine best-performing catalysts were used to evaluate hydrocarbon
yields produced from aspen wood at temperatures of 400, 500, and
600 C. These yields were determined based on the intensity of
respective spectrum lines compared to the calibration using toluene.
In addition to the batch experiments, semi-continuous tests were
initiated to observe the catalyst performance (product gas composition) as a function of the time-on-stream for three selected catalysts.
In these experiments 2 g of the catalyst was placed between quartz
wool plugs in the bottom of a 10 mm internal diameter tube heated by
an electric furnace as shown in Fig. 1. 34 mm long, 1 mm diameter

Table 1
Feedstock composition.
Elemental analysis, wt.% (m.f.)

Avicel

Lignin

Aspen

C
H
O
N
Ash

44.3
6.2
49.5
b 0.01
b 0.01

62.7
6.0
28.6
1.1
1.4

49.5
6.1
43.8
0.1
0.5

R. French, S. Czernik / Fuel Processing Technology 91 (2010) 2532

27

Table 2
List of catalysts used in biomass pyrolysis tests.
Catalyst numbera

Catalyst name

Producer

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40

BiZSM-5
CeZSM-5
H/[Co,Fe]ZSM-5
Co/Al2O3
H/[Co]ZSM-5
CoZSM-5
H/[Cu,Fe]ZSM-5
H/[Al,Fe]ZSM-5
H/[Fe]ZSM-5
H/FeZSM-5
GaZSM-5
H/ZSM-5
H/ZSM-5
H/ZSM-5/Al
MC-50
MC-508
Mn/Al2O3
Na/ZSM-5
ZSM-5/Al
ZSM-5/B
HZSM-5/B
NiZSM-5
BaX zeolite
CaX zeolite
BaY zeolite
CaY zeolite
NaY zeolite
LZY-8
Z-1000
ZSM-5
Al2O3
H/alumina
Kaolin
Silica gel
CBV 760 (Y zeolite)
CBV 720 (Y zeolite)
CBV 520 (Y zeolite)
SAPO-11
CBV 5524G
CBV 8014

NREL
NREL
U Utah
NREL
NREL
U Utah
U Utah
U Utah
U Utah
U Utah
NREL
NREL
U Utah
NREL
Mobil
Mobil
NREL
NREL
NREL
NREL
NREL
NREL
NREL
NREL
NREL
UOP
WR Grace
Union Carbide
Engelhardt
U Utah
Johnson Matthey
U Utah
NBS
Merk
Zeolyst
Zeolyst
Zeolyst
U Utah
Zeolyst
Zeolyst

a
b

Coke yieldb, wt.%

28.0

29.2
22.8
22.9

31.2
26.4

22.0

Fig. 1. Semi-continuous ow pyrolysis/catalytic cracking reactor.

24.6
26.0

Catalyst number in Fig. 5.

Catalytic pyrolysis of aspen wood at 600 C.

hardwood dowels were dropped onto the catalyst at 20 s intervals

(8 g/h, space velocity 4 h 1) and the product gases were swept to the
MBMS in a 10 L/min ow of helium. Amounts of char and coke were
determined by the gain in mass of the inner reactor piece measured at
the end of the test. The product gas composition was measured by
MBMS.
4. Results and discussion
Pyrolysis of biomass resulted in the formation of volatiles (gas and
vapors) that were analyzed by mass spectrometry and solids (char
and coke) whose amount was measured by weighing. The yields of
the solids are shown in Table 3. As expected, Avicel cellulose
volatilized almost completely (b1% residue) while lignin produced
signicant amounts of solid residue (char). The temperature increase
enhanced volatilization of biomass polymers, especially lignin. These
char yields are comparable to those reported in the literature for fast
pyrolysis of similar feedstocks [25].
Typical analyses of the volatiles produced by pyrolysis of biomass
feedstocks in quartz boats are shown in Fig. 2. The prominent peaks in
the spectra correspond to water (18) and carbon oxides (28 and 44)
that were produced from all studied feedstocks. The yields of H2O,
CO2, and CO from aspen wood were respectively 10 wt.%, 6 wt.%, and
5 wt.% accounting together for about 33% of biomass oxygen. The
other peaks represent different organic molecules that were formed
from cellulose and lignin resulting from the breakdown of their

polymeric structure. For aspen pyrolysis, they account for about

60 wt.% of feed and 50% of biomass oxygen. The top spectrum
obtained from pyrolysis of cellulose shows the typical carbohydrate
breakdown products such as hydroxyacetaldehyde and acetic acid
(60) (in this case, this spectrum line also represents a fragment ion of
levoglucosan (162) which is the major product of cellulose depolymerization), and furfuryl alcohol (98). The middle spectrum includes
lignin-derived aromatic monomers syringol (154), isoeugenol (164),
coniferyl alcohol (180), sinapyl alcohol (210), and heavier fragment
ions corresponding to dimers and trimers. The aspen wood pyrolysis
spectrum includes both cellulose and lignin-derived compounds. The
temperature effect on the volatile pyrolysis product in the range of
400600 C was not very signicant. Almost all pyrolysis products
were oxygenated compounds and only insignicant amounts
of hydrocarbons could be produced directly by simple thermal
decomposition of biomass at this temperature range (Fig. 2 and
Table 4, row 4).
In the presence of catalysts, the volatiles released by pyrolysis
underwent various reactions including deoxygenation (dehydration,
decarboxylation, decarbonylation) that resulted in the production of
hydrocarbons but also in additional carbonaceous solids coke. In our
tests we measured the combined amounts of solid residues then the
coke yields were determined by subtracting from total solids the
yields of char produced in non-catalytic experiments for respective
feedstocks assuming that the presence of the catalyst did not affect
the production of char, which is a primary non-volatile pyrolysis
product. The amount of coke varied depending on the feedstock, the
catalyst and the process temperature. For Avicel cellulose the amount
of coke left on the catalyst ranged from 30% to 50%, for aspen wood
from 10% to 30%, and for lignin from 5% to 15%. The yields of coke
produced by catalytic pyrolysis of aspen wood at 600 C using selected
nine catalysts is shown in Table 2. This data conrms the earlier
observation [10] that the coke production increases with a decrease of
Table 3
Yields of char (wt.%) produced by pyrolysis of biomass feedstocks.
Temperature, C

Avicel

Lignin

Aspen wood

400
500
600

1
b1
b1

46
39
29

16
13
10

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R. French, S. Czernik / Fuel Processing Technology 91 (2010) 2532

Fig. 2. Mass spectra of the volatile product from pyrolysis of Avicel cellulose (top), lignin (middle), and aspen wood (bottom) at 500 C; Y axis corresponds to the spectral line
intensity expressed in arbitrary units.

the effective hydrogen index, which equals 0 for cellulose, 0.16 for
aspen wood, and 0.47 for lignin. In general, higher coke production
was observed for the catalysts that also favored greater yields of
hydrocarbons, which is related to their dehydration activity. Though
lignin-derived vapors produced less coke than those from cellulose
and wood pyrolysis the total amount of solids (char and coke) could
reach 3060% of the feedstock. Lower amount of solids formed at
Table 4
Total hydrocarbon yields from catalytic pyrolysis of aspen wood.
Catalyst

NiZSM-5
Zeolyst 5524-G
Y zeolite
Al2O3

Hydrocarbon yield, wt.%

400 C

500 C

600 C

10
9
1.5
b1

12
14

16
16

600 C than at 400 C, which was mostly due to the reduced char
production at higher temperature, especially from lignin.
The catalytic pyrolysis spectra are very much different from those
for simple thermal process. Fig. 3 shows catalytic pyrolysis spectra
obtained from three biomass feedstocks using one of the best
catalysts, nickel-substituted ZSM-5. All the primary pyrolysis products
except water and carbon oxides appear to have converted mostly to
hydrocarbons of molecular mass less than 156 and to coke. The new
spectrum lines correspond to alkenes (27, 41, 42, 55, 56, 69, 70),
single-ring aromatics (78, 91, 92, 105, 106, 120), naphthalenes (128,
142, 156, 170), and methyl anthracene (192).
The spectra obtained using less active catalysts (silica, alumina or Y
zeolites) still showed some of the primary pyrolysis components
(mostly lignin-derived) as well as partially dehydrated oxygenates
furan (68), methyl furan (82), furfural (96), and methyl furfural (110).
Fig. 4 illustrates the difference of the product spectra obtained using
poor, medium, and good catalysts. No qualitative differences were

R. French, S. Czernik / Fuel Processing Technology 91 (2010) 2532

29

Fig. 3. Mass spectra of the volatile product from pyrolysis of Avicel cellulose (top), lignin (middle), and aspen wood (bottom) at 500 C, in the presence of NiZSM-5 catalyst; Y axis
corresponds to the spectrum line intensity expressed in arbitrary units.

observed in the spectra obtained for the same catalyst at different

temperatures though in most cases, the temperature increase resulted
in higher amounts of hydrocarbons. These spectra did not vary with
the catalyst loading because all the tests were performed using a large
catalyst excess. Interestingly, despite important differences in
chemical composition of primary pyrolysis products from cellulose
and lignin, the composition of volatiles from catalytic pyrolysis of all
three feedstocks was similar, at least for the best catalysts showing
mostly the same hydrocarbons with more alkenes obtained from
lignin than from cellulose and wood, most likely resulting from
splitting off propene side chains from aromatic lignin units.
The mass spectrometric data was evaluated using principal component analysis (PCA). The PCA application to biomass pyrolysis/
mass spectroscopy data has been described in detail by Evans and
Milne [24]. This multivariate pattern recognition technique reduces
the data complexity by nding correlated spectral intensities and
expressing them as new variables, the principle components. Usually
a few components account for the bulk of the variance in the data
because underlying chemical and physical relationships cause mass

intensities associated with a particular compound or family of

compounds to vary together as catalysts, conditions or feedstocks
change even when that is not obvious in the raw spectrum. Using the
Camo Unscrambler software we identied six principal components
that describe over 98% of the variance of the whole data set. The most
important principal components were associated with water (PC1),
hydrocarbons (PC2), and aromatic and furanoic oxygenates (PC3) and
accounted for 81% of the variance in the whole data set. Fig. 5 shows a
mass spectrum representing PC2 and its scores for all the catalysts
tested (only positive values of the scores are shown in Fig. 5b). The
catalysts for which the PC2 was high are considered to be the most
promising for the production of hydrocarbons from biomass pyrolysis
vapors. This group included laboratory-prepared catalysts: CeZSM-5,
CoZSM-5, CoHZSM-5, H[AlFe]ZSM-5, GaZSM-5, HZSM-5, and NiZSM-5
as well as the commercial Zeolysts 5524G and 8014. The preliminary
experiments conrmed that ZSM-5 type catalysts perform the best in
the process for converting oxygenated biomass pyrolysis vapors to
hydrocarbons. Contrary to some observations [26], larger-pore
zeolites proved less efcient in the deoxygenation of pyrolysis vapors

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R. French, S. Czernik / Fuel Processing Technology 91 (2010) 2532

Fig. 4. Mass spectra from catalytic wood pyrolysis using alumina (top), Z100 (middle), and Ga/ZSM-5 (bottom) at 500 C.

produced from all three types of feedstocks. Table 4 shows the

yields of hydrocarbons obtained by catalytic pyrolysis of wood in the
presence of selected best and less effective catalysts.
Semi-quantitative catalytic pyrolysis of aspen wood using nine
best catalysts showed only small performance difference between the
selected ZSM-5 zeolites. The yields of hydrocarbons were in the range
of 1016 wt.% and increased with temperature. This could be due to
both higher catalytic activity but also to more volatile pyrolysis
product (less char formed at higher temperature) available for the
secondary catalytic conversion. The highest yields of the desired
hydrocarbon product from wood, 16 wt.% including 3.5 wt.% of
toluene were obtained at 600 C using NiZSM-5 though the yields
produced by several other catalysts (gallium, cobalt, and ironsubstituted ZSM-5 zeolites as well as the commercial Zeolyst 8014)
were within the experimental error estimated at 3%. These yields
are comparable to those reported by Evans and Milne [23] for similar

zeolites. At this stage, we did not observe signicant differences in

the performance between laboratory-prepared HZSM-5 and metalsubstituted zeolites that were expected to have lower dehydration,
and consequently lower coking activity.
Tests performed using the semi-continuous ow reactor allowed
us to observe the change in the composition of the volatiles produced
by the pyrolysis/catalytic vapor cracking reactions as a function of the
catalyst time-on-stream. An example presented in Fig. 6 shows the
changes in the product slate represented by the intensity for selected
ions: m/z = 92 (toluene), m/z = 94 (phenol), and m/z = 60 (combined
acetic acid, hydroxyacetaldehyde, and levoglucosan) occurring during
the pyrolysis/catalytic cracking of hardwood at 500 C, using a HZSM5 catalyst. Despite the oscillation of the curves resulting from the nonuniform feeding rate of biomass to the reactor (especially between the
9th and 13th minute) a clear trend can be observed in the product
composition as a function of time. Initially, oxygenated compounds

R. French, S. Czernik / Fuel Processing Technology 91 (2010) 2532

31

Fig. 5. Mass spectrum (a) and scores of PC2 (b), the principal component representing hydrocarbons in aspen catalytic pyrolysis product at 400 C.

were not present in the toluene-rich product gas. In the rst minute
the product spectrum was very similar to that from Fig. 3. With time,
in addition to hydrocarbons, oxygenates such as phenol and cresol
showed up in the product. Finally, primary pyrolysis products became
dominant though the presence of hydrocarbons indicates that the
catalyst still retained some deoxygenation activity.
The semi-continuous tests, even of a relatively short duration
(30 min) showed that ZSM-5 catalysts could operate with high
deoxygenation activity for a short time after which they require
regeneration. Potentially, a circulating uidized bed system similar to
that used in uidized catalytic cracking of heavy oils could be applied
for the catalytic biomass pyrolysis to produce hydrocarbons.
5. Summary and conclusions

Fig. 6. Intensity of selected ions vs. time during hardwood pyrolysis/catalytic vapor
cracking at 500 C. Wood feed rate 0.13 g/min, 2 g of Mobil HZSM-5 catalyst.

We performed a preliminary study of biomass catalytic pyrolysis

to assess the efciency of selected catalysts for producing hydrocarbons that could be used as fuels or fuel blends. Batch mode tests
using three biomass feedstocks were conducted at the process

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R. French, S. Czernik / Fuel Processing Technology 91 (2010) 2532

temperature that ranged from 400 C to 600 C to identify the most

promising catalysts from a set of 40 selected for this study.
The molecular-beam mass-spectrometer was used to analyze the
product gas composition. The mass spectra were analyzed using
principal component analysis. The best-performing catalysts belonged
to the ZSM-5 group while larger-pore zeolites showed less deoxygenation activity. The highest yields of hydrocarbons from wood,
16 wt.% including 3.5 wt.% of toluene were obtained for the laboratoryprepared nickel-substituted ZSM-5 zeolite though a few other
laboratory-prepared ZSM-5 zeolites and a commercial Zeolyst 8014
performed almost as well.
Semi-continuous operation of the pyrolysis/vapor cracking process using a xed bed of a ZSM-5 catalyst at 500 C and a WHSV of 4
showed good deoxygenation performance for up to 4 min. At the end
of this time period the catalyst was partly deactivated and required
regeneration to maintain high activity.
Future tests will be conducted using a continuous ow system that
will allow us to collect the product and calculate mass balances for
different process conditions.
Acknowledgment
Financial support for this work was provided by the U.S.
Department of Energy Ofce of Biomass Programs.
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