Science of the Total Environment 754 (2021) 142192

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Science of the Total Environment

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

Hydrothermal carbonization of food waste after oil extraction

pre-treatment: Study on hydrochar fuel characteristics, combustion
behavior, and removal behavior of sodium and potassium
Hongcai Su a,d, Xuanyou Zhou a, Rendong Zheng b, Zhihao Zhou a, Yan Zhang a, Gaojun Zhu a, Caimeng Yu c,
Dwi Hantoko a, Mi Yan a,⁎
a
Institute of Energy and Power Engineering, Zhejiang University of Technology, Hangzhou 310014, China
b
Hangzhou Linjiang Environmental Energy Co. Ltd., Hangzhou 311222, China
c
Zhejiang Zheneng Xingyuan Energy Saving Technology Co. Ltd, Hangzhou 310013, China
d
State Key Laboratory of Clean Energy Utilization, Zhejiang University, Zheda Road 38, Hangzhou 310027, China

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

• Food waste after oil extraction pretreat-

ment was converted into hydrochar
by HTC.
• The hydrochars with higher C content,
fuel ratio and HHV were obtained.
• HTC process improved the combustion
behavior of hydrochars.
• High removal rate of Na (70.98%) and K
(84.05%) was achieved during HTC
process.

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

Article history: This study aims to convert oil extracted food waste (OEFW) into hydrochar as potential solid fuel via hydrother-
Received 31 May 2020 mal carbonization (HTC) process. The effect of HTC temperature and residence time on the physicochemical char-
Received in revised form 2 September 2020 acteristic, combustion behavior, and the removal behavior of sodium and potassium were evaluated. The raw
Accepted 2 September 2020
OEFW material was successfully converted into energy densified hydrochar with higher high heating value
Available online 03 September 2020
(HHV) (21.13–24.07 MJ/kg) and higher fuel ratio (0.112–0.146). In addition, carbon content in hydrochar in-
Editor: Daniel CW Tsang creased to 46.92–51.82% after HTC at various operating conditions. Compared with OEFW, the hydrochar had
more stable and longer combustion process with the higher ignition temperature and burnout temperature. Be-
Keywords: sides, the HTC process showed high removal rates of sodium and potassium. It was found that the HTC temper-
Hydrothermal ature resulted in a significant reduction of sodium and potassium in hydrochar as compared to the residence
Carbonization time. The highest removal rate of sodium (70.98%) and potassium (84.05%) was obtained. Overall, the results
Food waste show that the HTC is a promising alternative for conventional technologies (e.g., incineration and landfill) for
Hydrochar treatment and energy conversion of OEFW.
© 2020 Elsevier B.V. All rights reserved.

1. Introduction

As a result of an increasing world population and rapidly developing

industries, the awareness of searching renewable energy sources for re-
⁎ Corresponding author. placing fossil fuels has intrigued by the increasing demand for energy, as
E-mail address: yanmi1985@zjut.edu.cn (M. Yan). well as the serious environmental issues (Hu et al., 2020; Ibrahim and

https://doi.org/10.1016/j.scitotenv.2020.142192
0048-9697/© 2020 Elsevier B.V. All rights reserved.
2 H. Su et al. / Science of the Total Environment 754 (2021) 142192
Akilli, 2019). As the fourth-largest energy resource after coal, oil, and
natural gas in the world, the energy conversion of biomass resource
has been paid more and more attention (Morina, 2015). In China, the
biomass resources that can be used as sources of energy, such as agricul-
tural waste, forest residues and food waste, etc., which are equivalent to
approximately 460 million tons of standard coal annually (Nanda et al.,
2016; X. Zhang et al., 2020). Food waste is mainly obtained from house-
hold kitchens, restaurants, canteens, and food processing industries
(Barik and Paul, 2017), which is regarded as one of the largest groups
of organic solid wastes produced world-wide and the generation rate
is increasing steadily (Elkhalifa et al., 2019; Shen, 2020). Approximately
1.3 billion tons of the edible food is lost or wasted worldwide each year
(Xiong et al., 2019). The treatment of food waste has been the substan-
tial and growing global concern (Kim et al., 2020). Food waste usually
has a high content of lipids, especially in China, the combined pretreat-
ment process of “sorting, solid-liquid separation, oil extraction of liquid
part” was widely used for further biodiesel production (Ban et al., 2016;
Li et al., 2019). During the pretreatment process, the huge amount of
solid phase of food waste is generated, hereinafter called oil extracted
food waste (OEFW). Compared with the original food waste, the
OEFW contains much lower lipid content due to the oil extraction pro-
cess. In addition, after solid-liquid separation, the content of sodium
and potassium in OEFW is lower than original food waste, which is
due to the large amount of alkali/alkaline earth metals exist in the liquid
phase of original food waste. At present, landfill and incineration with
other municipal solid waste are still the main traditional technologies
for OEFW treatment in China (Hong et al., 2017). However, due to the
high moisture content and harmful bacteria in OEFW, these technolo-
gies have some limitations in low processing efficiency, as well as gen-
erating secondary pollution (Su et al., 2020). Therefore, how to
achieve efficient OEFW treatment and energy conversion has become
a major issue in urban environmental management and resource
utilization.
At present, two main energy conversion technologies widely used
for biomass waste, namely, biological and thermochemical conversions
Fig. 1. Technical route of 200 t/d food waste treatment in Hangzhou.
(C. Zhang et al., 2020). Compared with biological method, thermochem-
ical method has advantages of high product yield and treatment effi-
ciency (Zhang et al., 2019). Among thermochemical methods,
hydrothermal carbonization (HTC) has been considered as a promising
technology for high-moisture biomass owing to its unique advantages,
such as the absence of pre-drying process, milder reaction conditions,
fast reaction rates and low energy input (He et al., 2019; Lin et al.,
2016). At relatively low temperature (180–350 °C) and mild pressure
(2–10 MPa) for times ranging from 30 min to several hours, HTC can
convert biomass waste into value-added solid fuel (i.e., hydrochar)
through a series of reaction, such as hydrolysis reaction, dehydration,
decarboxylation and demethanation (Guo et al., 2015; Mumme et al.,
2011; Yao and Ma, 2018). During HTC process, the lower dielectric con-
stant of subcritical water favors the bio-polymers dissociation
(Emmerich, 2011; Ruiz et al., 2013; Suárez et al., 2020). Moreover, the
concentrations of alkali/alkaline earth metals, such as sodium and po-
tassium in some biomass are relatively high, which are responsible for
the furnace corrosion and slagging (Balakrishnan et al., 2015). Yao and
Ma (2019) studied the fate of several alkali/alkaline earth metals of
hydrochars which generated from HTC of Chinese fan palm. They
found that the HTC indicated the positive effect on removal of alkali/al-
kaline earth, but didn't have obvious effect on the removal of the heavy
metals. From an economical point of view, during HTC process, the need
for an energy-extensive pre-drying process involving extra cost is
completely avoided (Pauline and Joseph, 2020). The efficient conversion
of biowastes into solid fuel significantly increases the economic feasibil-
ity of HTC process (Shen, 2020). In addition, HTC also contributes to the
reduction of greenhouse gas emission for climate change mitigation, as
well as some additional socio-economic benefits (Wang et al., 2019a,
2019b).
In recent years, considerable attention has been paid to produce
solid fuel or materials from HTC of wet biomass wastes, such as water
hyacinth (C. Zhang et al., 2020), apple waste (Suárez et al., 2020), sew-
age sludge (Marin-Batista et al., 2020; Xu et al., 2020), microalgae (Liu
et al., 2019) and black liquor (Kang et al., 2012). The main organic
 H. Su et al. / Science of the Total Environment 754 (2021) 142192
components of OEFW are carbohydrates, lignin, protein, lipids (Luque,
2014; Tang et al., 2018), which indicates that it can be regarded as a
plausible resource for bio-fuel production via low-temperature HTC.
Previously, some researchers have studied the HTC of food waste.
Akarsu et al. (2019) carbonized food waste and its digestate in subcrit-
ical water under different operating conditions, and optimal tempera-
ture and duration were obtained. Wang et al. (2018) reported the co-
hydrothermal carbonization of food waste and woody biomass for bio-
fuel pellets production. Saqib et al. (2018) obtained the hydrochar
from HTC of food waste, then studied the co-combustion of hydrochar
and coal with three different ratios (5%, 10% and 15%). They found
that the higher reaction temperature of HTC favored lower activation
energy. As far, most of studies about HTC of food waste mainly focused
on a specific food waste or model mixed food waste. Recently, there are
a limited number of studies on the HTC of real urban food waste, espe-
cially the food waste after oil extraction pretreatment.
Fig. 1 shows the technical route of food waste treatment in Hang-
zhou. The major purpose of this study is to convert OEFW into
hydrochar, which is potentially used as a solid fuel. The specific objec-
tives were to: (1) study the effect of HTC temperature and residence
time on the yield and physicochemical characteristics of hydrochar;
(2) analyze the combustion behavior and thermal characteristics of
hydrochar by TGA and evaluate the feasibility of hydrochar as alterna-
tive bio-fuel; (3) study the effect of HTC temperature and residence
time on the removal behavior of sodium and potassium during the
HTC process. The results and observation obtained in this study is ben-
eficial for comprehensive and deep understanding of HTC of OEFW, es-
pecially for guiding the design of scale up facility and industrial
application.
2. Materials and method
2.1. Experimental materials
The OEFW was collected from a 200 t/d food waste treatment center
in Hangzhou, China, as shown in Fig. 2. Prior to HTC experiments, the
raw OEFW material was pretreated by removing the remaining inor-
ganic impurities, such as stone, waste plastic etc., which may cause in-
consistency of experimental materials. The obtained samples were
dried in a 105 °C oven overnight, then ground and screened through
100 meshes. In the OEFW, the content of cellulose, hemicelluloses, car-
bohydrates, lignin, protein and lipids is 3.12%, 22.76%, 34.21%, 2.68%,
23.28%, and 25.79%, respectively. The chemical characteristics of OEFW
materials are summarized in Table 1.
2.2. Hydrothermal treatment
The experiments of HTC were carried out in a 200 mL Hastelloy
batch reactor which mainly consisted of the electric heater, thermocou-
ples, stirrer, water cooling system and pressure relief valve. The experi-
mental temperature was controlled by with PID-temperature
controller. For each run, the mixture of 10 g feedstock and 100 mL de-
ionized water was loaded into reactor. Prior to the experiments,
Fig. 2. Original sample and hydrochar obtained from HTC process.
3
oxygen-free experimental condition was achieved by purging the reac-
tor with pure N2 (99.99%). The HTC reactor was heated by the electric
heater to reach the setting temperature with a rough heating rate of
10 °C/min. During the whole experimental process, the mixture was
stirred continuously by a magnetic stirrer. After maintaining at the de-
sired HTC temperature (210°С, 240°С, 270°С) for a certain residence
time (30 min, 60 min and 90 min), the reactor was quickly cooled
down to the room temperature by circulating cooling water. After
that, the gaseous product and solid-liquid mixture were collected. The
solid product (hydrochar) was separated using a vacuum filtration ap-
paratus with a 4.5 μm filtering paper. The obtained hydrochars were
dried at 105 °C for 12 h, then ground and screened through 100 meshes
for further analysis. The hydrochar was denoted as “HC-x-y”, in which x
and y represents HTC temperature and residence time, respectively.
2.3. Analytical methods
The elemental composition was determined by Vario EL III elemental
analyzer. The proximate analysis, combustion behavior and thermal
characteristics of hydrochar were determined by a thermogravimetric
analyzer (Discovery SDT 650). The detailed operating methods for prox-
imate analysis could be found in the literature (Gao and Goldfarb, 2019).
The heating process for combustion behavior was programmed as fol-
lows: the sample was heated from room temperature (~25 °C) to
950 °C at a heating rate of 10 °C/min under air atmosphere with a
flow rate of 100 mL/min. The surface morphology of hydrochar was an-
alyzed using field emission scanning electron microscope (FE-SEM,
Hitachi S-4700, Japan). The method of pH measurement reported by
(Liu et al., 2020) was used in this study. The hydrochar was digested
using the HNO3–HF–HClO4 acid digestion method in a PVC vessel prior
to the determination of sodium and potassium concentration by induc-
tively coupled plasma optical emission spectrometry (ICP-OES).
2.4. Product analysis
In order to better understand and evaluate the HTC process charac-
teristic, the process analysis, which were the HHV of hydrochar,
hydrochar yield, energy densification, energetic recovery efficiency
and removal rate of inorganics were calculated by using Eqs. (1)–(5)
as follows:
HHV ðMJ=kgÞ ¼ 0:349C þ 1:1783H
þ 0:1005S−0:1034O−0:0015N−0:0211Ash ð1Þ
where, the C, H, S, O, and N represent the mass percentage of carbon, hy-
drogen, sulful, oxygen, nitrogen elements in dry hydrochar, respec-
tively.
Mass of hydrochar
Hydrochar yield ð%Þ ¼  100 ð2Þ
Mass of feedstock
HHV of hydrochar
Energy densification ð%Þ ¼ ð3Þ
HHV of feedstock
4 H. Su et al. / Science of the Total Environment 754 (2021) 142192

Table 1
Chemical compositions and fuel characteristics of OEFW and hydrochars.

Parameter OEFW HC-210-30 HC-240-30 HC-270-30 HC-270-60 HC-270-90

Ultimate analysisa (wt%)

C 44.06 46.92 47.01 47.12 49.16 51.82
H 6.25 6.15 6.07 5.6 5.92 6.32
N 4.20 3.03 1.91 2.23 2.04 2.00
S 0.31 0.12 0.09 0.14 0.15 0.12
O 32.18 19.19 16.65 13.80 11.21 7.70
H/C 1.702 1.573 1.549 1.426 1.445 1.464
N/C 0.082 0.055 0.035 0.041 0.036 0.033
O/C 0.548 0.307 0.266 0.220 0.171 0.111

Proximate analysis (wt%)

Moisture 1.59 2.80 1.80 1.18 1.68 1.38
VM 80.30 65.27 61.94 59.53 58.48 58.11
FC 5.10 7.32 7.99 8.19 8.32 8.49
Ash 13.01 24.59 28.28 31.11 31.52 32.04
Fuel ratio (FC/VM) 0.064 0.112 0.129 0.138 0.142 0.146
HHV (MJ/kg) 19.16 21.13 21.24 20.97 22.32 24.07
pH 5.46 5.67 5.99 6.58 6.75 6.95
a
On the dry basis.

Energy yield ð%Þ ¼ Hydrochar yield  Energy densification
C f −Ci
Removal rate of element ðREx %Þ ¼  100
Cf
where, x represents the type of element, the Cf and Ci represent the con-
centration of inorganic elements in hydrochar and feedstock,
respectively.
A combustibility index S (%2/°C3·min2) was used as a criterion for
evaluating the combustion characteristic of hydrochar, and was defined
below as Eq. (6):
ðdw =dt Þmax ðdw =dt Þmean
S¼
T i2T b
where, (dw/dt)max and (dw/dt)mean refer to the maximum weight loss
rate and average rates of weight loss, respectively. Ti and Tb stand for
the ignition temperature and burnout temperature, respectively.
3. Results and discussion
3.1. Physicochemical properties of hydrochars
The proximate analysis, ultimate analysis and HHV of hydrochar
produced at various operating condition are summarized in Table 1.
Compared with the raw OEFW, the volatile matter (VM) content in its
hydrochars was lower, and showed a decreasing trend with the increase
of HTC temperature and residence time, while the fixed carbon (FC) and
ash content showed the opposite trend. The minimum VM content
(58.11%) and maximum FC content (8.49%) were obtained in HC-270-
90. The phenomenon was due to the dehydration and decarboxylation
reaction which happened in HTC process. The increase of FC content
was related to the released VM and the mass conversion during HTC
process (He et al., 2013). In addition, it was demonstrated in previous
studies (C. Zhang et al., 2020; Zhuang et al., 2018) that the part of re-
leased VM was also converted into gaseous phase, such as CO2. Similar
findings were also reported in the previous studies (Budyk and
Fullana, 2019; Lin et al., 2015). The fuel ratio (FC/VM) was usually
used to evaluate alternative of a solid fuel (He et al., 2013). As shown
in Table 1, when the residence was 30 min, with the HTC temperature
increased from 210 °C to 270 °C, the fuel ratio prominently increased
by 30.36% from 0.112 to 0.146, which was attribute to the increase of
FC and decrease of VM. When the residence time is lengthened to
90 min at 270 °C, the fuel ratio reached to 0.146 which was 128.13% in-
crease in comparison to the raw OEFW.
ð4Þ As shown in Table 1, the HTC temperature and residence time also
showed obvious effect on elemental composition of hydrochar. After
carbonization process, the carbon content in produced hydrochar was
ð5Þ
higher than raw OEFW. In order to evaluate the coalification degree of
the hydrochars, the atomic ratio of H/C and O/C were calculated and vi-
sualized in Van Krevelen diagram (Fig. 3), which shows the clear chem-
ical transformation of carbon into carbon-rich product during the HTC
process. In addition, the H/C and O/C atomic ratios of three typical
solid fuels, i.e., anthracite, coal, and lignite were exhibited in Fig. 3 for
comparison. As shown in Table 1, the obtained hydrochars from HTC
process exhibited lower H/C and O/C atomic ratio than the values in
the raw OEFW. Liu et al. (2013) reported that the low H/C and O/C
atomic ratio favored decreasing smoke and water vapor releasing dur-
ð6Þ
ing the hydrochar combustion. It is clearly known from Fig. 3 that the
decarboxylation and dehydration were the dominant reaction path-
ways during HTC of OEFW. When the reaction temperature increased
from 210 °C to 270 °C, the H/C and O/C atomic ratio showed a steady re-
duction and the position was closer to lignite regions, while the increas-
ing residence time presented slight effect on H/C atomic ratio.
Additionally, the relationship between N/C and O/C atomic ratios
under different HTC temperature and residence time was showed in
Fig. 3. Compared with the raw OEFW, lower N/C atomic ratio was ob-
tained in its hydrochars. According to the Fig. 3, it can be known that
the evolution of N/C and O/C atomic ratios from OEFW to hydrochars
followed the paths of reduction and denitrogenation.
Moreover, HHV is also an important characteristic of hydrochar,
which represents the amount of heat released from fuel combustion.
As shown in Table 1, the HHV was increased from 19.16 MJ/kg
(OEFW) to 21.13–24.07 MJ/kg (hydrochar), which were higher than
that of conventional lignite (15–20 MJ/kg) (Akkaya, 2013). The similar
observations were found in HTC of red seaweed (Cao et al., 2019),
olive wastes (Surup et al., 2020), cabbage (Theppitak et al., 2020), etc.
During the HTC process, the cleavage of low-energy chemical bonds
and the formation of high-energy chemical bonds may lead to the in-
crease of HHV (C. Zhang et al., 2020). During the HTC process, compared
with lignin, the cellulose and hemicellulose were easier to be
decomposed completely. In addition, due to the higher HHV of lignin,
the hydrochars with high HHV were obtained.
The pH values of all the hydrochars are showed in Table 1. The pH
value of OEFW were mildly acidic (5.46), which might be related to
the high content of rot or deteriorated fruit in the OWFW samples col-
lected from food waste treatment center. It could release various or-
ganic acids during pretreatment process (Zan et al., 2018). Compared
with the OEFW, the pH value of HC-210-30 presented a slight increase.
With the HTC temperature increased, the pH value of hydrochar
 H. Su et al. / Science of the Total Environment 754 (2021) 142192
Fig. 3. The H/C, N/C and O/C ratio of raw OEFW and hydrochars.
obviously increased, which was attributed to the further decomposition
of the organic acids at relatively higher temperature (Ghanim et al.,
2016). These phenomena were consistent with results reported by (Fu
et al., 2019). In addition, the residence time did not show a significant
effect on the change of pH value.
3.2. SEM analysis
SEM images of samples were presented to study the surface mor-
phology and physical structure change of hydrochars derived from
HTC process of OEFW with different temperature and residence time.
As shown in Fig. 4, the SEM images of the raw OEFW exhibits a relatively
well-defined and smooth surface structure. After HTC process, signifi-
cant changes on the surface morphology of hydrochars can be found.
Compared with the raw OEFW, HC-210-30 had rougher surface mor-
phology, and the degree of roughness increased with the increase of
temperature and residence time, which could be attributed to the en-
hanced decomposition reaction (C. Zhang et al., 2020). As shown in
Fig. 4(d–f), it could be found some cracks at HC-270-30, HC-270-60,
HC-270-90, which was likely due to the release of volatiles and gases
during HTC process (Zhao et al., 2017). With increasing the HTC temper-
ature, due to the decrease of water molecules polarity, the miscibility
between small organic compounds and high temperature water solvent
5
was promoted, which led to more small fragments presented on the
surface of hydrochars (Akiya and Savage, 2002; Chen et al., 2018). In ad-
dition, the monomer decomposition of the complex macromolecules
such as carbohydrates, proteins, and lipids may cause the surface struc-
ture transformations (Saqib et al., 2018).
3.3. Hydrochar yield and energy yield
The OEFW was subjected to HTC process at different reaction tem-
peratures (210–270 °C) and residence times (30–90 min). The effect
on hydrochar yield and energy yield are shown in Fig. 5. When the de-
sired residence time was 30 min, with the HTC temperature increased
from 210 °C to 270 °C, the hydrochar yield exhibited a decreasing
trend. It was ascribed to that the higher HTC temperature enhanced
the hydrolysis, dehydration and decarboxylation happened during
HTC process (Zhao et al., 2014). Moreover, it is worth mentioning that
the decreasing degree of hydrochar yield at the HTC temperature
range of 240–270 °C was smoother than that of the range of
210–240 °C. As mention above, the hemicelluloses and cellulose in
OEFW are easier degraded during HTC because of their low hydrolysis
temperature, which was 180–200 °C and above 220 °C, respectively
(Li et al., 2020). Therefore, when the reaction temperature increased
to 250 °C, most of hemicellulose and cellulose in OEFW had been
decomposed into glucose and xylose, while the lignin began to decom-
pose slowly, leading to the slower decrease rate of hydrochar yield
(Wang et al., 2020). On the other hand, as shown in Fig. 5, with increas-
ing residence time from 30 min to 90 min at a certain reaction temper-
ature of 270 °C, the hydrochar yield decreased by 5.51%. This might be
explained by the fact that after the reaction temperature reached the
desired value, the OEFW which has complex composition would be ex-
pected to require long residence time for completing thermal decompo-
sition reactions. Nevertheless, the results indicated that the residence
time showed not significant effect on hydrochar yield.
Based on the above discussion about HHV, and Eq. (3), the energy
densification exhibited the same trend with HHV. As shown in Fig. 5,
the minimum (1.24) and maximum (1.42) energy densification were
obtained at the operating condition of 210 °C, 30 min and 270 °C,
90 min, respectively. Besides, with the HTC increased from 210 °C to
270 °C, the energy yield decreased by 20.48% from 56.31% to 44.78%,
which was ascribed to the higher hydrochar yield at 210 °C though
the energy densification was lower. Nevertheless, when the HTC tem-
perature was 270 °C, with the residence time increased from 30 min
to 90 min, the energy yield increased by 8.44%, which was due to the
slight decrease of hydrochar yield and remarkable increase of energy
densification.
3.4. Combustion behavior and thermal characteristics of hydrochar
The TG and DTG curves of OEFW and hydrochars obtained from dif-
ferent HTC conditions are presented in Fig. 6. The combustion character-
istic parameters are shown in Table 2. The tangent intersection method
as reported in GB/T 33304-2016 was used to determine the ignition
temperature (Ti), maximum combustion rate temperature (Tm), and
burnout temperature (Tb). According to the weight loss rate at different
temperature in DTG curves, the combustion profile of OEFW and
hydrochars was divided into two stage, namely the devolatilization
and combustion (stage I), and the char combustion (stage II). The
(dw/dt)max1 and (dw/dt)max2 refer to the maximum weight loss rate
in stage I and stage II, respectively. The Tm1 and Tm2 refer to the maxi-
mum combustion rate temperature in stage I and stage II, respectively.
As shown in Fig. 6, compared with hydrochars, the DTG curve of
OEFW showed a wider covering range of Stage I. Moreover, the weight
loss peak in stage I gradually flattened out with the HTC and residence
time increasing. The highest (dw/dt)max1 was found in the DTG curve
of OEFW. These observations might be due to the high VM content in
the raw OEFW, and the decomposition of cellulose and hemicellulose
6 H. Su et al. / Science of the Total Environment 754 (2021) 142192

Fig. 4. SEM images of OEFW and hydrochars obtained from different operating conditions: (a) OEFW; (b) HC-210-30; (c) HC-240-30; (d) HC-270-30; (e) HC-270-60; (f) HC-270-90.

during HTC process (Gao et al., 2016; Liu et al., 2018). Nevertheless, for
the stage II, compared with OEFW, the Tm2 of hydrochars was higher,
which were attributed to the increase of FC content in hydrochars. Com-
pared with other hydrochars, the HC-270-90 presented the highest
(dw/dt)max (9.51%/min) and (dw/dt)mean (2.78%/min) due to the
highest FC content in HC-270-90. For the ignition characteristics of
fuel, the oxygen and VM content are the key factors. It can be seen
from Table 2 that the Ti of hydrochars was higher than OEFW. In addi-
tion, with the HTC temperature increased from 210 °C to 270 °C, the Ti
of hydrochar increased from 343.4 °C (HC-210-30) to 365.2 °C (HC-
270-30), which was attributed to the decrease of VM content in
hydrochar. Likely, when the HTC temperature was 270 °C, the HC-270-
90 showed the highest Ti. The observation had a good agreement with
the result of proximate analysis as mentioned in Table 1. Compared
with the Ti of lignite (300–400 °C), bituminous coal (400–550 °C), and an-
thracite bituminous coal (550–700 °C) (Zhang, 1981), the Ti of HTC
hydrochars in this study was closed to lignite. Xu and Sheng (2012) re-
ported that high Ti was expected to minimize potential fire and explosion
risks of fuel. Therefore, hydrochars obtained from HTC of OEFW have bet-
ter performance on the safe handling, storing and transportation. In addi-
tion, with the increase of HTC temperature, the Tb also increased.
Consequently, the increase of Ti and Tb indicates that HTC process is

Fig. 5. Effects of HTC temperature and residence time on energy densification, hydrochar yield and energy yield.
 H. Su et al. / Science of the Total Environment 754 (2021) 142192 7

Fig. 6. The TGA and DTG curves of OEFW and its hydrochars (Stage I: devolatilization and combustion, Stage II: char combustion).

Table 2
Combustion parameters of OEFW and its hydrochars.

Sample Ti Tb Tm1 (dw/dt)max1 Tm2 (dw/dt)max2 (dw/dt)mean S (%2/°C3·min2)

(°C) (°C) (°C) (%/min) (°C) (%/min) (%/min)

OEFW 311.3 520.7 322.2 3.93 465.7 7.33 2.31 3.75 × 10−7
HC-210-30 343.4 521.8 339.2 3.47 484.9 8.85 2.45 3.52 × 10−7
HC-240-30 362.4 535.6 260.4 2.33 496.2 7.83 2.53 2.83 × 10−7
HC-270-30 365.2 550.2 271. 9 1.65 504.2 7.21 2.56 2.52 × 10−7
HC-270-60 368.1 553.6 268.6 1.46 507.5 7.85 2.58 2.71 × 10−7
HC-270-90 384.5 542.3 260.1 1.32 501.5 9.51 2.78 3.29 × 10−7
8 H. Su et al. / Science of the Total Environment 754 (2021) 142192
beneficial to improve the combustion temperature of hydrochar and pro-
long the combustion process. Additionally, the combustibility index S of
OEFW was higher than hydrochars, which was related to the highest
VM (80.3%) in raw OEFW. In the previous studies, Chen et al. (2018)
also obtained the hydrochars with lower combustibility index S from
HTC of organic waste. To the best our knowledge, VM could improve
the flame burning and reaction activity, leading to unstable flame during
fuel combustion process, which may contribute to a large heat loss (He
et al., 2013). Thus, based on the above observation, it could be concluded
that the OEFW can be converted into the solid fuel with more stable flame
by HTC process.
3.5. The removal behavior of sodium and potassium
The existence of high-content sodium (Na) and potassium (K) may
cause furnace corrosion and they would lower the melting tempera-
tures (Teixeira et al., 2012). In order to investigate the removal behavior
of sodium and potassium of OEFW during HTC process, Fig. 7 shows the
content of sodium and potassium as well as their removal rate analyzed
by ICP-OES. The element content is the ratio of sodium and potassium
mass in samples to the mass of samples. It could be seen from Fig. 7,
the sodium content (1230 mg/kg) in the raw OEFW was much higher
than potassium content (514 mg/kg), which owing to the abundance
of sodium-containing food additives in the OEFW, such as NaCl,
NaCO3, NaHCO3. After hydrothermal treatment, compared with the
raw OEFW, the sodium and potassium content had a remarkable de-
crease in hydrochar. When the temperature was 210 °C, the removal
rate of the sodium and potassium was 58.62% and 77.43%, respectively.
The observation indicated that HTC process had a promising method for
removal of sodium and potassium from OEFW, which could be ex-
plained that the presence of subcritical water acted as a reacting me-
dium during HTC reaction, and the sodium and potassium with high
solubility contained in OEFW can be leached into the liquid phase (Lin
et al., 2015). In addition, with the HTC temperature increased from
210 °C to 270 °C, the removal rate of sodium and potassium increased
by 13.44% and 6.53%, respectively. The results indicated that higher tem-
perature enhanced the removal ability of sodium and potassium in
OEFW, which was related to that the potassium and sodium possessed
a higher affinity with the liquid phase at higher HTC temperature
(Wang et al., 2019a, 2019b). Nevertheless, when the temperature was
270 °C, the removal rate of sodium and potassium exhibited a slight
change trend with increasing the residence time. Compared with the
Fig. 7. The removal behavior of sodium and potassium of hydrochars during the HTC process.
raw OEFW, HTC-270-60 showed the highest removal rate of sodium
(70.98%) and potassium (84.05%).
4. Conclusion
In this work, the OEFW sample was collected from a 200 t/d food
waste treatment center in Hangzhou, and was utilized in HTC for solid
fuel conversion. The effects of various operating parameters including
HTC temperature and residence time were investigated. The main con-
clusions that can be established from this work are as follows:
(1) The carbon contents of hydrochars increased to 46.92–51.82%
after HTC at various operating conditions, while the oxygen con-
tents decreased to 7.70–19.19%.
(2) Compared with the raw OEFW, the obtained hydrochars proc-
essed lower VM (58.11–65.27%), higher FC (7.32–8.49%), higher
HHV (21.13–24.07 MJ/kg) and higher fuel ratio (0.112–0.146).
(3) The thermogravimetric analysis showed that the hydrochar had
more stable and longer combustion process with the higher igni-
tion temperature and burnout temperature.
(4) The HTC process contributed to the high removal rate of sodium
and potassium. Higher HTC temperature had relatively remarkable
effect on the improvement of the removal of sodium and potas-
sium, while the residence time had slight effect. The highest re-
moval rate of sodium (70.98%) and potassium (84.05%) was
obtained.
CRediT authorship contribution statement
Hongcai Su: Investigation, Methodology, Data curation, Writing -
original draft. Xuanyou Zhou: Investigation, Methodology, Data
curation. Rendong Zheng: Writing - review & editing, Methodology.
Zhihao Zhou: Resources, Investigation. Yan Zhang: Investigation,
Data curation. Gaojun Zhu: Resources, Investigation. Caimeng Yu: In-
vestigation, Methodology. Dwi Hantoko: Writing - review & editing.
Mi Yan: Conceptualization, Writing - review & editing, Supervision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
 H. Su et al. / Science of the Total Environment 754 (2021) 142192
Acknowledgement
The authors appreciate the financial support from the National Nat-
ural Science Foundation of China (51976196) and National Interna-
tional Cooperation Project, China (2017YFE0107600 and
2016YFE0202000), International Cooperation Project of Zhejiang Prov-
ince (2019C04026).
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