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Contents lists available at ScienceDirect

Process Safety and Environmental Protection

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

Oil palm waste: An abundant and promising

feedstock for microwave pyrolysis conversion into
good quality biochar with potential
multi-applications

Rock Keey Liew a , Wai Lun Nam a , Min Yee Chong a , Xue Yee Phang a ,
Man Huan Su a , Peter Nai Yuh Yek a,b , Nyuk Ling Ma c , Chin Kui Cheng d ,
Cheng Tung Chong e , Su Shiung Lam a,∗
a Pyrolysis Technology Research Group, Eastern Corridor Renewable Energy Group (ECRE), School of Ocean
Engineering, Universiti Malaysia Terengganu, 21030 Kuala Nerus, Terengganu, Malaysia
b School of Engineering and Technology, University College of Technology Sarawak, Lot 88, Persiaran Brooke, 96000

Sibu, Sarawak, Malaysia

c School of Fundamental Sciences, Universiti Malaysia Terengganu, 21030 Kuala Nerus, Terengganu, Malaysia
d Faculty of Chemical and Natural Resources Engineering, Universiti Malaysia Pahang, Lebuhraya Tun Razak, 26300

Gambang, Kuantan, Pahang, Malaysia

e Faculty of Mechanical Engineering, Universiti Teknologi Malaysia, 81310 Skudai, Johor, Malaysia

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

Article history: Oil palm waste (OPW), comprising mainly of empty fruit bunch, mesocarp fiber, frond, trunk,
Received 30 May 2017 and palm kernel shell generated from palm oil industry, was collected, characterized, and
Received in revised form 28 then pyrolyzed to evaluate their potential to be converted into biochar with desirable prop-
September 2017 erties for use in multi-applications. The OPW was detected to have considerable amounts
Accepted 9 October 2017 of carbon (43–51 wt%) and fixed carbon (30–39 wt%), showing potential to be converted into
Available online xxx carbon-rich biochar. Microwave pyrolysis of palm kernel shell as the selected OPW produced
a biochar with zero sulphur content and high heating value (23–26 MJ/kg) that is nearly com-
Keywords: parable to conventional coal, thus indicating its potential as an eco-friendly solid fuel. The
Oil palm waste biochar obtained was also showed low moisture (<3 wt%) and ash (3 wt%), and a highly
Microwave pyrolysis porous structure with high BET surface area (210 m2 /g), indicating the presence of many
Biochar adsorption sites and thus showing desirable characteristics for potential use as pollutant
Adsorbent adsorbent in wastewater treatment, or bio-fertilizer to absorb nutrient and promote plant
Bio-fertilizer growth. Our results demonstrate that OPW is a biowaste that shows exceptional promise to
Solid fuel be transformed into high-grade biochar rather than simply disposed by landfilling or burned
as low-grade fuel in boiler.
© 2017 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

∗
Corresponding author.
E-mail addresses: [email protected] (R.K. Liew), [email protected] (W.L. Nam), [email protected] (M.Y. Chong),
[email protected] (X.Y. Phang), [email protected] (M.H. Su), [email protected] (P.N.Y. Yek), [email protected] (N.L.
Ma), [email protected] (C.K. Cheng), [email protected] (C.T. Chong), [email protected], [email protected] (S.S. Lam).
https://doi.org/10.1016/j.psep.2017.10.005
0957-5820/© 2017 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article in press as: Liew, R.K., et al., Oil palm waste: An abundant and promising feedstock for microwave pyrol-
ysis conversion into good quality biochar with potential multi-applications. Process Safety and Environmental Protection (2017),
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1. Introduction the surface chemistry of biochar that has high carbon content can be
altered by introducing several chemical functional groups (e.g. hydroxyl
Oil palm plantations occupy the largest sector of agriculture in Malaysia and carbonyl) for specific adsorption purpose (Angin et al., 2013). Due to
with approximately 5.7 million hectares of plantation area in 2016 its unique characteristics, it has been researched for its application in
(MPOB, 2017). The subsequent processing to produce palm oil inadver- removal of heavy metal (Godinho et al., 2017; Johari et al., 2016), produc-
tently produces great amount of oil palm wastes (OPW) that generally tion of H2 gas using gasification (Lv et al., 2016), as catalyst in catalytic
comprise of 15% of mesocarp fibres (MF), 6% of palm kernel shells (PKS), pyrolysis reaction (Seng-eiad and Jitkarnka, 2016), as soil additive to
and 23% of empty fruit bunches (EFB) in one ton of fresh fruit bunch improve microbial respiration response (Lanza et al., 2016), or it can
(FFB) of oil palm (Loh, 2016; Omar et al., 2011). According to Malaysia further be upgraded into activated carbon that has wider applications
Palm Oil Board (MPOB) (Board, 2017), the total production of crude palm as supercapacitor, humidity regulator, and protector of electromagnetic
oil (CPO) in Malaysia was 3.4 million tonnes in 2016, hence about 25.5 radiation (Gupta et al., 2015; Tripathi et al., 2016b; Zhang et al., 2016).
million tonnes of OPW were generated since 75 wt% of the solid wastes In view of the large production of OPW and the advantages shown by
were produced from 10 wt% of CPO. the biochar produced from pyrolysis process, this study was performed
The majority of OPW (e.g. PKS and MF) are currently burned in boiler to investigate the potential of using OPW as a pyrolysis feedstock
to generate steam for sterilization of fresh fruit bunch, however this for recovery of biochar with desirable properties for use in multi-
method could lead to air pollution by releasing flue gases containing applications. This included some in-depth analyses of the elemental
ash, CO, and NOx into the atmosphere (Okoroigwe et al., 2013). OPW is and proximate composition of the OPW. The wastes were then ana-
also used as combustion feedstock for electricity generation in some lyzed via a thermogravimetrical approach to examine the different
palm oil mills, which leads to production of undesirable ash (Awalludin types and stages of chemical reactions (e.g. moisture evaporation,
et al., 2015). It is thus thought that an alternative method should be devolatilization, fragmentation) that could occur during their ther-
developed by transforming OPW into value-added materials such as mal decomposition by pyrolysis, and to propose the suitable pyrolysis
biochar or activated carbon to improve the recovery of OPW and divert temperature for optimal recovery of biochar. The OPW with desir-
these wastes from landfill or being a source of air pollution. able properties was selected and pyrolyzed to produce biochar over a
Pyrolysis, a thermal decomposition process under an inert environ- range of microwave power considered. The biochar obtained was then
ment, shows potential as an environmental friendly method to treat analysed for their various properties (i.e. chemical compositions, sur-
OPW (Lam et al., 2016a). Combustion of waste can release significant face morphology and porous characteristics) followed by examining its
amounts of greenhouse gases such as carbon dioxide (CO2 ), whereas applications as dye adsorbent and bio-fertilizer in mushroom cultiva-
pyrolysis method can limit the production of greenhouse gases and tion in order to assess its potential to be used in multi-applications.
decompose the waste to produce potentially useful products compris- There have been studies reported on pyrolysis of OPW, however most
ing of solid biochar, liquid bio-oil and biogas (Lam et al., 2016b). These of them focused on the recovery of bio-oil and biogas as fuels (Hossain
products can be used as chemical feedstock, fuel source, soil amend- et al., 2016a,b; Khanday et al., 2016; Tan et al., 2016; Yin et al., 2016). To
ment, catalyst, or further upgraded into activated carbon (He et al., the best of our knowledge, there has yet to be any studies reported on
2017; Lam et al., 2016d; Lee et al., 2017a; Tan et al., 2017). In particular, the use of vacuum environment to perform microwave pyrolysis. Pyrol-
microwave pyrolysis, a pyrolysis technique using microwave heating ysis performed under vacuum environment could provide advantages
as the heat source, has recently been investigated for its potential for in preventing uncontrolled heating inside the reactor and avoiding
waste recovery. adverse chemical reactions such as re-condensation of volatiles on the
Microwave pyrolysis offers a rapid and selective heating mechanism surface of the biochar.
over other thermal decomposition processes (e.g. conventional pyrol-
ysis, gasification and combustion) (Al-Salem et al., 2017; Lam et al., 2. Materials and methods
2017b; Salema et al., 2017). The use of microwave radiation targets
mainly to carbon-based material with good microwave absorbency. 2.1. Source and preparation of oil palm wastes (OPW)
When the carbon material is exposed to microwave radiation, dipole
rotation in atomic scale is occurred up to million times per second
Five types of OPW, namely empty fruit bunch (EFB), palm ker-
within the material. As a result, heat energy is rapidly generated from
nel shell (PKS), mesocarp fiber (MF), trunk, and frond, were
the frictions between the atoms and molecules within the material
which subsequently leads to fast heating of the material, thus shorter
collected from palm oil mill located in Kemaman, Terengganu,
process time (<30 min) is required to heat up the material to achieve Malaysia. The OPW collected were rinsed with tap water to
a desired high temperature (Lam and Chase, 2012; Wan Mahari et al., remove dirt particles and dried in an oven for 24 h at 105 ◦ C
2016). By comparison with the conventional pyrolysis that is heated to avoid rotting. The dried wastes were ground into smaller
by a furnace, the heating mechanism is non-selective where the heat pieces (1–2 mm in diameter) and stored inside an air-tight con-
energy targets everything within the chamber of the furnace. The heat tainer. The wastes needed to be processed to a smaller size
energy is transferred from the heating coil of the furnace to the sample in order to obtain a more accurate result on their thermal
mainly by conduction and convection mechanisms, which are com- decomposition behaviour during the pyrolysis using a ther-
paratively slower than microwave pyrolysis, thus longer process time
mogravimetric analyser (TGA). A large sample could decrease
(>1 h) is needed to heat up the sample until the desired temperature.
the efficiency of heat transfer from the surface of sample to its
In this study, the biochar produced from microwave pyrolysis of
core (Tripathi et al., 2016a), resulting in incomplete pyrolysis
OPW is of interest due to its potential to be used in many applications.
The characteristics and yield of the biochar obtained depend on the of the sample and hence producing inaccurate results from
types of feedstock used and process parameters involved. For instance, TGA.
the yield of biochar is significantly affected by process parameters such
as heating rate and residence time (Tripathi et al., 2016a). Fast heating 2.2. Analysis of OPW
rate (up to 100 ◦ C/min) with short residence time (from seconds to min-
utes) favour the formation of liquid bio-oil with less biochar obtained. Elemental analysis of the wastes were conducted using a
In contrast, slow heating rate (5–10 ◦ C/min) with long residence time FlashEA 1112 CHNS elemental analyzer to quantify the car-
(up to 1 h) were reported to enhance the yield of biochar (Collard and
bon, hydrogen, nitrogen and sulphur contents in the sample,
Blin, 2014).
whereas the oxygen content was determined by mass dif-
The biochar produced usually possesses better adsorption property
ference (i.e. O = 100 wt% –C–H–N–S) (Liu and Han, 2015). The
compare to its raw material due to the characteristic of porous surface
structure with wide range of surface area (10–300 m2 /g). In addition, wastes were dried in an oven at 105 ◦ C to remove any residual
moisture content. Next, the fruit wastes were combusted with

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oxygen at 1000 ◦ C to produce CO2 , H2 O, N2 , and SO2 as products 2.4. Characterization of biochar
of combustion. The contents of carbon, hydrogen, and sulphur
were detected quantitatively by the selective IR absorption The elemental and thermogravimetrical analyses of the
detectors whereas the content of nitrogen was measured by biochar were performed according to the aforementioned
a thermal conductivity detector. The results obtained were procedures (See Section 2.2). The heating value (HV) of the
presented in weight percent (wt%). biochars were estimated from their elemental composition
Thermogravimetrical analysis (TGA) of OPW were con- (i.e. carbon, hydrogen, and oxygen in wt%) using Eq. (2).
ducted using a Mettler Toledo Thermogravimetric analyser. According to Sheng and Azevedo (2005), the estimation of HV
The wastes were heated and pyrolyzed in N2 atmosphere from from elemental composition of biochar is more accurate than
ambient temperature to 900 ◦ C at a heating rate of 10 ◦ C/min the one estimated from proximate or lignocellulosic composi-
and a gas flow rate of 25 ml/min. The results obtained were tions.
presented as TGA-DTG curves in a form of weight percent
MJ 
(%) against temperature in degree Celcius (◦ C). The TGA HV ⁄kg = −1.3675 + 0.3137C + 0.7009H + 0.0318 O (2)
curves obtained from these pyrolysis experiments were used
to determine the stages of chemical reaction (e.g. moisture The biochars were analysed using a Perkin Elmer Spectrum
evaporation, devolatilization, charring) and estimate the suit- 100 Fourier Transform Infrared (FTIR) spectrometer to iden-
able pyrolysis temperature for optimal recovery of biochar tify and compare the changes of chemical functional groups
from OPW. The determination of the stages of chemical reac- present in the biochars obtained. A thin KBr (potassium bro-
tion is important to estimate the proximate contents of the mide) disc method was used in the FTIR analysis. Before the
wastes. This could in turn provides information on the possi- analysis was initiated, all analysis tools required were rinsed
ble types of products (e.g. char or bio-oil) to be recovered from with a small amount of acetone to remove any surface mois-
the wastes. ture that could interfere the results of FTIR. The analysis was
The moisture content was determined by the weight loss of performed at wavenumber ranging from 400 to 4000 cm−1
the wastes at 110 ◦ C while the volatile matter was determined for each sample (Lam et al., 2016b). The infrared spectrum
by the dramatic weight loss observed in the temperatures obtained was presented in a form of transmittance (%) against
between 200 until 450 ◦ C, whereas the ash content was deter- wavenumber (cm−1 ).
mined by combustion of the wastes in a muffle furnace at The surface of the biochars were scanned using JEOL
950 ◦ C with a holding time of 10 minutes (Lam et al., 2016b). JSM-6360LA scanning electron microscope (SEM) at 10 kV of
The fixed carbon was estimated by subtracting the contents of accelerating voltage to examine their surface morphology.
moisture, volatile matter and ash from the original dry mass The porous characteristics of biochars were obtained using
of the sample (i.e. fixed carbon = 100 wt% – moisture – volatile ASAP micromeritics 2020 porosimeter. Prior to nitrogen gas
matter – ash) (Lam et al., 2016c). adsorption measurement, the sample was degassed at 90 ◦ C
for 10 h with 10 ◦ C/min ramp rate under vacuum environment
2.3. Microwave pyrolysis of OPW to produce biochar to remove residual moisture. The analysis was then performed
using liquid nitrogen at −196 ◦ C to obtain N2 adsorption-
Selected OPW was subjected into pyrolysis experiment to desorption isotherm. The isotherm obtained was used to
investigate its potential to be converted into biochar. Pyrol- estimate BET surface area and estimation of the total pore
ysis of OPW was performed via a microwave pyrolysis set-up. volume at relative pressure of 0.99. The average pore size of
300 g of sample was measured in the reactor and placed inside the sample was estimated using Barrett–Joyner–Halenda (BJH)
the microwave oven. Before the pyrolysis was initiated, the air desorption method. The micropore volume was determined
inside the cavity of microwave oven was sucked out using a from the t-plot method, whereas the mesopore volume was
vacuum pump in order to create an inert condition for pyroly- calculated by difference (Mesopore volume (cm3 /g) = Total pore
sis to occur. After 10 min, the pyrolysis of OPW was performed volume − micropore volume).
over a range of microwave power (500–700 W) for 25 min. It had
been ascertained from trial experiment that no emission of 2.5. Adsorption of methylene blue using biochar
pyrolysis volatiles was observed after 20 min during the pyrol-
ysis of OPW, thus 25 min of microwave irradiation time was The biochar was tested for its adsorption performance using
chosen to allow the pyrolysis process to be completed. The methylene blue (MB). The adsorption test was performed in a
pyrolysis temperature was monitored using a Type-K thermo- beaker containing 1 g of biochar and 1 L of MB aqueous solution
couple that is in direct contact with the sample in the reactor with an initial concentration of 100 mg/L. The beaker added
during the pyrolysis experiment. biochar and MB solution was agitated at room temperature
The yield of the resulting biochar was calculated using Eq. at a mixer speed of 150 rpm for 10 min. The MB solution was
(1). centrifuged and the residual concentration of MB was ana-
lysed using a UV–Vis spectrophotometer at the wavelength of
Yield (wt%) = Wf ⁄Wi × 100 (1) 665 nm. The amount of MB adsorbed by the biochar was calcu-
lated using Eq. (3) to evaluate its efficiency as dye adsorbent.

Wf is the weight of biochar produced (g) and Wi is the weight of (Co − Ce ) V

OPW (g). The biochar obtained were termed ‘MC500’, ‘MC600’, qe = (3)
W
and ‘MC700’ in which the numerical indicates the microwave
power used to produce the biochar. The biochar was then where qe (mg/g) = adsorption efficiency of biochar; C0
stored inside a sample vial and ready for analysis. The pyroly- (mg/L) = initial concentration of MB solution; Ce (mg/L) = final
sis experiments were repeated for three times to ensure good concentration of MB solution; V = volume of MB solution in
reproducibility of the data. liter; W = mass of biochar used in gram.

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Fig. 1 – TGA-DTG curves of OPW. TGA curve is denoted by red line, and DTG curve is plotted with blue line.

2.6. Biochar as bio-fertilizer in Oyster mushroom 3. Results and discussions

cultivation
3.1. Characterization of OPW
The biochar produced was applied in Oyster mushroom
cultivation. 10 g of biochar was ground into powder using 3.1.1. TGA pyrolysis of OPW
grinder and then mixed with rice bran, calcium carbonate, Fig. 1 shows the TGA-DTG curves obtained from pyrolysis of
and sawdust to formulate the cultivation medium for Oyster OPW. It was observed from the curves that there were three
mushroom to grow. A polyethylene cylindrical bag was used to stages of decomposition occurred over different ranges of
make a baglog that was then filled with 1 kg of the cultivation temperatures during the pyrolysis of OPW, namely: (1) evapo-
medium, and then the Oyster mushroom spawn was injected ration of moisture (90–150 ◦ C), (2) de-volatilization (200–450 ◦ C)
into the baglog. The yield of Oyster mushroom was calcu- resulted from decomposition of the lignocellulosic compo-
lated (in gram) based on the total weight of the fresh mature nents (i.e. cellulose, hemicellulose and lignin) in OPW to form
mushroom harvested. Finally, the yield of Oyster mushroom condensable hydrocarbons (e.g. monomer units derived from
was compared between the data obtained from the cultiva- the lignocellulosic components) (Lam et al., 2016b), and (3)
tion medium added with and without biochar to evaluate its charring (450–900 ◦ C) that produces Cx Hy in the form of tar
potential as bio-fertilizer in Oyster mushroom cultivation. and incondensable gases such as CO, CO2 or H2 (Collard and
Blin, 2014).

Please cite this article in press as: Liew, R.K., et al., Oil palm waste: An abundant and promising feedstock for microwave pyrol-
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Table 1 – Proximate compositions (wt%) of OPW.

Samplea Moistureb Volatile matterc Fixed carbond Ashe

Empty fruit bunch (EFB) 6 60 30 4

Mesocarp fiber (MF) 7 60 30 3
Oil palm frond (OPF) 12 51 33 4
Oil palm trunk (OPT) 8 47 39 6
Palm kernel shell (PKS) 4 58 34 4

a
Dried basis.
b
Determine at 110 ◦ C.
c
Determine at 200–450 ◦ C.
d
Calculated by difference. (Fixed carbon = 100 wt% − moisture − volatile matter − ash).
e
Obtained by combustion in muffle furnace at 950 ◦ C for 10 min.

The weight of OPW slightly decreased (up to 12 wt%) when loss started to be observed. It can be observed from both the
the wastes were heated up to 110 ◦ C. This was likely due to TGA-DTG curves in Fig. 1 that the weight loss remained nearly
the evaporation of moisture from the waste materials (Lam constant at approximately 410 ◦ C for empty fruit bunch, 420 ◦ C
et al., 2016b). Their weight then dropped dramatically at tem- for mesocarp fiber, 430 ◦ C for palm kernel shell and oil palm
perature between 200–450 ◦ C, indicating the occurrence of trunk, and 520 ◦ C for oil palm frond. These temperatures indi-
devolatilisation from the decomposition of the wastes to pro- cate that most of the volatile matters in the OPW were released
duce volatiles and gases that led to the weight loss, leaving at a temperature ranging from 410 ◦ C to 520 ◦ C, thus suggesting
the non-volatile fraction in the form of biochar. It has been that a minimum temperature of 410 ◦ C is required to remove
reported in pyrolysis of biomass materials that the weight majority content of volatile matters from the wastes for sub-
loss observed between 200 and 450 ◦ C was derived from the sequent recovery as biochar.
depolymerization of lignocellulosic components (cellulose, Overall, the results from the pyrolysis of OPW indicate that
hemicellulose, and lignin) to produce organic volatiles such the waste would undergo several stages of chemical reactions
as levoglucosan (Patwardhan et al., 2011), furfural and fur- during their thermal decomposition by pyrolysis, comprising
furyl alcohol (Wang et al., 2013). These organic volatiles were moisture evaporation, devolatilisation from decomposition of
derived from the depolymerization reaction of cellulose at the lignocellulosic components (cellulose, hemicellulose and
around 300–390 ◦ C (Collard and Blin, 2014). Thus, it is thought lignin), and charring of the non-volatile fraction present in the
that the OPW being a biomass material also possess lignocel- form of biochar. This resulted in the production of volatile
lulosic components and followed the similar decomposition matter representing the majority content of the OPW, small
pattern as shown by the pyrolysis of biomass materials. amounts of moisture, and incondensable gases (e.g. CO, CO2
The three lignocellulosic components have different ther- and H2 ) and biochar. Therefore, the results suggest that pyrol-
mal stability and would decompose at different ranges of ysis of OPW should be performed at 410–520 ◦ C (depending on
temperatures. Hemicellulose that has the lowest thermal the wastes chosen) in order to obtain optimal yield of biochar
stability would decompose at 180–285 ◦ C followed by the with minimum content of volatile matters.
decomposition of cellulose over the range of 285–365 ◦ C.
Lignin, being the most thermally stable among the three com- 3.1.2. Proximate contents of OPW
ponents, would decompose at 365–500 ◦ C (Tzvetkov et al., Table 1 presents the moisture, volatile matter, fixed carbon,
2016). There were also studies reported that lignin would and ash contents of OPW obtained from proximate analysis.
decompose at a higher temperature up to 1000 ◦ C (Ferrara The results showed the volatile matter (47–60 wt%) represents
et al., 2014). The high temperature required to decompose the main component in the OPW followed by the fixed carbon
lignin component could be explained by its complex form of (30–39 wt%) and small amounts of moisture (4–12 wt%) and ash
polymer composing of different propylbenzene units linked (3–6 wt%).
with multiple ether and carbon to carbon linkages (Neutelings, High content of the volatile matter (up to 60 wt%) was
2011). detected in OPW. It represents an unwanted fraction in pro-
It was observed that the weight of the OPW then slightly ducing a desirable biochar with low volatile content, however,
decreased over a wide range of temperature from 450 to 900 ◦ C. they can also be recovered and transformed into bio-oil and
This could be due to the release of carbon containing species bio-gas for use as a potential fuel or chemical feedstock
with lower molecular weight such as COx gases, Cx Hy in the from pyrolysis process. Interestingly, it has been reported that
form of tar, or incondensable gases (e.g. H2 ) resulted from the the volatile matter could also contribute to increased forma-
charring of the non-volatile fraction (i.e. biochar) remained tion of biochar (10–20 wt%) during pyrolysis (Collard and Blin,
after the devolatilisation stage during the pyrolysis of biomass 2014), where the volatile matter, which was transformed into
(Lam et al., 2016b). This suggests that pyrolysis of the OPW volatiles and gases, could undergo condensation reactions to
should be performed at less than 450 ◦ C in order to obtain opti- form secondary biochar (Neves et al., 2011), thus adding to the
mal yield of biochar otherwise some of the biochar would be yield of the biochar formed. However, the condensation reac-
fragmented to produce COx gases, Cx Hy and incondensable tions would be favoured by prolonging the residence time of
gases beyond 450 ◦ C. the volatiles and gases inside the reactor.
In addition, the minimum temperature required to remove A considerable amount of fixed carbon (up to 39 wt%) was
majority of volatile matter from OPW can also be obtained detected in the OPW, indicating their potential to be converted
from the temperature at which the TGA curve starts to drop into carbonaceous materials such as biochar via pyrolysis.
steadily; this can also be estimated from the DTG curve at During pyrolysis of biomass, the fixed carbon components,
the temperature where a constant pattern of derivative weight which is non-volatile by its nature, would be transformed into

Please cite this article in press as: Liew, R.K., et al., Oil palm waste: An abundant and promising feedstock for microwave pyrol-
ysis conversion into good quality biochar with potential multi-applications. Process Safety and Environmental Protection (2017),
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Table 2 – Elemental compositions (wt%) of OPW.

OPW C H N Oa Sb O/C (N + O)/C

Empty fruit bunch (EFB) 43 6 10 41 0 0.7 0.9

Mesocarp fibre (MF) 46 7 9 38 0 0.6 0.8
Oil palm frond (OPF) 46 6 7 41 0 0.6 0.6
Oil palm trunk (OPT) 46 5 10 39 0 0.7 0.8
Palm kernel shell (PKS) 51 7 3 39 0 0.6 0.8

a
Calculate by difference.
b
Not detected.

biochar (Lam et al., 2016b). The biochar that contains fixed to divert the wastes from landfilling (with considerably the risk
carbon also indicates the possible development of adsorption of undesired production of greenhouse gas).
sites since the fixed carbon would form the carbon structure In addition, the gaseous product produced from pyroly-
that is then developed into pores (Dhorabe et al., 2016). Biochar sis of OPW could be more environmental friendly as there
is a main product of interest because it can be utilized for is no need to be concerned with the formation of sulphur-
soil amendment, heavy metal purification and dye removal containing compounds from the OPW that contain either zero
(Tripathi et al., 2016a), or it can further be upgraded into acti- or negligible content of sulphur. Overall, the OPW shows high
vated carbon that has wider applications. carbon and fixed carbon contents, indicating their potential to
Small amount of ash (up to 6 wt%) was detected in the OPW, be converted into carbon-dense material such as biochar.
suggesting that the OPW should be diverted from being burned
as a fuel in boiler to generate steam. The presence of ash could
lead to slag formation on the wall of the boiler reactor and 3.2. Product yield of biochar from microwave pyrolysis
decrease the efficiency and lifetime of the reactor (Öhman
et al., 2009). Alternatively, the OPW could be pyrolyzed to pro- Palm kernel shell (PKS) was selected as feedstock for biochar
duce biochar since the ash content may comprise of useful recovery due to its highest content of carbon (51 wt%; See
inorganic elements such as Na, K, Al, Fe, and Mn that could Table 2) and considerable high of fixed carbon (34 wt%; See
act as an inorganic catalyst during pyrolysis and enhance the Table 1). Hence, PKS was subjected into microwave pyrolysis to
pyrolysis cracking process to release more volatile matter (Lam produce biochar over a range of microwave power considered.
et al., 2015), thus producing biochar with a low volatile con- The product yield of biochar obtained at different microwave
tent and higher purity of fixed carbon that could shows higher powers of 500 W, 600 W, 700 W were 38 wt%, 35 wt%, 33 wt%,
adsorption efficiency. respectively.
The results showed that lower yield of biochar was
obtained at higher microwave power. The influence of
microwave power to the product yield obtained could be
3.1.3. Elemental content of OPW explained by the interaction between microwave energy and
Table 2 presents the results from CHNS elemental analysis of the microwave absorbent material (e.g. carbon-containing
OPW. Carbon (43–51 wt%) and oxygen (38–41 wt%) represent material such as biomass) (Lam et al., 2016c). Palm kernel
the major elements present in the OPW, whereas hydrogen shell (biomass material) represents a microwave absorbent
(5–7 wt%), nitrogen (3–10 wt%) were detected in low concen- material that can absorb microwave energy and convert into
tration. Sulphur was not detected in the OPW, probably due to heat energy within the material itself for pyrolysis reaction
the presence of a very low sulphur content that was below the to occur. This conversion of energy could be explained by the
detection limit of the CHNS analyser. polarization mechanism of the molecules present in the mate-
High carbon content was detected in all OPW, indicating rial. However, due to the complexity of components present
its potential as a feedstock to produce a carbon-rich biochar in the palm kernel shell (e.g. water, cellulose, hemicellulose,
(Brown, 2009). However, up to 41 wt% of oxygen was also lignin, and ash), the proposed polarization mechanism may
detected from the wastes, suggesting that the oxygen should not fully reflect the actual mechanism that occurred during
be removed by pyrolysis. The present of oxygen content could the microwave pyrolysis reaction.
contribute to the surface hydrophilicity and polar nature (as When the raw material (i.e. palm kernel shell) is exposed
indicated by both atomic ratios of O/C and (N+O/C), respec- to microwave radiation, the microwave would induce the
tively) of the OPW (Lam et al., 2016b). polarization effect on the material in which the chemical
Both surface hydrophilicity and polar nature indicates the bonds (e.g. covalent bond) that present within the lignocellu-
high tendency of OPW to mix or dissolve in the water as losic components (cellulose, hemicellulose and lignin) would
the oxygen-containing functional group (e.g. –OH) present in undergo oscillation (e.g. molecular bending). Fig. 2 illustrates
the OPW can bind and form hydrogen bonding with water the molecular bending motion of cellulose under microwave
molecule. Thus, it was inferred that if the OPW are sent for radiation. This oscillation will happen at up to million times
disposal in landfill, the wastes could undergo hydrolysis pro- per second, consequently the heating was generated from
cess with water molecules due to their nature of surface the rapid motion that probably resulted from strong frictional
hydrophilicity and polarity. The organic molecules present in force between the oscillating molecules. This could explain
OPW would react with water molecules in the landfill sites and the mechanism of heat generation within the microwave-
breakdown into simpler molecules (e.g. amino acids and fatty radiated material.
acids) and results in the formation of methane gas (i.e. green- When higher microwave power (700 W) was used dur-
house gas) by the conversion of bacteria. Efforts should be ing the pyrolysis process, the palm kernel shell will receive
made to transform the OPW into useful product (e.g. biochar) more microwave energy and generate heat energy within

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Fig. 2 – The molecular bending motions of cellulose during microwave radiation.

erated within the material and enhanced the carbonization

Table 3 – Proximate and elemental contents (wt%) of
biochar. of the palm kernel shell to produce a carbon-rich biochar.
During the carbonization process (i.e. conversion of palm ker-
Proximate content MC500 MC600 MC700
nel shell to biochar), there could be a few chemical reactions
Moisturea 1 2 3 (e.g. depolymerization, fragmentation, and cracking) occurred
Volatile matterb 35 19 10 simultaneously to break and re-form the chemical bonds
Fixed carbonc 61 76 85 within the lignocellulosic components (Collard and Blin, 2014).
Ashd 3 3 3
As a result, volatile matter that mainly consists of oxygenated
Element content compounds such as CO, CO2 , CH3 CHO and H2 O were released
Carbon 64 69 79 from the decomposition of palm kernel shell by pyrolysis. It
Hydrogen 5 4 3
was thought that the carbon-dense biochar obtained could be
Nitrogen 1 1 1
used as solid fuel. Combined with its zero-sulphur content and
Oxygene 30 24 17
Sulphurf 0 0 0 considerable high of heating value (23–26 MJ/kg) that is nearly
Heating value (MJ/kg)g 23 24 26 comparable to conventional coal such as lignite and anthrasite
(15–27 MJ/kg), the biochar represents as a more environmental
a
Determine at 110 ◦ C. friendly option to substitute the conventional coal for com-
b
Determine at 200–450 ◦ C.
c
bustion purpose since the burning of biochar will not release
Calculated by difference. (Fixed carbon = 100 wt% – moisture –
volatile matter – ash).
sulphur-containing compounds (e.g. sulphur dioxide) that can
d
Obtained by combustion in muffle furnace at 950 ◦ C for 10 min. contribute to acid rain formation.
e
Calculate by difference (Oxygen = 100 wt% − carbon − hydrogen – Interestingly, the moisture content of biochar increased
nitrogen – sulphur). with higher microwave power. This probably because more
f
Sulphur content is not detectable by the minimum detection limit moisture molecules were adsorbed on the abundant adsorp-
of the CHNS analyser (<0.05 wt%), and thus it is assumed to be
tion sites available from the biochar that obtained at higher
0 wt% in calculation.
g microwave power. It was envisaged that the MC700 produced
Estimated using Eq. 1 (−1.3675 + 0.03137C + 0.7009 H + 0.0318 O)
(Sheng and Azevedo, 2005). at 700 W has more adsorption sites been developed on the sur-
face compared with MC500 and MC600 which could have led
to more moisture being adsorbed on the surface. This con-
the material itself. The material will in turn be heated at
curred with the observation from the surface structure of the
higher temperature during the pyrolysis reaction, causing
biochar (See Fig. 4) in which more pores were observed from
more volatile matter to be released from the decomposition of
the surface of MC700. Despite there was increasing trend of
palm kernel shell to form biochar. Consequently, the biochar
moisture content observed from the biochar, the value is still
that was produced at 700W showed a lower yield (33 wt%) due
low (<3 wt%). Combined with the low ash detected (3 wt%),
to the loss of volatile matter.
the biochar shows desirable properties to be used as poten-
tial adsorbent material to remove pollutant molecules from
3.3. Characterization of biochar waste water or act as bio-fertilizer to adsorb nutrients and
promote plant growth since low contents of moisture and ash
3.3.1. Proximate and elemental contents of biochars of biochar would have higher adsorption capacity.
Table 3 shows the proximate and elemental contents of the
biochars obtained at different microwave power. The prox-
imate contents of biochars were contained mainly of fixed 3.3.2. Fourier transform infrared analysis
carbon (61–85 wt%) followed by volatile matter (10–35 wt%) Fig. 3 compares the FTIR spectrum of biochar produced at dif-
with small amount of moisture and ash (1–3 wt%). In addi- ferent microwave power with palm kernel shell (PKS). The
tion, the results of elemental of biochars show that carbon resulted wavenumbers and the classification of functional
(64–79 wt%) and oxygen (17–30 wt%) represent the major ele- groups present in biochar and PKS were tabulated in Table 4.
ments whereas hydrogen and nitrogen were detected in low It was shown from Fig. 3 that the spectrum obtained from
concentration (1–5 wt%). the biochar produced under different microwave power were
In general, the contents of fixed carbon and carbon were almost similar. Majority of the peaks of biochars were divided
inversely proportional to the contents of volatile matter and into different ranges of wavenumber which include the C H
oxygen respectively with increasing microwave power. This stretching, C C stretching, C H bending and C O bending.
could be attributed to the elimination of more volatile matter It was found that some of the peaks (i.e. O H stretching and
or oxygenated compounds from the pyrolysis reaction that C O bending) that originally present in the PKS were no longer
performed at higher microwave power (Kaifang et al., 2013). observed from the spectra of biochar. The broad peak of PKS
The use of higher microwave power (700 W) was likely to detected at 3000–3500 cm−1 (i.e. peak (a) in Fig. 3) attributes
have led to the exposure of more microwave energy to the to the O H stretching that indicates the presence of chemical
palm kernel shell. Consequently, more heat energy was gen- compounds with hydroxyl functional groups such as phenolic

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Fig. 3 – FTIR spectra of PKS and biochar produced at different microwave power.

Fig. 4 – SEM micrograph (magnification ×1500) of PKS and biochars produced at different microwave power.

or aliphatic alcohol and carboxylic acid in the PKS. It was found and 2855 cm−1 , indicating the asymmetric and symmetric
that this hydroxyl group was not detected from the biochar C H stretching of an alkane compound in PKS, respectively.
spectra, suggesting the hydroxyl-containing compounds were These peaks were likely to have derived from the C H stretch-
released as volatile matter (e.g. CH3 OH and CH3 COOH) prob- ing in methoxy group (–OCH3 ), methyl (–CH3 ), and methylene
ably via the fragmentation reaction of hemicellulose (Shen (–CH2 –). However, the peak intensities of these functional
et al., 2010) and cracking of alkyl-hydroxyl chain that present groups were lower in the biochar spectra (<5%). This could
in the lignin (Cao et al., 2013) during the carbonization process. probably due to the demethylation (i.e. removal of methyl and
At 2800–3000 cm−1 (i.e. peak (b) in Fig. 3), the peak pres- methylene groups) (Asmadi et al., 2011) and transformation
ence in this range was derived from chemical compounds with of methoxy group into carbon-containing species such as CO
C H stretching functional group. The two sharp transmittance and CO2 by breaking the ether bond (chemical bond between
peaks of C H stretching were detected at around 2925 cm−1

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Table 4 – Functional groups and the classification of compounds identified in oil palm shell biochar by FTIR analysis.
Transmittance peaks indicated by Wavenumber of Samples (cm−1 )a Functional groups Classification of compounds
the range of wavenumber (cm−1 )
PKSb MC500c MC600d MC700e

(a) 3000–3500 3421 – – – O H Stretching Alcohol, phenol or carboxylic acid

(b) 2800–3000 2925, 2855 2972 2934 2996 C H Stretching Alkanes
(c) 1700–1750 1744 – – – C O Stretching Aldehyde, ketone or carboxylic acid
(d) 1600–1700 1626 1658 1645 1624 C C Stretching Alkenes, aromatic ring
(e) 1300–1500 1376 1467 1500 1472 C H Bending (CH2 Alkanes
and CH3 )
(f) 1000–1200 1163, 1042 1094 1173 1166 C O Bending Alcohol, ether or carboxylic acid

a
The values shown are the peak value detected within the particular range of wavenumber.
b
Palm kernel shell.
c
Biochar obtained at 500 W.
d
Biochar obtained at 600 W.
e
Biochar obtained at 700 W.

carbon and oxygen) during pyrolysis (Cao et al., 2013), thus also concurred with the high carbon and fixed carbon detected
resulting in biochar with higher aromaticity. (Table 3) was indicated to have high resistivity to chemical
The transmittance peak shown at 1700–1750 cm−1 (i.e. peak reactions such as hydrolysis and acid-base reactions.
(c) in Fig. 3) indicates the presence of compounds with car-
bonyl (C O) stretching such as esters, ketones, aldehydes,
or carboxylic groups. However, this peak was only found in
3.3.3. Surface morphology of biochars
PKS spectrum and diminished in the biochar spectra. Besides,
Fig. 4 compares the surface morphology of PKS with the
a high transmittance peak (∼30%) of PKS spectrum for C O
biochar obtained under different microwave power. It was
bending (peak (f) in Fig. 3) at 1042 cm−1 was detected, indi-
observed that the surface of PKS was rugged and non-porous.
cating that alcohols, carboxylic acids, esters or ethers were
In contrast, pores were observed on the surface of all biochar
abundantly present within the PKS. On the other hand, the
after the carbonization process. This indicates that the car-
peak intensity of C O bending was reduced (10–20%) with
bonization process had led to the production and release of
increasing microwave power for the biochar spectra. The
volatile matter from the palm kernel shell; the remaining non-
absent of C O stretching and lower peak intensity of C O
volatile components were then transformed into biochar with
bending detected from biochar spectra could be resulted from
pores of different shapes and sizes observed on the surface.
the elimination of oxygenated compounds during the pyroly-
Besides that, there were more pores observed from the
sis conversion of PKS into biochar (Osman et al., 2016). During
biochar (MC700) obtained at higher microwave power com-
pyrolysis, these oxygenated compounds were resulted from
pared to the one obtained at lower microwave power (MC500),
the decomposition of lignocellulosic components in the form
suggesting microwave power is an influential process param-
of volatile matter and released, thus leaving the residual
eter in the development of surface porosity of biochar. When
carbon as the biochar with low oxygen content. This was con-
higher microwave power (700 W) was used, more heat energy
curred with the low oxygen content (17–30 wt%) detected from
was generated within the PKS which have then promoted
the biochars (Table 3).
the decomposition of lignocellulosic components into more
The band in the region between 1600–1700 cm−1 (i.e. peak
volatile matter. Consequently, more pores were formed that
(d) in Fig. 3) can be assigned to compounds with C C stretch-
resulted from the volatile matter released after the carboniza-
ing, which indicates the presence of alkene or aromatic
tion performed at higher microwave power.
compounds. The spectra of biochar have greater peak inten-
In addition, the pores on the surface of all biochar were
sity (∼15%) compared to the PKS spectrum (∼8%), indicating
clearly observed with less impurities. This could be attributed
the biochars have higher concentration of alkene or aromatic
to the use of vacuum environment instead of continuous flow
compounds than PKS. Hence, it was evident that the PKS
of nitrogen gas by the microwave pyrolysis approach in this
was transformed into biochar that has higher aromaticity
study. In vacuum condition, the pressure inside the reactor
after the carbonization process. This transformation could be
was lower. Hence, the volatile matter generated during the
occurred via a few proposed chemical reactions such as dehy-
pyrolysis was removed immediately from the reactor, reducing
drogenation by releasing H2 to form unsaturated compound,
the residence time of the volatile matter inside the reactor. As
demethylation of short substituents (e.g. –OCH3 and –CH3 )
a result, the possible re-condensation reaction of the volatile
to form polycyclic aromatic compound and dehydration by
matter on the surface of biochar that would have led to the
releasing H2 O to form alkene and aromatic compounds.
pores clogging can be prevented, leading to the formation of
Overall, the FTIR spectra of biochars obtained showed that
‘cleaner’ pores on the surface of biochar (Tripathi et al., 2016a).
the oxygenated compounds (alcohol, phenol, carboxylic, and
In contrast, the pores that present on the surface of biochar
ether) were reduced greatly after the carbonization process
could have clogged or blocked with the condensed volatile
that possibly involved a few chemical reaction pathways. It
matter when nitrogen gas is used during the pyrolysis reac-
was envisaged that the resulted biochar would contain mainly
tion. This could be due to the cooling effect of the nitrogen
of polycyclic structure components that has higher aromatic-
gas that can re-condense the volatile matter released on the
ity and low oxygen content since most of the oxygenated
surface of biochar and clogged the pores, resulting in lower
compounds were detected in low concentration. Thus, the
internal surface area obtained from the biochar. Fig. 5 illus-
present of polycyclic structure components in the biochar that
trates the effect of pyrolysis environments (i.e. vacuum and

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Fig. 5 – The effect of pyrolysis environments to the development of pores on the surface of biochar.

3.4. Application of biochar as dye adsorbent and

Table 5 – Porous characteristics of biochar.
bio-fertilizer in Oyster mushroom cultivation
Porous characteristics MC500c MC600d MC700e

BET surface area (m2 /g)a 80 130 210 Table 6 shows the results obtained when the biochar was
Total pore volume (cm3 /g)b 0.03 0.05 0.10 tested for adsorption of methylene blue (MB) and cultivation of
Average pore size (nm)b 4.2 4.7 3.8 oyster mushroom. It was found that the adsorption efficiency
a of biochar on MB dye was 20–48 mg/g. In addition, a higher
Multipoint Brunauer, Emmett & Teller (BET) method.
b
Barrett, Jovner & Halenda (BJH) desorption method. yield of oyster mushroom was harvested (300–450 g) when the
c
Biochar obtained at 500 W. biochar was applied as bio-fertilizer in the mushroom cultiva-
d tion compared to that obtained from control (230 g).
Biochar obtained at 600 W.
e
Biochar obtained at 700 W. It was observed that higher adsorption efficiency (48 mg/g)
on MB dye and higher yield of Oyster mushroom were obtained
from the biochar produced at higher microwave power (i.e.
MC700) compared to biochar obtained at lower microwave
nitrogen gas) to the development of pores on the surface of power (i.e. MC300). This could be due to the higher BET sur-
biochar. face area (210 m2 /g; Table 5) detected from MC700 that can
provide many adsorption sites for the MB dye to be adsorbed
onto, thus resulting in higher adsorption efficiency obtained.
3.3.4. Porous characteristics of biochars
In addition, the adsorption sites available on the MC700 could
Table 5 shows the porous characteristics of biochar obtained
also retain more nutrients (e.g. rice bran and calcium carbon-
under different microwave power. The biochars showed a BET
ate) and water provided for the growth of Oyster mushroom.
surface area ranging from 80 to 210 m2 /g and the average pore
This could then supply enough moisture and nutrients dur-
size (3.8–4.7 nm) falls in the category of mesoporous material.
ing fruiting stage of the mushroom, reducing the mortality of
It was found that the BET surface area of the biochar
young mushroom yield due to the shortage of water and nutri-
increased with increasing microwave power to 700 W, pro-
ents (Yang et al., 2013). Thus, higher yield of Oyster mushroom
ducing a biochar with a surface area of 210 m2 /g. At higher
was harvested from MC700. Overall, the results revealed that
microwave power, more heat energy was generated within
the biochar produced in this study shows potential to be used
the PKS for carbonization reaction, thus more volatile mat-
in several applications (i.e. dye adsorbent and bio-fertilizer for
ter was released. The release of volatile matter from the PKS
mushroom cultivation).
would have led to the creation of pores from the remain-
ing of non-volatile components that in turn transformed
into biochar. As a result, a biochar with higher BET surface 3.5. Comparison of process features with relevant
area was obtained from higher microwave power. In addi- literatures
tion, the MC700 obtained in this study shows considerable
high of BET surface area (210 m2 /g) compared with the other Table 7 shows the process features of microwave pyrolysis per-
biochar derived from hazelnut shell (14.7 m2 /g) and grapeseed formed in this study compared with the relevant literatures.
(14.5 m2 /g) (Özçimen and Ersoy-Meriçboyu, 2010), suggesting It was found that microwave pyrolysis shows advantage in
that the microwave pyrolysis approach could be a promising providing a shorter process time (25 min) over other conven-
method to produce biochar with high surface area. The MC700 tional pyrolysis using furnace heating (60–120 min), indicating
with high surface area indicates that it has many reaction sites that microwave pyrolysis could be a time-saving approach
available for adsorption process, thus showing potential to be and thus requiring lower processing cost compared to con-
used in waste water treatment or utilized as soil amendment ventional pyrolysis since less energy was also consumed due
to retain water and nutrients to facilitate plant growth. to shorter process time. Although there were also literatures

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Table 6 – Adsorption performance on methylene blue and yield of oyster mushroom obtained from biochar.
Application of biochar MC500a MC600b MC700c Without biochar (control)

Adsorption efficiency on methylene blue (MB) (mg/g) 20 28 48 –

Yield of Oyster mushroom (g) 300 370 450 230

a
Biochar obtained at 500 W.
b
Biochar obtained at 600 W.
c
Biochar obtained at 700 W.

Table 7 – Product feature comparison.

Process features This study Lee et al. (2017b) Aliyu et al. (2017)

Total process time 25 min 60 min 120 min

Source of heating Microwave Furnace Furnace
Types of pyrolysis environment Vacuum N2 gas N2 gas

reported on the use of microwave pyrolysis to produce biochar was supplied by a conventional microwave oven as heat-
from oil palm wastes (Mašek et al., 2013; Salema et al., 2013), ing source for the pyrolysis reaction. But, the conventional
there has yet to be any studies reported on the combined use microwave oven is not feasible to supply enough microwave
of microwave heating and vacuum environment to perform radiation to an industry-scale reactor. Thus, it is suggested
pyrolysis. In addition, the vacuum environment eliminates the that the conventional microwave oven could be replaced
cost to constantly use inert gas (e.g. N2 , argon) to maintain with a modified magnetron system as the direct source of
the pyrolysis condition. The vacuum environment could also microwave to supply higher microwave power for larger-scale
provide advantages in preventing uncontrolled heating inside of pyrolysis operation. However, the microwave limits the
the reactor and avoiding adverse chemical reactions such as types of materials that can be used in the construction of
re-condensation of volatiles on the surface of the biochar. a reactor. In addition, the high power of microwave radia-
tion could possess a potential unknown hazard although the
microwave can easily shielded within an appropriate Faraday
3.6. Potential difficulties of scale-up for industry use cage (Lam et al., 2017a), it is envisaged that the risk assessment
on the high power of microwave radiation to human health
Despite the advantages (e.g. fast heating rate and short pro- should be evaluated.
cess time) shown by laboratory-scale of microwave pyrolysis, In view of the economic feasibility on performing pyroly-
the scaling up of microwave pyrolysis to an industry-scale is sis operation using an industry-scale of microwave pyrolysis
hampered by a few potential difficulties such as the influences equipment, the costings that listed below need to be taken into
of key process parameters on the pyrolysis products, tech- considerations in which the total expenses should be lower
nical information for designing an industry-scale equipment than the market price of the commercialized products (e.g.
and the economic feasibility of a scale-up microwave pyrolysis biochar) in order to obtain profit.
system.
Before the construction of the scale-up prototype, it is
i) The production cost which include the cost incurred by
suggested that the influences of the key process parameters
the feedstock, transportation, consumables (e.g. chemi-
(e.g. microwave irradiation time, residence time of pyrolysis
cals), inert gas for pyrolysis environment (if required), and
volatiles, process temperature, and microwave power) on the
the electricity usage.
types of desired pyrolysis products should be well-understood.
ii) The human capital cost that includes the salary of equip-
For example, it is generally known from the conventional
ment operators, managers, technical and safety officers.
pyrolysis that the process conditions of longer residence
iii) The equipment cost which includes the first-time instal-
time of pyrolysis volatiles (up to 1 h) and slow heating rate
lation, fabrication, renovation and future maintenance.
(5–10 ◦ C/min) will produce more solid pyrolysis product (i.e.
biochar) while shorter residence time (from second to min-
utes) and fast heating rate (up to 100 ◦ C/min) will favours to Hence, it is thought that the microwave pyrolysis prototype
more liquid product (i.e. bio-oil) (Collard and Blin, 2014). How- is feasible to be scaled-up to a commercial level if the overall
ever, similar concept may not be fully applicable to microwave expenses could be minimized and lowered than the market
pyrolysis due to the different heating mechanisms. The cur- price of the commercialized product. It is proposed that the
rent understandings on the reaction mechanism between electricity usage could be reduced to minimize the production
microwave heating and the microwave absorbent materials cost. This could be done by installing an electricity generator
(e.g. biomass) are not well-established enough to accurately that could generate sufficient electricity to fully or partially
estimate the outcome of microwave pyrolysis. Thus, more supply the microwave pyrolysis operation. The electricity gen-
studies should be performed to explore and formulate the erator will be powered by solid fuel (e.g. biochar) in which part
optimized process parameters that can be used to produce of the biochar product obtained from the pyrolysis operation
desired pyrolysis products. could be used as feedstock for electricity generation, hence
With respect to designing an industry-scale of microwave the electricity usage of the whole pyrolysis operation would
pyrolysis equipment, there are several difficulties on the main be significantly reduced. In addition, the use of a continu-
components (i.e. source of microwave and material of the ous operation process would reduce the human capital cost
reactor) that need to be concerned. For the existing laboratory- due to several benefits such as simplified automatic control
scale equipment used in this study, the source of microwave of the pyrolysis operation and constant operating conditions

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(steady and continuous flow of feedstock into the reactor, and Collard, F.-X., Blin, J., 2014. A review on pyrolysis of biomass
continuous production of products out of the reactor from constituents: mechanisms and composition of the products
the conversion of the feedstock) (Lam et al., 2017b), thus less obtained from the conversion of cellulose, hemicelluloses and
lignin. Renew. Sustain. Energy Rev. 38, 594–608.
labours are needed for process monitoring.
Dhorabe, P.T., Lataye, D.H., Ingole, R.S., 2016. Adsorptive removal
of 4-mitrophenol from aqueous solution by activated carbon
4. Conclusion prepared from waste orange peels. J. Hazard. Toxic
Radioactive Waste 21 (2), 04016015.
Ferrara, F., Orsini, A., Plaisant, A., Pettinau, A., 2014. Pyrolysis of
Oil palm wastes can be a suitable feedstock for pyrolysis con-
coal, biomass and their blends: performance assessment by
version into biochar due to its high carbon content (up to thermogravimetric analysis. Bioresour. Technol. 171, 433–441.
51 wt%). The OPW should be pyrolysed at a minimum tem- Godinho, D., Dias, D., Bernardo, M., Lapa, N., Fonseca, I., Lopes, H.,
perature of 410 ◦ C in order to remove the majority content of Pinto, F., 2017. Adding value to gasification and co-pyrolysis
the volatile matter for recovery as a carbon-dense biochar. chars as removal agents of Cr3+ . J. Hazard. Mater. 321, 173–182.
Microwave pyrolysis of palm kernel shell as the selected Gupta, R.K., Dubey, M., Kharel, P., Gu, Z., Fan, Q.H., 2015. Biochar
OPW produced a yield of up to 38 wt% of biochar. The biochar activated by oxygen plasma for supercapacitors. J. Power
Sources 274, 1300–1305.
obtained at microwave power of 700 W (i.e. MC700) showed low
He, L.-L., Zhong, Z.-K., Yang, H.-M., 2017. Effects on soil quality of
oxygen (17 wt%) and volatile matter (10 wt%), indicating that biochar and straw amendment in conjunction with chemical
700 W of microwave power is suitable to remove most of the fertilizers. J. Integr. Agric. 16, 704–712.
oxygen and volatile matter from the palm kernel shell. The Hossain, M.A., Ganesan, P., Jewaratnam, J., Chinna, K., 2016a.
MC700 showed zero-sulphur content and high heating value Optimization of process parameters for microwave pyrolysis
of 26 MJ/kg, indicating it could be used as an eco-friendly solid of oil palm fiber (OPF) for hydrogen and biochar production.
Energy Convers. Manage. 133, 349–362.
fuel to substitute conventional coal in combustion. In addi-
Hossain, M.A., Jewaratnam, J., Ganesan, P., Sahu, J., Ramesh, S.,
tion, the MC700 produced was highly porous with ‘cleaner’
Poh, S., 2016b. Microwave pyrolysis of oil palm fiber (OPF) for
pores observed on its surface. Combined with the high BET hydrogen production: parametric investigation. Energy
surface area of 210 m2 /g and low contents of moisture and ash Convers. Manage. 115, 232–243.
(<3 wt%), this suggests that MC700 has many sites for adsorp- Johari, K., Saman, N., Song, S.T., Cheu, S.C., Kong, H., Mat, H.,
tion processes. The biochar showed a 48 mg/g of adsorption 2016. Development of coconut pith chars towards high
efficiency on methylene blue dye adsorption, and provided elemental mercury adsorption performance-effect of
pyrolysis temperatures. Chemosphere 156, 56–68.
good retention of water and nutrients to improve mushroom
Kaifang, F., Qinyan, Y., Baoyu, G., Yuanyuan, S., Liujia, Z., 2013.
growth (450 g of Oyster mushroom yield obtained), thus MC700 Preparation, characterization and application of lignin-based
could potentially be used in multi-applications such as an eco- activated carbon from black liquor lignin by steam activation.
friendly solid fuel, adsorbent material to remove pollutants Chem. Eng. J.
from wastewater treatment or bio-fertilizer to absorb nutri- Khanday, W.A., Kabir, G., Hameed, B., 2016. Catalytic pyrolysis of
ents and water for plant growth. oil palm mesocarp fibre on a zeolite derived from low-cost oil
palm ash. Energy Convers. Manage. 127, 265–272.
Lam, S.S., Chase, H.A., 2012. A review on waste to energy
Acknowledgement processes using microwave pyrolysis. Energies 5, 4209–4232.
Lam, S.S., Liew, R.K., Cheng, C.K., Chase, H.A., 2015. Catalytic
The authors acknowledge the financial support by the Univer- microwave pyrolysis of waste engine oil using metallic
siti Malaysia Terengganu for the conduct of the research. pyrolysis char. Appl. Catal. B: Environ. 176–177, 601–617.
Lam, S.S., Liew, R.K., Jusoh, A., Chong, C.T., Ani, F.N., Chase, H.A.,
2016a. Progress in waste oil to sustainable energy, with
References emphasis on pyrolysis techniques. Renew. Sustain. Energ. Rev.
53, 741–753.
Al-Salem, S., Antelava, A., Constantinou, A., Manos, G., Dutta, A., Lam, S.S., Liew, R.K., Lim, X.Y., Ani, F.N., Jusoh, A., 2016b. Fruit
2017. A review on thermal and catalytic pyrolysis of plastic waste as feedstock for recovery by pyrolysis technique. Int.
solid waste (PSW). J. Environ. Manage. 197, 177–198. Biodeterior. Biodegrad. 113, 325–333.
Aliyu, A.S., Abdullahi, N., Sulaiman, F., 2017. Pyrolysis of torrefied Lam, S.S., Liew, R.K., Wong, Y.M., Azwar, E., Jusoh, A., Wahi, R.,
oil palm wastes for better biochar. Malays. J. Fundam. Appl. 2016c. Activated carbon for catalyst support from microwave
Sci. 13. pyrolysis of orange peel. Waste Biomass Valorization 8,
Angin, D., Altintig, E., Kose, T.E., 2013. Influence of process 2109–2119.
parameters on the surface and chemical properties of Lam, S.S., Liew, R.K., Wong, Y.M., Yek, N.Y.P., Ma, N.L., Lee, C.L.,
activated carbon obtained from biochar by chemical Chase, H.A., 2017a. Microwave-assisted pyrolysis with
activation. Bioresour. Technol. 148, 542–549. chemical activation, an innovative method to convert orange
Asmadi, M., Kawamoto, H., Saka, S., 2011. Gas-and peel into activated carbon with improved properties as dye
solid/liquid-phase reactions during pyrolysis of softwood and adsorbent. J. Clean. Prod. 162, 1376–1387.
hardwood lignins. J. Anal. Appl. Pyrol. 92, 417–425. Lam, S.S., Mahari, W.A.W., Cheng, C.K., Omar, R., Chong, C.T.,
Awalludin, M.F., Sulaiman, O., Hashim, R., Nadhari, W.N.A.W., Chase, H.A., 2016d. Recovery of diesel-like fuel from waste
2015. An overview of the oil palm industry in Malaysia and its palm oil by pyrolysis using a microwave heated bed of
waste utilization through thermochemical conversion, activated carbon. Energy 115, 791–799.
specifically via liquefaction. Renew. Sustain. Energy Rev. 50, Lam, S.S., Mahari, W.A.W., Jusoh, A., Chong, C.T., Lee, C.L., Chase,
1469–1484. H.A., 2017b. Pyrolysis using microwave absorbents as reaction
Board, M.P.O., 2017. Production of crude palm oil for the month of bed: an improved approach to transform used frying oil into
March 2017, 1 April 2017 ed, Malaysia. biofuel product with desirable properties. J. Clean. Prod. 147,
Brown, R., 2009. Biochar production technology. Biochar Environ. 263–272.
Manage. Sci. Technol., 127–146. Lanza, G., Rebensburg, P., Kern, J., Lentzsch, P., Wirth, S., 2016.
Cao, J., Xiao, G., Xu, X., Shen, D., Jin, B., 2013. Study on Impact of chars and readily available carbon on soil microbial
carbonization of lignin by TG-FTIR and high-temperature respiration and microbial community composition in a
carbonization reactor. Fuel Process. Technol. 106, 41–47. dynamic incubation experiment. Soil Tillage Res. 164, 18–24.

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Lee, J., Kim, K.-H., Kwon, E.E., 2017a. Biochar as a catalyst. Renew. Shen, D., Gu, S., Bridgwater, A.V., 2010. Study on the pyrolytic
Sustain. Energ. Rev. 77, 70–79. behaviour of xylan-based hemicellulose using TG-FTIR and
Lee, X.J., Lee, L.Y., Gan, S., Thangalazhy-Gopakumar, S., Ng, H.K., Py-GC-FTIR. J. Anal. Appl. Pyrol. 87, 199–206.
2017b. Biochar potential evaluation of palm oil wastes Sheng, C., Azevedo, J., 2005. Estimating the higher heating value
through slow pyrolysis: thermochemical characterization and of biomass fuels from basic analysis data. Biomass Bioenergy
pyrolytic kinetic studies. Bioresour. Technol. 236, 155–163. 28, 499–507.
Liu, Z., Han, G., 2015. Production of solid fuel biochar from waste Tan, L., Wang, M., Li, X., Li, H., Zhao, J., Qu, Y., Choo, Y.M., Loh,
biomass by low temperature pyrolysis. Fuel 158, 159–165. S.K., 2016. Fractionation of oil palm empty fruit bunch by
Loh, S.K., 2016. The potential of the Malaysian oil palm biomass bisulfite pretreatment for the production of bioethanol and
as a renewable energy source. Energy Convers. Manage. 141, high value products. Bioresour. Technol. 200, 572–578.
285–298. Tan, X.-F., Liu, S.-B., Liu, Y.-G., Gu, Y.-L., Zeng, G.-M., Hu, X.-J.,
Lv, X., Xiao, J., Shen, L., Zhou, Y., 2016. Experimental study on the Wang, X., Liu, S.-H., Jiang, L.-H., 2017. Biochar as potential
optimization of parameters during biomass pyrolysis and sustainable precursors for activated carbon production:
char gasification for hydrogen-rich gas. Int. J. Hydrogen multiple applications in environmental protection and energy
Energy 41, 21913–21925. storage. Bioresour. Technol. 227, 359–372.
Öhman, M., Nyström, I., Gilbe, C., Boström, D., Lindström, E., Tripathi, M., Sahu, J.N., Ganesan, P., 2016a. Effect of process
Boman, C., Backman, R., Hedman, H., Samuelsson, R., Burvall, parameters on production of biochar from biomass waste
J., Shaojun, X., 2009. Slag formation during combustion of through pyrolysis: a review. Renew. Sustain. Energy Rev. 55,
biomass fuels. International Conference on Solid Biofuels. 467–481.
Mašek, O., Budarin, V., Gronnow, M., Crombie, K., Brownsort, P., Tripathi, M., Sahu, J.N., Ganesan, P., Jewaratnam, J., 2016b.
Fitzpatrick, E., Hurst, P., 2013. Microwave and slow pyrolysis Thermophysical characterization of oil palm shell (OPS) and
biochar—comparison of physical and functional properties. J. OPS char synthesized by the microwave pyrolysis of OPS.
Anal. Appl. Pyrol. 100, 41–48. Appl. Thermal Eng. 105, 605–612.
MPOB, M.P.O.B., 2017. Oil Palm Estates, January–December 2016. Tzvetkov, G., Mihaylova, S., Stoitchkova, K., Tzvetkov, P., Spassov,
Neutelings, G., 2011. Lignin variability in plant cell walls: T., 2016. Mechanochemical and chemical activation of
contribution of new models. Plant Sci. 181, 379–386. lignocellulosic material to prepare powdered activated
Neves, D., Thunman, H., Matos, A., Tarelho, L., Gómez-Barea, A., carbons for adsorption applications. Powder Technol. 299,
2011. Characterization and prediction of biomass pyrolysis 41–50.
products. Prog. Energy Combust. Sci. 37, 611–630. Wan Mahari, W.A., Zainuddin, N.F., Wan Nik, W.M.N., Chong, C.T.,
Okoroigwe, E.C., Ofomatah, A.C., Oparaku, N.F., Unachukwu, G.O., Lam, S.S., 2016. Pyrolysis recovery of waste shipping oil using
2013. Production and evaluation of activated carbon from microwave heating. Energies 9, 780.
palm kernel shells (PKS) for economic and environmental Wang, Z., McDonald, A.G., Westerhof, R.J., Kersten, S.R.,
sustainability. Int. J. Phys. Sci. 8, 1036–1041. Cuba-Torres, C.M., Ha, S., Pecha, B., Garcia-Perez, M., 2013.
Omar, R., Idris, A., Yunus, R., Khalid, K., Aida Isma, M.I., 2011. Effect of cellulose crystallinity on the formation of a liquid
Characterization of empty fruit bunch for microwave-assisted intermediate and on product distribution during pyrolysis. J.
pyrolysis. Fuel 90, 1536–1544. Anal. Appl. Pyrol. 100, 56–66.
Osman, N.B., Shamsuddin, N., Uemura, Y., 2016. Activated carbon Yang, W., Guo, F., Wan, Z., 2013. Yield and size of oyster
of oil palm Empty Fruit Bunch (EFB); core and shaggy. Procedia mushroom grown on rice/wheat straw basal substrate
Eng. 148, 758–764. supplemented with cotton seed hull. Saudi J. Biol. Sci. 20,
Özçimen, D., Ersoy-Meriçboyu, A., 2010. Characterization of 333–338.
biochar and bio-oil samples obtained from carbonization of Yin, L., Chen, Y., Li, D., Zhao, X., Hou, B., Cao, B., 2016.
various biomass materials. Renew. Energy 35, 1319–1324. 3-dimensional hierarchical porous activated carbon derived
Patwardhan, P.R., Dalluge, D.L., Shanks, B.H., Brown, R.C., 2011. from coconut fibers with high-rate performance for
Distinguishing primary and secondary reactions of cellulose symmetric supercapacitors. Mater. Des. 111, 44–50.
pyrolysis. Bioresour. Technol. 102, 5265–5269. Zhang, S., Hu, B., Zhang, L., Xiong, Y., 2016. Effects of torrefaction
Salema, A.A., Afzal, M.T., Bennamoun, L., 2017. Pyrolysis of corn on yield and quality of pyrolysis char and its application on
stalk biomass briquettes in a scaled-up microwave preparation of activated carbon. J. Anal. Appl. Pyrol. 119,
technology. Bioresour. Technol. 233, 353–362. 217–223.
Salema, A.A., Yeow, Y.K., Ishaque, K., Ani, F.N., Afzal, M.T.,
Hassan, A., 2013. Dielectric properties and microwave heating
of oil palm biomass and biochar. Ind. Crop. Prod. 50, 366–374.
Seng-eiad, S., Jitkarnka, S., 2016. Untreated and HNO3 -treated
pyrolysis char as catalysts for pyrolysis of waste tire: in-depth
analysis of tire-derived products and char characterization. J.
Anal. Appl. Pyrol. 122, 151–159.

Please cite this article in press as: Liew, R.K., et al., Oil palm waste: An abundant and promising feedstock for microwave pyrol-
ysis conversion into good quality biochar with potential multi-applications. Process Safety and Environmental Protection (2017),
https://doi.org/10.1016/j.psep.2017.10.005