Journal of Environmental Chemical Engineering 8 (2020) 104561

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Journal of Environmental Chemical Engineering

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Characteristics of pyrolysis products from pyrolysis and co-pyrolysis of

rubber wood and oil palm trunk biomass for biofuel and
value-added applications
Patipan Sakulkit a, Arkom Palamanit a, b, *, Racha Dejchanchaiwong c, Prasert Reubroycharoen d
a
Energy Technology Program, Faculty of Engineering, Prince of Songkla University, 15 Karnjanavanich Rd., Hat Yai, Songkhla, 90110, Thailand
b
Interdisciplinary Graduate School of Energy Systems, Prince of Songkla University, 15 Karnjanavanich Rd., Hat Yai, Songkhla, 90110, Thailand
c
Department of Chemical Engineering, Faculty of Engineering, Prince of Songkla University, 15 Karnjanavanich Rd., Hat Yai, Songkhla, 90110, Thailand
d
Department of Chemical Technology, Faculty of Science, Chulalongkorn University, Phyathai Rd., Pathumwan, Bangkok, 10330, Thailand

A R T I C L E I N F O A B S T R A C T

Editor: Yunho Lee This study investigated the yields and characteristics of bio-oil, biochar and pyrolysis gas obtained from pyrolysis
and co-pyrolysis of rubber wood sawdust (RWS) and oil palm trunk (OPT) by using an agitated bed pyrolysis
Keywords: reactor. Co-pyrolysis of RWS and OPT was performed at the mixing ratio of 50:50 (wt.). The biomass samples
Biochar were pyrolyzed at temperatures of 400, 450, and 500 ◦ C under specific conditions. The results indicated that the
Biomass
yields of the bio-oil, biochar and pyrolysis gas were in the ranges of 38.5-46.5, 22.27-28.68 and 30.1-36.9 wt.%,
Bio-oil
respectively. Pyrolysis of RWS at 500 ◦ C provided the most bio-oil. Co-pyrolysis of RWS and OPT could improve
Co-pyrolysis
Pyrolysis the product yield and quality. The bio-oil had relatively high water content, while its pH was low. The main
Pyrolysis products compounds of bio-oil were oxygenated compounds such as acetic acid, phenols and 2-Propanone, 1-hydroxy-,
determined by GC-MS. The higher heating value (HHV) of bio-oil ranged from 16.1 to 20.36 MJ/kg. The biochar
had high carbon content and low oxygen content in proximate and ultimate analysis, and based on FTIR. The
HHV of biochar was in the range from 26.35 to 29.6 MJ/kg. The biochar also was highly porous, which was
revealed by SEM and BET. The pyrolysis gas mainly contained CO, CO2, H2 and CH4, and its heating value was in
the range from 3.23 to 6.7 MJ/m3. Based on these results, the RWS and OPT are alternative and challenging
biomasses for conversion to biofuels and value-added products via pyrolysis.

1. Introduction applications in many countries, both developed and developing coun­

The applications of organic wastes and biomasses for biofuels, bio­
energy or biorefining are gaining interest due to the concerns of
depleting fossil fuel resources and their environmental impacts [1,2].
The heavy reliance on fossil resources not only affects security and
environment, but it also influences sustainability and economics,
particularly in countries that need to import the fossil fuels. Thus, uti­
lization of organic wastes and biomass for biofuels, bioenergy and bio­
refining based on the potential of each area, region or country is
motivated [3]. This is due to the fact that the potential of biomass by
region or country is different, depending on many factors such as loca­
tion, weather, as well as agricultural and industrial activities. The
biomass has high potential for biofuels, bioenergy and biochemical
tries. Previously, biomass has been applied to generate heat, power, as
well as to produce biofuels (solid, gaseous and liquid biofuels).
Currently, biomass is considered a renewable alternative resource for
energy and biochemical products in many countries, including Thailand
[3,4].
In Thailand, biomass plays an important role in bioenergy and bio­
economy systems, because this is an agro-industrial country, with high
potential biomass resources. The main sources of biomass in Thailand
are from growing, harvesting, processing, as well as replanting of crops
and plants. The rubber wood and oil palm biomasses are widely avail­
able in the southern region of Thailand. In 2018, the plantation areas of
rubber and oil palm trees in Thailand were 3.66 and 0.88 million
hectares, respectively [5,6]. The replantation of rubber trees generates a

* Corresponding author at: Energy Technology Program, Faculty of Engineering, Prince of Songkla University, 15 Karnjanavanich Rd., Hat Yai, Songkhla, 90110,
Thailand.
E-mail address: arkom.p@psu.ac.th (A. Palamanit).

https://doi.org/10.1016/j.jece.2020.104561
Received 23 May 2020; Received in revised form 25 September 2020; Accepted 27 September 2020
Available online 1 October 2020
2213-3437/© 2020 Elsevier Ltd. All rights reserved.
P. Sakulkit et al.
big source of wood and biomass. The previous studies reported that
replanting of rubber trees and processing of rubber wood generated a lot
of rubber wood biomass [7]. The rubber tree roots, rubber tree branches,
rubber wood slabs and rubber wood sawdust are examples of rubber
wood biomass. The higher heating value (HHV) of rubber wood biomass
is in the range 17.1-22.25 MJ/kg [7,8]. Some of these biomasses have
been applied in heat and power generation. However, the rubber wood
biomass still has high potential for biofuels, bioenergy and biochemical
applications. The oil palm biomass is non-wood biomass and the main
sources of this biomass are from processing of fresh fruit bunches and
replanting old oil palm trees. The processing of fresh fruit bunches
provides many residues and wastes, including empty fruit bunches, oil
palm pressed fiber, oil palm kernel shell, decanter cake, waste water and
sewage sludge [3,9]. The replantation of old oil palm trees generates a
huge source of oil palm fronds, oil palm leaves, oil palm trunks and oil
palm roots [10]. The empty fruit bunches, oil palm pressed fiber and oil
palm kernel shells have been used as solid fuel for heat and power
generation in industries and power plants. The higher heating value of
mentioned oil palm biomass is in the range from 12.8 to 18.7 MJ/kg [3,
11]. However, there is still only little applications of oil palm fronds, oil
palm leaves, oil palm trunks and oil palm roots for biofuels, bioenergy
and biochemical products [9]. Thus, these biomasses have high poten­
tial for biofuels, bioenergy and biorefinery applications.
The applications of biomass for biofuels and biorefinery are chal­
lenging because the choice of conversion process among the options
depends on many factors such as utilization target, conversion cost,
available technology, storage and transportation, as well as biomass
properties and composition [3,10,12]. The properties and composition
of biomass are the main factors that directly influence to the quantity
and quality of the obtained products [3]. Most biomasses obtained from
woods, plants and crops are lignocellulosic with cellulose, hemicellulose
and lignin. The lignocellulosic biomass is gaining interested as a
promising feedstock for biofuels, energy and biorefinery applications
[10,12]. This is due to the fact that growth of biomass absorbs carbon
dioxide (CO2) that is released from biomass or biofuels combustion, thus
utilization of bioenergy is considered carbon neutral [2,12]. The ligno­
cellulosic biomass can be classified as woody or non-woody depending
on its origin. The contents of cellulose, hemicellulose and lignin in
woody and non-woody biomasses are normally different due to many
factors such as variety, type, age, weather and growth conditions [13,
14]. The conversion of lignocellulosic biomass into biofuels, bioenergy
and biochemical products can be performed by several processes such as
mechanical, biological, thermochemical, and combined processes [10,
12].
Pyrolysis is one of alternative routes to produce the biofuels and
bioproducts for replacing the fossil resources [4,10]. It is widely applied
to many lignocellulosic biomasses such as wood from forestry, agricul­
tural residues and industrial wastes. Pyrolysis is the thermal decompo­
sition of raw materials or biomass under the absence of oxygen or air at
elevated temperature higher than 400 ◦ C. The main products obtained
from pyrolysis include bio-oil, biochar and pyrolysis gas [4,10,15].
There are normally two types of pyrolysis processes, including slow
pyrolysis and fast pyrolysis, which are classified by heating rate, py­
rolysis temperature and vapor residence time. These pyrolysis processes
provide different yields and quality of pyrolysis products. The bio-oil
obtained from pyrolysis is a complex mixture of aromatics, carbohy­
drate and oxygenated compounds, which are generated from the frag­
mentation of cellulose, hemicellulose and lignin [15]. The bio-oil with
appropriate water content can be used directly as fuel for boiler or
upgraded as liquid fuel for engine, as well as refined to value-added
biochemical products. The biochar from pyrolysis has high carbon
content, leading to high energy content, so it is suitable for use as solid
fuel for heat and power generation. The biochar also can be applied as a
sorbent for contaminant management in soil and water [10]. The py­
rolysis gas with appropriate heating value can be used as gas fuel for
heating pyrolysis or other processes. The quantity and quality of
2
Journal of Environmental Chemical Engineering 8 (2020) 104561
pyrolysis products not only depend on types of pyrolysis reactor and
pyrolysis conditions, but they are also influenced by biomass properties
and compositions [4].
Applications of pyrolysis to produce bio-oil and biochar from various
single species biomasses of both woody and non-woody types, such as
corn cobs, wheat straws, rice straws and rice husks [15] oil palm
biomass [16], rubber wood [8] and wood sawdust [4] have been re­
ported. However, there are not many studies related to the pyrolysis of
rubber wood biomass or oil palm trunks for producing bio-oil, biochar
and pyrolysis gas [3,10,11]. Besides pyrolysis, the co-pyrolysis of
lignocellulosic biomasses is challenging and of increasing interest.
Co-pyrolysis not only helps increase the utilization of low potential and
low grade feedstocks, but it may also help improve the yield and quality
of pyrolysis products as compared to pyrolysis of a single low-grade
feedstock. Previously, most studies of blended biomass pyrolysis have
mixed biomass either with coal, sewage sludge or plastic wastes [17].
There are very few or no studies on the co-pyrolysis of woody and
non-woody biomasses, such as rubber wood biomass and oil palm trunk.
Therefore, the aim of this study was to investigate the yield and quality
of pyrolysis and co-pyrolysis products, including bio-oil, biochar and
pyrolysis gas obtained from oil palm trunk (OPT), rubber wood sawdust
(RWS) and OPT mixed with RWS (OPT:RWS) by using an agitated py­
rolysis reactor.
2. Materials and methods
2.1. Biomass preparation
The biomass used in this study included OPT, RWS and OPT mixed
with RWS (OPT:RWS). The fresh OPT was obtained from an old oil palm
tree harvested at 22 years age. The oil palm tree was grown at Klong
Thom District, Krabi Province, Thailand. The RWS was obtained from
the rubber wood processing factory located at Khlong Ngae, Sadao
District, Songkhla province, Thailand. The fresh OPT was prepared by
reducing the size using the saw and chopping machine (MCH-420,
Machinery 789, Thailand). The chopped OPT and RWS were dried with
solar greenhouse dryer to reduce the moisture content below 10 wt.%
(wet basis). The dried chopped OPT and RWS was then ground with
grinding machine (YPS-102, Bonny, Thailand) to reduce the particle
size. The ground biomass samples had particle size smaller than 2 mm.
The mixed OPT and RWS was prepared by mixing of OPT and RWS with
the ratio of 50:50 (wt.). The prepared biomass samples were kept in
sealed plastic bags prior to the experiments.
2.2. Determination of biomass properties and compositions
2.2.1. Particle size distribution and bulk density of ground biomass samples
The particle size distributions of ground biomass samples were
determined by using a vibratory sieve shaker (Analysett 3 pro, Fritsch,
Germany). It was equipped with seven sieve sizes, including 0.08, 0.11,
0.15, 0.21, 0.30, 0.60, 1.18 mm and a bottom pan (<0.08 mm). The
determination was performed following the sieve standard of ASTM E11
[3,18]. It was done in triplicate and the result are presented as weight
percentages (wt.%). The bulk densities of the ground biomass samples
were determined based on the mass and volume ratio using a modifi­
cation of the method of Basu [19]. The ground biomass sample was filled
into the cylindrical container with 1000 mL volume. Then, the mass of
the ground biomass sample was weighted and the bulk density of
biomass was determined as the ratio of mass and volume (kg/m3) [3,
11].
2.2.2. Proximate and ultimate analysis
The gross compositions in terms of moisture content, volatile matter,
fixed carbon content and ash content of biomass were determined by
proximate analysis. The analysis was performed by using the macro
thermogravimetric analyzer (TGA 701, LECO, USA) following the
P. Sakulkit et al.
Fig. 1. Schematic diagram of the pyrolysis reactor.
procedure of ASTM D7582 [3,10]. The determination was carried out in
triplicate and results are presented as mean value with standard devia­
tion, on as received basis (wt.%, as received basis). The elemental
compositions of biomass samples were determined by ultimate analysis
using CHNS/O Analyzer (Flash 2000, Thermo Scientific, Italy),
following the ASTM D4239 and EN 15104 standard. The determination
was performed in triplicate and the mean value with standard deviation
are reported for contents of carbon (C), hydrogen (H), nitrogen (N),
oxygen (O) and sulphur (S) based on dry basis (wt.%, dry basis) [3,10].
2.2.3. Energy content and potential use as energy equivalent with fossil
fuels
The energy content or heating value of biomass samples is reported
in terms of higher heating value (HHV). The HHV of biomass was
determined directly by using bomb calorimeter (IKA C5000, Germany)
according to EN 14918 procedure. The HHV of biomass samples ob­
tained from bomb calorimeter was then converted to the potential en­
ergy equivalent with fossil fuels, including coal (bituminous), crude oil,
natural gas (NG) and liquefied petroleum gas (LPG). The reference HHV
of coal, crude oil, NG and LPG was 28.87 MJ/kg, 38.78 MJ/L, 38.95 MJ/
m3 and 50.08 MJ/kg, respectively [3,20,21].
2.2.4. Thermogravimetric analysis
The thermal decomposition behavior of biomass sample under inert
condition was observed via thermogravimetric analysis (TGA) and de­
rivative thermogravimetric analysis (DTG) using the thermogravimetric
analyzer (Perkin Elmer, USA), according to ASTM E1131 procedure. The
biomass sample of 10 mg was subjected to temperature ranging from 50
◦
C to 1000 ◦ C, at heating rate of 10 ◦ C/min under a nitrogen (N2) gas
atmosphere [3,10].
2.2.5. Lignocellulosic composition
The biomass samples were determined for chemical compositions in
terms of cellulose, hemicellulose and lignin contents. These contents
were determined via the method developed by Georing and Van Soest
[22], Van Soest [23], Reza et al. [24], and Kambo and Dutta [25]. Ac­
cording to this method, the acid detergent fiber (ADF), acid detergent
lignin (ADL) and neutral detergent fiber (NDF) were determined, and
then the percentages of cellulose, hemicellulose and lignin were calcu­
lated using the equations (1)–(3). The part of extractives was calculated
by difference method as shown in equation (4). All results are presented
as mean value and standard deviation on dry basis (wt.%, dry basis) [3,
10,11].
3
Journal of Environmental Chemical Engineering 8 (2020) 104561
Cellulose = ADF-ADL (wt.%, dry basis) (1)
Hemicellulose = NDF-ADF (wt.%, dry basis) (2)
Lignin = ADL (wt.%, dry basis) (3)
Extractives = 100- Cellulose - Hemicellulose - Lignin (wt.%, dry basis) (4)
2.3. Experimental set-up
The schematic diagram of agitated pyrolysis reactor used in this
study is shown in Fig. 1 (modified from Palamanit et al. [10]). The main
components of this reactor include a reaction chamber, heater with
controller, high torque direct current motor, agitated blade connected to
a magnetic coupling drive, motor speed controller, hopper and control
valve, cyclone, shell and tube condensers, water cooling bath, nitrogen
gas tank with regulation system, nitrogen gas flow meter, and flow
meter for cold water. The shape of reactor chamber was cylindrical and
it was made from stainless steel with a diameter, height and wall
thickness of 13,15 and 0.5 cm, respectively. The reaction chamber was
heated by electrical heater with the power of 3 kW. The temperature of
biomass sample during pyrolyzing can be measured by K-type thermo­
couple equipped with stainless steel shield. The PID-controller was used
to control the temperature of biomass. The biomass sample was fed into
reaction chamber via hopper equipped with control valve. During py­
rolyzing, the biomass sample inside reaction chamber was mixed by
mixing blade connected to electrical motor (4RK25GN-C, Zhengke
Electromotor Co., Ltd., China) via magnetic coupling drive connector.
The speed of agitated blade can be controlled by adjusting the motor
shaft speed using the controller. The nitrogen (N2) gas was supplied to
the reactor through the bottom of the reactor. The flow rate of N2 gas can
be controlled by controlled valve and its flow rate was measured by flow
meter (RMA-21-SSV, Dwyer, USA). The vapor of pyrolyzed biomass
exited from the top of reactor and flowed to the cyclone, which was used
to remove the solid particles from pyrolysis vapor. The vapor was
condensed in three shell and tube condensers. The bio-oil was collected
at collectors of condensers. Cold water was supplied to each condenser
from cooling water bath (CBD-30-P, Scientific Promotion Co., Ltd,
Thailand). The flow rate of cold water can be controlled by balancing
valve and measured by rotameter. The incondensable vapor could be
recycled to use as carrier gas by control valve or released to environment
P. Sakulkit et al.
through the wet scrubber.
2.4. Experimental procedure
The experiments of this study were of batch type runs. For each batch
experiment, 150 g of biomass was pyrolyzed. The experiment was
started by heating the reaction chamber to a temperature of 97 ◦ C, then
the biomass was fed into the reaction chamber via the hopper and
control valve. The valve was closed and the biomass sample was heated
continuously to desired temperature (400, 450 and 500 ◦ C). These
temperatures were selected based on the thermal decomposition
behavior of biomass samples, which were indicated by TGA and DTG
analyses. The results showed that most thermal decomposition of
biomass occurred at temperatures ranging from 200 to 400 ◦ C. Thus, the
pyrolysis needs to have temperature above 400 ◦ C to make sure that the
hemicellulose and cellulose are mostly decomposed. The pyrolysis
temperatures were also referred from the previous study of Palamanit
et al. [10]. During heating, the biomass was continuously mixed by
mixing blade at the speed of 10 rpm. When the biomass temperature was
increased to 250 ◦ C, the N2 gas with the flow rate of 2 L/min was purged
into the reaction chamber to maintain an inert atmosphere inside the
reactor. When the biomass temperature reached the set point tempera­
ture, the N2 gas flow rate was increased to 5 L/min. The vapor produced
during pyrolyzing was immediately condensed in condensers with cold
water at temperature of 10 ◦ C and a flow rate of 8 L/min. The biomass
sample was pyrolyzed at set point temperature for 30 min for each
experiment. The condensable and incondensable vapors were consid­
ered bio-oil and pyrolysis gas, respectively. The solid residue remaining
in reaction chamber was considered biochar. The yields of bio-oil and
biochar were directly determined by weighing. The weight of pyrolysis
gas was determined by the difference method. The sum of all pyrolysis
products was considered 100 wt.% based on the mass balance of whole
pyrolysis process. The investigated properties and compositions of
bio-oil, biochar and pyrolysis gas were then determined and analyzed.
2.5. Characteristics of bio-oil
2.5.1. Water content, pH value and density
The water content of the bio-oil was determined by volumetric Karl-
Fischer titration technique using a Mettler Toledo V20 automatic titrator
[10,26]. The pH value of bio-oil was measured by a pH meter (UB-10
Denver Instrument) at room temperature. Before measurement, the in­
strument was calibrated with standard liquid with pH of 4, 7, and 10
[10,27,28]. The density of bio-oil was determined based on the weight
and volume ratio using a density bottle at room temperature [16,26].
The determination was performed in triplicate and the result was re­
ported as mean value with standard deviation value.
2.5.2. Solid and ash content
The solid content was determined by vacuum filtration technique.
The bio-oil with 3 g was filtered through a pre-dried Whatman No. 2
filter paper. The filter paper was then washed with of 99.9 % ethanol
until the filtrate was clear to ensure that there was no bio-oil left on the
filter paper. The filter paper with the solid residue was pre-dried with
ambient air for 15 min and then it was dried with hot air in an oven at
temperature at 105 ◦ C for 30 min. The dried filter paper was cooled in
the desiccator prior to weigh and the solid content was calculated and
reported as mass ratio (wt.%) [10,27,28]. The ash content of bio-oil was
determined by burning method. The sample of bio-oil was burned in a
furnace at temperature of 775 ◦ C with air for 24 hours. The solid residue
remaining in crucible was considered as ash [16,27]. The determination
was performed in triplicate and the result was reported as mean value
with standard deviation value.
2.5.3. Ultimate analysis and energy content
The elemental composition of bio-oil was determined by ultimate
4
Journal of Environmental Chemical Engineering 8 (2020) 104561
analysis using the same method described in previous section. The en­
ergy content of bio-oil was considered in terms of higher heating value
(HHV). It was determined by a bomb calorimeter using the same method
described in previous section. Before determining the HHV of bio-oil, the
sample of bio-oil was dried in a hot air in oven at 60 ◦ C until its weight
was constant [10]. The Van Krevelen diagram (H/C and O/C atomic
ratios) of water-free bio-oil (dry basis) was also compared to conven­
tional oils, including crude oil and heavy fuel oil [29,30].
2.5.4. Chemical compounds
The chemical compounds of the bio-oil were determined by using gas
chromatography-mass spectroscopy (GC-MS) (Agilent, USA). The
GC–MS system was equipped with the column of Agilent CP9205 VF-
WAXms. The specification of column was 30 m × 250 μm × 0.25 μm
(length × ID × film thickness). The stationary phase was polyethylene
glycol. The helium gas was used as carrier gas at the flow rate of 1 mL/
min. The injection port and detector were both operated at temperature
of 250 ◦ C. The GC oven was heated to 70 ◦ C for 2 min, and then it was
heated to the temperature of 250 ◦ C for 10 min at a heating rate of 5 ◦ C/
min. The injection was performed with 10 μl of bio-oil sample. The
chemical compounds of bio-oil sample were then identified based on the
peak matching of the mass spectra from the National Institute of Stan­
dards and Technology (NIST) mass spectral library [14,31,32].
2.6. Characteristics of biochar
2.6.1. Particle size distribution, proximate analysis, ultimate analysis and
energy content
The particle size distribution, proximate analysis and ultimate
analysis of biochar were determined by using the same method
described in the previous sections. The energy content of biochar was
reported as HHV. The energy content of biochar was reported as HHV.
They were determined by calculating with the equations (eq. 5) [33]:
HHV = 0.341C + 1.322H – 0.12O – 0.12 N + 0.0686S – 0.0153Ash
(MJ/kg) (5)
where, C, H, O, S and Ash are the components of biomass obtained
from ultimate analysis and proximate analysis [33]. The Van Krevelen
diagram (H/C and O/C atomic ratios) of biochar was compared between
biomass and coal [34].
2.6.2. Surface morphology
The scanning electron microscope (SEM) (JSM-5800 LV, JEOL,
Japan) was used to observe the surface morphology of the biomass and
biochar sample. Prior to observation with SEM, the sample was coated
with gold by sputtering method. The SEM was performed under high
vacuum condition with accelerating voltage of 20 kV, and a secondary
electron (SE2) detector with magnification of 500X [10].
2.6.3. Surface area and average pore diameter
The surface area of the biomass and biochar sample was determined
by Brunauer– Emmett–Teller (BET) method (ASAP2460, Micromeritics,
USA) using the static volumetric N2 gas adsorption method. The sample
was pretreated under vacuum condition at temperature of 80-200 ◦ C for
15 hours. The adsorption-desorption isotherm was determined by the
static volumetric method. The N2 gas was used as carrier gas and
adsorbed gas. The pore volume was obtained from the adsorption
isotherm with the multi condensation point (p/p0 = 0.05-0.03, 10-20
points). The pore structure was determined from the adsorption
isotherm and the average width was calculated by using the formula 4
V/A (“V” represents the pore volume while “A” denotes the adsorbed bet
specific surface area) [10].
2.6.4. Functional groups
The Fourier Transform Infrared Spectroscopy (FTIR) technique was
used to characterize the organic functional groups of biochar. In this
study, the biochar obtained from pyrolysis temperature of 500 ◦ C was
P. Sakulkit et al. Journal of Environmental Chemical Engineering 8 (2020) 104561

Table 1
Bulk density, and proximate, and ultimate analysis results of ground biomass
samples
Biomass type
Characteristic
OPT RWS OPT:RWS

Proximate analysis (wt.%, as received basis)

Moisture content 9.65 ± 0.03 4.95 ± 0.02 7.3 ± 0.03
Volatile matter 74.1 ± 0.3 77.65 ± 75.87 ±
0.36 0.33
Fixed carbon 13.96 ± 15.3 ± 0.47 14.63 ±
0.31 0.39
Ash content 2.3 ± 0.03 2.1 ± 0.18 2.2 ± 0.11
Ultimate analysis (wt.%, dry basis)
Carbon 41.63 ± 45.43 ± 43.53 ±
0.17 0.04 0.11
Hydrogen 5.99 ± 0.23 6.01 ± 0.05 6.00 ± 0.14
Nitrogen 0.15 0.09 0.12
Sulphur 0.10 0.07 0.09
Oxygen 43.02 ± 41.72 ± 42.37 ± 0.2
0.12 0.28
Lignocellulosic compositions (wt.
%)
Cellulose 46.24 ± 56.6 ± 0.8 51.42 ±
Fig. 2. Particle size distributions of ground biomass samples.
0.04 0.42
Hemicellulose 20.84 ± 17.4 ± 0.26 19.12 ±
analyzed for functional groups by the FTIR (Vertex70, Bruker, Ger­ 0.12 0.19
Lignin 4.95 ± 0.08 17.56 ± 11.25 ± 0.3
many). Each spectrum was an average of 32 scans from 400-4000 cm-1 at
0.52
4 cm-1 spectral resolution. The FTIR data interpretation of each spec­ Extractive 27.97 ± 8.45 ± 0.18 18.21 ±
trum was based on a literature survey using extensive elucidation. 0.38 0.28
Higher heating value (MJ/kg) 16.31 ± 17.7 ± 0.09 16.85 ±
0.05 0.02
2.7. Pyrolysis gas compositions and heating values Bulk density (kg/m3) 189 ± 0.27 290.4 ± 267.7 ±
0.45 0.56
A sample of gas obtained from pyrolysis temperature of 500 ◦ C was
collected in gas bag. Then, composition of the gas was determined
rate of carrier gas had risk of decreased to bio-oil yield. The small
immediately by gas chromatography (GC) (GC-2014, Shimadzu). This
biomass particles are easily carried out from the reaction zone before
GC was equipped with a thermal conductivity detector (TCD). The col­
pyrolysis reaction is complete. The loss of small biomass particles also
umn of CG was a 2.0 m packed column (Shin carbon ST 100/120 Restek)
led to bio-oil with a high solids content. In the case of pyrolysis of large
for indicating the concentrations (vol. %) of H2, CO2, CO, and CH4. The
biomass particles, a previous study found that the bio-oil and pyrolysis
temperature of injection port, oven and detector was 120, 50 and 100
gas yields were decreased by increased biomass particles size, while the
◦
C, respectively. The argon gas was used as carrier gas at a flow rate of
biochar yield increased. Thus, in practice the biomass particle size for
15 mL/min. The gas sample with the volume of 0.5 mL was injected to
pyrolysis may ranges from micrometers to centimeters, depending on
GC [35]. The heating value of the pyrolysis gas was then calculated as
the reactor type and operating conditions. However, the preparation of
follows (Eq. 6) [10,36]:
biomass particles needs to consider the related aspects such as cost,
Heating value = 13.1(%CO/100) + 13.2(%H2/100) + 41.2(%CH4/100) (MJ/ energy consumption, transportation, storage, as well as the feeding
m 3) (6) system of pyrolysis reactor [3,37].
The bulk density of ground biomass samples is shown in Table 1. It is
where CO, H2, and CH4 are the percentages (vol.%) of carbon monoxide, seen that the bulk density of the biomass samples was in the range of
hydrogen, and methane in the pyrolysis gas product. 189– 290.4 kg/m3. The ground RWS had the highest bulk density (290.4
kg/m3), followed by the ground OPT:RWS (267.7 kg/m3) and ground
3. Results and discussion OPT (189 kg/m3). The bulk density of ground biomass samples was
corresponding to the biomass particles size as discussed in previous
3.1. Characteristics of raw biomass paragraph. The bulk density of ground OPT was low due to its fibrous
structure [3]. Generally, the bulk density of biomass depends on the
3.1.1. Particle size distribution and bulk density of ground biomass sample particle size, shape, moisture content, particle density and surface
Fig. 2 depicts the particle size distributions of the ground biomass characteristics. The previous studies indicate that the bulk density of
samples. The results showed that most of the ground biomass samples different biomasses, including non-woody biomass such as cereal grains
had particle sizes ranging from 0.3 to 1.18 mm. For RWS, its particle size and straws ranged from 15 to 200 kg/m3, 280 - 480 kg/m3 for woody
was in the range of 0.3-0.6 mm, which was relatively smaller than the biomass [38] and 152-896 kg/m3 for oil palm biomass [3]. As compared
ground OPT and OPT mixed with RWS (0.6-1.18 mm). The size of to the bulk density of coal, it is clear that the bulk density of lignocel­
biomass particle a physical property that influences yield and quality of lulosic biomass is lower [14]. For pyrolysis applications, the bulk density
pyrolysis products. This is because the biomass particle size affects heat of biomass particles directly affects the biomass volume present in the
transfer during pyrolyzing. Pyrolysis of biomass with small particles reaction chamber, consequently it influences the heat transfer behavior
provides high heat transfer rate because the surface area of small par­ during pyrolyzing. The bulk density of biomass particles also relates to
ticles is larger than of large biomass particles. For bio-oil production, the energy density (MJ/m3), storage area, and handling and transportation
heat transfer rate or heating rate not only affected the bio-oil yield but it costs [10,14].
also influenced the quality of bio-oil both in fixed bed and moving bed
pyrolysis reactors [26,27]. A previous study indicated that pyrolysis of
very small biomass particles with moving bed reactor or using high flow

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P. Sakulkit et al. Journal of Environmental Chemical Engineering 8 (2020) 104561

3.1.2. Proximate and ultimate analysis results

Table 1 shows the results of proximate and ultimate analysis of the
OPT, RWS and OPT:RSW. The proximate analysis indicated that the
moisture content, volatile matter, fixed carbon content and ash content
of biomass samples were in the ranges of 4.95-9.65, 74.09-77.65, 13.96-
15.3, and 2.1-2.3 wt.%, respectively. The biomass samples had low
moisture contents (<10 wt.%), which is appropriate for pyrolysis ap­
plications [4,10]. This is because the moisture content of biomass
strongly affects the yield and quality of bio-oil [39]. Moreover, a high
moisture content of biomass also consumes extra heat for evaporating
the moisture and increasing the vapor temperature to desired set point
temperature. Thus, pyrolysis of moist biomass gives bio-oil with high
water content, and has a large thermal energy consumption for pyrolysis
reactor [40]. Regarding volatile matter, it is seen that the volatile matter
of RWS was higher than OPT and OPT:RWS. This result indicates that the
volatile matter of these biomasses was not much different from other
biomasses, for example switchgrass, macadamia shells, coconut shells,
rice straw, redwood, wheat straw, corn stover, corn cob and oil palm
biomass [3,11,14,15]. The volatile matter is the main component in
biomass for producing bio-oil by pyrolysis. The higher volatile matter in
biomass is favorable for bio-oil production with pyrolysis since the
bio-oil tends to depend on the volatile matter [41]. Considering the fixed
carbon content of biomass samples, it indicated that the RWS had higher
fixed carbon content as compared to OPT and OPT:RWS. The fixed
carbon of biomass is the component that can be converted into biochar.
Thus, the biochar yield of pyrolysis products depends on the fixed car­
bon content of that biomass. For producing the biochar, the biomass
with high fixed carbon content is appropriate. The inorganic composi­
tions of biomass are considered as ash. The biomass used in this study
had low ash content (2.1-2.3 wt.%). The ash content of RWS was lower
than OPT and OPT:RWS. Some previous studies indicated that the ash
content of woody biomass was lower than of non-woody biomass [14].
The low ash content of biomass also enhanced the quality and quantity
of bio-oil by avoiding the secondary reaction of condensable vapors
[42], as well as the reduction of solid content in bio-oil.
For the elemental composition of biomass samples, the ultimate
analysis showed that the contents of C, H, N, S, and O of OPT, RWS and
OPT:RWS were in the ranges of 41.63-45.43, 5.99-6.01, 0.09-0.15, 0.07-
0.1, and 41.72-43.02 wt.%, respectively. The contents of C and H in RSW
were higher than in OPT, while the N, S and O of RSW were lower than in Fig. 3. TGA (a) and DTG (b) of ground biomass samples.
OPT. The result of ultimate analysis was consistent with the result of
proximate analysis. As compared to the other biomasses, it indicated the
were 46.24-56.6, 20.84-17.4, 4.95-17.56, and 8.45-27.97 wt.%,
carbon and hydrogen contents of RSW and OPT were relatively high
respectively. The main component in biomass samples was cellulose.
compared to cassava rhizomes, cassava stalk, wheat straw, corn stalk,
The hemicellulose content of RWS was lower than lignin content. But,
wood sawdust, corncob, and rice husk, bamboo, oak wood and birch
the lignin content of OPT was relatively similar to the hemicellulose
wood [4,14,15,27,28]. Normally, biomass with high carbon and
content. The previous studies indicated that the biomass with high cel­
hydrogen content provides a high HHV and LHV [10,30]. In the part of
lulose and hemicellulose is favorable for producing bio-oil using pyrol­
oxygen content, it was relatively high. For pyrolysis process, the oxygen
ysis process. This is because these compositions promote high yield of
content of biomass should be low, while the carbon and hydrogen
bio-oil as compared to the use of biomass with high lignin content
contents need to be high. This is due to the fact that the carbon and
[10,44]. Pyrolysis of biomass with high lignin content usually provides
hydrogen in biomass can be converted into useful aromatic compounds
high biochar yield. This is due to the thermal decomposition of cellulose
in bio-oil. On the other hand, the oxygen will be bonded with the hy­
and hemicellulose that occurs at a lower temperature comparing to the
drocarbon molecules during pyrolysis process as oxygenated com­
lignin [10,11]. The effects of lignocellulose content of biomass on bio-oil
pounds, which reduce the quality of bio-oil. Moreover, the pyrolysis of
and biochar yield were studied by many authors. Qu et al. [45] found
biomass with high oxygen content is also risk to obtain the bio-oil with
that the pyrolysis of cellulose provided a high bio-oil yield as compared
high water content. This is because water can be formed from the re­
to pyrolysis of hemicellulose because cellulose is more volatile than
action between hydrogen and oxygen [43]. The nitrogen and sulphur
hemicellulose. Kim et al. [46] concluded that there was a higher bio-oil
content of biomass samples were low. The low nitrogen and sulphur
yield when using biomass with higher cellulose and hemicellulose
contents of biomass help avoid the partial formation of NOx and SOx
contents. Quan et al. [47] pyrolyzed cellulose, hemicellulose, and lignin
during oxidation of nitrogen and sulphur with oxygen in biomass. Most
at 500 ◦ C and they found that the pyrolysis of these components pro­
of sulphur and nitrogen remain in the biochar [4,10].
vided liquid yields of 18.67, 30.83, and 0.5 wt.%, respectively. In
addition to the bio-oil yield, variations in the composition of the cellu­
3.1.3. Lignocellulosic compositions
lose, hemicellulose, and lignin in the biomass also influence the chem­
Table 1 shows chemical composition of biomass samples in term of
ical compounds of the bio-oil or liquid product [44]. In addition, Wang
cellulose, hemicellulose, lignin and extractives. The results indicated
et al. [48] reported that the extractives in biomass could enhance the
that cellulose, hemicellulose, lignin and extractives of biomass samples

6
P. Sakulkit et al. Journal of Environmental Chemical Engineering 8 (2020) 104561

Table 2
Commercial fuel equivalents for same energy as one kilogram of biomass
Fossil fuel amount with equivalent energy
Type of
biomass HHV (MJ/ Crude oil Coal LPG NG
kg) (L) (kg) (kg) (m3)

OPT 16.31 0.42 0.56 0.33 0.42

RWS 17.7 0.46 0.61 0.35 0.45
OPT:RWS 16.85 0.43 0.58 0.34 0.43

bio-oil yield and suppress the char and gas production when using corn
stalks and wheat straws as feedstocks for pyrolysis.

3.1.4. Thermal decomposition behaviour

The thermal decomposition behavior of biomass samples was
observed via TGA and DTG as shown in Fig. 3(a) and (b), respectively.
These figures clearly indicate that there were four main stages of ther­
mal decomposition of biomass samples. The first stage occurred at
temperatures of 50-120 ◦ C, in which the weight of biomass samples
slightly decreased. The mass reduction was less than 10% due to evap­ Fig. 4. Effects of pyrolysis temperature on product yields from OPT.
oration of the moisture present in biomass. In the second stage which
occurred at temperatures of 120-200 ◦ C, the weight of the biomass
samples was relatively constant due to less evaporation of the light
volatile compounds. The thermal energy supplied to the biomass at this
stage was used to increase its temperature. The third stage is the main
thermal decomposition of the biomass samples as clearly depicted in
Fig. 3(a) and (b). This stage occurred at temperatures of 200-400 ◦ C,
with a mass loss rate of about 65-70%. Most of the volatile organics,
including cellulose and hemicellulose were decomposed by heat to
condensable and incondensable vapors or gases, which correspond to
the thermal decomposition of general lignocellulosic biomass [3,10].
The last stage was present at temperatures above 400 ◦ C, and the ther­
mal degradation of the biomass samples was relatively slow at this stage.
The mass loss at temperatures 400-1000 ◦ C was about 10-15% due to the
decomposition of the lignin. The thermal decomposition trend of
biomass samples was consistent with the proximate analysis results and
lignocellulosic components as shown in previous sections. The previous
studies indicated that the thermal decomposition of hemicellulose, cel­
lulose and lignin of biomass occurred in temperature ranges of 250-350,
325-400 and 300-900 ◦ C, respectively [4,10,44].
Fig. 5. Effects of pyrolysis temperature on product yields from RWS.
3.1.5. Energy content and potential use as energy equivalent with fossil
fuels
The energy content and potential use as energy equivalent with fossil
fuels of biomass samples is shown in Table 1 and 2. The energy content
of biomass samples was presented as higher heating value (HHV). The
results showed that the HHV of OPT, RWS and OPT:RWS was 16.31,
17.7 and 16.85 MJ/kg, respectively. The heating value of biomass de­
pends on many factors such type, composition, age and plantation re­
gion and conditions. The composition of biomass is one of most
important factors that influences its heating value. Based on this result,
it is observed that the HHVs of biomass samples were consistent with the
proximate and ultimate analysis results. Previous studies also indicated
that the biomass with high cellulose and lignin tended to have high
HHV. Demirbaş [49] reported that the lignin has HHV better than cel­
lulose and starch. For the pyrolysis process, the heating value of the
biomass did not clearly affect the heating value of the bio-oil. This is
because different types of biomass with the same heating value may
have different compositions of volatile matter, fixed carbon content and
lignocellulose content. Thus, these components can be converted into
condensable vapors under different conditions during the pyrolysis
process [10,50]. The potential use of the biomass samples as energy
Fig. 6. Effects of pyrolysis temperature on product yields from OPT:RWS.
equivalent with crude oil, coal, LPG, and NG were 0.42-0.46 L, 0.56-0.61
kg, 0.33-0.35 kg, and 0.42-0.45 m3, respectively. It indicated that
biomass samples had relatively low potential for use as energy since the
energy content of biomass was low. However, utilization or

7
P. Sakulkit et al. Journal of Environmental Chemical Engineering 8 (2020) 104561

Table 3 should have the most volatile matter, leading to an increase in the bio-oil
Basic properties of bio-oil yield [10]. The lower bio-oil yield of OPT is due to high ash content in
Property the biomass samples. The same trend also occurred in the study of Fahmi
Pyrolysis et al. [51]. Also, the RWS have high density and particle size was smaller
Biomass temperature Water pH Solid Ash Density
content value content content (kg/m3) than of OPT and RWS mixed with OPT, as shown in Fig. 2. The smaller
(◦ C)
(wt.%) (wt.%) (wt.%) particle size of biomass sample led to good heat transfer rate, which
2.45
strongly affects the bio-oil yield [3]. However, previous studies reported
76.36 ± 0.33 ± 0.3 ± 1006 ± that the bio-oil yield of pyrolysis not only depends on biomass compo­
400 ±
0.11 0.05 0.05 0.06
0.02 sition and properties, but is also influenced by the operating parameters
2.32 and reactor type [16,52,53]. The pyrolysis of biomass at a high heating
73.54 ± 0.64 ± 0.42 ± 1002 ±
OPT 450
0.7
±
0.04 0.05 0.16 rate using moving bed reactors provided bio-oil yield exceeding 47 (wt.
0.01
2.84 %) [16,37]. Pyrolysis of biomass with moving bed reactors normally
74.12 ± 0.82 ± 0.44 ± 1005 ±
500 ± provides higher bio-oil yield as compared to fixed bed reactors [53–54].
0.96 0.06 0.06 0.07
0.01 In contrast, pyrolysis of biomass with high fixed carbon content led
65.48 ± 0.27 ± 0.3 ± 1008 ± to high yield of biochar. In the case of biochar, the highest biochar yield
400 2.35
0.5 0.02 0.03 0.05
2.28
was obtained from RWS (28.68 wt.%) and the lowest from OPT (24.2 wt.
63.78 ± 0.31 ± 0.37 ± 1018 ± %). The biochar yield was high at lower temperature (400 ◦ C) and it was
RWS 450 ±
0.53 0.08 0.01 0.31
0.02 significantly decreased when increase in temperature [39,55]. This is
500
63.17 ± 2.4 ± 0.4 ± 0.4 ± 1024 ± due to a greater thermal decomposition of lignocellulosic components at
0.71 0.02 0.05 0.04 0.15
higher temperature [50,52]. However, the gas yield showed the oppo­
67.4 ± 0.57 ± 0.3 ± 1008 ±
400
0.65
2.66
0.06 0.09 0.46 site trend, it decreased with increasing temperature due to the con­
75.66 ± 0.64 ± 0.36 ± 1011 ± densable gases contributing to bio-oil. The highest and lowest yield for
OPT: 450 2.75
RWS
0.35 0.04 0.07 0.22 the gas were 36.9 wt.% and 30.1 wt.% obtained from OPT and RWS at
2.58 500 ◦ C, respectively.
71.5 ± 0.74 ± 0.4 ± 1019 ±
500 ±
0.81 0.08 0.01 0.22
0.02
3.3. Properties of bio-oil

co-utilization of biomass as bioenergy can help reduce the reliance on
fossil fuels and environmental impacts.
3.2. Distribution of pyrolysis product yields
Fig. 4–6 depict the product yields obtained from the pyrolysis of
OPT, RWS, and OPT:RWS at temperatures of 400, 450, and 500 ◦ C. The
results showed that the product yields of the bio-oil, biochar and py­
rolysis gas were in the ranges of 38.5-46.5, 22.27-28.68 and 30.1-36.9
wt.%, respectively. These results indicated that pyrolysis temperature
and biomass type affected the product yields. As can be seen in that
Figures, an increase in pyrolysis temperature from 400 ◦ C to 500 ◦ C led
to obtain more bio-oil for all biomass samples. The higher bio-oil led to
lower biochar and pyrolysis gas yield. Considering the effect of pyrolysis
temperature, it is clearly seen that pyrolysis at temperature of 500 ◦ C
provided the highest bio-oil yield, while the biochar was highest at
temperature of 400 ◦ C for all biomass samples. An increase in pyrolysis
temperature provided the higher bio-oil yield due to more thermal
decomposition of lignocellulosic components, particularly the hemicel­
lulose and cellulose as discussed in section 3.1.4. In the case of biomass
types, the results indicated that pyrolysis of RWS obtained the highest
liquid yield and co-pyrolysis of OPT with RWS helped to improve the
bio-oil yield as compared to pyrolysis of OPT only. However, it is
observed that at each pyrolysis temperature, the biomass type had
smaller effect on the products yields than pyrolysis temperature. This is
because the compositions of biomass samples are not much different as
indicated by volatile matter, fixed carbon content and lignocellulosic
composition. Based on these compositions, the yields of bio-oil and
biochar products were consistent with the proximate analysis results and
the lignocellulosic components of the biomass samples. The previous
studies revealed that pyrolysis of the biomass with high volatile matter
and low ash content resulted in a high amount of bio-oil [10,27]. The
results of the pyrolysis products also correspond to the lignocellulose
content of the biomass samples. As can be seen in Table 1, the RWS
contained high hemicellulose and cellulose content, while the lignin and
extractives were low. Thus, the pyrolysis of the RWS provided the
highest amount of bio-oil. Qu et al. [45] reported that the cellulose is
more volatile, therefore, the RWS with the largest amount of cellulose
3.3.1. Water content
Table 3 presents the water contents of bio-oil obtained from pyrolysis
of OPT, RWS and OPT:RWS at different pyrolysis temperatures. The
results showed that the water content of the bio-oil was in the range of
63.17-76.36 wt.%. These results indicated that pyrolysis of OPT, RWS
and OPT:RWS at different pyrolysis temperatures had a small effect on
the water content of the bio-oil. The water content in the bio-oil was
consistent with the moisture content of raw biomass samples, as well as
their oxygen and hydrogen contents. The bio-oil obtained from pyrolysis
of RWS contained less water than that from OPT and OPT:RWS. This is
because the moisture content of RWS was lower than of other biomass
samples. The previous studies reported that the water content of bio-oil
is depended on the moisture content of raw biomass and is also influ­
enced by the oxygen content in biomass [55,56]. The pyrolysis of
biomass with a high oxygen content has risk of producing bio-oil with
high water content. This is because water can be formed from the re­
action between hydrogen and oxygen of biomass [43]. The results ob­
tained from this study indicated that the water content of the bio-oil was
higher than 50 wt.%. The high water content of bio-oil is due to the used
pyrolysis reactor providing a low heating rate, which was about 14
◦
C/min. However, the water content of bio-oil obtained from this study
was relatively similar with many previous studies. Chen et al. [57]
report that the water content of the obtained bio-oil was 64.4-75.1 wt.%.
Gómez et al. [58] found that the slow pyrolysis of biomass provided
bio-oil with water content higher than 50 wt.%. Recently, Palamanit
et al. [10] showed that the slow pyrolysis of oil palm biomass provided
liquid products with the water content ranging from 61.1 to 68.3 wt.%.
In the case of fast pyrolysis, the water content of the bio-oil usually
varies in the range 10-40 wt.% (wet basis), depending on the biomass
type and composition, as well as the pyrolysis conditions [10,59].
Moreover, the water content in bio-oil not only depends on the moisture
content and oxygen content of raw biomass but is also influenced by
pyrolysis conditions such as heating rate, reactor type, vapor residence
time and pyrolysis temperature [10,59]. The water content in bio-oil has
both positive and negative impacts. The bio-oil with low water content
provides high HHV and good stability, while the high water content in
bio-oil helps improve the flow ability [26,27].

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P. Sakulkit et al. Journal of Environmental Chemical Engineering 8 (2020) 104561

Table 4
Ultimate analysis results and higher heating value of bio-oil
Ultimate analysis (wt.%, as received basis)
Biomass Pyrolysis temperature (◦ C) HHV (MJ/kg)
Carbon Hydrogen Nitrogen Sulphur *Oxygen

400 ◦
C 13.8 ± 0.2 9.91 ± 0.19 0.07 <0.01 76.21 ± 0.39 17.3 ± 0.06
OPT 450 ◦
C 14.63 ± 0.3 9.92 ± 0.21 0.08 <0.01 75.36 ± 0.24 19.51 ± 0.08
500 ◦
C 15.81 ± 0.21 9.44 ± 0.17 0.16 <0.01 74.58 ± 0.37 20.3±0.34
400 ◦
C 16.93 ± 0.18 9.83 ± 0.23 0.59 ± 0.18 <0.01 72.64 ± 0.41 18.07 ± 0.26
RWS 450 ◦
C 20.97 ± 0.13 9.49 ± 0.12 0.10 ± 0.01 <0.01 69.43 ± 0.24 20.33 ± 0.15
500 ◦
C 21.53 ± 0.36 9.22 ± 0.26 0.23 ± 0.01 <0.01 69.01 ± 0.24 20.36±0.08
400 ◦
C 17.62 ± 0.25 9.74 ± 0.07 0.16 ± 0.01 <0.01 72.47 ± 0.28 16.1 ± 0.34
OPT:RWS 450 ◦
C 18.33 ± 0.08 9.90 ± 0.21 0.70 ± 0.01 <0.01 71.06 ± 0.3 18.48 ± 0.05
500 ◦
C 22.62 ± 0.1 9.12 ± 0.18 0.18 ± 0.01 <0.01 68.07 ± 0.09 19.24 ± 0.1
*
Oxygen by difference.

3.3.2. pH, solids content, ash content and density

The pH, solids content, ash content and density of bio-oil are also
shown in Table 3. It is seen that the pH, solids content, ash content and
density of bio-oil were in the ranges 2.28-2.84, 0.27-0.82 wt.%, 0.3-0.44
wt.%) and 1002-1024 kg/m3, respectively. These results imply that
biomass type and pyrolysis temperature had small effects on these
properties of bio-oil. The pH of bio-oil obtained from this study was
similar to pH of the bio-oil from previous studies [10,26]. This is because
bio-oil contains a high amount of organic acids, including acetic acid
and formic acid [16,35]. Other groups of chemical compounds in bio-oil
that influence the acidity include phenolics and fatty, resin and hydroxy
acids. Recently, Chorazy et al. [60] reported that the pH of bio-oil from
lignocellulosic biomass was in the range 2-3. The presence of acids in
bio-oil was due to the degradation of hemicellulose and cellulose of
biomass, which has high oxygen content. The high acid value of bio-oil is
a disadvantage of this product for direct use or applications, since it can
cause corrosion of materials during storage and applications [60].
In the part of solids content, it is seen that biomass types and py­
rolysis temperature had small effect on the solids content of bio-oil. The
solids content of the bio-oil samples obtained from this work was rela­
tively low as compared to other types of moving bed reactors such as
fluidized bed and twin screw reactors [26,28]. The solids content in
bio-oil obtained from RWS was lower than that obtained from OPT and
OPT:RWS. This may be because the bulk density of RWS was higher than
of OPT and OPT:RWS, consequently less solid particles were carried out
from reaction chamber during pyrolyzing. At a higher pyrolysis tem­
perature, the solids content in bio-oil was also high. This is due to the
fact the biomass particles were more pyrolyzed at higher temperature,
leading to lower weight of that biomass particles and then the biochar
particle can be carried out from reaction chamber. The result of solids
content in bio-oil was similar to the pyrolysis of wood, rice straw, cas­
sava and oil palm biomass [10,55]. The solids present in bio-oil can
cause erosion and blockages in pumping or supplying equipment [61].
The ash content of bio-oil ranged from 0.3 to 0.44 wt.%. It was found
that an increased pyrolysis temperature led to higher ash content in
bio-oil, which was consistent with the results of solids content in bio-oil.
This ash was the solid remaining after burning bio-oil under oxidation
condition. The composition of ash was inorganic components from
biomass sample. High ash content in bio-oil can cause high wear in
pumps and injectors, as well as deposition and corrosion in equipment
due to the presence of alkali metals in ash. The density of bio-oil was in
the range of 1002-1024 kg/m3. The previous studies reported that the
density of bio-oil was in the range of 900-1,300 kg/m3, depending on the
its composition [10,61].
3.3.3. Ultimate analysis results and energy content of bio-oil
Table 4 summarizes the ultimate analysis results and higher heating
values (HHV) of bio-oil. The results reveal that the contents of C, H, N, S
and O of bio-oil were in the ranges 13.8-22.62, 9.12-9.92, 0.07-0.7,
<0.01 and 68.07-76.21 wt. %, respectively. These results indicated
that biomass types and pyrolysis temperatures had small effect on the
Fig. 7. Van Krevelen diagram (H/C and O/C atomic ratios) for water-free bio-
oil (500 ◦ C) and conventional oils.
hydrocarbon content of bio-oil. Pyrolysis of RWS provided bio-oil with
contents of carbon and hydrogen higher than the bio-oil obtained from
OPT. As can be observed, co-pyrolysis of OPT and RWS improved the
hydrocarbon content of bio-oil as compared to OPT only. The carbon
content of bio-oil was increased at higher pyrolysis temperature, but
hydrogen content tended to decrease. This is due to the decarboxylation
and dehydration reactions [62]. In addition, Pattiya and Suttibak [27]
reported that the elemental compositions of bio-oil might be influenced
by the solids content and water content. The high water content in
bio-oil led to high hydrogen content. The bio-oil obtained from this
study consisted mainly of water and oxygen-containing compounds. The
oxygen present in bio-oil is from the cellulose, hemicellulose and lignin
fractions of the biomass [10,27]. The obtained hydrocarbon from this
study was similar with the result of Alvarez et al. [63]. They found that
the hydrocarbon of bio-oil was only 15-27 wt.%. In the case of fast py­
rolysis, the hydrocarbon content of bio-oil with low water content can
range within 60-80 wt.% [52]. The higher hydrocarbon content and
lower oxygen content of bio-oil enhances its fuel value. For the content
of nitrogen and sulphur, it was found that the bio-oil contained low
amounts of nitrogen and sulphur since the biomass used in this study
had low nitrogen and sulphur contents. When the organic elements of
water-free bio-oil samples were presented in the form of atomic ratios in
a Van Krevelen diagram as shown in Fig. 7, it is seen that the atomic
ratios of H/C and O/C of water-free bio-oil samples were in the ranges of
0.62-1.2 and 0.3-0.9, respectively. The bio-oil samples had low H/C and
high O/C atomic ratios as compared to conventional oils [29,30]. This is
because the bio-oil samples contained with low hydrogen and carbon
contents, while their oxygen content were relatively high. The HHV of
bio-oil shown in this study was the HHV of water-free bio-oil as shown in

9
P. Sakulkit et al. Journal of Environmental Chemical Engineering 8 (2020) 104561

Table 5
Main chemical compounds in bio-oil from pyrolysis at 500 ◦ C
Peak area (%)
Compounds
OPT RWS OPT: RWS

Acids
Acetic acid 41.17 37.26 41.19
Propanoic acid 1.87 1.63 1.97
Phenols
Phenol 11.48 3.97 7.5
Phenol, 2-methoxy- 0.95 2.38 1.59
Phenol, 2,6-dimethoxy- 4.14 5.28 5.05
5-tert-Butylpyrogallol 0.68 1.22 1.09
Creosol N/D 1.33 0.76
3,5-Dimethoxy-4-hydroxytoluene 0.8 2.29 1.6
Ketones
2-Propanone, 1-hydroxy- 9.54 8.47 9.19
2-Cyclopenten-1-one 1.76 1.34 1.69
1-Hydroxy-2-butanone 1.29 1.62 1.55
2-Cyclopenten-1-one, 3-methyl- 1.07 0.64 1.08
2-Cyclopenten-1-one, 2,3-dimethyl- 0.83 0.72 1.13
3-Ethyl-2-hydroxy-2-cyclopenten-1-one 0.82 0.69 0.83
2-Cyclopenten-1-one, 2-hydroxy-3-methyl- 2.93 3.34 3.38 Fig. 8. Particle size distributions of biochars from pyrolysis at 500 ◦ C.
Syringylacetone 1.27 1.44 1.37
Aldehydes
2-furan-carboxaldehyde 2.42 2.11 1.63 Table 6
Carbohydrates Proximate analysis results of biochars
Anhydro-sugar 2.85 4.11 3.73
1,4:3,6-Dianhydro-alpha-d-glucopyranose 2.16 1.04 1.61 Proximate analysis (wt.%, as received basis)
Pyrolysis
1,6-anhydro-beta-D-Glucopyranose 4.04 2.79 2.53 Biochar Moisture Volatile Fixed Ash
temperature (◦ C)
Others 7.93 16.33 9.53 content matter carbon content
Total 100 100 100
19.26 ± 68.85 ± 8.27 ±
*N/D = Not detected 400 3.62 ± 0.08
0.55 0.54 0.04
18.29 ± 69.47 ± 8.79 ±
OPT 450 3.45 ± 0.17
0.03 0.08 0.12
Table 4. It was found that the HHV of bio-oil was in the range of
14.15 ± 74.26 ± 8.32 ±
16.1-20.36 MJ/kg3, which was consistent with the hydrocarbon content 500 3.27 ± 0.09
0.3 0.29 0.12
of bio-oil. The HHV of bio-oil obtained from RWS was higher than that of 25.79 ± 68.72 ± 5.48 ±
400 3.45 ± 0.11
OPT and OPT:RWS. The obtained HHV of bio-oil from this study was 0.22 0.13 0.02
also compared to previous studies, including Palamanit et al. [10], Sir­ 20.5 ± 69.82 ± 6.4 ±
RWS 450 3.28 ± 0.16
0.15 0.17 0.15
ijanusorn et al. [26], Pattiya et al. [27], Kabir et al. [52], Chang et al. 19.52 ± 73.4 ± 7.76 ±
[64], and Varma et al. [65]. These studies reported that the HHV of 500 2.92 ± 0.1
0.35 0.29 0.21
bio-oil was in the range 17-39 MJ/kg. The HHV of bio-oil obtained from 24.57 ± 65.55 ± 6.03 ±
400 3.85 ± 0.06
this study was relatively low compared to some previous studies. This is 0.37 0.06 0.06
OPT: 18.16 ± 71.88 ± 6.97 ±
because of the differences in pyrolysis process and biomass composi­ 450 2.98 ± 0.18
RWS 0.36 0.08 0.08
tions. However, the HHV of bio-oil from this study was similar to the 15.17 ± 74.86 ± 7.35 ±
500 2.62 ± 0.12
study of Palamanit et al. [10] who performed slow pyrolysis of oil palm 0.34 0.04 0.04
biomass, and they found that the HHV of bio-oil was in the range of
19-23 MJ/kg. These results make clear that the HHV of bio-oil is lower
than of conventional petroleum fuels (40-50 MJ/kg) [54]. alkali metals with the pyrolysis vapor catalyzed the conversion of the
levoglucosan to light organic compounds such as acetic acid and
3.3.4. Chemical compounds furfural. The amounts of acidic compounds in the obtained bio-oil
Table 5 lists the major chemical compounds of bio-oil obtained from indicated that the pyrolysis product is highly acidic, which is consis­
OPT, RWS and OPT:RWS at pyrolysis temperature of 500 ◦ C. The results tent with the pH of 2.28-2.84, as shown in Table 3. Bio-oil with a low pH
indicated that the main chemical compounds of the bio-oil samples were value is not appropriate for direct use because it encourages aging and
oxygenated compounds such as acetic acid, phenols, 2-Propanone,1-hy­ corrosion [66].
droxy-, and 1,6-anhydro-beta-D-Glucopyranose. The concentrations of
these compounds were in the ranges 37.26-41.17, 3.97-11.48, 8.47-9.54
3.4. Characteristics of biochar
and 2.53-4.04 %, respectively. It is seen that the concentration of each
compound in the bio-oil depended on the biomass type and composition,
3.4.1. Particle size distribution and proximate analysis results
particularly on the lignocellulosic components as depicted in Fig. 3. The
Fig. 8 depicts the particle size distributions of biochar obtained from
obtained results were relatively similar with the previous studies. They
OPT, RWS and OPT:RWS at pyrolysis temperature of 500 ◦ C. It is seen
reported that the chemical compounds in the bio-oil is strongly influ­
that the particle size distribution of most biochars was in the range of
enced by biomass compositions [10,52]. They also indicated that the
0.2-0.3 mm. The results indicate the particle size distribution of biochar
cellulose and hemicellulose in the biomass could decompose to gluco­
was consistent with the particle size distribution of raw biomass sam­
pyranoses (anhydro-sugars) and heterocyclic compounds (furan and
ples. The particle size of biochar was lower due to the shrinkage of
furan derivatives, and acetic acid). In the part of lignin, it was devola­
biomass particle caused by thermal decomposition during pyrolysis. The
tilized to pervade the resulting bio-oil with oxygenated aromatic com­
shrinkage of biochar particle is mainly influenced by the nature of the
pounds such as phenols and phenolic derivatives [52,55]. Besides the
biomass and the pyrolysis conditions [67]. For the proximate analysis
lignin content, the alkali metals of the biomass also influenced the
results of biochar, it is shown Table 6. This table shows the proximate
compounds of the bio-oil. Kabir et al. [52] explained that the contact of
analysis results of the biochar obtained from OPT, RWS, and OPT: RWS

10
P. Sakulkit et al. Journal of Environmental Chemical Engineering 8 (2020) 104561

Table 7
Ultimate analysis results and higher heating values of biochars
Ultimate analysis (wt.%, dry basis)
Biochar Pyrolysis temperature (◦ C) HHV (MJ/kg)
Carbon Hydrogen Nitrogen Sulphur *Oxygen

400 74.14 ± 0.16 3.16 ± 0.03 0.58 ± 0.01 0.06 13.48 ± 0.18 27.65 ± 0.01
OPT 450 75.12 ± 0.1 3.01 ± 0.07 0.56 ± 0.01 0.06 12.15 ± 0.22 27.94 ± 0.14
500 77.45 ± 0.24 2.38 ± 0.06 0.51 0.06 11 ± 0.22 28.05 ± 0.11
400 71.63 ± 0.24 3.28 ± 0.05 0.4 0.03 18.98 ± 0.2 26.35 ± 0.07
RWS 450 77.1 ± 0.21 3.11 ± 0.01 0.39 ± 0.01 0.03 ± 0.01 12.75 ± 0.2 28.73 ± 0.08
500 80.38 ± 0.43 2.56 ± 0.01 0.41 ± 0.01 0.04 8.62 ± 0.45 29.6 ± 0.21
400 73.29 ± 0.36 3.53 ± 0.08 0.45 ± 0.01 0.04 16.48 ± 0.41 27.54 ± 0.18
OPT:RWS 450 76.55 ± 0.12 3.01 ± 0.02 0.51 ± 0.01 0.05 12.7 ± 0.11 28.4 ± 0.23
500 78.60 ± 0.09 2.45 ± 0.03 0.46 ± 0.02 0.05 10.89 ± 0.18 28.57 ± 0.04
*
Oxygen by difference.

Table 8
BET surface areas and average pore diameters of biomasses and biochars (500
๐
C)
Type of biomass/ BET surface area (m2/g) Average pore diameters
biochar (nm)

OPT 3.1 11.46

RWS 2.0 13.9
OPT:RWS 2.58 12.68
OPT biochar 2.1 21.2
RWS biochar 1.5 32.8
OPT:RWS biochar 1.3 24.63

biomasses and pyrolysis temperatures. It is seen that the C, H, N, S and O

Fig. 9. Van Krevelen diagram (H/C and O/C atomic ratios) of biomass, biochar
(500 ◦ C) and coal.
at various pyrolysis temperatures. As can be seen the moisture content,
volatile matter, fixed carbon content, and ash content of the biochar
were in the ranges 2.92-3.85, 14.15-25.79, 65.55-74.86 and 5.48-8.79
wt.%, respectively. These results indicate that differences in the type
of oil palm biomass and pyrolysis temperature affected the composition
of the biochar. Based on the obtained results, it is observed that the
moisture content of biochar samples was not zero after pyrolysing,
which was similar to previous studies [10,52]. They reported that the
moisture content of biochars was in the range of 2.40-4.42 wt.%. The
volatile matter of biochar decreased with pyrolysis temperature. This is
because the volatile matter was more decomposed to low molecular
weight liquid and gas at higher temperature [10]. However, the volatile
matter of the biochar remained between 14.15-25.75 wt.%, indicating
incomplete pyrolysis of the biomass under the investigated pyrolysis
temperatures and time. This is because the biomass samples contained
some lignin, which decomposes at high temperatures. The lower volatile
matter led to higher fixed carbon content of biochar. The high fixed
carbon content of biochar is favorable for solid fuel application due to
high energy content [10,55]. The high fixed carbon content of biochar
also helps improve stability during storage as compared to the raw
biomass, which is easily biologically decomposed during storage. The
ash content of OPT was higher than RWS and OPT: RWS, which was
consistent with the gross component of raw biomass. The ash in biomass
and biochar is a non-volatile matter and non-combustible components.
The increase in ash content of biochar resulted from the destructive
volatilization of lignocellulose components at higher temperature [68].
content of the biochar was in the range of 74.14-80.38, 2.38-3.53, 0.41-
0.58, 0.03-0.06 and 8.62-18.98 wt.%, respectively. The results of ulti­
mate analysis were consistent with the proximate analysis results as
indicated by the relation between fixed carbon content and volatile
matter, and carbon and hydrogen content. The carbon content of OPT
and OPT: RWS was lower than that of RWS. Pyrolysis temperature
showed more significant effect on biochar. These results clearly showed
that the pyrolysis of biomass produced biochar with a high carbon
content and a low oxygen content, which is similar to the results from
previous studies [10]. As depicted by Van Krevelen diagram in Fig. 9, the
ratio of H/C and O/C of biochar was clearly improved as compared to
raw biomass. The reduction of hydrogen and oxygen content at higher
pyrolysis temperature was attributed to the dehydration and decar­
boxylation reactions [55]. That ratios of biochar were close to the values
of each coal, thus the biochar normally can be called “biocoal”. In
practice, the lower ratio of O/C and H/C is favorable for solid fuel
application via combustion or co-firing. The nitrogen and sulfur content
of biochar was relatively low. However, as compared to the raw biomass
the biochar had higher nitrogen content. This is due to the combination
effect of nitrogen into complex structures and nitrogen bond is also
resistant to heat and not easily volatilized [68]. The higher carbon
content and lower oxygen content of the biochar led to superior HHV

3.4.2. Ultimate analysis results and energy content of biochar

Table 7 shows the elemental compositions of the biochar at different
Fig. 10. FTIR spectra of biochars from pyrolysis at 500 ◦ C.

11
P. Sakulkit et al.
Fig. 11. SEM photographs of (a) OPT, (b) OPT biochar, (c) RWS, (d) RWS biochar, (e) OPT: RWS, (f) OPT: RWS biochar. The biochars are from pyrolysis at 500 ◦ C.
[3]. As can be seen in Table 8, the HHV of biochar was in the range of
26.35-29.6 MJ/kg. The HHV of RWS biochar was higher than OPT and
OPT: RWS biochar, which is consistent with the HHV of biomass. The
higher carbon content and lower oxygen content of the biochar led to
superior HHV as compared to raw biomass. Previous studies showed that
the HHV of biochar obtained from woody and non-woody biomasses was
in the range of 14-33 MJ/kg, depending on the type of used biomass and
the pyrolysis conditions. The previous studies also indicated that the
HHV of biochar from woody biomass was better than of biochar from
non-woody samples [10,52,53,64]. As compared to the hydrochar, the
HHV and carbon content of biochar was better than hydrochar [69].
12
Journal of Environmental Chemical Engineering 8 (2020) 104561
Thus, the low moisture content, low ratio of O/C and H/C, combined
with high HHV of biochar are desirable for solid fuel applications for
both heat and power generation since these properties help to reduce the
airborne waste and energy loss [70].
3.4.3. FTIR analysis results
The FTIR analysis results of the biochar obtained from pyrolysis of
OPT, RWS and OPT:RWS at temperature of 500 ◦ C are shown in Fig. 10.
This figure showed that there were many components present in the
obtained results. This is because the biochar still contained structures of
carbon, hydrogen and oxygen, which mostly remained in the form of
P. Sakulkit et al.
Fig. 12. Composition and heating value of pyrolysis gas at 500 ◦ C.
lignin. The result of FTIR are consistent with the proximate and ultimate
analysis results of biochar discussed previously. The spectra of each
biochar sample were not different because of the elemental composition
of biochar samples was relatively similar as indicated by the content of
carbon, hydrogen and oxygen. The peaks can be explained as follows.
The first peak appeared at 3385-3386 cm− 1 and was attributed to the
stretching of OH groups [69]. It is also attributed to acceleration in
dehydration reaction of biomass. The small peaks at 2850-3011 cm-1
were associated with the C-H stretching vibration of aliphatic and aro­
matics structures. The observed peak at 1685 cm− 1 is attributed the
presence of carbonyl and carboxyl groups in carbohydrates [71]. The
aromatic C = C ring stretching vibration occurred at 1565–1566 cm-1
[55]. At 1378-1402 cm-1, the peak is assigned mainly to stretching vi­
brations of aliphatic C–H and CH2 bending in biochar, respectively. The
bands in the range 1260-1261 cm-1 represent the stretching of aromatic
C–O and phenolic OH. The weak vibrations of C-H bond in aromatic and
heteroaromatic compounds are visible as a band between 611-873 cm− 1
[71,72].
3.4.4. Surface morphology and surface area
Fig. 11(a)–(f) show the surface features of the biomass and biochar
obtained from OPT, RWS, and OPT:RWS at a pyrolysis temperature of
500 ◦ C. These images clearly showed the difference between biomass
and biochar surface features. The surface of biomass samples was rela­
tively rough with small pores as shown in Fig. (a), (c) and (e). It is seen
that the surface of RWS biomass was relatively rougher than OPT
biomass. After pyrolysis process, the morphology of biochar revealed
pores created over the surface, with the size and shape of the pores
clearly seen in Fig. (b), (d) and (f). The RWS biochar had rough surface
with non-uniform shape of pores as compared to OPT biochar. The shape
of the OPT biochar pores at the surface appears like a honeycomb with
cylindrical and polygonal pores. The average pore diameter of RWS
biochar was bigger than OPT biochar. The surface feature of OPT bio­
char obtained from this study was similar to the result of Palamanit et al.
[10], and Bensidhom et al. [53]. The creation of large pores is caused by
the volatilization of organic compounds or lignocellulosic components.
When the pore was larger, the number of pores might be lower, leading
to reduced surface area [55]. The BET surface area of biomass and
biochar was determined and shown in Table 8. It is observed that the
surface area of OPT, RWS and OPT:RWS biochar was lower as compared
to the raw biomass sample. This is because the thermal decomposition of
biomass led to larger pore size, in which the number of pores might be
lower. Comparing between biomass types, it was found that the BET
surface area of OPT was higher than RWS and OPT:RWS. This is prob­
ably due to thermal decomposition of RWS was better than OPT as
shown in TGA graph. The large pores are caused by the progressive
13
Journal of Environmental Chemical Engineering 8 (2020) 104561
degradation of the lignocellulosic components including cellulose,
hemicelluloses and lignin. At higher temperature, it also facilitates the
release of volatile materials and created more pores, resulting in larger
pore size of biochar [10]. Previous study also reported that at heating
rate higher than 10 ◦ C/min, the volatile vapor was generated inside the
biomass particles and then it released from surface, which resulted in
open fiber structure leading to the formation of cavities. The high porous
structure of biochar may be beneficial for bio-filter applications and soil
mixing, in addition to use as solid fuel [8,73].
3.5. Pyrolysis gas composition and heating value
Fig. 12 shows the main compositions and heating values of the py­
rolysis gas products obtained from pyrolysis temperature of 500 ◦ C. The
results showed that the pyrolysis gas mainly contained H2, CO, CH4 and
CO2. The concentrations of these gases were in the ranges 4.42-9, 1.34-
17.96, 4.76-7.62, and 6.8-29.54 vol. %, respectively. With obtained
concentration of combustible pyrolysis gases, the heating value of py­
rolysis gas was in the range of 3.23-6.7 MJ/m3. The obtained pyrolysis
gas contained lower concentrations of combustible gases as compared to
the results from previous studies [53,61,63]. The concentration of
combustible pyrolysis gas was relatively low due to the slow pyrolysis
process and batch runs used in this study. In addition, the N2 gas flow
rate supplied to the reactor was also relatively high. Considering the
effects of biomass type on pyrolysis gas composition, the results showed
that pyrolysis of OPT provided more H2, CO and CH4 than that obtained
from RWS and OPT:RWS. This was attributed to the lignocellulosic
compositions of biomass samples [10,61]. The amount of hemicellulose
combined with cellulose in OPT was lower than in RWS. Consequently,
RWS is mostly converted as condensable vapor, while the incondensable
vapor of OPT was high. Thus, at pyrolysis temperature of 500 ◦ C the OPT
provided higher concentration of H2, CO and CO2 than RWS and OPT:
RWS. This result was also consistent with the TGA results. The result of
this study are similar to Paenpong and Pattiya [61], who showed that
pyrolysis of biomass with high hemicellulose and cellulose led to high
concentration of combustible gases. Moreover, gas composition may be
influenced by the secondary reactions of condensable vapor with ash
during the process [73,74]. This result led to high gas yield and gas
concentration such in the case of OPT. However, it is noted that the
composition and concentration of the pyrolysis gas also depend on other
factors such as the reactor type, pyrolysis temperature, pyrolysis type
and N2 gas flow rate [10,74].
4. Conclusion
The yields and characteristics of bio-oil, biochar and pyrolysis gas
obtained from pyrolysis and co-pyrolysis of RWS and OPT were inves­
tigated by using an agitated pyrolysis reactor. The co-pyrolysis was
performed at the mixing ratio of 50:50 (wt.). The biomass samples were
pyrolyzed at temperatures of 400, 450, and 500 ◦ C under specific con­
ditions. The yield and characteristics of bio-oil, biochar and pyrolysis
gas were then determined and analyzed. The results indicated the py­
rolysis temperatures had more effect on the yield and characteristics of
bio-oil and biochar than biomass types. The yields of the bio-oil, biochar
and pyrolysis gas were in the ranges of 38.5-46.5, 22.27-28.68 and 30.1-
36.9 wt.%, respectively. Pyrolysis of RWS at 500 ◦ C provided the highest
yield. The bio-oil had high water content and low pH. The main com­
pounds of bio-oil were oxygenated compounds such as acetic acid,
phenols and 2-Propanone,1-hydroxy- as indicated by GC-MS. The high
water content of bio-oil led to low HHV (16.1-20.36 MJ/kg). The bio­
char had high carbon and low oxygen contents, matching proximate and
ultimate analysis and FTIR. The HHV of biochar was in the range of
26.35-29.6 MJ/kg. Besides this, the biochar also had porous structure,
which was indicated by SEM and BET. The pyrolysis gas obtained from
500 ◦ C mainly contained CO2, CO, H2 and CH4, and its heating value was
in the range 3.23-6.7 MJ/m3. Based on these results, OPT and RWS are
P. Sakulkit et al.
alternative biomasses for biofuel, biochemical and bio-product pro­
duction via pyrolysis and co-pyrolysis processes.
CRediT authorship contribution statement
Patipan Sakulkit: Conceptualization, Investigation, Visualization,
Writing - original draft. Arkom Palamanit: Conceptualization, Re­
sources, Writing - review & editing, Supervision. Racha Dejchanchai­
wong: Writing - review & editing, Supervision. Prasert
Reubroycharoen: Writing - review & editing, Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper
Acknowledgements
The authors would like to thank to the Interdisciplinary Graduate
School of Energy Systems, Prince of Songkla University (Contract
number: 1-2018/06) and Provincial Electricity Authority (PEA) of
Thailand for their financial support. This study was also partially sup­
port by Graduate Student Fund (Contract number: 033/2562) from
Energy Conservation Promotion Fund, Energy Policy and Planning Of­
fice (EPPO), Ministry of Energy, Thailand. The authors thank to
Research and Development Office (RDO), Prince of Songkla University,
and Assoc. Prof. Dr. Seppo Karrila for support an English correction.
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