Journal of Analytical and Applied Pyrolysis 114 (2015) 68–78

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Journal of Analytical and Applied Pyrolysis

journal homepage: www.elsevier.com/locate/jaap

Slow pyrolysis of paulownia wood: Effects of pyrolysis parameters on

product yields and bio-oil characterization
Sait Yorgun ∗ , Derya Yıldız
Department of Chemical Engineering, Engineering and Architecture Faculty, Eskişehir Osmangazi University, 26480 Eskişehir, Turkey

a r t i c l e i n f o a b s t r a c t

Article history: Pyrolysis experiments of paulownia wood (P. tomentose) were performed in a fixed-bed reactor under
Received 18 September 2014 static and nitrogen atmospheres. The effects of the final pyrolysis temperature (623–873 K), heating
Received in revised form 30 April 2015 rate (10 and 50 K min−1 ), particle size (0.224–1.8 mm), and sweep gas flow rate (100–300 mL min−1 )
Accepted 9 May 2015
were investigated on the pyrolysis conversion and product yields. The maximum pyrolysis conversion of
Available online 12 May 2015
77.4% was obtained at a final pyrolysis temperature of 773 K. The highest liquid product yield of 54.0 wt%
was obtained at the pyrolysis temperature of 773 K with a heating rate of 50 K min−1 , particle size of
Keywords:
0.425 < Dp <1 mm and a nitrogen flow rate of 100 mL min−1 . In addition, the bio-oil and fractions of the
Biomass
Paulownia wood
bio-oil were examined using elemental analysis and, chromatographic and spectroscopic techniques.
Pyrolysis The empirical formula of the bio-oil with heating value of 28.6 MJ kg−1 was established as CH1.57 O0.29 .
Bio-oil The obtained bio-oil can be considered a potential source for energy or fuels and a valuable chemical
Characterization feedstock.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction fossil fuel resources [2,10,11], and it is a renewable resource with

The world energy demand is currently met mainly by conven-
tional fossil energy sources such as coal, crude oil and natural
gas. Despite of the high costs of fossil fuels, global climate change
and predicted future reduction of fossil fuel feed stocks, over 90%
of the energy in most developing countries is obtained from fos-
sil fuels [1,2]. In the future, world energy systems will need to
be renewable and sustainable, efficient, cost-effective, convenient
and safe [3]. To meet rapidly increasing energy demands, alter-
native energy sources must be utilized effectively. Industrialized
nations have initiated long-term plans to replace their current
energy sources with clean and sustainable energy sources. Renew-
able energy sources are destined to play a very important role in
the world energy balance [4]. Among these sources, biomass is
the world’s largest and most sustainable energy resource [5], with
an estimated ∼2.2 × 1011 Mg of dry biomass worldwide annually
[6,7]. Biomass has been proposed to play a central role in future
sustainable-energy scenarios [8]. It has been estimated that, by
2050, biomass could provide nearly 38% of the world’s direct fuel
and 17% of the world’s electricity [9]. Biomass has been recognized
as a major world renewable energy source to supplement declining
∗ Corresponding author. Tel.: +90 222 239 37 50 36 66; fax: +90 222 239 36 13.
E-mail address: syorgun@ogu.edu.tr (S. Yorgun)
large potential, economic viability and various social and environ-
mental benefits [2,9,10,12–14]. It contains negligible amounts of
sulfur, nitrogen and ash, which means that it emits less SO2 , NOx
and soot than fossil fuels [1,15,16]. Biomass appears to have posi-
tive environmental properties that result in no net release of CO2
[10,13,14,17].
Examples of biomass feedstocks include wood/wood wastes and
forestry residuals [5,7,13,18–29], agricultural crops and their by
product and wastes [2,4,13–16,22,30–32], municipal solid wastes
(MSW) [25,33], wastes from food processing [14,34], urban and
solid industrial wastes [35–37], animal wastes, aquatics and algae,
and energy plants including perennial or annual crops with high
yields [13,17,38–43]. All of these feedstocks can be utilized as
sources of biofuels in the form of solid, liquid and gaseous fuels.
They may also be used as the sources of energy, chemicals and acti-
vated carbons. The majority of biomass energy is produced from
wood and wood wastes (64%), followed by MSW (24%), agricultural
wastes (5%), and landfill gases (5%) [44]. The processing of wood
generates lignocellulosic biomass in the form of wood sawdust, off-
cuts and chips, which can amount to 20% of the total input mass
[45]. In total, 2.8 × 108 Mg of wood residues are produced world-
wide annually [18]. Wastes obtained from clearing forests and from
the wood processing industry could amount to large quantities of
biomass, and these wastes may play an important role in find-
ing new alternative energy sources and fuels. Wood wastes can be

http://dx.doi.org/10.1016/j.jaap.2015.05.003
0165-2370/© 2015 Elsevier B.V. All rights reserved.
 S. Yorgun, D. Yıldız / Journal of Analytical and Applied Pyrolysis 114 (2015) 68–78
burned for heating in various industrial and domestic applications
or for producing steam to generate electricity [10,15,18,20,44].
Much research has focused on sustainable and environment-
friendly energy from biomass to replace conventional fossil fuels
[44]. In recent years, there has been an increased focus on using bio-
chemical and thermochemical technologies which convert biomass
to valuable liquid, gaseous, and solid fuels and chemicals of higher
value [5–7,13,19,20,41,44]. Amongst the thermochemical conver-
sion processes (e.g. pyrolysis, gasification and combustion), the
pyrolytic process is recognized as the most promising because it
can be used either as an independent process for fuels and other
valuable chemical products or an initial step prior to gasifica-
tion or combustion [46]. Pyrolysis processes are mainly classified
into carbonization (very slow), conventional (slow), fast and flash
depending on the operating conditions that are used [47]. The major
operating parameters include the type of reactor, final pyrolysis
temperature, heating rate, sweep gas velocity, residence times, par-
ticle size, catalyst, volatile matter, mineral matter, and the moisture
content of raw materials [48]. The yield of the pyrolysis product
depends upon the properties of biomass, type of the pyrolysis pro-
cess and operating parameters. Pyrolysis has received increased
attention because the process conditions can be optimized to max-
imize the production of solid, liquid and gaseous fuels [5,7,11,12].
The lower pyrolysis temperature and low heating rate lead to the
formation of char product. Higher final pyrolysis temperatures,
lower heating rate and longer residence times increase the biomass
conversion to gas product. The intermediate final pyrolysis temper-
atures (773–823 K), high heating rate and short vapour residence
time usually maximize the liquid yield. Three products are always
produced, but the proportions can be varied over a wide range by
adjustment of the pyrolysis parameters [47,48]. The major objec-
tive of biomass pyrolysis is to produce liquid fuel [48].
The liquid product is composed of two phases, namely, the bio-
oil and aqueous phases. The bio-oil is complex mixture of organic
compounds from different chemical groups such as aliphatic, aro-
matic, hydrocarbons and oxygenated compounds.
Bio-oil has value as a fuel because, as a liquid, its handling, stor-
age, transportation and utilization are similar to the methods of
processing petroleum-based oils [34]. It can also be upgraded to
refined fuels or added to petroleum refinery feedstocks [12,48],
and it can contain chemicals in economically recoverable concen-
trations [7]. It can serve as a substitute for fuel oil or diesel fuel
in many applications including boiler/burner/furnace systems for
heat generation and diesel engines/turbines for power/electricity
generation [5,8,13,22,36,48–50]. Alternatively, bio-oils can be used
as raw materials for obtaining hydrocarbons in the boiling range
by hydrotreating or catalytic transformation [14,51]. Bio-oils could
serve as a raw material for the production of different chemi-
cals [14,22]. The yield and composition of bio-oil depends on the
biomass feedstock and processing parameters [48].
Biomass energy sources are extensively found throughout
Turkey. Turkey’s annual biomass potential is approximately 1.41 EJ,
of which the total recoverable bio-energy potential is estimated
to be approximately 0.75 EJ. This energy also comprises approx-
imately 13% of the total energy used in Turkey [16]. For many
years, Turkey has used wood, animal wastes, agricultural crop
residues, forestry-wood processing residues and municipal wastes
as fuels for direct combustion [16]. In Turkey, establishing modern
energy forests and adding energy crops to forests and agricul-
tural lands will bring many advantages such as reducing the use
of fossil fuels to protect natural forests and environments, dimin-
ishing soil erosion, and providing significant sources for a wide
range of useful chemicals, materials, and energy [38]. Paulownia is
an economically important genus in the family Scrophulariaceae,
with nine species of very adaptable and fast-growing timber trees
[52]. Turkey’s geographical and climatic conditions are suitable
69
for Paulownia plantation. In recent years, Paulownia has received
increasing attention as a genus suitable for use as a short-rotation
woody crop in Turkey. Paulownia trees have been used to produce
leaves useful as fodder or fertilizer, flowers for medicine or honey
production, wood for solid products, and pulp to produce fine paper
[52–54]. Paulownia wood is a potential resource for energy gen-
eration, chemical production, and production of activated carbon
[24,27]. Up to now, no satisfactory information has been found in
the literature about the pyrolysis of paulownia wood (P. tomen-
tose). In this study, paulownia wood was pyrolyzed in a fixed-bed
reactor. The influences of final pyrolysis temperature, heating rate,
sweep gas flow rate and particle size range on the pyrolysis prod-
uct yields were investigated. In addition, the bio-oil was examined
using elemental analysis and chromatographic and spectroscopic
techniques.
2. Experimental
2.1. Materials
The paulownia wood used as a raw material in this study was
obtained from Çorum, the Black Sea region of Turkey. Prior to
use, Paulownia tree stems were debarked and the debarked, stems
were reduced to a size of 10–20 mm. The chips were then dried
to approximately 10% moisture at room temperature for approx-
imately 2 weeks and then ground in a high speed rotary cutting
mill and subsequently screened to produce particle size fractions of
0.224 < Dp < 0.425, 0.425 < Dp < 1, 1 < Dp < 1.8 and Dp > 1.8 mm. The
sample fractions were kept in glass jars for use in further experi-
ments. All samples were dried in an oven at 378 K for 24 h before
pyrolysis experiments. Ultimate analyses of the raw material, bio-
oil and n-pentane fraction were carried out using an elemental
analyser (LECO, CHNS 932). Moisture, ash, volatile matter con-
tent and higher heating value were determined according to ASTM
test methods. Fixed carbon was calculated from the difference.
Cellulose, hemicellulose, lignin and extractives of the wood were
analyzed according to Turkish Standards and ASTM standards. The
results of ultimate, proximate and component analyses of the raw
material are given in Table 1, and the elemental compositions of
the wood, bio-oil and n-pentane fraction are given in Table 2.
2.2. Pyrolysis
The slow pyrolysis experiments were performed in a fixed-bed
reactor, which is a lab-scale pyrolysis system. The 316 stainless-
steel fixed-bed reactor (70 mm i.d. and 140 mm length) with a
sweep gas (N2 ) connection was externally heated by an electrical
furnace. In the pyrolysis system, the heating rate, final pyrolysis
temperature and sweep gas flow rate were controlled. The tem-
perature was measured with a Ni–Cr thermocouple inside the bed.
The connecting pipe between the reactor and the cooling system
Table 1
Main characteristics of paulownia wood.
Characteristics Raw material (wt%) ASTM test standard
Proximate analysis (as received)
Moisture 6.50 D 4442–92
Ash 1.06 D 1102–84
Volatile matter 71.80 E 987–82
Fixed carbona 20.64
Component Analysis (as received)
Cellulose 44.25 TS 324
Hemicellulosea 24.79
Lignin 22.61 D 1106–96
Extractives 8.35 D 1105–96
a
By difference.
70 S. Yorgun, D. Yıldız / Journal of Analytical and Applied Pyrolysis 114 (2015) 68–78

Table 2 fate to remove the remaining water, and then the solvent (DCM)
Elemental compositions and fuel properties of wood, bio-oil and n-pentane sub-
was removed from the bio-oil by a rotary evaporator at 313 K and
fraction.
at a reduced pressure of 10 kPa and the quantity of the bio-oil
Analyses Wood (wt%) Bio-oila (wt%) n-Pentane eluatea (wt%) was measured by weighing. The bio-oil yield was calculated. The
C 44.73 66.12 84.18 water content of the bio-oil was determined be Karl-Fisher titra-
H 6.12 8.67 12.39 tion (ASTM E 203). After the experiments, the furnace was turned
N 0.87 – – off and the reactor system was purged with nitrogen with a flow
Oa 48.28 25.21 3.43
rate of 100 mL min−1 for 60 min. The reactor was removed from the
H/C molar ratio 1.64 1.57 1.77
O/C molar ratio 0.80 0.29 0.03 furnace at the end of this time and cooled down to room temper-
HHV(MJ kg−1 )b 20.7 28.6 43.0 ature to avoid the oxidation of char with compressed air at a rate
Water contentc none of 20 K min−1 . The remaining solid (char) was removed from the
Empirical formula CH1.64O0.8 N0.02 CH1.57O0.29 CH1.77O0.03
reactor and weighed. The gas yield was calculated from a material
a
Obtained at a pyrolysis temperature of 773 K, with a heating rate of 50 K min−1 balance. All the yields are expressed on a dry ash free (daf) basis, and
and nitrogen flow rate of 100 mL min−1 . the average yields from at least three experiments are presented,
b
ASTM D 3280.
c with experimental error less than ±1 wt%.
ASTM E 203.

2.3. Characterization
was heated to 673 K to avoid the condensation of tar vapor. More
detailed descriptions of the pyrolysis procedure can be found else-
The chemical class composition of the bio-oil was determined by
where [24,35,38].
liquid column chromatographic fractionation. Approximately 1 g
The pyrolysis experiments were performed in two different
of bio-oil was separated into two fractions, n-pentane soluble and
atmospheres, static (without using purging gas) and nitrogen in
insoluble compounds (asphaltenes), by using 100 mL n-pentane
a fixed-bed reactor. Prior to the pyrolysis experiments, the fixed-
as the solvent. The n-pentane soluble material was further sepa-
bed reactor was purged with nitrogen gas with a flow rate of
rated on activated silica gel (70–230 mesh) pretreated at 378 K for
100 mL min−1 for 10 min to create an oxygen-free condition. In the
2 h prior to introduction in a 20 cm height and 2.5 cm i.d. column.
static atmosphere experiments, to determine the effects of the final
The column was eluted successively with n-pentane, toluene and
pyrolysis temperature and the heating rate on the pyrolysis con-
methanol to obtain fractions enriched in aliphatic, aromatic and
version and product yields, 20 g of wood, reduced and sieved to the
polar chemical class fractions, respectively. Each fraction was dried
range of 0.425 < Dp <1 mm particle size, was placed in the reactor.
and weighed [38,41].
The air in the fixed-bed reactor was purged out with a nitrogen
The FTIR spectra of the bio-oil, n-pentane, toluene and methanol
flow of 100 mL min−1 for 10 min before each static pyrolysis exper-
fraction were recorded using a PerkinElmer 100 spectrophotometer
iment and then the sweeping gas flow was cut off. The temperature
with the range of 4000–400 cm−1 . 1 H NMR analysis was used for
was separately raised at both 10 and 50 K min−1 heating rates to the
determination of types of hydrogen in the bio-oil. 1 H NMR spectra
final pyrolysis temperatures of 623, 673, 723, 773, 823 and 873 K. At
of the bio-oil were obtained at an H frequency of 300 MHz using a
each of the final pyrolysis temperature values, the experiment was
Bruker Biospin UltrashieldTM instrument in deuterated chloroform
continued for an additional 30 min while the temperature was kept
(CDCl3 ) with tetrametylsilane [(CH3 )4 Si] as the internal standard.
constant to ensure that the total conversion of the raw material was
GC–MS analysis of the fractions of bio-oil were performed with
reached. In these experiments, the optimum heating rate and final
an Agilent 6850 GC equipped with an Agilent 7890 MS, using a
pyrolysis temperature values were determined to be 50 K min−1
0.25 mm × 30 m HP-5 capillary column with 0.25 ␮m film thickness
and 773 K, respectively, because the maximum liquid yield was
and the GC oven temperature was programmed from 343 K to 543 K
obtained under these conditions.
at 293 K min−1 and held at 543 K for 40 min. Helium was used as a
The second group of experiments was performed under static
carrier gas. The mass spectrometer was set at an ionizing 70 eV
atmosphere to determine the effect of particle size on the pyrolysis
with mass range (m/z) of 50–550. The compound identified using
conversion and product yields. Particle sizes of 0.224 < Dp < 0.425,
the database of the GC–MS (WILEY 7n.1).
0.425 < Dp < 1, 1 < Dp < 1.8 and Dp > 1.8 mm were used, and these
experiments were carried out at the most convenient conditions
of 773 K pyrolysis temperature with a heating rate of 50 K min−1 , 3. Results and discussion
based on the results of the first group of experiments.
In the third group of experiments (under nitrogen atmosphere), 3.1. Characterization of the raw material
to investigate the effect of the sweep gas velocity on the pyrolysis
conversion and product yields, the experiments were conducted at As shown in Tables 1 and 2, paulownia wood mainly consisted
a sweep gas flow rates of 100, 200 and 300 mL min−1 . The residence of cellulose, hemicellulose and lignin. The cellulose and hemi-
times for these sweep gas flow rates were 0.09, 0.045 and 0.03 s, cellulose components of wood were mainly responsible for the
respectively. By this way, the secondary reactions were minimized volatile portion of the pyrolysis products while lignin was the
due to the low residence times. In these experiments, the pyroly- main contributor to char [13]. These results reveal that higher
sis temperature, heating rate and particle size were taken as 773 K, volatile matter content resulted in higher bio-oil yield from the
50 K min−1 and 0.425 < Dp < 1 mm, respectively, based on the max- pyrolysis of wood [55]. The component and elemental analy-
imum liquid product yield values determined by the results of the ses of paulownia (P. tomentosa) wood were similar to those of
second group of experiments. Volatiles were passed through an other paulownia wood which contains cellulose (43.3 wt%), hemi-
ice-water condenser where the aqueous and bio-oil phases were cellulose (25.2 wt%), lignin (23.4 wt%) and extractives (8.2 wt%).
condensed at approximately 273 K using salted ice and recovered The elemental analysis is 45.5 wt% carbon, 6.3 wt% hydrogen and
by washing with dichloromethane. The aqueous phase of the liquid 48.2 wt% oxygen [27].
product was separated from the organic phase (bio-oil) by decanta- Forestry biomass has much lower ash content compared with
tion using a separatory funnel. The water content was measured, agricultural species. Volatile matter is in the range of 61–76%, and
and thus water yield was determined. The mixture of bio-oil and forestry biomass has somewhat higher volatile matter then agri-
dichloromethane (DCM) was filtered over anhydrous sodium sul- cultural biomass [56]. Paulownia wood has the advantages of low
 S. Yorgun, D. Yıldız / Journal of Analytical and Applied Pyrolysis 114 (2015) 68–78 71

55 product yields. When final pyrolysis temperature was increased

Char Gas Bio-oil Liquid from 623 to 873 K the pyrolysis conversion increased from 65.5% to
50
74.6% and from 70.5% to 76.0% for the heating rates 10 K min−1 and
45 50 K min−1 , respectively. Increasing the pyrolysis temperature and
heating rate increased the pyrolysis conversion. However, at high
40 pyrolysis temperature (873 K), increasing the heating rate from 10
to 50 K min−1 had no significant difference in the pyrolysis conver-
Yield (%)

35
sion yields. According to the results, the maximum conversion yield
30 of 76.0% was reached at a final pyrolysis temperature of 873 K with
a heating rate of 50 K min−1 . Similar results have been reported in
25 the literature [12,15,30,34,36,42].
As shown in Figs. 1 and 2, as the pyrolysis temperature increased
20
from 623 to 873 K, the char yields decreased from 34.5% to 25.4%
15 and from 29.5% to 24% at a heating rates of 10 K min−1 and
600 650 700 750 800 850 900 50 K min−1 , respectively. Higher char yields were obtained for
Pyrolysis temperature (K) lower heating rates over the entire temperature range. These higher
yields may be related to the rapid heating rate, which promotes
Fig. 1. Effect of final pyrolysis temperature on product yields at a heating rate of the fast depolymerization of the solid material to primary volatiles,
10 K min−1 and 0.425 < Dp <1 mm. (Liquid contains bio-oil, water and water-soluble while at the lower heating rate, dehydration to more stable anhy-
components).
drocellulose is limited and very slow. The char yields always
decreased with increasing final pyrolysis temperature and heating
ash content and high volatile matter, which make it the ideal raw rate, because the decomposition of the wood or secondary decom-
material for pyrolysis and gasification [7,56]. Wood with low mois- position of the char leads to higher conversion with increasing final
ture content is suitable for thermochemical conversion processes. temperatures [11,18]. Similar results have been reported in the lit-
In addition, the lower nitrogen content and absence of sulphur in erature [11,30,36]. The gas product yields consistently increased
paulownia wood compared with coal are especially important for with increasing pyrolysis temperature. When the final pyroly-
environmental protection [56]. As a result, paulownia wood can be sis temperature was increased from 623 to 873 K, the gas yields
considered as a suitable feedstock for pyrolysis to produce bio-oil. increased from 25.3% to 29.2% and from 22.4% to 27.1% at heating
rates of 10 K min−1 and 50 K min−1 , respectively. The increase in
3.2. Influence of pyrolysis parameters on the product yields the gaseous product is thought to be predominantly due to the
secondary cracking of the pyrolysis vapours at higher tempera-
The yield and quality of the pyrolysis products mainly depend tures. However, the secondary decomposition of the char at higher
on operating parameters, type of biomass and type of the pyrolysis temperatures may also generate non-condensable gaseous prod-
process. The operating parameters include final pyrolysis temper- ucts. Similar observations have been made by other researchers
ature, heating rate, residence time, sweep gas flow rate, moisture [15,34,36,42].
content, mineral matter, and catalyst [36,48,50]. The liquid product was composed of aqueous and bio-oil phases.
The pyrolytic aqueous phase, including all the water soluble organic
3.2.1. Effect of final pyrolysis temperature and heating rate on the compounds, consisted of water coming from both moisture in
product yields the wood and the dehydration reactions occurring the pyroly-
Figs. 1 and 2 show the product yields from the pyrolysis of wood sis process [57]. In this study, it was observed that the main
in the fixed-bed reactor at varying final pyrolysis temperatures constituent of the aqueous phase was water (∼90 wt%). The water-
between 623 and 873 K with heating rates of 10 and 50 K min−1 soluble organic compounds were mainly formic and acetic acids,
and a particle size of 0.425 < Dp < 1 mm in a static atmosphere. and it contained low molecular-weight oxygenated organic com-
The pyrolysis temperature greatly affected the pyrolysis conver- pounds such as aldehydes, ketones, alcohols, phenols and others
sion and product yields. Heating rate was also important for the [13,46,57,58]. All the water-soluble organic compounds could be
recovered as useful chemicals [58]. As the final pyrolysis temper-
60 ature increased from 623 to 873 K, the pyrolytic aqueous phase
fraction increased from 19.9% to 21.1% and from 21.4% to 22.5% at
Char Gas Bio-oil Liquid
55 heating rates of 10 K min−1 and 50 K min−1 , respectively. As shown
50 in Figs. 1 and 2, at both heating rates of 10 and 50 K min−1 , the bio-
oil yield increased as the final pyrolysis temperature was increased
45 from 623 K to 773 K. On the other hand a decrease was observed
40 in bio-oil yield at a much higher final pyrolysis temperature of
Yield (%)

873 K. The bio-oil yield reached a maximum value of 29.5% with

35 a heating rate of 50 K min−1 and at the final pyrolysis tempera-
30 ture of 773 K. At high heating rates, the high bio-oil yield mainly
owes to short residence time to prevent the secondary reactions,
25 tar cracking and repolymerization [48]. As shown in Figs. 1 and 2,
20 at the lower heating rate of 10 K min−1 , the liquid yield was 43.1%
at a pyrolysis temperature of 623 K. The liquid yield reached max-
15 imum value of 45.7% at the temperature of 773 K and decreased
600 650 700 750 800 850 900 to 45.3% at 873 K. For the heating rate of 50 K min−1 , liquid yields
Pyrolysis temperature (K) were obtained at the level of 48.1–48.9% for pyrolysis temperatures
of 623–873 K. The maximum liquid yield of 51.0% was obtained
Fig. 2. Effect of final pyrolysis temperature on product yields at a heating rate of
50 K min−1 and 0.425 < Dp <1 mm. (Liquid contains bio-oil, water and water-soluble at the pyrolysis temperature of 773 K, and the yield decreased to
components). 48.9% at 873 K. Smaller quantities of liquid were obtained at higher
72 S. Yorgun, D. Yıldız / Journal of Analytical and Applied Pyrolysis 114 (2015) 68–78
Fig. 3. Effect of particle size on the product yields at heating rate of 50 K min−1 and
pyrolysis temperature of 773 K. (Liquid contains bio-oil, water and water-soluble
components).
temperatures than 773 K. It may be concluded that secondary reac-
tions of the volatile liquid product and further decomposition of
the char particles proceeded in the reactor with increasing pyrol-
ysis temperature [30]. Increasing the heating rate from 10 K min−1
to 50 K min−1 increased the liquid yield from 45.6% to 51.0%. This
increased yield may be due to the higher heating rate overcoming
the heat and mass transfer limitations in the pyrolysis atmosphere,
preventing secondary reactions and resulting in maximum liquid
product yields. The maximum liquid product yield of 51.0% was
obtained at a final pyrolysis temperature of 773 K with a heating
rate of 50 K min−1 [30]. Similar trends in the liquid product yield
have been noticed for the pyrolysis of different types of raw mate-
rials. Previous studies [11,12,15,30,34,36,48] suggest that a final
pyrolysis temperature between 773 and 873 K for biomass pyroly-
sis maximizes the liquid product yield.
3.2.2. Effect of particle size on the product yields
The particle size is another parameter that affects the pyrolysis
product distribution. The particle size also influences the heat and
mass transfer rates and the extent of secondary reactions inside
the particles. The useful particle size of the raw material may vary
depending up on the type of biomass and type of the pyrolysis
process. In general, small particle sizes are preferred in the rapid
pyrolysis system. This may be due to the fact that the smaller par-
ticles heat up uniformly [48] and therefore release more volatile
matter with more bio-oil and gas product yields. It is expected that
an increase in particle size (Dp >1.8 mm) leads to greater temper-
ature gradients inside the particle so that at a given time the core
temperature would be lower than that at the surface of the particle.
This likely gives rise to an increase in the liquid and char yields and
a decrease in the bio-oil and gas product yields [11].
The effect of particle size on the product yields at the con-
stant temperature of 773 K and at a heating rate of 50 K min−1 is
shown in Fig. 3. As observed in Fig. 3, the pyrolysis conversion, char,
gaseous, liquid and bio-oil product yields were found in the ranges
of 72.7–74.1%, 27.3–25.9%, 21.8–24.3%, 50.9–49.8% and 28.6–28.8%,
respectively, as the particle size increased from less than 0.224 to
above 1.8 mm. No significant effect of the particle size was observed
on the pyrolysis conversion and product yields. Similar results were
obtained from pyrolysis of different types of biomass [11,15,28,38].
The highest bio-oil yield of 29.5% was obtained with a particle size of
0.425 < Dp <1 mm at 773 K with a heating rate of 50 K min−1 under
static atmosphere.
65
60 Char Gas Bio-oil Liquid
55
50
45
Yield (%)
40
35
30
25
20
15
50 100 150 200 250 300 350
Nitrogen flow rate (mL min-1)
Fig. 4. Effect of nitrogen flow rate on product yields at a heating rate of 50 K min−1
and pyrolysis temperature of 773 K. (Liquid contains bio-oil, water and water-
soluble components).
3.2.3. Effect of sweep gas flow rate on product yields
The effects of sweep gas flow rate on the conversion and product
yields are given in Fig. 4. As shown in Fig. 4, the pyrolysis conversion,
char, liquid and gas product yields varied between 74.4 and 77.4%,
25.5 and 22.6%, 54.0 and 50.6% and 20.4 and 26.8%, respectively, as
the nitrogen flow rate increased from 100 to 300 mL min−1 . The
nitrogen flow affects the residence time of volatile matter pro-
duced by pyrolysis. The vapour residence time was calculated as
the ratio of the reactor volume to the carrier gas flow rates. Accord-
ing to this, vapour residence time was in the range of 0.09–0.03 s.
The rapid carrier gas flow (i.e. small residence time) serves to
remove the volatile products quickly from the reactor to minimize
secondary reactions such as thermal cracking, depolimerization,
recondensation and char formation and to maximize liquid yield
[11,30,34,36,41]. The maximum liquid product yield of 54.0% was
obtained at a sweep gas flow rate of 100 mL min−1 . The increase in
the nitrogen flow rate from 100 mL min−1 to 300 mL min−1 reduced
the bio-oil yield from 32.5% to 28.2%. The highest bio-oil yield
obtained as 29.5% at 773 K with a heating rate of 50 K min−1 under
static atmosphere increased to 32.5% with sweep gas at flow rate
of 100 mL min−1 . In other words, approximately a 10.2% increase
was observed in the bio-oil yields by the use of sweeping gas. As
reported in the literature [12,34], the sweeping gas removed the
volatile matters from hot zone to minimize the secondary reactions
and to maximize the bio-oil yield.
The char and gas yields were obtained as 27.3% and 22.8%,
respectively, without any sweeping gas. These values decreased to
25.6% and 20.4%, respectively, using the sweep gas at a flow rate of
100 mL min−1 . The sweeping gas flow rate of 100 mL min−1 had no
significant effect on the pyrolysis conversion yield, remaining con-
stant at about 74%. The pyrolysis conversion and gas yield increased
as the sweep gas flow rate increased from 100 to 300 mL min−1 .
The char and liquid yields decreased as the nitrogen flow rate was
increased from 100 to 300 mL min−1 . The reason for the decrease
in liquid product yield and increase in gaseous product yield was
either poor cooling or uncondensed volatiles leaving the pyrolysis
system as gaseous products [11,30]. Similar observations have been
made other studies [11,15,30,34,36,41].
3.3. Bio-oil characterization
The pyrolytic liquid following removal of the aqueous phase is
often referred to as oil or bio-oil. Bio-oil is usually a very complex
mixture of oxygenated aliphatic and aromatic hydrocarbons [31].
It has high viscosity, high corrosiveness, high oxygen content, low
 S. Yorgun, D. Yıldız / Journal of Analytical and Applied Pyrolysis 114 (2015) 68–78
Table 3
Comparison of column chromatography fractions of the bio-oils.
Biomass type Pentane soluble materials (%)
Paulownia wood 48.9
Potato skin 62.62
Hazelnut bagasse 54.42
Olive bagasse 80.41
Onopordum acanthium L. 43.0
Miscanthus × giganteus 64.2
heating value and low stability [50,51]. The composition and prop-
erties of bio-oil differ considerably from those of petroleum-based
fuels. Some of the negative properties of bio-oil can be eliminated
by upgrading the bio-oil. Various methods for upgrading include
solvent fractionation, hydroprocessing and catalytic cracking [51].
Chemical characterization of bio-oil is useful and necessary so that
these oils can be treated as mixtures of a few groups instead of
mixtures of more than 300 different organic compounds [23]. The
chemical content of bio-oil was determined using liquid column
chromatographic fractionation. As shown in Table 2, the carbon and
hydrogen contents of the n-pentane fraction of the oil were very
high compared to the composition of the bio-oil as a whole. More-
over, this fraction had a high calorific value (MJ/kg), and the H/C
molar ratio was between that of light and heavy crude oils (1.5–1.7).
The pentane eluate contained predominantly paraffins and olefins.
The toluene eluate contained low molecular weight aromatics, usu-
ally benzene or its derivatives, and the methanol eluate contained
oxygenated compounds. The results of the column chromatography
fractions of the bio-oil are presented in Table 3. The yield of pentane
plus toluene eluates in the bio-oil was higher than the pentane plus
toluene eluate yields of potato skin [36], hazelnut bagasse [35], Ono-
pordum acanthium [42], and Miscanthus x giganteus [41]. The polar
fraction obtained in this study was significantly lower compared to
the polar fractions found in potato skin [36], hazelnut bagasse [35],
Onopordum acanthium [42], and Miscanthus x giganteus [41].
The FTIR spectra of the bio-oil, n-pentane, toluene and methanol
fractions are shown in Fig. 5. The FTIR functional groups and
the indicated compounds of the bio-oil, n-pentane, toluene and
methanol fractions are given in Table 4. Symmetrical and asym-
metrical C H stretching vibrations of aliphatic CH3 and CH2 groups
(3050–2800 cm−1 ) and C H bending vibrations between 1475 and
1350 cm−1 indicate the presence of alkane groups in the bio-oil
and all fractions. The typical carbonyl group (C O) stretching vibra-
tions at approximately 1703 cm−1 in bio-oil suggests the presence
of aldehydes, ketones or carboxylic acids. The C C stretching vibra-
tions at approximately 1607 cm−1 in the bio-oil proves the presence
of alkanes. The presence of aromatic compounds is confirmed
by the aromatic C C stretching vibrations between 1460 and
1455 cm−1 . The existence of a C O stretch within 1075–1020 cm−1 ,
(1033 cm−1 ) indicates the presence of primary, secondary and ter-
tiary alcohols, phenols, and/or esters. Similar results were observed
in previous studies [59]. As shown in Fig. 5 and Table 4, bio-oil is
a complex mixture, containing mostly aliphatic and aromatic com-
pounds. The presence of hydrocarbon groups indicates that bio-oil
has the potential to be used as a fuel or a source of chemicals.
The bio-oil was further analyzed by 1 H NMR (proton nuclear
magnetic resonance). The 1 H NMR spectrum is divided into
three regions of interest based on the chemical shifts of specific
proton types. Aliphatic resonance occurs in the chemical shift
region 0.7–4.6 ppm, and olefinic resonance occurs between 4.6
and 6.3 ppm. Resonances between 4.6 and 6.3 ppm have been
attributed to non-conjugated olefins. Aromatic resonance occurs in
the 6.3–9.6 ppm region. The hydrogen distribution obtained from
the 1 H NMR spectrum is given in Table 5. The olefinic proton (peaks
73
Pentane eluate (%) Toluene eluate (%) Methanol eluate (%) Reference
43.1 32.2 24.7 Our study
20.89 22.39 56.72 [36]
33.29 14.81 51.90 [35]
35.84 40.45 23.71 [35]
∼21.0 ∼20 ∼50 [42]
37.9 22.7 39.4 [41]
in 4.6–6.3 pp chemical shift range) was the least abundant. The bio-
oil has the greatest portion (37.5%) of protons in the ␣ position to
an aromatic ring. The aliphatic content of the bio-oil was 66.4%.
The fractions of the bio-oil were analysed by GC–MS. The GC–MS
chromatogram of the n-pentane, toluene and methanol fractions
are given in Fig. 6. The n-pentane fraction consisted of normal alka-
nes, alkenes and branched hydrocarbons. As shown in Fig. 6, the
carbon distribution was between C10 and C30 . The distribution of
straight chain alkanes exhibited an increase in the range of C13 –C20
and a decrease in the range of C20 –C30 in the bio-oil. The bio-oil
contained mostly C13 –C20 aliphatic hydrocarbons. The results of
spectroscopic techniques were consistent with results from chro-
matography, confirming that the hydrocarbons of the n-pentane
fraction of the bio-oil are mixture of alkanes and alkenes.
In general bio-oils are mainly composed of aromatic, aliphatics,
aldehydes, ketons and phenolic compounds. Phenols and deriva-
tives such as 2-methoxy phenol (guaiacol), 2,6-dimethoxy phenol
(syringol) are primarily form by decomposition of lignin unit of
biomass and the esters, aldehydes, alcohols and ketons are formed
by degradation of cellulose and hemicellulose fraction of biomass
[27]. GC/MS techniques were applied to identify the chemical com-
position of the aliphatic, aromatic and polar subfractions of bio-oil.
Identified compounds can be divided into four different classes
of monoaromatics, aliphatics, oxygenated compounds and pol-
yaromatic compounds. Monoaromatic compounds include toluene,
furans, phenols, benzene and their derivatives. Aliphatics are
mainly consist of alkanes and alkenes and their derivatives. Oxy-
genated compounds composed of aldehydes, ketones, carboxylic
acid and esters [11]. The identification of the peaks was made using
the database of the GC–MS (WILEY 7n.1). The retention time, names
and areas of the identified compounds are listed in Table 6 and
only the compounds with more than 0.4% of total area was given.
As seen from Table 6, polyaromatic hydrocarbons (PAHs) (48.8% of
total area of n-pentane fraction) and alkanes (36.3% of total area of
n-pentane fraction) are the major compounds of n-pentane subfrac-
tion of bio-oil. Aliphatic subfraction contains mostly hydrocarbons
such as eicosane (C20 H42 ), heneicosane (C21 H44 ) and PAHs such as
naphthalene, 1,6,7-trimethyl- (C13 H14 ). The carbon distribution of
the n-pentane fraction ranged from C12 to C29 . Benzene derivatives
and phenolic compounds such as phenol, 2-methoxy- (Guaiacol),
phenol, 2-methoxy-4-methyl (Creosol) are the main compounds
identified in the toluene subfraction. The carbon distribution of the
toluene fraction ranged from C7 to C10 . Bio-oil can be used not only
as a fuel in engines but also as a chemical feedstock, phenols could
be considered as one of them because of their commercial values.
Methanol subfraction of the bio-oil contains mostly oxygenated
compounds (48% of total area of methanol fraction) and phenols
(41% of total area of methanol fraction). 2-Cyclopenten-1-one, 2-
hydroxy-3-methyl- and phenol, 2,6-dimethoxy- (Syringol) are the
most abundant compounds (according to their area%) identified in
methanol fraction. The carbon distribution of the methanol fraction
ranged from C2 to C21 . Table 6 gives peak areas of identified com-
pounds in percents, which represented the relative concentrations
rather than the actual concentrations of the detected compounds.
74 S. Yorgun, D. Yıldız / Journal of Analytical and Applied Pyrolysis 114 (2015) 68–78

Fig. 5. Infrared spectra of the bio-oil (a), n-pentane (b), toluene (c) and methanol (d) fractions.

Table 4
Results of FTIR spectra for bio-oil, n-pentane, toluene and methanol fractions.

Frequency range (cm−1 ) Functional groups Bio-oil Pentane Toluene Methanol Class of compounds

3500–3200 O H stretching + – + + Polymeric O H, water impurities

3050–2800 C H stretching + + + + Alkanes
1750–1650 C O stretching + – + + Aldehydes, ketones, carboxylic acids, quinones, etc.
1645–1500 C C stretching + + + + Alkenes
1475–1350 C H bending + + + + Alkanes
1300–1150 C O stretching + – + + Primary, secondary and tertiary alcohols
1300–1150 O H bending + – + + Phenols, esters and ethers
1150–1000 C H bending + – + + Alkenes
900–675 O H bending + + + + Aromatic compounds
 S. Yorgun, D. Yıldız / Journal of Analytical and Applied Pyrolysis 114 (2015) 68–78 75

Fig. 6. GC–MS chromatogram of the n-pentane, toluene and methanol fractions.

76 S. Yorgun, D. Yıldız / Journal of Analytical and Applied Pyrolysis 114 (2015) 68–78

Table 5
1
H NMR results of the bio-oil.

Type of hydrogen Chemical shifts (ppm) Bio-oila [mol% (% of total hydrogen)]

␤-CH3 , CH2 and CH␥ or further from an aromatic ring 0.7–1.4 11.51
CH3 , CH2 and CH␣ to an aromatic ring 1.8–3.3 37.55
Ring-join methylene (Ar–CH2 –Ar) 3.3–4.6 17.36
Total aliphatics 0.7–4.6 66.42
Phenolic (OH) or olefinic proton 4.6–6.3 14.53
Aromatic 6.3–9.6 19.05
a
Bio-oil obtained at 773 K, 50 K min−1 under nitrogen flow rate of 100 mL min−1 .

Table 6
Identification and peak area (%) of n-pentane, toluene and methanol subfractions of the bio-oil.

RT (min) Name of the compound (n-pentane) Formula Peak area (%)

25.13 Naphthalene, 1,7-dimethyl C12 H12 1.17

25.51 Naphthalene, 1,6-dimethyl- C12 H12 0.83
25.59 Naphthalene, 2,7-dimethyl- C12 H12 0.82
26.00 Naphthalene, 2,6-dimethyl- C12 H12 0.51
26.40 Naphthalene, 1,3-dimethyl- C12 H12 0.51
26.94 Naphthalene, 1,2,3,4-tetrahydro-1,4,6-trimethyl- C13 H18 0.64
27.17 1,1 -Biphenyl, 4-methyl- C13 H12 0.43
27.30 Naphthalene, 1,2,3,4-tetrahydro-2,2,5,7-tetramethyl- C14 H20 1.62
27.54 Pentadecane C15 H32 0.7
27.66 3-(2-Methyl-propenyl)-1H-indene C13 H14 0.43
28.25 Naphthalene, 1,4,6-trimethyl- C13 H14 1.1
28.94 Naphthalene, 2,3,6-trimethyl- C13 H14 1.13
29.37 Naphthalene, 1,6,7-trimethyl- C13 H14 9.93
30.68 Hexadecane C16 H34 1.65
32.35 [1,1 -Biphenyl]-4-carboxaldehyde C13 H10 O 0.59
32.68 Naphthalene, 1,2,3,4-tetramethyl- C14 H16 1.72
33.86 Azulene, 7-ethyl-1,4-dimethyl- C14 H17 4.28
33.98 9H-Fluorene, 2-methyl- C14 H12 1.9
34.18 Heptadecane C17 H36 3.18
34.49 2,2 -Dimethylbiphenyl C14 H14 2.22
35.04 4-Carbomethoxy-3-methoxy-4-methyl-2,5-cyclohexadien-1-one C10 H12 O4 1,00
35.22 Benzene, 1-methyl-3-[(4-methylphenyl) methyl]- C15 H16 0.51
35.83 Phenanthrene C14 H10 1.36
36.17 1-Octadecene C18 H36 1.25
36.31 Octadecane C18 H38 4,05
37.80 1H-Cyclopropa[l]phenanthrene,1a,9b-dihydro- C15 H12 2.28
37.90 Nonadecane C19 H40 3.22
38.02 Phenanthrene, 1-methyl- C15 H12 3.13
38.27 Hexadecanoic acid, methyl ester C17 H34 O2 2.26
39.13 1-Heptadecene C17 H34 1.25
39.21 Eicosane C20 H42 8.48
39.45 Phenanthrene, 3,6-dimethyl- C16 H14 2.69
40.09 Hexadecane C16 H34 1.2
40.31 8,11-Octadecadienoic acid, methyl ester C19 H34 O2 4.55
40.35 Heneicosane C21 H44 4.4
40.60 Pyrene C16 H10 0.76
40.63 Octadecanoic acid, methyl ester C19 H34 O2 0.62
41.31 1-Nonadecene C19 H38 0.99
41.37 Docosane C22 H46 3.61
41.89 Pyrene, 1-methyl- C17 H12 2.83
42.25 9-Tricosene, (Z)- C23 H46 0.75
42.31 Tricosane C23 H48 2.46
43.29 1-Heneicosene C21 H42 0.44
43.35 Tetracosane C24 H50 2.18
46.77 Heptacosane C27 H56 3.27
47.50 Octacosane C28 H58 0.98
48.19 Nonacosane C29 H60 1.82

Name of the compound (toluene)

7.37 Cyclohexane, ethyl- C8 H16 1.35
8.29 Benzene, ethyl- C8 H10 1.16
12.63 Phenol C6 H6 O 0.71
15.08 Phenol, 2-methyl- C7 H8 O 1.75
16.30 Phenol, 2-methoxy- (Guaiacol) C7 H8 O2 16.26
18.02 Phenol, 2,4-dimethyl- C8 H10 O 1.53
18.94 2-Methoxy-6-methylphenol C8 H10 O2 2.35
19.49 Phenol, 2-methoxy-4-methyl (Creosol) C8 H10 O2 17.49
21.33 Phenol, 2-ethyl-6-methyl- C9 H12 O 1.73
21.96 Benzene ethanol, 2-methoxy- C9 H12 O2 21.4
24.03 Phenol, 2-methoxy-3-(2-propenyl)- C10 H12 O2 6.7
24.09 2-Methoxy-4-Ethyl-6-Methylphenol C10 H14 O2 1.57
24.28 Phenol, 2-methoxy-4-propyl- C10 H14 O2 6.1
24.49 1,3-Benzodioxole, 5-(1-propenyl)- C10 H10 O2 2.24
 S. Yorgun, D. Yıldız / Journal of Analytical and Applied Pyrolysis 114 (2015) 68–78 77

Table 6 (Continued)

RT (min) Name of the compound (n-pentane) Formula Peak area (%)

25.14 Benzaldehyde, 4-hydroxy-3-methoxy C8 H8 O3 5.18

25.32 Phenol, 2-methoxy-4-(1-propenyl)- C10 H12 O2 4.19
47.34 [1,1 -Binaphthalene]-4,4’-diol C20 H14 O2 1.04
47.96 Phenol, 2-methoxy-4-(2-propenyl) C10 H12 O2 0.49
49.29 2,24-Dihydroxytetracosanoic acid C20 H38 0.58
50.97 3-(8-methoxycarbonyl-7-tetralyl)-2-(6-tetralylmethyl) propanoic acid C26 H30 O4 0.68

Name of the compound (methanol)

2.67 Acetic acid C2 H4 O2 3.05
5.01 Propanoic acid, 2-methyl- C4 H8 O2 0.84
8.07 2-Furanmethanol C5 H6 O2 1.34
11.93 2-Furancarboxaldehyde, 5-methyl- C6 H6 O2 1.71
14.31 2-Cyclopenten-1-one, 2-hydroxy-3-methyl- C6 H8 O2 6.43
15.31 3,5-Dımethyl Cyclopentenolone C7 H10 O2 0.98
16.21 Phenol, 2-methoxy- C7 H8 O2 1.15
16.41 4-Ethyl-2-hydroxycyclopent-2-en-1-one C8 H14 O 0.73
17.31 Ethyl Cyclopentenolone C7 H10 O2 1.95
19.39 Phenol, 2-methoxy-4-methyl- C8 H10 O2 1.41
19.78 1,2-Benzenediol C6 H6 O2 2.65
21.48 1,2-Benzenediol, 3-methoxy- C7 H8 O3 3.5
21.77 2,3-Dihydroxy-Acetophenone C8 H8 O3 0.78
21.86 Phenol, 4-ethyl-2-methoxy- C9 H12 O2 1.24
22.46 1,2-Benzenediol, 4-methyl- C7 H8 O2 1.17
22.81 4-vinyl-2-methoxy-phenol C9 H10 O2 0.87
23.35 1,3-Benzodioxole-5-carboxaldehyde C8 H6 O3 1.26
24.06 Phenol, 2,6-dimethoxy- (Syringol) C8 H10 O3 18.7
24.55 2,5-Dihydroxypropiophenone C9 H10 O3 0.89
24.86 4-Ethylcatechol C8 H10 O2 1.22
25.25 Benzaldehyde, 4-hydroxy-3-methoxy- C8 H8 O3 2.29
26.51 Ethanone, 1-(2,4,6-trihydroxyphenyl)- C8 H8 O4 0.74
27.12 1,2-Dihydroxy-4-(1-propyl) benzene C9 H12 O2 1.06
27.40 Ethanone, 1-(4-hydroxy-3-methoxyphenyl)- C9 H10 O3 1.11
28.56 2,4-Dimethyl-3-(methoxycarbonyl)-5-ethylfuran C10 H14 O3 9.76
28.71 Homovanillyl alcohol C9 H12 O3 1.87
29.64 2,6-Dimethyl-3-(methoxymethyl)-p-benzoquinone C10 H12 O3 1.08
31.09 Phenol, 2,6-dimethoxy-4-(2-propenyl)- C11 H14 O3 5.03
33.27 Benzaldehyde, 4-hydroxy-3,5-dimethoxy- C9 H10 O4 2.47
35.08 Ethanone, 1-(4-hydroxy-3,5-dimethoxyphenyl)- C10 H12 O4 1.3
35.93 2-Pentanone, 1-(2,4,6-trihydroxyphenyl) C11 H14 O4 2.7
36.84 Benzene, 4-(dimethoxymethyl)-1,2-dimethoxy- C13 H20 O4 0.73
48.82 11H-Cyclopenta[a]phenanthrene-15-carboxylic acid C21 H20 O4 0.79

4. Conclusion References

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• Paulownia wood seems to be a suitable raw material for pyrolysis
conversion into liquid and gaseous products.
• The presence of aliphatic and aromatic hydrocarbon in bio-oil is
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