Waste Management 141 (2022) 16–26

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Waste Management
journal homepage: www.elsevier.com/locate/wasman

Effects of torrefaction on product distribution and quality of bio-oil from

food waste pyrolysis in N2 and CO2
Hoang Vu Ly a, b, Byeongwan Kwon a, Jinsoo Kim b, *, Changho Oh c, Hyun Tae Hwang d,
Jung Suk Lee e, Seung-Soo Kim a, *
a
Department of Chemical Engineering, Kangwon National University, 346, Joongang-ro, Samcheok, Gangwon-do 25913, Korea
b
Department of Chemical Engineering (Integrated Engineering), Kyung Hee University, 1732 Daegyeong-daero, Giheung-gu, Yongin, Gyeonggi-do 17104, Korea
c
Daekyung Esco, M-1903, 32, Songdowahak-ro, Yeonsu-gu, Incheon 21984, Korea
d
Department of Chemical and Materials Engineering, University of Kentucky, 4810 Alben Barkley Drive, Paducah, KY 42002, USA
e
Department of Mechatronics, Inha Technical College, 100 Inha-Ro, Namgu, Incheon 22212, Korea

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

Keywords: Waste food utilization to produce bio-oil through pyrolysis has received increasing attention. The feedstock can
Mixed food waste be utilized more efficiently as its properties are upgraded. In this work, the mixed food waste (MFW) was pre­
Fast pyrolysis treated via torrefaction at moderate temperatures (250–275 ◦ C) under an inert atmosphere before fast pyrolysis.
Fluidized-bed
The pyrolysis of torrified MFW (T-MFW) was performed in a bubbling fluidized-bed reactor (FBR) to study the
Torrefaction
CO2 utilization
influence of torrefaction on the pyrolysis product distribution and bio-oil compositions. The highest liquid yield
of 39.54 wt% was observed at a pyrolysis temperature of 450℃. The torrefaction has a significant effect on the
pyrolysis process of MFW. After torrefaction, the higher heating values (HHVs) of the pyrolysis bio-oils (POs)
ranged from 31.51 to 34.34 MJ/kg, which were higher than those of bio-oils from raw MFW (27.69–31.58 MJ/
kg). The POs mainly contained aliphatic hydrocarbons (alkenes and ketones), phenolic, and N-containing de­
rivatives. The pyrolysis of T-MFW was also carried out under the CO2 atmosphere. The application of CO2 as a
carrier gas resulted in a decrease in the liquid yield and an increase in the gas product yield. In addition, the
carbon and nitrogen content of POs increased, whereas the oxygen was reduced via the release of moisture and
CO. Using CO2 in pyrolysis inhibited the generation of nitriles derivatives in POs, which are harmful to the
environment. These results indicated that the application of CO2 to the thermal treatment of T-MFW could be
feasible in energy production as well as environmental pollution control.

hazards such as polluting leachate and toxic gaseous emissions derived

1. Introduction
Nowadays, food waste, along with biomass, is regarded as one of the
promising renewable energy sources to alternate fossil fuels. Food waste
is produced from mixed leftovers (e.g., fruits, meat, fish, and/or bones),
used cooking oil, vegetable residue, dairy wastes, etc. According to Food
and Agriculture Organization (FAO) report in 2011, 1.3 billion tons of
food waste per year were produced throughout the food supply chain
(Lee et al., 2020; Pham et al., 2015). Handling this massive amount by
traditional methods such as anaerobic fermentation to produce fertilizer
or conversion into animal feed requires a large area of land and a long
time for digestion (Elkhalifa et al., 2019, Ly et al., 2015). However, the
utilization of considerable amounts of food waste can generate renew­
able energy and value-added products while reducing environmental
from the landfill disposal.
Various thermochemical conversion technologies, including incin­
eration, combustion, pyrolysis, and gasification, have been demon­
strated to generate bioenergy from food waste. Pyrolysis has received
considerable interest among these techniques due to its environmental
friendliness, efficient conversion into biofuels and chemicals, and
reasonable operating costs without complexity (Ly et al., 2021). The
pyrolysis has been applied to a variety of waste sources such as soybean
proteins (Tang et al., 2018), spent coffee waste (Ly et al., 2022, Ngo
et al., 2015;), agriculture waste (Lee et al., 2017a), animal bones
(Alkurdi et al., 2020), waste frying oil (Kraiem et al. 2017), and mixed
food waste (Elkhalifa et al., 2019; Lee at al., 2020; Ly et al., 2021).
Generally, the distribution and composition of the pyrolyzed products
depend on the type of food waste and the condition of the pyrolysis

* Corresponding authors.
E-mail addresses: jkim21@khu.ac.kr (J. Kim), sskim2008@kangwon.ac.kr (S.-S. Kim).

https://doi.org/10.1016/j.wasman.2022.01.013
Received 11 August 2021; Received in revised form 30 December 2021; Accepted 11 January 2022
Available online 25 January 2022
0956-053X/© 2022 Elsevier Ltd. All rights reserved.
H.V. Ly et al.
Nomenclature
AQ Aqueous phase
HHV Higher Heating Value, MJ/kg
MFW Mixed food waste
OCAQ Organic compounds in the aqueous phase
POs Pyrolysis bio-oils
T-MFW Torrefied mixed food waste
T250-MFW Mixed food waste torrefied at 250 ℃
T275-MFW Mixed food waste torrefied at 275 ℃
Umf Minimum fluidization flow rate of nitrogen, L/min
process.
However, like conventional bio-oils from biomass feedstocks, the
bio-oils from food waste have high moisture and oxygen contents, which
lowers the quality of the bio-oils. Therefore, various upgrading tech­
niques, including catalytic pyrolysis and hydrotreatment (hydro­
deoxygenation or hydrocracking), have been proposed to reduce the
oxygen content in the bio-oils (Meng et al., 2012). During the upgrading
processes, oxygen species are eliminated in the form of CO, CO2, and/or
moisture (H2O), ameliorating the bio-oil properties (Ly et al., 2019,
2021). Unfortunately, applying these approaches on a large scale re­
quires large amounts of hydrogen consumption and catalysts.
The quality of bio-oil can be affected by the properties of initial
feedstock materials, such as oxygen content and hygroscopicity (Wang
et al., 2018), which also affects the conversion efficiency of feedstock
into energy. For these reasons, pretreatment steps, such as densification,
chemical processes, or torrefaction, are essential to improving the
properties of feedstock materials before introducing them into the py­
rolysis process (Arias et al., 2008; Poudel et al., 2015; Wang et al., 2018).
Among these pretreatment techniques, torrefaction has the advantage of
improving the uniformity of product quality even with simple opera­
tions (Arias et al., 2008). Torrefaction is a thermal pretreatment process
in which the biomass or feedstock materials are heated at moderate
temperatures between 200 and 300 ℃ in inert gas under atmospheric
pressure (Boateng and Mullen, 2013; Fu et al., 2021; Wang et al., 2018).
During the torrefaction process, the moisture content is reduced via
evaporation and partial dehydration. In addition, low-weight volatile
components are emitted by decomposing light aliphatic compounds,
hemicellulose, and part of carbohydrate or cellulose. As a result, the
torrefied materials have less moisture, better hydrophobicity, high
carbon content, and improved heating value (Fu et al., 2021; Pahla et al.,
2018; Ren et al., 2013).
Torrefaction has been proposed for the pretreatment of various
biomass samples prior to pyrolysis. For example, Ren et al. (2013)
studied the influence of torrefaction on bio-oil and syngas from the
pyrolysis of Douglas fir sawdust. They found that biomass pretreated by
torrefaction favored the production of phenols and sugars in pyrolysis
bio-oil. In addition, the quality of syngas was remarkably improved by
increasing CH4 and H2 while reducing CO2 formation. Zheng et al.
(2013) have studied the fast pyrolysis of torrefied corncobs in a
fluidized-bed reactor. They also found that the HHV and pH of the bio-
oil improved when the torrefaction was applied as pretreatment. In
addition, the phenolic compounds, primarily derived from decomposi­
tion of lignin, increased with increasing torrefaction temperature. Chen
et al. (2015) reported that compared to bio-oil by pyrolysis of dried
cotton stalk, the water content in that of the torrefied sample (at 280 ℃)
decreased by 41.8%, while phenolic contents increased, leading to an
increase in the heating value by 50.9%. Ukaew et al. (2018) investigated
the influence of torrefaction and acid pretreament on the quality of bio-
oil from the fast pyrolysis of rice straw in Py-GC/MS. They found that the
torrefaction process helps improve the quality of the bio-oil by reducing
its acidity, moisture, and reactive oxygenate compounds, promoting
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Waste Management 141 (2022) 16–26
aging reaction in bio-oil storage. The torrefaction temperature of 225 ◦ C
with the pyrolysis temperature of 550 ◦ C was found to be optimal in
their study. Besides the high quality of bio-oil obtained from the fast
pyrolysis of torrefied arecanut husk, Gogoi et al. (2017) also reported
that the torrefied arecanut husk biochar showed higher efficiency in
removal of As(V) than raw arecanut husk biochar. Currently, many re­
searches have been conducted on the torrefaction behavior of different
types of food waste (Pahla et al., 2018; Poudel et al., 2015), however, the
pyrolysis of torrefied mixed food waste has not been investigated
sufficiently.
Recently, CO2 has been demonstrated as a favorable environment for
deeper decomposition of biomass than an inert medium such as N2
(Kwon et al., 2019; Lee et al., 2017a). CO2 as a reaction medium in
pyrolysis enhances the thermal conversion of biomass. The introduction
of CO2 in the pyrolysis process improved the production of CO while
reducing the formation of high-molecular-weight organic substances,
known as tar, by hindering the polymerization reaction of pyrolysis
vapor (Lee et al., 2017a; Ly et al., 2015a; Oh et al., 2017). Several studies
have been conducted on the utilization of CO2 for the pyrolysis of wastes
feedstock, including food waste, wood waste, and animal manure
(Guizani et al., 2014; Lee et al., 2017a; Oh et al., 2017). This treatment is
effective for waste management, energy recovery, and mitigation of
climate change by reducing CO2 emissions.
In this study, the torrefaction technique was applied as a thermal
method for pretreating mixed food waste (MFW) samples. In addition,
the torrefied mixed food waste (T-MFW) was further investigated as
feedstock material of the fast pyrolysis. The fast pyrolysis of T-MFW was
performed in a fluidized-bed reactor (FBR). To evaluate the efficiency of
pyrolysis, the conversion of T-MFW, product distribution, and the
quality of the pyrolysis bio-oil were measured under different carrier
gases (N2 and CO2). Finally, these results were compared to those
derived from the pyrolysis of the raw MFW in our previous work (Ly
et al., 2021)
2. Materials and methods
2.1. Sample preparation
MFW samples provided by Daekyung Esco (South Korea) were dried
at room temperature. The resulting samples were ground and sieved to
obtain 0.7–1.1 mm fractions. After drying the sample in an oven at 105
℃ for 12 h, it was stored in a desiccator to maintain the equilibrium
moisture before the pyrolysis. To study the effect of torrefaction on the
fast pyrolysis product yields and bio-oil quality, the prepared MFW
sample was first torrefied in the tubular reactor under N2 atmosphere.
Specifically, 100 g of MFW sample was put into a metal woven net
container with a pore size of 180 μm before placing in a tubular reactor.
N2 as a sweeping gas continuously flowed during the process with a flow
rate of 500 mL/min. The MFW was torrefied at two different tempera­
tures, 250 ℃ (T250-MFW) and 275 ℃ (T275-MFW), for 1 h. The char­
acteristics of T-MFW were analyzed by scanning their functional groups
using a Fourier-transform infrared spectrometer (FT/IR-4600, JASCO).
The pyrolysis characteristics of T-MFW were also determined based on
their thermal degradation using a thermogravimetric (TG) analyzer (N-
1000, SINCO). During this analysis, the temperature was increased from
20 to 700℃ at a heating rate 10 ℃/min under a flow rate of 20 mL/min
N2.
2.2. Experimental setup
The fast pyrolysis with T-MFW materials was conducted in an FBR,
assembled by a stainless steel tube (50 cm in height and 3.3 cm in I.D.)
with a porous metal gas distributor. Silica sand (with a mean diameter of
180 μm) was employed as the fluidizing bed material. The torrefied
samples were decomposed in the fluidizing medium, and the fluidization
velocity was adjusted by the mass flow controllers. In each experiment,
H.V. Ly et al.
100 g of silica sand was placed into the reactor, which was heated
externally by an electric furnace. The temperature of the FBR was
measured by two K-type thermocouples at the center of the reactor and
the bed material layer. The reaction temperature was chosen based on
the thermal decomposition properties of two torrefied samples from
TGA.
The experiments were carried out at reaction temperatures between
400 and 550 ℃, at a feed rate of 100 g/h for 60 min under the N2 at­
mosphere (N2-pyrolysis). According to our prior work for raw MFW, the
velocity of N2 sweeping gas was fixed at 2.0 × Umf (minimum fluidizing
velocity of silica sand, Umf = 5.0 L⋅min− 1). Then, the fast pyrolysis of the
two T-MFW samples was also investigated with a CO2 medium under the
same conditions (CO2-pyrolysis). As in the N2-pyrolysis case, the ve­
locity of CO2 in the FBR was maintained at 2.0 × Umf. To avoid the
condensation of pyrolysis volatiles, the tube from a cyclone to a
condenser was maintained at 300 ℃. After the reaction, the solid
products, including char and sand, were collected from the reactor and
the cyclone collector. The pyrolysis volatiles condensed into both the
organic (bio-oil) and aqueous phases (AQ) were collected from two
condensers that were continuously kept at – 10 ℃ by a chiller with
ethylene glycol as the cooling agent. The aerosols in the gas stream were
captured by electrostatic precipitation. The cotton wool trap was used to
filter the remaining aerosols in the non-condensable gases before leaving
the system. The mass balances were calculated based on the initial
weight of samples and product yields of liquid and char. The gas yields
were determined by difference (i.e., gas yield (wt%) = 100 – char yield
(wt%) – liquid yield (wt%)). The experimental details are discussed in
our previous studies (Ly et al., 2015a, 2020; Tran et al., 2021).
2.3. Analytical method
The properties of the T-MFW samples, bio-oils, and bio-char were
characterized following the ASTM standard methods (i.e., elemental
analysis and moisture and ash contents) (Ly et al., 2018, 2021). The
acidity of liquid products was measured by a pH meter (Thermo Sci­
entific, Orion 3-Star). The organic phase (bio-oils) and aqueous phase
were separated from the liquid products. The moisture content in each
phase was analyzed using a Karl-Fischer titration (TitroLine 7500KF). In
addition, dichloromethane was used as a solvent to extract the organic
compounds in the aqueous phase (OCAQ). The chemical compositions of
the bio-oil products and OCAQ were identified using a gas
chromatograph-mass spectrometer (GC–MS, Agilent GC/7890A-MS/
5975C) equipped with a capillary column HP-5MS. Prior to GC–MS
analysis, the bio-oil products and OCAQ were diluted with methanol.
The higher heating values (HHVs) of the bio-oil and biochar were
determined by a bomb calorimeter (SDC715, Calorimeter System). The
functional groups present in the organic compounds were identified by
an NMR spectrometer. The dimethyl sulfoxide-d6 (DMSO‑d6) solvent
was used to dilute the bio-oil sample for 13C NMR analysis, and the
spectra were recorded at 300 MHz. The compositions of the gaseous
products were directly analyzed and quantified by gas chromatography
(YL 6500GC) with dual detectors (flame ionization and thermal con­
ductivity detectors). Detailed procedures for the operation of GC can be
found in our previous studies (Ly et al., 2018, 2020).
Table 1
Characteristics of MFW samples (on dry basis).
Proximate analysis (wt%) Solid Moisture (%) Ash (%) Volatile matter
recovery
(wt.%)
Raw MFW* 100 0.24 ± 0.19 11.07 ± 0.11 68.17
T250-MFW 75.94 2.73 ± 0.24 13.14 ± 0.15 61.95
T275-MFW 60.82 3.36 ± 0.4 15.76 ± 0.11 54.25
*Re-calculating elemental analysis of raw MFW (Ly et al., 2021) according to dry basis.
(Ash + C + H + N + S + O = 100%).
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Waste Management 141 (2022) 16–26
3. Results and discussion
3.1. Characterization of T-MFW materials
Table 1 shows the weight loss of raw MFW at different torrefaction
temperatures. Compared to raw MFW, the weight loss increased to 24.06
and 39.18 wt% with increasing torrefaction temperature to 250 and 275
℃, respectively. It is likely that a part of the carbohydrates and proteins
were decomposed during the torrefaction process. The moisture and ash
contents of raw MFW were reported to be 0.24 and 11.07 wt% in our
prior work (Ly et al., 2021). After the torrefaction process, the moisture
contents increased to 2.73 and 3.36 wt%, and the ash content to 13.14
and 15.76 wt% for T250-MFW and T275-MFW, respectively. However,
the volatile matter decreased from 68.17 to 61.95 (T250-MFW) and
54.25 wt% (T275-MFW), corresponding to 9.21 and 20.42% reduction
in volatile components. Table 1 also shows the analysis of chemical el­
ements including C, H, N, S, and O. The C, H, N, S, and O contents of the
raw MFW were measured to be 41.86, 5.71, 4.24, 1.32, and 35.80 wt%,
respectively (on a dry basis). After the torrefaction pretreatment at 250
℃ (T250-MFW), the C content increased to 43.31 wt% while other
contents decreased. With an increase in torrefaction temperature to 275
℃ (T275-MFW), the C contents increased further to 44.06 wt%, and
contents of other elements decreased. As a result, the HHVs of T250-
MFW and T270-MFW increased to 21.54 and 23.11 MJ/kg after the
torrefaction of the raw MFW (18.43 MJ/kg) (Ly et al., 2021). These
HHVs are comparable to those of other torrefied materials, including
cotton stalk (18.85 MJ/kg) (Chen et al. 2015), beechwood (20.74 MJ/
kg), and loblolly pine (22.7 MJ/kg) (Meng et al. 2012). The FT-IR
spectra of MFW before and after torrefaction are shown in Fig. 1. The
absorption spectra were similar between the MFW samples, but the peak
intensities differed. As torrefaction temperature increases, the absor­
bance band corresponding to O-H group between 3100 and 3500 cm− 1
becomes weak, indicating that the moisture was reduced via dehydra­
tion reaction during the thermal pretreatment process (Ma et al., 2018;
Miglio et al., 2013; Özsin and Pütün, 2017). The absorbance band be­
tween 2800 and 3000 cm− 1 is assigned to CH3− and -CH2− functional
groups in fatty acid chains (Miglio et al., 2013). In addition, C=O
stretching in carboxyl groups (1650 – 1750 cm− 1) and C-O and C-C
bonds (1475 – 1000 cm− 1) bands assigned to esters and carbohydrate
decrease by torrefaction (Ma et al., 2018; Miglio et al., 2013; Özsin and
Pütün, 2017).
The thermogravimetric behavior of torrefied samples is shown in
Fig. 2. As seen in the figure, the TG curves of the torrefied samples were
slightly shifted to the left side (lower temperatures), compared to that of
the raw MFW. Starting at ~ 230 ℃, the pyrolysis of the T-MFW feed­
stocks nearly finished at ~ 530 ℃ (with more than 95% conversion).
The results also confirmed that the thermal pretreatment by torrefaction
reduces the volatile substances of the original MFW material. The dif­
ferential thermogravimetric (DTG) analysis shows that the primary
conversions occurred over a range from 280 to 500 ℃, with the
maximum decomposition at 320 ℃ (for the T275-MFW) and 317 ℃ (for
the T275-MFW). Each DTG curve was separated into three small peaks
based on the deconvolution of DTG curves which were applied to
separate clearly all peaks corresponding to degradation of each
Fixed carbon Elemental analysis (wt%) HHV
(MJ/kg)
C H N S O
20.52 41.86 5.71 4.24 1.32 35.80 18.43 ± 0.26
22.18 43.31 5.54 4.18 – 33.83 21.54 ± 0.17
26.63 44.06 5.22 4.04 – 30.92 23.11 ± 0.10
H.V. Ly et al. Waste Management 141 (2022) 16–26

Fig. 1. FT-IR spectra of raw MFW and T-MFW samples.

Fig. 2. Thermogravimetric (TG) curves and deconvolution of differential thermogravimetric (DTG) curves: (a) raw MFW, (b) T250-MFW, and (c) T275-MFW (at
heating rate = 10 ℃/min).

component in the sample material. The first peak centered at 320 – 340 materials. It might be attributed to the decomposition of carbonates in
℃ is likely due to carbohydrate and protein degradation and becomes the feedstock (Ly et al. 2015b).
narrower after the torrefaction process. The second peak (390 – 400 ℃)
assigned to the decomposition of lipids was observed at 390 – 400 ℃ (Jo
et al., 2017). Finally, the third peak appeared more clearly in the T-MFW

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H.V. Ly et al. Waste Management 141 (2022) 16–26

3.2. Product distribution from pyrolysis of T-MFW samples
It is well known that yield of pyrolysis products is significantly
influenced by the reactor temperature (Ly et al., 2018, 2020). In this
study, the pyrolysis of the T250-MFW sample (N2-pyrolysis) was con­
ducted under the same temperatures at which the raw MFW was
examined (Ly et al., 2021). The product yields from the fast pyrolysis of
T250-MFW are given in Table 2. With increasing temperature from 400
to 450 ℃, the liquid yield increased from 37.08 to 39.54 wt% and
decreased to 32.75 wt% with a further increase in temperature to
550 ◦ C. The decrease of the liquid yields at higher temperatures is most
likely because of increased gas yields via the emission of CO2, CO, H2,
and C1-C4 gases by the cracking of pyrolyzed volatiles (Ly et al., 2019,
2020, 2021). With an increase in temperature, the gas yield increased
from 12.29 to 23.65 wt% while decreasing the char yields from 50.63 to
43.59 wt%, which are higher than that from pyrolysis of raw MFW
feedstock (31.13 wt%).
To clarify the effect of torrefaction temperature on pyrolysis of MFW,
pyrolysis of the T275-MFW sample was also examined under the same
conditions used for the T250-MFW. Table 2 also shows the product
distribution from the fast pyrolysis of T275-MFW at 450 and 475 ℃. It
can be seen that the char yields slightly increase (to 49.52 wt% at 450
and 47.74 wt% at 475 ℃) as the torrefied temperature increases. The
product yields of the T-MFW are comparable to those from other tor­
refied materials. Ren et al. (2013) studied the pyrolysis of torrefied wood
waste from Douglas fir in a microwave. They obtained a maximum bio-
oil yield of 40.25 wt% (torrefied at 275 ℃ in 8 min) at a pyrolysis
temperature of 480 ℃. Similar tendencies were observed in pyrolysis of
torrefied rice straw at temperatures between 450 and 550 ℃ (Ukaew
et al., 2018). With increasing pyrolysis temperature of the feedstock
torrefied at 250 ℃, the yield of bio-oil increased from 16 wt% (at 450
℃) to 23 wt% (at 500 ℃) and then decreased to 22 wt% (at 550 ℃).
Besides, the liquid yields reduced with the torrefaction temperature. The
maximum bio-oil yield of 26 wt% was obtained from sample torrefied at
225 ℃ at the pyrolysis temperature of 550 ℃. Meng et al. (2012)
investigated the pyrolysis of torrefied loblolly pine at 500 ℃. Liquid and
char yields from the pyrolysis of the raw sample were measured to be
44.30 and 9.70 wt%, respectively. It was observed that the liquid yields
decreased, but the char yields increased after the torrefaction pretreat­
ment. They found char yield increased from 22.2 to 43.3 wt% while
decreasing liquid yield from 37.1 to17.9 wt% with increasing the tor­
refaction temperature from 275 to 330 ℃.
Compared to the raw MFW, the torrefied samples showed lower
liquid and gas yields but higher char yield during the pyrolysis. In
addition, char yields were much higher than liquid yields. The higher
yield in char product might be resulted from the C-C cross-linking
formed via the dehydration of carbohydrate molecules in the MFW
during torrefaction. These cross-links rarely break down because they
are stable under pyrolysis conditions (Ukaew et al., 2018; Wigley et al.,
2016). The decrease in liquid yields is due to the removal of thermally-
reactive compounds derived from carbohydrate, proteins, and fatty acid
ester via the dehydration, volatilization, and carbonization reactions
during the torrefaction (Ukaew et al., 2018).
3.3. Effect of CO2 on the pyrolysis
As mentioned in the introduction, several studies investigated the
effect of CO2 in the pyrolysis of biomass. Lee et al. (2017b) found that
thermal cracking of volatile organic carbon from pyrolysis of peat was
enhanced in the presence of CO2. The biochar derived from this process
showed a larger surface area, compared to that produced in a N2 at­
mosphere. The role of CO2 as a sweeping medium in the pyrolysis of food
waste was also investigated by Lee et al. (2020). They reported that the
use of CO2 as a pyrolysis environment affected the composition of both
non-condensable gases and condensable vapors. They concluded that
the introduction of CO2 probably inhibited the formation of cyclic

Table 2
Product distribution of T-MFW at different pyrolysis temperatures in N2 atmosphere (gas velocity = 2.0 × Umf).
Feedstock Raw MFW T250-MFW T275-MFW

Temperature [℃] 475 ℃ 400 ℃ 450 ℃ 475 ℃ 500 ℃ 550 ℃ 450 ℃ 475 ℃

Gas 19.82 12.29 14.02 15.72 21.96 23.65 12.02 13.32

Product yield [wt%] Char 31.13 50.63 46.44 44.98 43.88 43.59 49.52 47.74
Total liquid 49.05 37.08 39.54 39.30 34.16 32.76 38.46 38.94
Moisture (%) 74.23 44.94 46.58 47.85 48.53 49.17 44.76 46.01
Aqueous phase
Organic (%) 25.77 55.06 53.42 52.15 51.47 50.83 55.24 53.99
Moisture (%) 9.33 7.11 6.58 6.94 6.17 5.82 4.96 5.31
Organic phase
Organic (%) 90.67 92.89 93.42 93.06 93.83 94.18 95.04 94.69

C 38.88 35.48 36.18 36.81 37.84 39.26 36.88 37.34

H 6.89 6.17 6.52 6.58 6.89 7.05 6.22 7.01
Elemental analysis of OCAQ [wt%]
N 7.59 7.38 8.28 8.33 9.33 9.50 8.35 9.62
O 47.64 50.97 49.02 48.28 45.94 44.19 48.05 46.03

C 67.10 66.40 66.93 67.94 68.73 69.30 68.45 67.70

H 9.63 9.60 9.57 9.53 9.44 9.39 9.27 9.39
Elemental analysis of bio-oil [wt%]
N 6.06 5.64 5.74 5.79 6.10 6.50 6.36 6.61
O 17.21 18.36 17.76 16.74 15.73 14.81 15.56 16.30
HHV of bio-oil [MJ/kg] 29.69±0.33 31.51±0.10 32.82±0.14 33.52±0.15 33.89±0.09 34.12±0.11 33.03±0.20 34.34±0.14
pH of bio-oil 3.27±0.03 3.87±0.10 3.98±0.02 4.02±0.08 4.10±0.01 4.17±0.05 4.12±0.02 4.21±0.06

CO 6.01 13.82 15.72 18.78 20.88 22.96 18.02 19.02

CO2 81.68 71.18 66.06 58.79 52.60 48.51 59.80 51.58
H2 2.04 2.19 3.11 3.58 5.58 7.08 1.01 1.26
CH4 4.19 5.67 7.16 7.32 8.03 8.16 8.75 11.01
Gas selectivity [mol%]
C2H4 1.22 1.39 1.49 1.98 2.14 2.21 2.24 2.83
C2H6 2.75 3.21 3.68 4.40 4.96 5.09 5.20 6.96
C3H6 0.71 0.83 0.85 1.52 1.74 1.81 1.41 2.45
C3H8 0.89 1.02 1.09 1.72 1.89 1.94 1.49 2.79
n-C4H8 0.33 0.43 0.49 1.67 1.92 1.96 0.86 1.0
i-C4H10 0.18 0.26 0.35 0.24 0.26 0.28 1.22 1.10
Total volume of gas product (L/gsample) 0.12 0.08 0.09 0.10 0.16 0.18 0.08 0.09
HHV of gas (MJ/m3)a 8.91 11.28 14.01 16.86 21.00 23.61 14.40 18.50
a
The HHV of gas product (Ly et al. 2015).

20
H.V. Ly et al. Waste Management 141 (2022) 16–26

components, which are hazardous to the environment and human
health. In our study, the pyrolysis of T250-MFW and T275-MFW samples
was investigated in an FBR reactor using CO2 as a carrier gas at 450 and
475 ℃ to understand the influence of CO2 sweeping gas on the pyrolysis
of torrefied materials. Table 3 reveals the contents of gas, liquid, and
char products produced from pyrolysis of the T-MFW samples under N2
and CO2. Similar patterns were observed in gas and solid yields in both
N2 and CO2 atmospheres with changing pyrolysis temperatures. In the
CO2-pyrolysis, the yields of gas and liquid products increased with re­
action temperature for both T250-MFW and T275-MFW samples, indi­
cating that the presence of CO2 in pyrolysis of T-MFW hindered the
secondary char formation (via tar cracking), enhancing the conversion
into the gas and liquid products.
Interestingly, the type of sweeping gas has little effect on the char
yields for all temperatures examined in this study. In other words, as
seen in Table 3, the differences in gas and liquid yields between N2– and
CO2-pyrolysis are similar. For instance, the liquid yield decreases from
39.54 to 37.04 wt%, while the gas yield increases from 14.02 to 16.09 wt
% when a carrier gas is switched from N2 to CO2 in the pyrolysis of T250-
MFW at 450 ℃. This result reveals that replacing N2 with CO2 could
hinder the formation of tar on char by promoting the cracking of high
molecular weight compounds in pyrolysis vapor, leading to the forma­
tion of more light molecules and non-condensable gases (Lee et al.,
2020). These results are in good agreement with the literature (Kwon
et al., 2019; Lee et al., 2017b; Lee et al., 2020; Oh et al., 2013).
3.4. Composition of the gas products
Table 2 shows the compositions in the gaseous products from the
pyrolysis of T250-MFW under the N2 atmosphere. The gas products
mainly contain CO, CO2, H2, and a small amount of hydrocarbon gases
from C1 to C4. In comparison with the gas products from the pyrolysis of
raw MFW in our previous study (Ly et al., 2021), the gas compositions
from the torrefied sample produced lower CO2 ranging from 48.51 to
71.18 wt% and a significant amount of CO in the range of 13.82–22.96
wt%. Compared to T250-MFW pyrolysis, the CO2 formation was lower,
but a higher concentration of hydrocarbon (C1-C4) fractions was ob­
tained in the pyrolysis of T275-MFW. During the torrefaction of MFW,
most of the oxygen was removed via primary reactions, such as dehy­
dration, devolatilization, and depolymerization of carbohydrates, a part
of proteins, and fatty acid esters, resulting in changes in the chemical
structure of raw material. This stage is known as the early stage of py­
rolysis (Shen et al., 2009; Pahla et al., 2018). The evolutions of CO2 and
CO were attributed to the open pyranose rings reaction of a glucan unit
in the carbohydrates of the MFW feedstock (Ly et al., 2015b; Ma et al.,
2018). In the pyrolysis of MFW samples, CO2 was observed to be the
majority among the gas products. During the pyrolysis of T-MFW, the
formation of CO2 and CO can be attributed to the O-removal via the
cleavage of heterocyclic oxygen, decarbonylation of aldehyde-contained
intermediate components, and decomposition of carboxyl groups (acidic
structure) in O-containing compounds. These are known as secondary
decompositions of high molecular weight compounds in pyrolysis vapor
(Ma et al., 2018; Shen et al., 2009; Yuan et al., 2012). An increase in
reaction temperature could be the reason for the enhanced production of

Table 3
Product distribution from pyrolysis of T-MFW in different atmospheres (gas velocity = 2.0 × Umf).
Pyrolysis atmosphere N2-pyrolysis CO2-pyrolysis
b b
T250-MFW T275-MFW T250-MFW T275-MFW

Temperature [℃] 450 ℃ 475 ℃ 450 ℃ 475 ℃ 450 ℃ 475 ℃ 450 ℃ 475℃

Gas 14.02 15.72 12.02 13.32 16.09 17.23 14.48 15.44

Product yield [wt%] Char 46.44 44.98 49.52 47.74 46.87 44.61 48.83 47.13
Total liquid 39.54 39.30 38.46 38.94 37.04 38.16 36.99 37.43
Moisture (%) 46.58 47.85 44.76 46.01 47.13 48.21 47.08 47.83
Aqueous phase
Organic (%) 53.42 52.15 55.24 53.99 52.87 51.79 52.92 52.17
Moisture (%) 6.58 6.94 4.96 5.31 6.94 7.32 6.31 6.66
Organic phase
Organic (%) 93.42 93.06 95.04 94.69 93.06 92.68 93.69 93.34

C 36.18 36.81 36.88 37.34 43.50 43.26 44.02 44.28

H 6.52 6.58 6.22 7.01 7.73 7.82 7.57 7.69
Elemental analysis of OCAQ [wt%]
N 8.28 8.33 8.35 9.62 10.37 10.38 10.91 10.93
O 49.02 48.28 48.05 46.03 38.40 38.54 37.49 37.08

C 66.93 67.94 68.45 68.70 67.29 69.63 68.99 70.78

H 9.57 9.53 9.27 9.39 8.76 9.60 9.09 8.66
Elemental analysis of bio-oil [wt%]
N 5.74 5.79 6.36 6.51 6.90 6.48 6.83 6.53
O 17.76 16.74 15.92 15.40 17.05 14.29 15.09 14.03
HHV of bio-oil [MJ/kg] 32.82 33.52 33.03 34.34 31.19 32.23 32.50 34.23
±0.14 ±0.15 ±0.20 ±0.14 ±0.27 ±0.18 ±0.18 ±0.19
pH of bio-oil 3.98±0.02 4.02±0.08 4.12±0.02 4.21±0.06 4.08±0.03 4.14±0.01 4.19±0.02 4.28±0.02

CO 46.32 45.57 44.83 38.37 49.26 51.16 56.27 51.83

CO2 – – – – – – – –
H2 9.16 8.69 2.51 2.61 4.37 4.55 3.07 3.13
CH4 21.10 17.76 21.77 23.45 18.48 18.71 18.04 19.49
Gas selectivity [mol%]
C2H4 4.39 4.80 5.57 5.87 3.28 3.42 2.99 3.10
C2H6 10.84 10.68 12.94 14.43 9.67 9.80 8.05 10.22
C3H6 2.50 3.69 3.51 5.08 3.38 3.56 3.07 3.25
C3H8 3.21 4.17 3.71 5.79 5.239 4.66 4.24 4.38
n-C4H8 1.44 4.05 2.14 2.07 4.07 2.52 2.19 2.41
i-C4H10 1.03 0.58 3.03 2.32 2.25 1.61 2.08 2.19
CO/H2 5.05 5.25 17.84 14.68 11.27 11.24 18.33 16.56
Total volume of gas product 0.14 0.17 0.12 0.13 0.16 0.17 0.14 0.15
(L/gsample)
HHV of gas (MJ/m3)a, b 41.28 40.91 35.83 38.58 35.49 34.93 31.48 33.41
a
The HHV of gas product (Ly et al. 2015).
b
Re-calculating gas selectivity with the removal of CO2 component.

21
H.V. Ly et al.
CO and hydrocarbon gases in this stage.
In the pyrolysis under the CO2 atmosphere, the composition of the
gas products shown in Table 3 was calculated after excluding a CO2
medium. However, the amount of CO2 produced by pyrolysis is much
smaller than that of CO2 as a medium. For this reason, it was not simple
to calculate reliable CO2 yields due to the high uncertainty of produced
CO2 measurements. For T250-MFW, as reactor temperature increased
from 450 to 475 ℃, the concentration of CO increased, and there was no
significant change in the other gases. It may be due to the enhanced
thermal cracking of pyrolysis volatiles under the presence of CO2. Ac­
cording to Eq. (1), CO2 can react with hydrocarbon volatiles to form CO
through a gas reforming reaction (Guizani et al., 2014).
y fractions: water-insoluble (organic phase or bio-oils) and water-soluble
Cx Hy + xCO2 →2xCO + H2 (1)
2
In addition, to compare the constitute of produced gases between the
N2– and CO2-pyrolysis processes, the gas compositions (mol%) of N2-
pyrolysis were recalculated, excluding the CO2 component. As shown in
Table 3, the formation of CO was enhanced at all the examined tem­
peratures for both T250-MFW and T275-MFW samples when CO2 was
used instead of N2. Based on the elemental analysis of the T-MFW
samples, the chemical formula of the samples can be expressed as
C4.78H7.35O1.85 (i.e., CH1.53O0.38) for T250-MFW and C5.2H7.72O1.5 (i.e.,
CH1.48O0.29) for T275-MFW. These results suggest that the CO concen­
tration cannot exceed the H2 concentration without supplemental C and
O sources. However, the CO/H2 ratio was calculated to be higher in the
CO2-pyrolysis than in the N2-pyrolysis. Therefore, it is evident that the
most likely source of the C and O was the CO2 medium, and the CO
constituent in the CO2-pyrolysis was generated by the reaction shown in
Eq. (1).
The total volume of gas products can be determined according to the
mole fraction of gas components (Blank et al., 2020). As shown in
Table 2, the total volumes of gas product from the N2-pyrolysis of T-
MFW are between 0.08 and 0.18 L/gsample. At the same temperature
(475 ℃), the total gas volume from the N2-pyrolysis of T-MFW (0.10 L/
gsample) is lower than that of raw MFW (0.12 L/gsample). This result is in
agreement with the gas yield from the N2-pyrolysis of T-MFW and raw
MFW samples at the same conditions.
The HHVs of the gas products can be calculated based on each
component’s mole fraction and HHV (Bob Fegan, 2001; Engineering
ToolBox, 2005; Ly et al., 2015a). As shown in Table 2, the HHVs of gas
products from the N2-pyrolysis of T-MFW are in the range of
11.28–23.61 MJ/m3. As given in Table 3, for CO2-pyrolysis, the HHVs,
excluding CO2 in the calculations, ranged from 31.48 to 35.49 MJ/m3,
whereas the HHVs, excluding CO2 in the recalculations for N2-pyrolysis,
ranged from 35.83 to 41.28 MJ/m3.
3.5. Characterization of the bio-oils
Tables 2 and 3 show the total liquid yield from pyrolysis of T-MFW
samples for both N2 and CO2 mediums. With increasing pyrolysis tem­
perature from 450 to 475 ℃, the C content in the bio-oil fraction
increased, while the O content decreased. For example, in the N2-py­
rolysis of T250-MFW, the C content increased from 66.93 to 67.94 wt%,
whereas the O content reduced from 17.76 to 16.74 wt%. It can also be
seen that the POs from T275-MFW contain slightly higher C content but
lower O content than those of T250-MFW. During the torrefaction pro­
cess, the O element can be removed via dehydration. Increasing the
torrefaction temperature is likely to promote the dehydration reaction,
resulting in enhanced O elimination. The HHVs of the POs from T-MFW
were in the range of 31.19–34.34 MJ/kg, which are higher than those for
raw MFW (27.69–31.58 MJ/kg) (Ly et al., 2021), indicating that a tor­
refaction pretreatment improved properties of the feedstock. In addi­
tion, the HHVs of the POs from T-MFW are comparable to those of other
feedstock, including spent coffee waste (27.91–37.80 MJ/kg) (Vu Ly
et al., 2022) and other lignocellulosic biomass: tulip tree (24.37 MJ/kg)
22
Waste Management 141 (2022) 16–26
and bamboo (24.65–26.95 MJ/kg) (Ly et al. 2018, 2020). These results
are also comparable to POs from catalytic fast pyrolysis of MFW in our
previous study, which were 35.69, 34.07, and 35.31 MJ/kg at 550 ℃
with dolomite, red mud, and HZSM-5 catalyst, respectively (Ly et al.
2021). In the present study, the pH value of the POs was in the range
from 3.87 to 4.28, which is higher than that of raw MFW (3.03–3.69),
suggesting that the acid components were removed during torrefaction
(Chen et al., 2015, Ukaew et al., 2018). The T-MFW may be deeply
decomposed in CO2-pyrolysis, resulting in more decomposition of pro­
tein components, which can increase the N content in POs. As a result,
the pH value of the liquid product increases in CO2-pyrolysis.
The liquid products obtained from pyrolysis were separated into two
(aqueous phase, AQ) fractions. The AQ contains a high water content
which is emulsified with organics. The organic fraction (low molecular
weight oxygenates) in the aqueous phase (OCAQ) was extracted using
dichloromethane as a solvent. The elemental analysis of OCAQ is pre­
sented in Table 3. The pyrolysis of T-MFW in the CO2 medium exhibited
a carbon distribution different from that of N2-pyrolysis. It was observed
that the OCAQ by CO2-pyrolysis contains higher C but lower O content
than the OCAQ by N2-pyrolysis. This result can be explained that the
participation of CO2 in pyrolysis promotes the thermal cracking of
macromolecular organic matter to form lighter condensable compounds
and more non-condensable gases (e.g., a large amount of CO, which is
also produced by the elimination of O elements during pyrolysis) (Kim
et al., 2019, Lee et al., 2020). Condensable constituents from CO2-py­
rolysis have low molecular weight and are water-soluble. Therefore,
they are more soluble in dichloromethane solvent (water-soluble) than
those obtained by N2-pyrolysis. As a result, more organic fraction was
recovered from the aqueous phase by CO2-pyrolysis.
The carbon and oxygen distributions in different types of products
are shown in Table S1 (Supplement). The C/O ratio of pyrolysis products
was calculated based on the elemental analysis of each phase. It was
found that the C/O ratio of bio-oils was enhanced when CO2 was used as
a sweeping medium in pyrolysis instead of N2. Although the C and O
contents (wt%) of bio-oils were decreased by using a CO2 medium,
however, the C/O ratio was increased. This result shows that oxygenates
were removed in gaseous form (e.g., CO and moisture) via deoxygen­
ation and dehydration reactions. Compared to the T-MFW samples
before pyrolysis, total C and O contents in the products were lower, as
given in Table S1. This deficiency might be explained that: (i) there are
some gaseous components that GC systems cannot detect and (ii)
dichloromethane used to extract the OCAQ cannot recover whole water-
soluble compounds in the aqueous phase.
Table 4 presents the compositions of the organic phase and OCAQ
derived from the torrefaction of MFW. It was found that these phases
mainly consist of fatty components such as esters of fatty acids, sugar
(dianhydromanitol), flavor-enhancing agent, furan, and pyrazine de­
rivatives that were removed from MFW during the torrefaction process.
These results are in good agreement with the observation from the FT-IR
analysis of MFW and T-MFW samples. Table 4 also shows the GC–MS
analysis of the POs obtained from N2 and CO2-pyrolysis of two T-MFW
samples at different temperatures and the same fluidization velocity
(2.0 × Umf). As shown in Table 4, the main components in POs include
fatty acids (oleic acid and palmitic acid), N-containing compounds,
phenolic derivatives, and aliphatic hydrocarbons. In comparison with
POs of MFW, the amount of fatty acid components in POs from T-MFW
decreased, but high selectivity of fatty acids was obtained. The fatty
acids are currently used as a source for pharmaceutical ingredients,
cosmetics, and bio-lubricants (Ly et al., 2021). Compared to POs of raw
MFW, less acid acetic, ketones, and furans were found in POs of T-MFW.
It is likely because they were removed during the torrefaction process. In
addition, the torrefaction pretreatment was expected to modify the
structural and chemical properties of MFW, causing changes in reaction
pathways during the pyrolysis process. A large number of low-weight
components (i.e., aliphatic hydrocarbon compounds) are produced
H.V. Ly et al. Waste Management 141 (2022) 16–26

Table 4
Analysis of pyrolysis bio-oils from T-MFW by GC–MS (gas velocity = 2.0 × Umf, feed rate = 100 g/hr) (Area%).
Compositions Torrefied MFW at 275 ℃ Compositions N2-pyrolysis CO2-pyrolysis

T250-MFW T275-MFW T275-MFW

QCAQ Organic phase 475 ℃ 550 ℃ 475 ℃ 475 ℃

Acetic acid 9.54 10.29 2,2-dimethoxy propane 1.11

Methyl-2-hydroxy propanoate 4.30 1.69 Acetic acid 1.84 1.32
Propanoic acid 2.65 Propionic acid 1.61
Pyridine Phenol 3.10 4.61 4.52 1.94
Methyl pyridine 1.81 Pyrrole 1.24 0.6
2-Furanmethanol 5.09 17.55 2-hydroxy-3-methyl-2-cyclopenten-1-one 1.05 1.67
1-Hydroxy-2-pentanone 1.24 2,3-Dimethyl − 2-Cyclopenten-1-one 0.79 1.61 0.85
4-Hydroxy-4-methyl-2-pentanone 2.06 2-Furanmethanol 1.17 0.6
2,6-Dimethyl pyrazine 1.0 2-methoxy phenol 3.02 2.15 4.15 1.84
D-Manitol 1.76 2-methyl-2-cyclopenten-1-one 1.98 1.65 1.59 1.96
3-Ethyl-2,5-dimethyl pyrazine 1.59 2-Methyl phenol 2.6 2.93 2.79 2.63
2-Hydroxy-3-methyl-2-cyclopenten-1-one 3.45 4-Methyl phenol 7.36 7.99 7.84 6.66
1,5-Dimethyl piperidine-3-ol 3.26 4-Ethyl phenol 4.55 2.52 4.01 2.74
2-Hydroxy-3-ethyl-2-cyclopenten-1-one 3.41 11.68 2,4-Dimethyl phenol 2.99 4.51 3.08 1.84
1-(2-Furanyl)-Ethanone 4.09 Maltol 2.17 1.96 1.40 0.58
Phenol 3.35 Udecane 1.38 1.78 0.95 1.89
2-Furanmethanol acetate 1.48 3-ethyl-2-cyclopenten-1-one 1.23
Trimethyl pyrazine 2.30 Dodecane 1.90 4.58 3.90
4(2-Propenyl)- phenol 2.10 2.99 Tridecene 2.49
2-Methoxy phenol 2.83 Tridecane 3.09 1.49 1.66
Maltol 4.70 19.94 Tetradecene 2.89 2.96 2.48
Dianhydromanitol 26.05 Tetradecane 2.53 2.86 2.56 3.30
Methyl tetradecanoate 2.60 1-Indole 1.52 2.04 1.37
Methyl hexadecanoate 26.61 2-Furyl methyl ketone 1.02
Methyl 9-Octadecanoate 3.91 Indolizine 1.52 1.27 1.97
Dianhydromannitol 2.17
Methyl Indole 2.96 1.20
Pentadecane 2.53 5.15 1.56
Hexadecane 2.1 1.55 1.30 1.51
8-Heptadecene 1.78 2.46
Heptadecane 2.64 5.72 4.51 5.69
Pentadecanonitrile 3.45 2.66 1.67
Oleonitrile 2.78 1.16 2.82 1.25
Oleamide 1.15 2.03 4.31
Methyl palmitate 2.17 1.77 2.37
Palmitinic acid 1.11 5.95 5.19 2.16
Oleic acid 7.52 4.84 5.80 3.96
Methyl Oleate 2.84 2.12 2.37 1.20
Pentadecanoic acid 1.07
Hexadecanamide 2.76 4.31
Octadecanenitrile 2.07 4.01 1.14

during pyrolysis instead of aromatic compounds. The POs also contain a
considerable amount of N-containing compounds (e.g., nitrile and amide
derivatives) derived from the decomposition of the proteins. Although
nitrile derivatives have been used in sensor technology and the dye in­
dustry, these components may be unfriendly to the environment (Lee
et al. 2020). In this context, pretreating MFW by torrefaction is helpful
because it can reduce the selectivity of nitriles in POs. The decrease in
nitriles is attributed to the removal of thermally-reactive compositions
derived from proteins during the torrefaction. Moreover, the pyrolysis in
the CO2 atmosphere can further hinder the formation of these com­
pounds. This phenomenon can be explained that CO2 participated as an
intermediate (via CO2 + H2O ↔ 2H+ + CO32–) in the hydration of the
nitrile group to generate amide substances (Ma et al., 2013; Tomishige
et al., 2020). Amide derivatives are the other N-containing compounds
found in POs. Among them, oleamide has various industrial uses,
including an antifouling coating on submerged surfaces and a medical
agent for mood and sleep disorders (Getachew et al., 2016; Ovidi et al.,
2020). Moreover, the amide derivatives will be converted into hydro­
carbons which can be used directly as transportation fuel by the
following upgrading process of the POs (Chiaberge et al., 2013). As
presented in Table 4, the selectivity of amides was found to be higher in
POs from CO2-pyrolysis than that from N2-pyrolysis.
The functional groups in organic compositions of the POs were
identified by 13C NMR spectroscopy. The peaks with different intensities
appeared in the spectrum regions of 0–55 ppm (aliphatic hydrocarbon),
55–95 ppm (carbohydrate, esters, phenolic methoxy), 95–165 ppm
(phenol and olefins), and 165–180 ppm (carboxylic acids), as presented
in Fig. 3. The figure shows that the torrefaction temperature signifi­
cantly influences the components in the organic phase derived from the
torrefaction of MFW, closely relating to the pyrolysis product distribu­
tion. Torrefaction at higher temperatures is expected to remove more
components in the raw feedstocks. Peaks with relatively higher in­
tensities are observed in the aliphatic hydrocarbon region for all the POs
of T-MFW samples. Different intensities of the peaks in this region are
attributed to the concentration of alkanes, alkenes, or hydrocarbons
generated by the cracking of long-chain hydrocarbon in esters and fatty
acids. The presence of CO2 is likely to promote the breaking of long or/
and side aliphatic chains into shorter hydrocarbons or hydrocarbon
gases. In addition, the tar cracking by CO2 to produce more CO may
occur according to Eq. (1). These results also account for lower in­
tensities of signals in the range of 0–55 ppm in CO2-pyrolysis. The high
intensities of signals in 13C NMR spectra of OCAQ from torrefaction
could be justified by removing components from raw materials. This also
explains the low peaks in the 55–180 ppm region and no signals in
180–210 ppm (ketones and aldehyde). The results from the 13C NMR
spectra of POs are in agreement with those observed from GC–MS
analysis.

23
H.V. Ly et al.
13
Fig. 3. C NMR spectra of bio-oil produced from pyrolysis of T-MFW samples.
3.6. Characterization of the biochar
The biochar produced by the pyrolysis of T-MFW was also analyzed
in this study. The char yield decreased with increasing reaction tem­
perature because of the thermal decomposition of organic components
in the biomass material. Table 5 shows the elemental analysis of biochar
from N2– and CO2-pyrolysis of two T-MFW samples. It can be seen that
the C, H, and N constituents decrease with pyrolysis temperature in both
N2– and CO2-pyrolysis. This trend was similarly observed in T-MFW
samples. This result is because organic volatiles (proteins and lipids) in
the T-MFW are thermally converted into liquid and gas products as
pyrolysis temperature increases. Similar behavior was reported by Lee
24
Waste Management 141 (2022) 16–26
et al. (2018). The biochar from T-MFW was found to contain a lower ash
content than that of the raw MFW because of a higher char yield from
the pyrolysis of T-MFW. The elemental analysis in Table 5 also shows
that the C content in biochar from CO2-pyrolysis is lower than that from
N2-pyrolysis. This result may be attributed to the reaction between CO2
and organics compounds (tar cracking), hindering the secondary char
formation during CO2-pyrolysis (Guizani et al., 2014). The decrease in C
content may be due to the gasification of char in CO2, known as the
Boudouard reaction (Eq. (2)). However, this reaction may not occur at
the reaction temperature below 650 ℃:
CO2 + C ↔ 2CO (2)
H.V. Ly et al. Waste Management 141 (2022) 16–26

Table 5
Characteristics of biochar from pyrolysis of T-MFW (gas velocity = 2.0 × Umf, feed rate = 100 g/hr).
Elemental analysis (wt%) N2-pyrolysis CO2-pyrolysis
Raw T250-MFW T275-MFW T250-MFW T275-MFW

475 ℃ 400 ℃ 450 ℃ 475 ℃ 500 ℃ 550 ℃ 450 ℃ 475 ℃ 450 ℃ 475 ℃ 450 ℃ 475℃

C 23.77 35.35 31.49 27.05 26.45 25.86 30.33 28.34 31.43 27.1 30.15 28.26
H 1.58 3.31 3.14 2.21 1.71 1.50 2.23 2.22 2.74 2.68 2.94 2.88
N 2.36 3.65 3.38 2.92 2.90 2.61 3.21 3.10 2.90 2.78 3.17 3.03
O 21.81 23.41 23.36 24.44 25.25 26.20 25.15 23.96 23.16 24.92 27.45 25.50
Ash 43.15 34.29 38.62 43.38 43.69 43.83 39.08 42.38 39.77 42.52 36.29 40.33
HHV of char(MJ/kg) 19.76 19.28 17.35 16.84 16.13 15.41 15.97 15.54 17.94 17.39 17.04 16.88
±0.23 ±0.10 ±0.13 ±0.11 ±0.08 ±0.10 ±0.18 ±0.13 ±0.13 ±0.17 ±0.14 ±0.13

The HHVs of the biochar were ranged from 15.41 to 19.28 MJ/kg,
which is at a similar level to that obtained by pyrolysis of raw MFW.
These HHVs are comparable to those of other solid fuels: coals (15 ~ 27
MJ/kg) (Ngo and Kim, 2014), wood (12 ~ 18 MJ/kg), and lignite
(15–18 MJ/kg) (Bae et al., 2011). The produced biochar from the py­
rolysis of T-MFW contained high C and ash contents, which can be uti­
lized as fertilizer or additives for farmland (Ly et al., 2016).
4. Conclusions
The fast pyrolysis of two T-MFW samples was systematically studied
in a bubbling FBR. The highest bio-oil yield of 39.54 wt% was achieved
at 450 ℃ with a fluidization velocity of 2.0 × Umf and particle size
(0.7–1.1 mm). Torrefaction has a significant effect on product distri­
bution and quality of pyrolysis products. After torrefaction of MFW, the
quality of POs increased due to improved aliphatic hydrocarbon and
phenol contents. The HHVs of POs (at 475 ℃) increased from 29.69 MJ/
kg for raw MFW to 33.5 and 34.34 MJ/kg for T250- and T275-MFW,
respectively. When a carrier gas CO2 was replaced with N2, the liquid
yield decreased, whereas the bio-oil quality increased. In addition, the
selectivity of alkanes, alkenes, and phenol derivatives also increased.
Furthermore, the presence of CO2 in pyrolysis favored a cracking reac­
tion to produce more CO in the gaseous products. Finally, CO2 in py­
rolysis inhibited the formation of nitriles derivatives, which are harmful
to the environment, suggesting that the application of CO2 to pyrolysis
of T-MFW can contribute to the mitigation of climate change by
reducing CO2 emission and developing of waste management.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This research was supported by the Korea Institute of Energy Tech­
nology Evaluation and Planning (KETEP) and the Ministry of Trade,
Industry, & Energy (MOTIE) of the Republic of Korea (No.
20173010092430).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.wasman.2022.01.013.
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