Journal of Hazardous Materials 395 (2020) 122636

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Journal of Hazardous Materials

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

Engineered biochar via microwave CO2 and steam pyrolysis to treat T

carcinogenic Congo red dye
Peter Nai Yuh Yeka,b,c,1, Wanxi Penga,1, Chee Chung Wongc, Rock Keey Liewd, Yee Ling Hob,
Wan Adibah Wan Maharib, Elfina Azwarb, Tong Qi Yuane, Meisam Tabatabaeif,g,
Mortaza Aghbashloh, Christian Sonnei,a, Su Shiung Lamb,a,j,*
a
Henan Province Engineering Research Center For Biomass Value-Added Products, School Of Forestry, Henan Agricultural University, Zhengzhou, 450002, China
b
Pyrolysis Technology Research Group, Institute of Tropical Aquaculture and Fisheries (AKUATROP), Universiti Malaysia Terengganu, 21030 Kuala Nerus, Terengganu,
Malaysia
c
University College of Technology Sarawak, Department of Engineering, 96000, Sibu, Sarawak, Malaysia
d
NV WESTERN PLT, No. 208B, Jalan Macalister, Georgetown, 10400, Pulau Pinang, Malaysia
e
Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry University, No.35 Tsinghua East Road Haidian District, Beijing, 100083, China
f
Faculty of Plantation and Agrotechnology, Universiti Teknologi MARA (UiTM), 40450 Shah Alam, Selangor, Malaysia
g
Department of Microbial Biotechnology, Agricultural Biotechnology Research Institute of Iran (ABRII), AREEO, Karaj, Iran
h
Department of Mechanical Engineering of Agricultural Machinery, Faculty of Agricultural Engineering and Technology, College of Agriculture and Natural Resources,
University of Tehran, Karaj, Iran
i
Aarhus University, Department of Bioscience, Arctic Research Centre (ARC), Frederiksborgvej 399, PO Box 358, DK-4000, Roskilde, Denmark
j
Anhui Juke Graphene Technology Co., Ltd., Bozhou, 233600, China

G R A P H I C A L A B S T R A C T

A R T I C LE I N FO A B S T R A C T

Editor: Rinklebe Jörg We developed an innovative single-step pyrolysis approach that combines microwave heating and activation by
Keywords: CO2 or steam to transform orange peel waste (OPW) into microwave activated biochar (MAB). This involves
CO2 carbonization and activation simultaneously under an inert environment. Using CO2 demonstrates dual functions
Microwave in this approach, acting as purging gas to provide an inert environment for pyrolysis while activating highly
Pyrolysis porous MAB. This approach demonstrates rapid heating rate (15–120 °C/min), higher temperature (> 800 °C)
Microwave-activated biochar and shorter process time (15 min) compared to conventional method using furnace (> 1 h). The MAB shows

Abbreviations: OPW, orange peel waste; MAB, microwave activated biochar; CO2, carbon dioxide; CO, carbon monoxide; H2, hydrogen gas; CH4, methane gas; CR,
Congo red; BET, Brunauer Emmett Teller; SBET, Brunauer Emmett Teller surface area; MAB-CO2, microwave-activated biochar produced by carbon dioxide gas; MAB-
Steam, microwave-activated biochar produced by steam; KOH, potassium hydroxide; NaOH, sodium hydroxide; H3PO4, phosphoric acid; ZnCl2, zinc chloride; TGA,
Thermogravimetric analysis; C, carbon; H, hydrogen; N, nitrogen; S, sulphur; △H, enthalpy
⁎
Corresponding author at: Henan Province Engineering Research Center for Biomass Value-Added Products, School of Forestry, Henan Agricultural University,
Zhengzhou, 450002, China.
E-mail address: lam@umt.edu.my (S.S. Lam).
1
These authors contributed equally to this work and act as co-first authors.

https://doi.org/10.1016/j.jhazmat.2020.122636
Received 20 January 2020; Received in revised form 27 March 2020; Accepted 1 April 2020
Available online 08 April 2020
0304-3894/ © 2020 Elsevier B.V. All rights reserved.
P.N.Y. Yek, et al.
Steam higher mass yield (31–44 wt %), high content of fixed carbon (58.6–61.2 wt %), Brunauer Emmett Teller (BET)
surface area (158.5–305.1 m2/g), low ratio of H/C (0.3) and O/C (0.2). Activation with CO2 produces more
micropores than using steam that generates more mesopores. Steam-activated MAB records a higher adsorption
efficiency (136 mg/g) compared to CO2 activation (91 mg/g), achieving 89–93 % removal of Congo Red dye. The
microwave pyrolysis coupled with steam or CO2 activation thereby represents a promising approach to trans-
form fruit-peel waste to microwave-activated biochar that remove hazardous dye.
1. Introduction
World production of citrus achieves 100 million tonnes annually, of
which 55–60 % of the production turns into orange peel waste (OPW).
These OPW are currently disposed at landfill or converted into low
value organic fertilizer. It also shows potential to be transformed into
activated biochar via thermochemical process (e.g. pyrolysis) (Farhat
et al., 2011; Lam et al., 2016). Biochar is a porous carbon-based ma-
terial (Maneerung et al., 2016) produced either by one step (carboni-
sation and activation are performed simultaneously) or two steps ap-
proach (carbonisation and activation are performed at separated steps)
using pyrolysis process. The generation of biochar from biomass such as
fruit peel waste could undergo several reaction stages at different
temperature ranges during the pyrolysis process. Firstly, evaporation of
moisture (101–120 °C) would occurred, followed by de-volatilization,
de-polymerization and fragmentation of lignocellulosic components at
temperature above 180 °C (Wang et al., 2013; Eom et al., 2012). Then,
charring (> 550 °C) would occur that involves cracking, recombination
/ re-condensation to form a carbonaceous solid product (Wei et al.,
2006; Morf et al., 2002), and subsequently activation process involving
the use of gasification media (e.g. steam and CO2) to gain access and
remove the internal carbon atoms in order for generating new pores and
widening the existing pore.
After the moisture evaporation, the lignocellulosic components of
fruit peel waste would decompose over a range of temperatures during
the pyrolysis process. Hemicellulose formed by complex carbohydrate
polymer undergoes depolymerisation reaction and rearranges glyco-
sidic ring structure to produce condensable vapours and non-con-
densable volatiles (CO2, CO, H2, CH4) at 180–285 °C due to low thermal
stability of the amorphous structure (Lange, 2007). The cellulose,
formed by polysaccharide in a plant tissue, has linear polymer and
composes of glucose sub-units connected to form long chains by hy-
drogen bonding and Van der Waals forces (Chen, 2014). Cellulose un-
dergoes partial decomposition because its crystalline structure is re-
sistant to thermal depolymerisation, resulting in production of its
monomer unit (i.e. β-glucopyranose), and then fragmentation reaction
would occur to form gases, liquids and char products at a higher tem-
perature from 240 to 350 °C. The lignin, comprising polymer which is
relatively hydrophobic and aromatic (Chen, 2014), decomposes at a
wider temperature (200–700 °C) due the stable and complex poly-aro-
matic structure (Ferrara et al., 2014). During the subsequent charring
stage of pyrolysis, secondary cracking would occur and some of the
volatiles would further release to form biogas (CO, H2, CH4) and re-
cover light organic molecules into bio-oil (Collard and Blin, 2014).
Microwave pyrolysis is a thermal degradation in an inert environ-
ment using electromagnetic radiation as heat source. The use of mi-
crowave radiation induces dipole rotation of particles and generates
heat within the materials (Deng et al., 2009). This allows both internal
and volumetric heating compared to conventional heat transfer from
the surface to the inner part through conduction mechanism (Lam et al.,
2015). Microwave pyrolysis is reported to show advantages in pro-
viding rapid and targeting heating mechanism (Lam et al., 2017a; Wan
et al., 2016). Thus, it provides potentially short process time and sub-
sequently lower production cost to produce desired products as com-
pared to conventional pyrolysis (Kundu et al., 2015; Menéndez et al.,
2004). This provides the motivation for using microwave pyrolysis to
convert biomass to produce biochar from biomass.
2
Journal of Hazardous Materials 395 (2020) 122636
The activation stage is a crucial part as high temperature (above
700 °C) and proper activating agents are usually required to assure
optimal production of desirable engineered biochar. The activation of
engineered biochar has been carried out chemically using KOH, NaOH,
H3PO4, ZnCl2 (Hui and Zaini, 2015; Sangchoom and Mokaya, 2015), or
physically using CO2 and steam (Pallarés et al., 2018). Biochar syn-
thesized through chemical activation with metal carbonates or alkali-
based activating agent reacts with carbon structure via reduction-oxi-
dation. Then, metallic atoms penetrate into the internal biochar struc-
ture via intercalation and in turn expand the existing pores and also
generate new pores (Foo and Hameed, 2012). Extra washing steps are
required to remove the excess chemicals remained within the product
after chemical activation, hence this approach is costly and time con-
suming. The washing steps also produce wastewater in large volumes
during mass production of activated biochar using chemical activation.
Hence, this provides the motivation to develop an approach combining
microwave heating and physical activation using steam or CO2 as ac-
tivating agents to produce MAB.
Carbon dioxide (CO2) is an abundant greenhouse gas in the atmo-
sphere, and its emission is rapidly increasing to nearly 391 ppm due to
man-made activities that include fossil fuel combustion among others
(Yamada et al., 2013; Hosseini et al., 2013). Thus, having efforts that
utilise CO2 in different applications is highly necessary. In the con-
struction field, CO2 is used to produce ready-mixed concrete where CO2
injected during concrete mixing stage improve the concrete compres-
sive strength and reduce the concrete binder needs (Monkman and
MacDonald, 2017). In addition, CO2 has the potential to grow micro-
algae generating renewable biodiesel (Demirbas, 2011). Study on CO2
biofixation by microalgae shows that direct utilisation of CO2 is a cli-
mate-friendly biological process and a possible solution for global
warming problems (Demirbas, 2011). So far, there have been limited
studies reporting on the application of microwave heating combining
CO2 or steam as activating agents in a single step physical activation
(Chang et al., 2000; Mahamud et al., 2014; Plaza-Recobert et al., 2017).
For the single step microwave pyrolysis, the processing is simplified
whereby the carbonisation and activation are performed simulta-
neously in one step to convert orange peel waste into MAB. This can
potentially reduce the consumption of heating energy and the proces-
sing time required compared to that required in two steps activation
(i.e. carbonisation is first performed followed by activation as the
second processing step). As a result, the overall processing cost of single
step activation is potentially lower than the two steps activation.
CO2 aids in the production of biochar with high degrees of porosity
from loquat stones (Plaza-Recobert et al., 2017), sewage sludge char
(Alvarez et al., 2016), rice husk char (Alvarez et al., 2015) and corn cob
(Chang et al., 2000) using conventional heating. Pallarés et al. (2018)
reported that biochar produced from barley straw through CO2 acti-
vation showed microporosity with high surface area (789 m2/g),
whereas the use of steam activation led to enlarging of pores and in-
crease in mesoporosity (552 m2/g) (Pallarés et al., 2018). Xin-hui et al.
(2011) reported that CO2 activation produced higher yied of activated
carbon compared to steam activation. The authors stated that micro-
wave heating with steam/CO2 showed significant lower temperature,
flow rate and shorter processing time compared to that shown by
conventional heating (Xin-hui et al., 2011).
Most research reported on the use of chemical activation as acti-
vation agents, and fewer research have been reported on the
P.N.Y. Yek, et al. Journal of Hazardous Materials 395 (2020) 122636

application of physical activation methods, and in particular, no re-
search have been reported on the combined use of microwave pyrolysis
and steam/CO2 utilisation in single step to produce porous carbon
products. This study aims to fill the knowledge gap by demonstrating
microwave pyrolysis integrated with activation using either steam or
CO2 as activation agent in producing MAB. The MAB produced via CO2
(MAB-CO2) and steam (MAB-Steam) activation was then investigated
and evaluated for its potential and efficiency as an adsorbent to remove
Congo Red (CR) dye – a carcinogenic dye contaminating the wastewater
from the textile industry that is hard to degrade and toxic to the animals
and human (Faouzi Elahmadi et al., 2009).
of N2 adsorption-desorption of MAB was carried out using liquid ni-
trogen to analyze the N2 adsorption-desorption isotherm in order to
calculate the BET surface area and total pore volume. The Barrett-
Joyner-Halenda (BJH) desorption method and t-plot method are used to
estimate the average MAB pore size and micropores volume, respec-
tively, whereas the mesopores volume is calculated by the difference of
total volume and micropore. The Zetasizer (Malvern, Model: Nano ZS)
were used to determine the zeta potential of produced MAB.
2.2. Single step microwave pyrolysis using CO2 and steam as an activating
agent

Fig. 1 shows the single step microwave pyrolysis system using a

2. Materials and methods
1 kW power supply (Wepex, Model 1000) and 2450 MHz of magnetron
(Samsung, Model:OM75-P-11EDYF) to produce MAB from OPW using
2.1. OPW and MAB characterization
either CO2 or steam as gasification agents. The OPW was heated up by
microwave to 100 °C in an open-top quartz funnel, after which pyrolysis
OPW from local fruit stalls was rinsed with distilled water and then
was performed on the OPW under CO2 or steam purging for 15 min
dried in oven at 105 °C for 24 h. The dried peels were crushed into 4 mm
which created an inert pyrolysis environment that was subjecting the
in size and kept in air-tight container before being subjected to mi-
OPW to de-volatilization, charring, pyrolysis and gasification reactions.
crowave pyrolysis. Proximate analysis was carried out using
A Teflon seal was used to prevent the leakage of pyrolysis volatiles into
Thermogravimetric analysis (TGA) (Mettler Toledo) according to ASTM
the microwave cavity and damaging the microwave magnetron. The
D5142-02a to measure the content of moisture, volatile matter, and ash.
thermometer with data logger (Omega, Model: RDXL4SD) and ther-
Moisture content and volatile matter were calculated from the weight
mocouple (Omega) were used to record the temperature profile of mi-
difference of the sample after heating at 110 °C and pyrolyzed at
crowave heating.
150–600 °C in N2 purging environment (García et al., 2013). The ash
OPW (100 g) was pyrolysed under CO2 (supplied by Linde Industrial
content was weighted after combustion of the char at 950 °C under
Gases, Malaysia, purity of 99.5 %) and steam purging for 15 min at a
oxygen purging for 20 min (Lam et al., 2017b). The fixed carbon was
constant flow rate of 5 L/min from 100 to 700 °C. MAB produced via
obtained by the difference (Lam et al., 2016). The elemental composi-
activation by CO2 and steam were labelled as MAB-CO2 and MAB-
tion was quantified by CHNS elemental analyser (FlashEA 1112) (Ismail
Steam. Eq. (1) was used to determine the MAB mass yield (Y), where mi
et al., 2013). Scanning electron microscope (JEOL 6360LA) at magni-
refers to the OPW mass and Mf refers to the produced MAB mass. The
fication of 200X was used to examine the surface morphology of MAB.
resulting MAB was subsequently cooled in desiccator and weighted
Micrometric ASAP 2020 was used to examine the porous characteristics
using electronic balance.
of MAB via adsorption and desorption of nitrogen gas (Manyà, 2012).
The MAB sample was in a degassed environment to remove the residual
Y = mf mi x 100% (1)
moisture at 100 °C for 10 h under vacuum condition. The investigation

Fig. 1. Single step microwave pyrolysis using CO2 / steam for activation.

3
P.N.Y. Yek, et al.
2.3. Adsorption isotherm and kinetics model of Congo Red adsorption
The MAB was tested for its potential and efficiency to treat and
adsorb Congo Red (CR). Stock solution of CR with concentrations of
1000 mg/L was prepared and adjusted to pH 2–3 with HCl for further
batch adsorption test. The performance of MAB in CR removal was
carried out with 300 mL of prepared CR as adsorbate, and 1.0–3.0 g/L
of MAB as adsorbent. The beakers were stirred at 120 rpm using jar test
mixer at room temperature for 24 h to ensure homogeneity. After ad-
sorption test, the remained CR concentration was measured using Hash
6000 UV–vis spectrophotometer at a wavelength of 493 nm. Equation
S1 and S2 in the Supporting Information were used to calculate the CR
removal (%) and adsorption efficiency (qe) respectively. Equation S3
and S4 were applied to determined Langmuir and Freundlich isotherm
models respectively at three different CR concentration (500, 250 and
125 mg/L) for 24 h in order to reach the equilibrium of adsorption. The
concentration with highest adsorption capacity has been selected for
further kinetics model analysis. Equation S5 and S6 were used to ana-
lysed the Pseudo-first-order and pseudo-second-order kinetic models at
four different durations (60, 180, 360 and 1440 min).
3. Results and discussion
3.1. Temperature profile and reaction stages during microwave pyrolysis
and activation
Fig. 2 shows the temperature profiles of microwave pyrolysis and
activation using CO2 or steam. OPW was directly heated up at a mi-
crowave power of 1000 W from room temperature to 700–800 °C
without addition of microwave absorbent. At 100 °C, CO2 gas or steam
was injected to purge from the bottom of the reactor to create inert
environment for pyrolysis and function as activating agents. The tem-
perature profile by CO2 activation showed steady increase of tem-
perature at a rate of 50 °C/min until 700 °C and become consistent for
another 200 s. The temperature during steam activation showed a rapid
increase compared to CO2 activation. The temperature profile of steam
activation is divided into four reaction stages occurred according to
different heating rate achieved during the process. These are (1) drying
(70 °C/min), (2) further heating (15 °C/min), (3) pyrolysis (120 °C/
min), and (4) activation (40 °C/min).
The initial drying stage caused the release of the moisture from
OPW and showed a heating rate of around 70 °C/min, recording a
temperature up to 210 °C after 180 s. The high heating rate achieved
indicated that the moisture had functioned as a good microwave
Fig. 2. Temperature profile of single step microwave pyrolysis using CO2 and steam as an activating agent.
4
Journal of Hazardous Materials 395 (2020) 122636
absorbent that in turn heated up and increased the process temperature
rapidly (Mushtaq et al., 2015; Intani et al., 2016). This is because the
dielectric loss factor of water is higher than that biomass, causing im-
proved microwave absorbance and conversion into heat and this in-
creased the process temperature. Moreover, dielectric property of bio-
mass increased with higher moisture content and temperature (Zhu and
Guo, 2017; Kol, 2009).
The second stage shows further heating and the temperature profile
slightly dropped to 190 °C and then raised again to 350 °C, recording a
lower heating rate at 15 °C/min. As biomass is dried after the release of
its moisture content, there was no moisture left to act as good micro-
wave absorbent to absorb and convert microwave radiation into heat,
resulting in the relatively low heating rate (Salema et al., 2017; Antunes
et al., 2018).
At the third stage, pyrolysis reaction started at 350–700 °C with the
highest heating rate of 120 °C/min recorded because of the occurrence
of exothermic reactions comprising devolatilisation of lignocellulose
(Bates and Ghoniem, 2013; Chen et al., 2014) and carbonisation
(Bridgeman et al., 2008). The release of volatile matter led to increased
extent of exothermic reaction and in turn caused the increment of the
process temperature (Cerfontain et al., 1987). The carbonisation gra-
phitised the carbon structure of OPW with better microwave absor-
bency and electric conductivity that in turn increased the conversion
efficiency of microwave electromagnetic radiation into heat energy
(Zhou et al., 2016), leading to increased heating rate and process
temperature. As a result, high process temperature (700 °C) was
achieved and this caused extensive pyrolysis and carbonization of OPW
for subsequent activation stage to occur.
The activation stage (the fourth stage) occurred when the process
temperature achieved 500 °C above under the purging of CO2 or steam
(Yek et al., 2019; Braghiroli et al., 2018). The use of CO2 had caused the
temperature to increase rapidly to around 100 °C within 100 s and then
remained steadily at this high temperature for another 300 s. However,
steam activation shown higher heating rate compared to CO2 activa-
tion, possibly due to the lower energy (+117 kJmol−1) required by
steam to produce CO and H2 as shown in the Eq. (2). Moreover, the
exothermic reaction of CO and H2O produced hydrogen rich syngas that
could also cause the temperature to increase rapidly to around 850 °C
(Sattar et al., 2014), then become consistent at 750 °C for continuous
steam activation process.
It was revealed that the microwave pyrolysis approach provided a
rapid heating mechanism and simultaneously allowing carbonisation
and physical activation to occur in one step to transform OPW into
microwave activated biochar (MAB). The total process time of
P.N.Y. Yek, et al. Journal of Hazardous Materials 395 (2020) 122636

transforming OPW to MAB was only 15 min, while also offered a higher contained higher mesopores volume (0.22 cm3/g) and lower micro-
heating rate (40−120 °C/min) compared to conventional pyrolysis pores volume (0.08 cm3/g). This indicates that the utilisation of steam
method heated by a furnace (1–7 h) (Lam et al., 2017c), suggesting that has the effect of widening the micropores generated to form mesopores
microwave pyrolysis is a fast approach and potentially energy efficient (Chang et al., 2000). However, MAB-CO2 is beneficial in producing
to produce MAB due to the high heating rate and shorter duration product with higher mass yield (44 wt %) and more micropores
achieved. (0.04 cm3/g). It was also revealed that the CO2 performed dual func-
tions in this approach, acting as purging gas to provide an inert en-
3.2. Microwave activated biochar vironment for pyrolysis cracking and thereby also serving as an acti-
vating agent in generating microporous MAB-CO2.
3.2.1. Mass yield, proximate and elemental content The adsorption isotherms of MAB exhibited the combinations of
Table 1 compares mass yield, proximate content and elemental Type I, type II and hysteresis loop of H4 (Fig. S1) by International Union
composition of MAB via CO2 and steam as an activating agent in single of Pure and Applied Chemistry (IUPAC). This indicates that MAB ex-
step microwave pyrolysis. The release of volatile matter was the pri- hibits unrestricted monolayer-multilayer adsorption and adsorbent-ad-
mary reason for weight loss in the production of MAB from OPW. MAB- sorptive interactions on the slit-shapes micro-mesoporous structure
Steam (31 wt %) has relatively lower mass yield due to the burn off at (Thommes et al., 2015).
higher temperature achieved (Fig. 2) during the activation stage Fig. 3 presents the micrograph of the OPW and MAB obtained from
(Rodríguez-Reinoso et al., 1995). It was also likely that steam diffused microwave pyrolysis using CO2 and steam as activating agent. The OPW
more into the MAB, enlarged the existing pores and also formed addi- surface was coarse and less-porous. Further heating of OPW caused de-
tional pores through removal of the internal carbon atoms (Pallarés volatilization and created pores in the MAB. CO2 activation exhibited
et al., 2018). The proximate content of OPW is mainly occupied by more uniform porous structure compared to steam activation, probably
61.0 wt % of volatile matter, 17.0 wt % of ash, 15.0 wt % of fixed due to complete devolatilisation of the volatile matters via the use of
carbon and 7.0 wt % of moisture. Both MAB-CO2 and MAB-steam CO2. There are small amount of impurities of volatile matter (e.g. mi-
showed reduced volatile matter (19.3–19.5 wt %) and high fixed carbon nerals and extractives) released and remained on the surface during
(58.6–61.2 wt %). The de-volatilization process of OPW likely degrade carbonization (Yek et al., 2019; Asadieraghi and Wan Daud, 2014). The
lignocellulosic composition to form bio-oil and syngas (Tihay and production of MAB with a porous structure is desirable for use as ad-
Gillard, 2010; Lopez-Gonzalez et al., 2013). However, the high ash sorbent.
content of MAB (16–17 wt %) indicates that it is no suitable for use as
fuels but may be utilised as bio-adsorbent (Yang et al., 2007). Lower 3.3. Activation mechanism of MAB with microwave heating
moisture content of MAB (3–5 wt %) was noticed compared to OPW
(7 wt %) as the hydrophobicity and moisture uptake of OPW was re- This work develops an innovative single-step approach combining
duced after heat treatment. Low moisture content is preferable to in- microwave pyrolysis and CO2 (or steam) to convert orange peel waste
crease the availability of the adsorption site of MAB for use as adsorbent into MAB. CO2 and steam were examined for its ability to provide dual
(Lam et al., 2017a; Sadasivam and Reddy, 2014). functions for the microwave pyrolysis approach: (1) Acting as purging
The elemental analysis showed that OPW was dominated by carbon gas to provide an inert environment for pyrolysis reactions, and (2) as
(43.0 wt %) and oxygen (50.5 wt %) and small amounts of hydrogen activating agent to generate porous biochar (MAB). It is envisaged that
(5.5 wt %), nitrogen (1.0 wt %), and sulphur-free. Decarboxylation re- CO2 and steam could aid the removal of the carbon atoms located in the
actions were likely to occur during microwave pyrolysis and activation interior part of the biochar, leading to formation of new pores and in-
process of MAB-CO2 and MAB-Steam (Liu et al., 2011). This reduced the creasing the porosity.
oxygen content (19.0–24.0 wt %) and increased the carbon content The mechanism involved in physical activation for pores formation
(73.4–78.4 wt %) while exhibiting lower H/C (0.3) and O/C (0.2) ratio. is explained by gasification, Boudouard reaction, and water-gas shift
The high carbon content, low H/C and O/C ratio of MAB indicate im- reaction (Pallarés et al., 2018; Hunt et al., 2013; Zheng et al., 2014).
proved resistance toward oxidation and chemical reactions due to the Stoichiometric equations of Eq. (2) explain the Boudouard reaction of
presence of strong carbon bonding (Lam et al., 2016; Li et al., 2016). carbon char with carbon dioxide (CO2) to produce carbon monoxide
The low H/C and O/C ratio indicate that there are higher carbon con- (CO), and Eq. (3) could explain the gasification of steam (H2O) with
tent than the hydrogen and oxygen contents. The H/C ratio also implies carbon char to "extract" carbon atoms from the carbon structure. Both
the types of chemical bonding (e.g. single bond and double bond) where
lower H/C ratio indicate an increase in double bonds (Lam et al., 2016). Table 1
In this study, the MAB with low H/C ratio indicates the presence of Mass yield, proximate and elemental contents of OPW, MAB-CO2 and MAB-
more double bonds (600 kJ), which possesses higher bond energy than Steam.
single bond (350 kJ) (Liew et al., 2018). Thus, the bonds are harder to OPW Biochar MAB-CO2 MAB-Steam
be broken by chemical reactions, hence showing higher resistance to-
wards oxidation and chemical reactions. Mass yield (wt %) – 48 44 31
Proximate Contenta
Moisture 7.0± 3.0 4.0± 3.0 3.0±2.0 5.5± 2.0
3.2.2. Porous characteristic and surface morphology Volatile matter 61.0± 9.0 22.3±5.0 19.3± 6.0 19.5± 4.0
Table 2 shows the characteristics of biochar and MAB derived from Fixed carbonb 15.0± 15.0 56.7±11.0 61.2± 9.0 58.6± 7.0
N2 adsorption-desorption. The Brunauer Emmett Teller (BET) surface Ash 17.0± 3.0 17.0±3.0 16.5± 1.0 16.4± 1.0
area of biochar was 95.6 m2/g, whereas the BET surface area of MAB-
Elemental Content
Steam and MAB-CO2 was 305.1 m2/g and 158.5 m2/g, respectively.
Carbon 43.0± 9.0 63.0±8.0 73.4± 6.0 78.4± 7.0
This shows that using steam and CO2 as activation agent both increase Hydrogen 5.5± 0.8 4.5± 0.8 2.0±0.5 2.1± 0.6
the surface area of the char product. This is likely via promoting the de- Nitrogen 1.0± 0.6 0.8± 0.6 0.6±0.4 0.5± 0.3
volatilization of volatile components from OPW and the function of Oxygenb 50.5± 10.4 31.7±9.4 24.0± 6.9 19.0± 7.9
steam and CO2 as carbon scavenger in reducing tar formation (Cho Sulphur 0.0 0.0 0.0 0.0
H/C 1.5± 0.5 0.9± 0.3 0.3±0.1 0.3± 0.1
et al., 2018; Li et al., 2016) that could otherwise block the pores formed O/C 0.9± 0.4 0.4± 0.2 0.2±0.1 0.2± 0.1
within the MAB. Hence, this led to the production of MAB with in-
creased pore formation and higher surface area. MAB-Steam with a
Dry weight basis (dwb).
b
higher surface area is desirable for use as adsorbent. The MAB-Steam Calculate by mass difference.

5
P.N.Y. Yek, et al. Journal of Hazardous Materials 395 (2020) 122636

Table 2
Porous characteristics of MAB produced from microwave pyrolysis using CO2
and steam as activating agent.
Biochar Steam Activation CO2 Activation

SBET (m2/g) 95.6 305.1 158.5

Micropores (m2/g) 60.0 184.4 102.0
VMicropores (cm3/g) a 0.02 0.08 0.04
VMesopores (cm3/g) b 0.03 0.18 0.01
Average pore diameter (nm) 3.3 1.9 1.3

a
Determined by t-plot method.
b
VMesopores = Vtotal – VMicropore.

carbon dioxide and steam are gasification agents that can penetrate into
the interior of the carbon material to enhance the porosity. Both the
reactions of carbon with carbon dioxide and steam are endothermic and
thus it is necessary to supply extra energy to maintain reaction tem-
peratures. For this purpose, the utilization of microwave heating was
beneficial in providing a fast heating mechanism in the current study
compared to conventional oven or furnace heating in order to perform
improved activation at high temperature (> 700 °C).
Moreover, Hunt et al. (2013) has reported that microwave heating
has reduced the activation energy and apparent enthalpy of Boudouard
reaction compared to conventional heating. Hence, microwave-induced
heating has catalysed the gas-carbon reactions (Hunt et al., 2013);
carbon atoms were removed individually from their surface to form
carbon monoxide and hydrogen in the gas phase through Boudouard
and gasification reactions. Furthermore, the exothermic water-gas shift
reaction between steam and carbon monoxide could occur to produce
CO2 and H2 as catalysed by the surface of the carbon as shown in Eq. (4)
(Marsh and Rodríguez-Reinoso, 2006).

C + CO2 ⟷ 2CO (△ H = + 159kJmol−1) (2)

C + H2 O = CO + H2 (△ H = + 117kJmol−1) (3)

CO +H2 O ⟷ CO2 + H2 (△ H = − 41kJmol−1) (4)

3.4. Adsorption isotherm of Congo red (CR)

Table 3 exhibits the adsorption efficiency of biochar, MAB-CO2 and

MAB-Steam in removal of CR dye (a carcinogenic dye) in acidic con-
dition (pH 2–3); the acidic condition was selected to prevent aggrega-
tion of CR dye occurred in alkali solution (Mall et al., 2005; Rafi et al.,
2018) that will otherwise reduce the adsorption efficiency. It has been
reported that the adsorption efficiency of CR is greatly affected by the
pH where lower adsorption efficiency is usually observed at pH > 3
(Shaban et al., 2018). A lower number of positively charge ions (H+) in
less acidic condition (pH 3–7) would assist in binding between ad-
sorbent and CR, whilst the presence of negatively charge ions (OH−) in
alkali condition (pH > 7) would compete with CR for attaching to the
adsorption sites on the adsorbent (Lafi et al., 2019). Hence, the ad-
sorption efficiency of MAB-CO2 and MAB-Steam in removal of CR dye Fig. 3. Surface morphology of (a) orange peel, (b) MAB-CO2 and (c) MAB-
Steam.
was performed in acidic condition (pH 2–3). Maximum adsorption ef-
ficiency of 136 mg/g was attained by MAB-Steam and 91 mg/g by MAB-
CO2. Removal percentage of Congo Red achieved 93 % and 89 % with
3.0 g/L dosage of MAB-Steam and MAB-CO2, respectively. MAB-Steam Table 3
showed higher adsorption efficiency due to the higher surface area Congo-Red adsorption efficiency and removal % of MAB-Steam and MAB-CO2.
functioned as adsorption sites.
Biochar MAB-Steam MAB-CO2
Fig. S2 exhibited the Langmuir and Freundlich isotherm models
plotted under 125–500 mg/L CR dye concentrations and both constant Maximum Adsorption Efficiency (mg/g) 136 91
of Freundlich and Langmuir isotherm were calculated and presented in
Table 4. The MAB-Steam presents the Langmuir isotherm (R2 > 0.95) Removal (%)
Dosage: 1.0 g /L 5% 39 % 34 %
of single layer adsorption on the MAB’s surface. The Qmax of
Dosage: 2.0 g/L 8% 63 % 59 %
192.308 mg/g is the highest capacity of single layer adsorption. KL of Dosage: 3.0 g/L 11 % 93 % 89 %
0.019 L/mg referring to the affinity between the MAB-Steam and CR.

6
P.N.Y. Yek, et al. Journal of Hazardous Materials 395 (2020) 122636

Table 4 applicable and efficient in dye wastewater treatment. The CR removal is

Constant value of isotherm models. influenced by pH, initial CR concentration and MAB amount. Higher
Adsorbate Langmuir constants Freundlich constants adsorption efficiency was achieved in previous study during acidic
conditions (Lafi et al., 2019), which was adopted during the application
2
Qmax (mg/g) KL (L/mg) R KF (mg/g)/ 1/n R2 of the MAB in CR removal. The change in CR adsorption over the pH
(mg/L)n range is accounted by the mechanisms of surface electrostatic and π - π
MAB-Steam 192.308 0.019 0.972 47.589 0.210 0.888 interaction between the MAB and CR. The MAB exhibits better CR
MAB-CO2 131.579 0.005 0.834 6.207 0.433 0.879 adsorption efficiency at low pH (Ausavasukhi et al., 2016). An initial
concentration of CR of 500 mg/L and above, as well as a duration of
24 h, are recommended in order to achieve optimal adsorption effi-
However, MAB-CO2 shows relatively higher R2 for the Freundlich iso- ciency when applied in wastewater treatment.
therm, implying that CR was adsorbed as multilayer on the surface. The
Freundlich constants of 1/n (0.433) and KF (6.207) indicate the driving 4. Conclusion
force and strength of adsorption.
An innovative single-step pyrolysis approach was developed com-
3.5. Adsorption kinetics of Cong red adsorption bining the utilisation of either steam or CO2 and microwave heating in
producing microwave-activated biochar from orange peel waste.
Adsorption kinetic analysis presents the speed of adsorption process. Microwave pyrolysis combined with steam activation showed higher
Fig. S3 exhibits the plots of kinetic model plots. Table 5 shows the heating rate whereas that combined with CO2 activation presented a
constant values of pseudo-first and second-order. The qe obtained from steady increase of temperature profile. The steam activation produced
the experimental work for MAB-Steam and MAB-CO2 were and 136 and MAB containing mesopores while the CO2 activation produced MAB
91 mg/g, respectively. Table 5 shows that kinetic adsorption of both with more micropores. The adsorption isotherm of MAB-Steam fitted
MAB-Steam and MAB-CO2 is better explained by pseudo-second order the Langmuir model whereas MAB-CO2 fitted the Freundlich isotherm
(R2 > 0.95); a chemisorption mechanism between dye and active model. Both MAB-CO2 and MAB-Steam are pseudo-second-order ki-
surfaces of the adsorbent (Hasan et al., 2019). Fig. S4 shows the plots of netics, showing good adsorption efficiency on Congo red dye. Our
CR removal rate in 24 h. Initially, high removal rate of CR was due to findings demonstrated the suitability of using the MAB as promising
the high accessibility of MAB active sites and adsorption efficiency adsorbent for treatment of hazardous Congo red dye wastewater from
become constant over time (Eom et al., 2012). the textile industry.

3.6. Mechanism of CR dye adsortpion CRediT authorship contribution statement

The adsorption mechanisms of CR dye onto MAB are mainly due to Peter Nai Yuh Yek: Conceptualization, Methodology, Investigation,
adsorption and electrostatic interation of surface charge of the ad- Writing - review & editing. Wanxi Peng: Investigation, Writing - review
sorbent in aqueous solution (Lafi et al., 2019; Tran et al., 2017). The & editing, Funding acquisition. Chee Chung Wong: Writing - review &
point of zero charge (isoelectric point) of the MAB-Steam and MAB-CO2 editing. Rock Keey Liew: Writing - review & editing. Yee Ling Ho:
was found at about pH 6 and 6.5, respectively. Zeta potential of MAB- Investigation, Writing - review & editing. Wan Adibah Wan Mahari:
Steam and MAB-CO2 measured at pH 2 was 36.0 mV and 34.7 mV, re- Writing - review & editing. Elfina Azwar: Writing - review & editing.
spectively, during the adsorption of the anionic dye possibly through Tong Qi Yuan: Writing - review & editing. Meisam Tabatabaei:
electrostatic forces of attraction (Rafi et al., 2018). The acidic condition Writing - review & editing. Mortaza Aghbashlo: Writing - review &
has greatly increased the attractive forces between the carbon surface editing. Christian Sonne: Writing - review & editing. Su Shiung Lam:
(positively charged) and anionic dyes (CR). Furthermore, the sulfonic Conceptualization, Methodology, Writing - review & editing,
groups (–SO3–) of CR is favorable for adsorption onto the positively Supervision, Funding acquisition.
charged MAB (Lafi et al., 2019). As the specific surface areas of MAB-
Steam (305.1 m2/g) is larger than MAB-CO2 (158.5 m2/g) then the Declaration of Competing Interest
maximum adsorption efficiency were as follows: MAB-Steam (136 mg/
g) > MAB-CO2 (91 mg/g). Therefore, the surface charge and surface The authors declare that they have no known competing financial
area show significant effect to the CR adsorption efficiency which are interests or personal relationships that could have appeared to influ-
associated with the attractive and repulsive forces between carbon ence the work reported in this paper.
surface charges and ionic dyes.
Acknowledgements
3.7. Comparison CR dye removal via adsorption
The authors thank the technical support provided by the University
Table 6 compares the characteristics during CR removal by MAB College of Technology Sarawak, Henan Agricultural University,
obtained from microwave steam and CO2 pyrolysis. The production of Universiti Malaysia Terengganu. The authors acknowledge the financial
MAB using microwave heating significantly reduced the activation support of FRGS research grant (Vot 59512) by the Ministry of
temperature (700 °C) and duration to 10 min. This shows that the mi-
crowave steam/CO2 activation is an energy-saving method to generate Table 5
biochar of higher surface area compared to conventional carbonization Constant value of kinetics models.
at higher temperatures (normally 900 °C) for 5 h (Ausavasukhi et al.,
Adsorbates Adsorbent Pseudo-first order Pseudo-second order
2016). It was found that the MAB-Steam in this study has similar BET
surface area and adsorption efficiency with commercial activated C0 qe,exp k1 qe,cal R2
K2 qe,cal R2
carbon (Mall et al., 2005), and also showed Langmuir isotherm and (mg/ (mg/
Pseudo second-order kinetics model during CR adsorption analysis (Lafi L) g)
et al., 2019).
500 91 MAB-CO2 0.0004 2.99 0.4967 0.0063 97.1 0.990
The MAB, comparable to those reported in the literature, achieved 500 136 MAB-steam 0.0004 110.0 0.8437 0.0062 142.9 0.997
91–136 mg/g of CR adsorption efficiency. This indicates that the MAB is

7
P.N.Y. Yek, et al. Journal of Hazardous Materials 395 (2020) 122636

Table 6
Comparison of CR dye removal.
Absorbent & Characteristics Adsorption efficiency Reference

Orange peel waste • CR concentration: 500 mg/L Current study

• CO2 activation in microwave heating • Amount: 3000 mg/L
• 700 °C, 10 min • Duration: 24 h, pH 2–3
• SBET = 158.5 m2/g • Adsorption efficiency: 91 mg/g
• Fixed carbon=61.2 wt % • Isotherm model: Freundlich
• Kinetics model: Pseudo second-order
Orange peel waste • CR concentration: 500 mg/L Current study
• Steam activation in microwave heating • Amount: 3000 mg/L
• 700 °C, 10 min, SBET = 305.1 m2/g • Duration: 24 h, pH 2 – 3
• Fixed carbon=58.6 wt% • Adsorption efficiency: 136 mg/g
• Isotherm model Langmuir
• Kinetics model: Pseudo second-order
Bagasse fly ash • CR concentration: 30 mg/L Mall et al. (2005)
• SBET = 169 m2/g • Amount: 1000 mg/L
• Fixed carbon=48.56 wt % • Duration: 4h
• Adsorption efficiency: 99.4 %
Activated carbons: (commercial grade) • CR concentration: 30 mg/L Mall et al. (2005)
• SBET = 390 m2/g • Amount: 2000 mg/L
• Fixed carbon=68.12 wt % • Duration: 4h
• Adsorption efficiency: 30.1 %
Activated carbons (laboratory grade) • CR concentration: 30 mg/L Mall et al. (2005)
• SBET = 492 m2/g • Amount: 2000 mg/L
• Fixed carbon=72.10 wt % • Duration: 4h
• Adsorption efficiency: 79.8 %
Pigeon drop • CR concentration: 125 mg/L Harpreet Kaur (2014)
• Amount: 8000 mg/L
• Duration: 105 min
• Adsorption efficiency: 14 mg/g
Coffee waste activated carbon • CR concentration: 120 mg/L Lafi et al. (2019)
• SBET = 220 m2/g • Amount: 4000 mg/L, pH = 3
• oxygen-containing functional groups • Duration: 180 min
• Adsorption efficiency: 90.9 mg/g
• Isotherm model: Langmuir
• Kinetics model: Pseudo second-order
Low-rank coal (leonardite) • CR concentration: 100 mg/L Ausavasukhi et al. (2016)
• Carbonization: 900 °C, 5 h • Volume: 200 mL, pH = 5
• Carboxylic groups: 0.005 mmol/g • Amount: 0.25 g
• Lactonic groups: 0.002 mmol/g • Duration: 240 min
• Phenolic groups: 0.071 mmol/g • Isotherm model: RedlichePeterson
• SBET = 82.05 m2/g • Kinetics model: Pseudo second-order
• Pore volume = 0.1587 cm2/g • adsorption was an endothermic and spontaneous process.
• pHpzc: 9.1

Education Malaysia, Golden Goose Research Grant (Vot 55191) by
Universiti Malaysia Terengganu, and the University College of
Technology Sarawak for the conduct the research under the University
Grant Scheme: UCTS/RESEARCH/ < 4/2018/12 > (01).
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jhazmat.2020.122636.
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