Fuel 129 (2014) 6167

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Pyrolysis and catalytic upgrading of pine wood in a combination

of auger reactor and xed bed
Li Bosong, Lv Wei, Zhang Qi, Wang Tiejun, Ma Longlong
Key Laboratory of Renewable Energy and Gas Hydrate, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou, Guangdong 510640, PR China

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 Pyrolysis and catalytic upgrading of

pine wood was studied in a combined

system.
 The system included an auger
pyrolysis reactor and a xed-bed
catalytic reactor.
 HZSM-5 catalyst was evaluated for
catalytic cracking.
 HZSM-5 was suitable for converting
pine wood to phenols and aromatics.

a r t i c l e

i n f o

Article history:
Received 21 September 2013
Received in revised form 3 March 2014
Accepted 20 March 2014
Available online 5 April 2014
Keywords:
Bio-oil
Auger reactor
Catalytic upgrading
HZSM-5
Phenols

a b s t r a c t
A combined system of auger pyrolysis reactor and xed-bed catalytic reactor was designed and used for
continuous pyrolysis and catalytic upgrading of pine wood in this paper. HZSM-5 (Si/Al = 38) catalyst was
evaluated for catalytic cracking. The distributions of liquid and gaseous products at the pyrolysis temperatures of 400600 C and the catalytic cracking temperatures of 450650 C were determined. The results
showed that HZSM-5 catalyst, at a catalytic temperature of 650 C, was suitable for converting pine wood
to phenols, aromatics and gaseous hydrocarbons. The phenols and aromatics increased from 6% (peak
area) for non-catalytic pyrolysis to 41%. The decrease in oxygen content of bio-oil and the increase in
alkenes and alkanes of gaseous products are desirable for the pyrolysis and catalytic upgrading of
biomass.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
The development of renewable energy as replacements for fossil-based fuels is rapidly progressing. Lignocellulosic biomass is
being studied worldwide as a feedstock for producing liquid fuels
and chemicals to replace petroleum because of its renewability
and large availability [13]. Pyrolysis is one of the main methods
Corresponding author. Tel.: +86 20 87057790.
E-mail address: mall@ms.giec.ac.cn (L. Ma).
http://dx.doi.org/10.1016/j.fuel.2014.03.043
0016-2361/ 2014 Elsevier Ltd. All rights reserved.

from biomass to bio-oil production, and it has caused great attention and sparked interest extensively in recent years. However,
bio-oil from biomass pyrolysis, is a mixture of more than 200
highly oxygenated compounds. Bio-oil is thermally unstable and
must be upgraded if to be used as fuels.
Various approaches have been applied to the improvement of
bio-oil quality, including hydrodeoxygenation [4,5], catalytic cracking [6,7], emulsication [8,9], steam reforming [10], esterication
[11], etc. One option for bio-oil upgrading is to use biomass-derived
feedstocks in a petroleum renery, such as catalytic cracking.

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B. Li et al. / Fuel 129 (2014) 6167

Catalytic cracking of bio-oil is an upgrading process of deoxygenation, which can improve the quality of bio-oil. Various types of
zeolite catalysts have been studied in the catalytic cracking of biomass in the past 20 years, such as ZSM-5, Beta, Y, Al-MCM-41, and
SBA-15. Catalysts for bio-oil upgrading have been well reviewed by
many researchers [12,13]. Among these catalysts, HZSM-5 performs as a good catalyst for catalytic conversion of biomass due
to its moderate internal pore space and steric hindrance [14]. It
has been found to dramatically change the composition of bio-oils
by both reducing the amounts of oxygenated compounds via deoxygenation reactions and simultaneously increasing the aromatic
species, producing a lighter faction, while decreasing the bio-oil
molecular weight [15].
Several types of reactors have been used in catalytic pyrolysis/
upgrading of biomass [1618]. In bench-scale reactors, currently
only bubbling uidized beds (BFBs) and circulating uidized beds
(CFBs) can be applied to continuous production, and there is mixing of solid biomass with the solid catalyst. There are two drawbacks on uidized bed reactors. (1) The uidized beds need large
volumes of inert carrier gases, which dilute the pyrolytic gases
and reduce the thermal efciency of the process. (2) The presence
of char (especially the ash in char) in the catalyst reduces the capability of the catalyst.
Auger pyrolysis reactors, with/without the use of sand as a heat
carrier, are among the most popular reactors being evaluated today
[19,20]. These reactors do not require large volumes of carrier
gases, and can produce pyrolysis vapors continuously. If a catalysis
bed is connected to the auger pyrolysis reactors, the pyrolysis vapors will pass through the catalyst and there is no mixing of solid
biomass with the solid catalyst, which called catalytic upgrading of
pyrolysis vapors. Thus, the combined system of auger pyrolysis
reactor and xed-bed catalytic reactor can overcome the drawbacks of uidized bed systems.
In this paper, a combined system of auger pyrolysis reactor and
xed-bed catalytic reactor was applied to achieve biomass continuous pyrolysis and catalytic upgrading of pyrolysis vapors. HZSM-5
zeolite was evaluated for catalysis cracking upgrading using pine
wood as feedstock. The reaction parameters were optimized with
a focus on the effects of reaction temperatures. Furthermore, the
properties and components were investigated before and after
upgrading.
2. Experimental
2.1. Characterization of feedstock and catalysts
The pine wood feedstock was from Guangdong province, China.
Feedstock was ground and sieved to a particle size <1 mm. The
pine wood samples were oven-dried overnight to 68% moisture
content at 105 C before tests. Elemental analyses of pine wood
samples were carried out using a Vario EL cube. The ash content
was determined according to ASTM D-482. Thermogravimetry
(TG) analysis of feedstock was carried out under a nitrogen ow
rate of 30 ml/min with STA 449 C thermal analyzer (NETZSCH,
Germany) by using 10 mg samples and a 30 C/min temperature
increase.
HZSM-5 zeolite catalyst with a Si/Al ratio of 38 was from the
Nankai University Catalyst Co. Ltd. (Tianjin, China). The shape of
catalysts was cylindrical with the diameter of 3 mm and the length
of 10 mm. Before using, the catalysts were calcined at 550 C for
6 h in air. NH3 temperature-programmed desorption (NH3-TPD)
analysis was carried out in a quartz tube reactor with a thermal
conductivity detector (TCD). 200 mg of catalyst was pretreated in
a ow of helium (25 ml/min) at 500 C for 1 h, and after cooling
to 120 C, ammonia adsorption was carried out. Subsequently,
excessive physisorbed ammonia was removed by purging with he-

lium at 100 C for 1 h. Tests were carried out by increasing the temperature from 100 to 700 C at a rate of 10 C/min and a helium
ow rate of 25 ml/min.
2.2. Pyrolysis and catalytic cracking upgrading
Pine wood was pyrolysed and catalytic cracking upgrading
using a combined system of auger pyrolysis reactor and xedbed catalytic reactor as shown in Fig. 1. The dried biomass was
introduced into the hopper of the feeder and fed into the auger
reactor at a feeding rate of 25 kg/h. The pine wood was pushed
through the hot zone of the reactor with an auger screw driven
by a 1.5 kW variable speed motor. All the tests were conducted
at auger speeds of 5 rpm which corresponds to a solid residence
time inside the reactor of 8 min. Outside the auger screw, a stainless-steel tube with a length of 300 cm (heating zone was 240 cm)
and a diameter of 16 cm was heated by a hot blast stove. A diesel
burner (Riello 40 G3, Italy) was the heat resource of the hot blast
stove. The temperature of the external wall in the pyrolysis reactor
was recorded and maintained at set temperatures. The temperature of the pine wood sample pyrolysed was also quantied. Due
to the structure of the reactor and the blowing direction of hot
wind, the varied temperature values existed along the reactors
axis. Owing to the relatively low heat transfer coefcient between
the wall and the biomass moving bed, a signicant temperature
gradient was established between the biomass bed and the wall
of the reactor. Fig. 2 shows the timetemperature prole for the
pyrolysis of pine wood and the wall of the reactor. After pyrolysis,
the charred particles were collected, left to cool for 2 h and
weighed in a char pot. The pyrolysis vapors were sucked into a
xed-bed catalytic reactor which was loaded zeolite catalysts.
The xed-bed catalytic reactor (a stainless-steel tube with a length
of 130 cm and a diameter of 78 cm) was heated by an electrical furnace to the desired temperature (450650 C) before experiments.
After upgrading, the pyrolysis vapors were condensed in two condensation units. The rst unit was a vertical tube with cooling
water coils where pyrolysis vapors were cooled to approximately
25 C. The second condensation unit consisted of two traps in series immersed in water cooled by ice. The pressure inside the reactor was kept by a Roots vacuum pump with a frequency converter.
The Roots vacuum pump with a frequency converter to regulate
the suction had two purposes: (1) helping to suck the pyrolysis vapors from the reactor, and (2) controlling the velocity of ow to adjust the residence time of vapors inside the pyrolysis reactor and
catalyst bed. The yield of liquid was determined by weighing the
rst condenser and the traps. The non-condensable gases were calculated by difference.
2.3. Product analysis
Gas chromatography mass spectroscopy (GC/MS) analysis of
bio-oil was performed on a gas chromatograph (7890A, Agilent
Technologies, USA) coupled with a mass spectrometer (5975C, Agilent Technologies, USA). A HP-INNOwax capillary column was used
for the chromatographic separation of chemical components in
bio-oil. The injector temperature was 260 C, and a split ratio
20:1 was used. The GC oven temperature program was 2 min at
60 C, and to 240 C in a rate of 10 C/min with a dwell time of
10 min. The mass spectrometer was operated in the electron impact mode at 70 eV. After a solvent delay of 2.8 min, full scan mass
spectra were acquired from 12 to 500 m/z. The identication of the
main peaks was made from NIST11 MS Library and previously published literatures.
The water content of the bio-oil was determined by Karl
Fischer titration (ASTM D 1744) with a Metrohm 787 KF
Titrino. The analysis was carried out three times to conrm the

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B. Li et al. / Fuel 129 (2014) 6167

Fig. 1. Scheme of a combination of auger pyrolysis reactor and xed-bed catalytic reactor.

X gas

massgas
 100%
masssample  masschar  massliquid  masscoke

Xgas the total yield of gas released (wt.%)

Yield of gas released (mol/kg biomass) was calculated based on
the formula (3):

Yield of gas released P

X gas
 Sel:gas
molecular mass  Sel:gas

 1000

3. Results and discussion

3.1. Pine wood and HZSM-5 zeolite characterization

Fig. 2. Timetemperature prole for the pyrolysis of pine wood and the wall of the
reactor.

reproducibility and average values were calculated for each identied product.
Gas chromatography (GC) analysis of gas products was performed on a gas chromatograph (7890A, Agilent Technologies,
U.S.A.). A series of columns were used the chromatographic separation of chemical components in gas, which were J&W GS-GASPRO,
Agilent Mol. sieve 5A, and Agilent Hayesep Q. The injector temperature was 200 C, and a split ratio 20:1 was used. The GC oven temperature program was 3 min at 60 C, and 15 C/min to 250 C.
Hydrocarbons were analyzed by a ame ionization detector (FID),
CO2 and CO were analyzed by a thermal conductivity detector
(TCD1), and H2 was analyzed by TCD2.
The concentration of gas (vol.%) was calculated according to Eq.
(1):

V gas
Sel:gas P
 100%
V gas

The elemental composition of the pine wood used in the experiments was 45.29% C, 6.24% H, 0.20% N, 0.01% S, and 48.26% O. The
ash content of pine wood was 2.60%. The TG and differential thermal gravity (DTG) curves (Fig. 3) were obtained for the pine wood
pyrogenation under N2 at the heating rate of 30 C/min. From
Fig. 3, the TG curve of the pine wood pyrogenation shows that
thermal reaction occurred over a wide temperature range. The pine
wood sample had a char yield of 24.50 wt.% at the ending temperature of 600 C. From the DTG curve, there was a primary peak of

Sel.gas the concentration of gas (vol.%); Vgas the volume of gas

(L).
The total yield of gas released (wt.%) was calculated according
to Eq. (2):

Fig. 3. TG and DTG curves for pine wood at a heating rate of 30 C/min.

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B. Li et al. / Fuel 129 (2014) 6167

mass loss at the temperature of 375.5 C, and the temperature

range of mass loss was from 215 C to 430 C. Thus, the pyrolysis
temperature of 500 C was enough to make sufcient pyrogenation
for the pine wood sample.
The pore structure properties of the HZSM-5 catalyst sample
were that the specic surface areas were 325 m2/g, and the pore
volume was 0.22 cm3/g. Fig. 4 shows the NH3-TPD curve of the
HZSM-5 catalyst used in this study. It can be seen that two obvious
desorption peaks occur over the HZSM-5 zeolite. The one at 230 C
could be attributed to weak adsorption of NH3 on the bronsted acid
site and NH3 association with Si-OH, and the other peak at 440 C
could be ascribed to a strong description of NH3 adsorbed on the
acidic SiOHAl group [2124].

Table 1
The product distribution obtained under various pyrolysis and upgrading temperatures using the HZSM-5 catalyst. Data are the average of results from three
experiments, the experimental error is 62.0%.

Sample temp. (C)

Catalyst bed temp. (C)
Char (wt.%)
Gas (wt.%)
Oil (wt.%)
Water content (wt.% in oil)

Without catalyst

HZSM-5

400

45.1
24.7
30.2
40.2

500
450
30.0
37.5
32.5
50.4

500

30.3
35.7
34.0
45.6

600

25.2
41.7
33.1
60.5

500
550
30.2
39.8
30.0
60.2

500
650
30.5
42.5
27.0
70.8

3.2. Pyrolysis and catalytic upgrading of pyrolytic vapors from pine

wood
Table 1 shows the product distribution obtained under various
pyrolysis and upgrading temperatures using the HZSM-5 catalyst.
When pyrogenation without catalyst, a higher temperature caused
more char to be converted into gases via secondary decomposition
reactions, but the bio-oil yield maintained more or less unchanged.
Based on this result and TG result, the pyrolysis temperature was
set at 500 C during the catalytic upgrading experiments. When
the HZSM-5 catalyst was loaded in the catalytic upgrading bed,
the bio-oil yield reduced due to catalytic cracking, which lead to
an increased gas yield and an increased water content in bio-oil.
The water content in the bio-oil increased obviously to 70.8% on
increasing the catalytic cracking temperature to 650 C. As mentioned above in NH3-TPD results, the strong acid sites existed in
HZSM-5, which showed excellent cracking performances. This resulted in the deoxygenation of oxygenates in the bio-oil, which
contained carbonyl and carboxyl groups, indicating that the catalytic upgrading improved the bio-oil quality [3]. The main deoxygenation pathway of bio-oil is dehydration, which can be used as
a basis for the evaluation of bio-oil produced from lignocellulosic
biomass [25].
3.3. Chemical composition of upgraded bio-oils
The GCMS results of the bio-oil obtained from pyrolysis and
catalytic upgrading are shown in Fig. 5. More than 50 compounds
in bio-oil were identied by GCMS. Compared with non-catalytic
pyrolysis, the composition of the bio-oil from catalytic upgrading

Fig. 4. NH3-TPD prole of HZSM-5 catalysts.

Fig. 5. The GCMS results of the bio-oil obtained from pyrolysis and catalytic
upgrading. A: non-catalysis, B: catalytic temp. 450 C, C: catalytic temp. 550 C, D:
catalytic temp. 650 C.

was changed obviously. However, not all the experimental conditions could change the composition of bio-oil effectively. When
the catalyst bed temperature was lower (e.g. 450 or 550 C), the
peak curves were similar with the non-catalysis curves. This outcome may be related to the temperature of catalytic cracking because a higher temperature provides more energy, which favors
the break of bonds in large molecules of bio-oil.
The compositions of the bio-oil obtained from pyrolysis and catalytic upgrading are shown in Table 2. In the raw bio-oil, acids, ketones, phenolics and D-allose were shown to be the main products,
while the distribution of products resulting from catalytic cracking
over HZSM-5 at 650 C was different. The primary products of upgraded bio-oil were mono-phenols, and the peak area percentage
was more than 30%. Aromatics, such as xylene and indene, were
also observed. With the use of catalysts, acetic acid decreased from
33% for non-catalytic pyrolysis to 13.8%, while phenols and alkyl
phenols increased from 5.8% for non-catalytic pyrolysis to 34.4%.
D-allose was not detected in the upgraded bio-oil.
In this study, mono-phenols (phenol and alkyl phenols, not
including guaiacol derivatives) and aromatics were regarded as
desirable chemicals, and oxygenates were chosen as the criteria

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B. Li et al. / Fuel 129 (2014) 6167

Table 2
The compositions of the bio-oil obtained from pyrolysis and catalytic upgrading.
R.T./min

Name

Raw bio-oil/Area%

Upgraded bio-oila/Area%

4.19
6.03
6.51
7.26
7.42
8.50
8.73
8.98
9.41
9.46
9.66
11.11
12.10
12.31
12.39
13.02
13.32
13.38
14.37
14.47
14.84
14.87
15.56
15.62
16.49
17.31
18.06
19.92
20.70

p-Xylene
Furan, 2,5-diethoxytetrahydro2-Propanone, 1-hydroxy2-Cyclopenten-1-one
2-Cyclopenten-1-one, 2-methylAcetic acid
Furfural
Indene
Furan, 2,4-dimethyl2-Cyclopenten-1-one, 3-methylPropanoic acid
2-Furanmethanol
1H-Indene, 1-methylene2(5H)-Furanone
1,2-Cyclopentanedione
2-Cyclopenten-1-one, 2-hydroxy-3-methylNaphthalene, 1-methylPhenol, 2-methoxyPhenol, 2-methoxy-4-methylNaphthalene, 2,6-dimethylPhenol, 2-methylPhenol
Phenol, 2,5-dimethylPhenol, 4-methylPhenol, 3-ethylPhenol, 2,6-dimethoxyBenzoic acid, 4-hydroxy-3-methoxyVanillin

7.05
1.35

33.07
2.95

1.32
1.90
1.55

1.17

2.48

1.88
1.39

1.01
2.79

2.03

4.17
2.61
1.02
7.21

5.46
4.75
5.69
3.59
1.40
13.79
1.36
1.77
1.13

2.40

2.81

1.84
2.95
2.56
3.35

1.79
4.36
11.67
2.28
11.71
1.24
1.33

D-Allose

Compounds listed are those represented by more than 1% of the total peak area.
a
Upgrading temperature condition: 650 C.

species to assess the degree of deoxygenation. Changes in the biooil composition as a result of catalytic upgrading are shown in
Fig. 6. In general, catalytic upgrading resulted in a reduction of
the oxygen content and an increase in the phenols and aromatics
contents, which were high value-added. In this study, with the
HZSM-5 catalyst, at the higher temperature (650 C), the main oxygenate compounds, such as acids, alcohols, carbonyls and carbohydrates, were removed effectively, while it was not effective at
lower temperatures. Oxygenates decreased from 71% for noncatalytic pyrolysis to 48%, while phenols and aromatics increased
from 6% for non-catalytic pyrolysis to 41%. It is concluded that
HZSM-5 catalyst with micropores and strong acid were the most
effective for removing oxygenates and producing phenols and

Fig. 6. Main chemical compounds in bio-oils. A: non-catalysis, B: catalytic temp.

450 C, C: catalytic temp. 550 C, D: catalytic temp. 650 C.

aromatics. This agrees with the results of other researches [3,26].

The high value-added condensables could be used as high quality
aromatic fuel additives or chemicals after a distillation or extraction process.
3.4. Gas products
The composition of gas products obtained by pyrolysis and catalytic upgrading is shown in Table 3. And Fig. 7 shows the yield of
gas released at different experimental conditions. Compared with
bubbling uidized beds and circulating uidized beds, there are
no inert gases in the gas products by the combined system of auger
pyrolysis reactor and xed-bed catalytic reactor. CO and CO2 were
the main gas products both in non-catalytic and catalytic pyrolysis,
which took up 7590 volume percentages. The formation of CO and
CO2 is another well known pathway of the deoxygenation of biooil. Another interesting result was that employing a catalyst considerably increased the concentration and yield of C2+ alkenes, as
well as water and CO. This observation suggests that HZSM-5 contains Brnsted acid sites and is a system of two perpendicularly
intersecting channels. The larger of the two channels has a near circular pore structure with dimensions of 0.54  0.56 nm2. The smaller channels have a geometry of 0.51  0.54 nm2. The intersection
of these channels which contains the proposed active site is
approximately a 0.9 nm cavity [27]. Several reactions occur inside
the zeolite including dehydration, decarboxylation, isomerization
and decarbonylation thereby removing oxygen as water, carbon
monoxide and carbon dioxide and converting the carbon and
hydrogen into olens and aromatics [1,17]. In addition, alkanes
and hydrogen increased when catalytic upgrading. This result indicated that in the present of catalysts, the bonds in the side chains
of bio-oil molecules broken up and released more gas molecules.
Therefore, it is considered that HZSM-5 catalyst was effectual to
produce alkenes and alkanes, which improved the quality of
pyrolysis gases.

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B. Li et al. / Fuel 129 (2014) 6167

Table 3
The composition of gas products obtained by pyrolysis and catalytic upgrading.
Pyrolysis temp. (C)

Catalyst bed temp. (C)

500
500
500
500

450
550
650

The concentration of gas (vol.%)

CH4

C2 + alkane

C2 + alkene

C6H6

CO2

CO

H2

6.17
6.17
4.89
9.64

0.83
0.83
0.78
1.54

1.26
1.26
2.14
9.80

0.11
0.11
0.02
0.33

46.74
46.74
51.16
37.43

43.75
43.75
39.92
37.95

1.14
1.14
1.08
3.32

the Cooperation Project of ChinaEuropean Union Founded by

MOST of China-China (246772).

References

Fig. 7. The yield of gas released at different experimental conditions. A: noncatalysis, B: catalytic temp. 450 C, C: catalytic temp. 550 C, D: catalytic temp.
650 C. Data are the average of results from three experiments, the experimental
error is 62.0%.

4. Conclusions
The general conclusion from this study is that the high
value-added condensables and pyrolysis gases can be produced
from biomass by a combined system of auger pyrolysis reactor and
xed-bed catalytic reactor. This means a signicant development in
the progress of continuous catalytic pyrolysis for the treatment of
lignocellulosic biomass. The combined system can overcome the
drawbacks of uidized bed systems: No requirement of carrier gases
and no mixing of solid biomass with the solid catalyst.
HZSM-5 (Si/Al = 38) catalyst loaded in xed-bed catalytic reactor shows high activity for biomass catalytic pyrolysis. Using
HZSM-5 catalyst, the higher catalytic temperature (650 C) is suitable for converting pine wood to phenols, aromatics and gaseous
hydrocarbons. This work proves that the properties of bio-oil can
be effectively improved and the oxygen content can be markedly
reduced though continuous catalytic pyrolysis.
The combined system of auger pyrolysis reactor and xed-bed
catalytic reactor used in this work must be viewed as a research
prototype. Future work in this area will focus on two elds. The
one is the efciency analysis facing to the industry application.
The other one is the stability and reactionregeneration cycles of
the catalysts.

Acknowledgements
This research was sponsored by the National Natural Science
Foundation of China-China (51106166), the National Science &
Technology Pillar Program of China-China (2011BAD22B07), and

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