Bioresource Technology 282 (2019) 28–36

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Hydrothermal carbonization of Chinese fan palm T

Zhongliang Yao, Xiaoqian Ma
⁎

Guangdong Key Laboratory of Efficient and Clean Energy Utilization, School of Electric Power, South China University of Technology, Guangzhou 510640, People’s
Republic of China

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Keywords: This study provided a detailed observation on hydrothermal carbonization (HTC) of Chinese fan palm. The
Hydrothermal carbonization heating value and chemical exergy was calculated. As the reaction severity increased, both heating value
Chinese fan palm (18.84–27.61 MJ/kg) and chemical exergy (21.07–29.06 MJ/kg) had increase trend. The effect of temperature
Biomass upgrading on HTC process was more significant than residence time. Due to the dehydration and decarboxylation, the O/C
Combustion characteristics
and H/C atomic ratios decreased gradually. However, the N/C ratio was not linear change. When the tem-
perature was 240 °C, and reaction time was above 60 min, the fuel properties of hydrochar were close to lignite.
The water uptake rate (7.22–3.59%) also had very decreased trend. The SEM and XRD analysis showed the
surface morphology of hydrochar treated at 240 °C much differed from that of raw sample, the structure is
partially destructed. Combustion characteristics of CFP and hydrochar was detected, the 180–60 had optimal
combustion characteristics.

1. Introduction
With the speeding up of China’s urbanization process, biomass
waste disposal has become a thorny issue. Every year about 10 million
tons waste biomass were produced. For a long time, there were no laws
and regulations to deal with these waste products in China. In southern
china, the china fan palm (CFP) is the most widely spread plant. The
huge dead leaves which are the main component of biomass wastes are
difficult to deal with. Meanwhile, there existed much moisture, and
alkali/alkaline earth metals in the CFP, which cause severe fouling and
agglomeration inside combustion boilers (Liu et al., 2013). What’s
more, direct combustion of CFP can cause a large amount of fly ashes,
leading to the air pollution. Thus, how to make use of the dead leaves of
CFP is a major problem affecting the sustainable development of urban
environment. The conversion of the huge dead leaves to value-added
fuel for combustion or activated carbon (Laginhas et al., 2016) might be

⁎
Corresponding author.
E-mail address: epxqma@scut.edu.cn (X. Ma).

https://doi.org/10.1016/j.biortech.2019.02.130
Received 24 January 2019; Received in revised form 20 February 2019; Accepted 21 February 2019
Available online 01 March 2019
0960-8524/ © 2019 Elsevier Ltd. All rights reserved.
Z. Yao and X. Ma Bioresource Technology 282 (2019) 28–36

a viable CFP treatment scheme in order to reduce fossil energy con- province, was adopted as parent feedstock. Dirt and impurities on the
sumption as well as energy efficient utilization. Up to now, there are leaves of were washed off. The washed CFP samples were ground using
two main conversion technologies widely used for biomass wastes, a small grinder and screened small size less than 178 μm for HTC. The
namely, thermochemical and biological conversions. Compared with screened particles were dried in an oven at 105 °C for 24 h.
biological conversion, thermochemical treatment has several ad-
vantages of high product yields and short processing times. Among 2.2. Hydrothermal carbonization
thermochemical conversion methods, direct combustion, co-combus-
tion and pyrolysis are widely studied, as these methods are very mature, The HTC experiments of CFP were carried out by using an autoclave
and have the high potential among short term options for realizing 250 ml reactor which has reported in our previous paper (Yao et al.,
biomass energy utilization (Lin et al., 2016). However, the wide di- 2016c). The reactor was filled with 8 g of completely mixed CFP and
versity of physical shapes, compositions and energy densities serious 150 ml of deionized water. Before each experiment, a large amount of
challenges in sizing, transportation and storage of feedstocks (Liu et al., nitrogen is injected into the reactor to isolate the air. According to our
2013). Season changes also have influence on the availability of bio- previous paper (Lin et al., 2015; Yao et al., 2016c), the maximum en-
mass feedstocks. To solve the problem, it is important to pre-treat or ergy recovery efficiency was obtained at the HTC temperature of
modify the biomass feedstock prior to combustion to homogenize dif- ∼210 °C. In this paper, relatively low reaction temperature was se-
ferent biomass feedstocks. In this way, hydrothermal carbonization lected. The reactor was heated up to the desired temperature (180, 210
(HTC) provides environmental, social and economic benefits of biomass and 240 °C) and maintained for a designated residence time (30, 60,
energy. Furthermore, the HTC process can greatly move the alkali and and 100 min). The stirring rate was set to 500 rpm throughout the re-
alkaline earth metals (Lin et al., 2015). Compared with combustion and action process. After reaction, the reactor was rapidly cooled to ambient
pyrolysis, the HTC has great advantages of mild reaction condition and temperature with air and water. The collection of the solid, liquid and
low energy input (Lin et al., 2016). So, HTC is a good scheme to convert gas products was reported in our previous paper (Lin et al., 2016). After
biomass feedstock into high performance fuel or other upgraded solid complete reaction, the pressure relief valve was open and the reactor
products. The CFP has enormous potential as a feedstock to produce was immediately cooled to room temperature, and the gaseous products
hydrochar. were collected in an aluminum foil gas collecting bag. The liquid pro-
In the past few years, considerable attention has been paid to pro- ducts and hydrochar were separated by filtration through a pre-
duce hydrochar from HTC of wet waste biomass, such as moist agro- weighted filter paper, then dried in dry oven at 105 °C for 12 h. The
industrial wastes (Benavente et al., 2015), food waste, municipal solid hydrochars were marked as ‘xxx-xx’ in accordance with HTC tempera-
waste (Lu et al., 2011) and sewage sludge (He et al., 2013; Zhai et al., ture (°C) and residence time (min), respectively. The fraction dissolved
2016). Because of its simplicity to perform, the elimination of an en- in the aqueous phase was recovered as a solid referred as stable liquid
ergy-extensive drying process, the wide availability of raw materials, fuels (SLF) through drying oven at ∼105 °C to completely remove the
and fewer greenhouse gas emissions, HTC has been suggested as a re- water. Like the asphaltene in the oil industry, the dark brown color
latively novel and promising technique to treat high-moisture solid presented a visual demonstration of intrinsic properties.
materials (Kambo and Dutta, 2015). HTC occurs at relatively low
temperatures (180–280 °C) under autogenous pressures in hot com- 2.3. Fuel analysis
pressed liquid water for times ranging from 30 min to several hours
simultaneously generating gas, a liquid phase, and a carbon-rich solid To understand the HTC process characteristics and optimum ex-
residue. The HTC process mainly contains dehydration, decarboxyla- perimental conditions for the energy balance, the High heating value
tion and demethanation reaction (Guo et al., 2015). During HTC, vo- (HHV) (MJ/kg), low heating value (LHV) (MJ/kg), Chemical exergy
latile oxygen-rich compounds of biomass are removed from the struc- (MJ/kg) were calculated by the following Eqs (Channiwala and Parikh,
ture, leaving behind stable carbon-rich micro–nano particles 2002; Song et al., 2012; Zhang et al., 2018):
(hydrochar). After HTC, the specific surface area and oxygen-containing
HHV = 0.3491Cm + 1.1783Hm 0.1034Om 0.0151Nm 0.211Ash (1)
functional groups of hydrochar were had significant increase (Jain
et al., 2016). The hydrochar has the wide application in many fields. It LHV = HHV 21.978Hm (2)
is a good raw material which can be used as premium fuel, activated
where Cm, Hm, Om, Nm are the mass percentages for C, H, O and N,
carbon and soil remediation agent (Hoekman et al., 2011; Huang and
respectively.
Yuan, 2016; Laginhas et al., 2016).
Chemical exergy can be expressed as follows (Guo et al., 2017;
Up to date now, though as a typical biomass in southern china, few
Peduzzi et al., 2016):
papers are available about hydrochar production from HTC of CFP with
the specific intention of solid fuel and other application. Nowadays, CE = LHV (3)
many authors have studied hydrothermal carbonization of other bio-
where is a proportional value and can be calculated as the form
mass (Parshetti et al., 2013; Yao et al., 2016c, 2017). In this study, the
below:
HTC of CFP and mass balance were studied. Effects of temperature and
time on product characteristics were comprehensive evaluated through
parametric analysis. The structural and morphological properties were biomass =
1.0412 + 0.2160· Cm
H
m
O
(
0.2499· Cm · 1 + 0.7784· Cm
m
H
m )
investigated. The metals removal and accumulation behavior during
N
+ 0.0450· Cm
m
the HTC were investigated. The results obtained in this paper could lead
to deeper understanding of hydrothermal carbonization CFP and pro- Om
/ 1 0.3035·
vide reference for the resource utilization of it. From the perspective of Cm (4)
efficient energy use, the HTC of CFP seems to be a feasible solution. Hm O N
= 1.0437 + 0.1896· + 0.0617· m + 0.0428· m
hydrochar
Cm Cm Cm (5)
2. Materials and methods

2.1. Materials 2.4. Analytical methods

In this study, as the main part of the plant, the huge dead leaves of The gaseous phase composition was quantitatively analyzed using a
CFP purchased from the urban district of Guangzhou, Guangdong gas chromatography system (Agilent 7890B) that was equipped with a

29
Z. Yao and X. Ma
thermal conductivity detection (TCD) device. The elemental composi-
tion was determined by an Elementar (Vario EL cube). Proximate
analysis and decomposition behavior of solid products were performed
using an Industrial analyzer (Henan Hengke). The proximate analysis
and ultimate analysis were tested according to National Standard in
China GB/T 28731-2012 and General rules for elemental analyzer JY/T
017-1996, respectively. The Fourier transform infrared (FTIR) spec-
trometry (Nicole, Model iS10) was employed to analyze various func-
tional groups contained in the samples. The FTIR spectra were collected
using a mixture of sample and KBr in a sample/KBr ratio of 1:100. FTIR
spectra were recorded from 4000 to 500 cm−1 by the software OMNIC.
The thermogravimetric analysis was carried out by the thermal ana-
lyzer (TGA, METTLER TOLEDO). The flow rate of the gas mixture was
80 ml/min, which was adopted the air atmosphere. The experiment
temperature remained at 105 °C for 3 min to remove moisture, and then
increased to 650 °C at a heating rate of 20 °C/min. Bruker D8 ADVANCE
X-ray diffractometer (XRD) was used to measure the samples. The test
conditions were as follow: Cu Kα radiation (1.5418 nm), the generator
voltage of 40 kV, the generator current of 40 mA, the scanning range of
5–50°. The water uptake rate test was conducted in the air condition
room of the humidity of 60%, the weight of the samples is recorded by
every hour, until the weight is constant.
2.5. ICP-OES analysis
Metal elements in the samples was detected in an Inductively
Couple Plasma – Optical Emission Spectrometry (ICP-OES, Agilent
Technologies Co. Ltd, U.S.A) after microwave digestion. The super-
natant was detected because there still existed precipitation.
The following equations was used to calculate the fate of metal
elements:
The enrichment rate/removal rate = (1 Chydrochar /Craw ) × 100% (6)
where Chydrochar and Craw were the contents of hydrochars and the raw
samples, respectively. When the Chydrochar is higher than that of Craw, it
presents the enrichment phenomenon. However, the Chydrochar is lower
than that of Craw, it presents the removal phenomenon.
3. Results and discussion
3.1. Gross product distributions
The HTC process included hydrolysis of cellulose, hemicellulose and
lignin. Then, with the dehydration, radical reaction and fracture of CeC
bonds, many intermediate products (acids, alcohols, furfurals and al-
dehydes), gas and liquid products have been produced. Simultaneously,
the hydrochar formatted through aromatization, condensation, and
solid–solid reaction (He et al., 2018; Kumar et al., 2018).
The gross product distributions were shown in Fig. 1a, with the
reaction temperature and residence time increasing, the proportion of
hydrochar were decreased, while more and more feedstock was dis-
solved in aqueous phase in the form of bio oil. The composition of SLF is
properly stable oxygenated compounds, for instance, furfurals, phenols,
sugars, acids and lignin derivatives (Liu et al., 2018; Mazar et al.,
2018). However, during the recovery of SLF from water, some small
molecules, such as ketones, formic acid and the water from in-
tramolecular dehydration may volatilize from the aqueous phase. This
part was defined as mass loss. In addition, the gas evolved from the HTC
and mass loss also had the increase trend, due to degradation, dehy-
dration and CeC bond fracture of the CFP. Fig. 1b showed the gas
products in different experimental severities by gas chromatography.
The results showed that CO2 and CO were the dominant gaseous spe-
cies, which occupied ＞95% of the volume. This revealed that dec-
arboxylation reaction occurred during the HTC of CFP. At 210 °C,
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Bioresource Technology 282 (2019) 28–36
almost all the gas products were composed of CO2 (∼90%) and CO.
When the temperature increased to 240 °C, the CO2 production de-
creased significantly while the CO production increased. This phe-
nomenon could be concluded that the decarboxylation reaction oc-
curred at relative low temperatures, while high temperatures tended to
favor decarbonylation. Most oxygen atoms were removed via dehy-
dration and decarboxylation reactions. The existence of a small amount
H2 is attributed to the aromatization of hydro aromatic compounds in
lignin. The remaining gas was mostly CH4, especially for 240 °C. This
suggested that the demethylation reaction only occurred at relative
high temperature. Generally speaking, the gas products occupied small
proportion (∼5%) in the gross products (Lin et al., 2017a).
3.2. Ultimate and proximate characteristics
As shown in Table 1, fixed carbon (FC), ash and volatile matter
(VM) content had a slight change. Due to dehydration and decarbox-
ylation reactions in HTC process, VM content declined from 80.4% to
68.54%, while the FC and Ash content respectively increased from
15.43% to 23.19% and 4.17% to 8.27%, with the increasing of tem-
perature and residence time. The similar phenomenon were also re-
ported in the previous literature (Kang et al., 2012). As we know, ash
played the main role of the slag in the combustion boiler due to the high
contents of alkali metals and alkali earth metals, so the appropriate
reaction conditions need to be chosen. Due to the decomposition,
cracking and then extraction of oxygenated components, the oxygen in
CFP diminished (Kambo and Dutta, 2015; Mau et al., 2016). Mean-
while, the fuel ratio significantly increased from 0.20 to 0.34 as the
reaction temperature and time rose, which is an important parameter to
evaluate of the fuel properties. As shown in Table 2, The HHV and
chemical exergy increased from 20.44 to 29.41 MJ/kg and 21.07 to
29.06 MJ/kg, with a great promotion of 43.88% and 37.92%, respec-
tively. For all hydrochar samples, the rise in the carbon and hydrogen
concentrations led to the overall increase of heating value (Escala et al.,
2013). On the other hand, lignin has the highest thermal stability
among the three model compounds (cellulose, hemicellulose and
lignin) of biomass, which was not easy to be decomposed. The high
lignin content of hydrochar also led to the higher heating value. The
HHV of lignin (∼26 MJ/kg) was the highest among three model com-
pounds followed by hemicellulose and cellulose in between that of
17–18 MJ/kg (Kambo and Dutta, 2015). Meanwhile, as the HTC tem-
perature was between 180 °C and 210 °C, the nitrogen content declined.
And then it was increased, when the temperature was up to 240 °C. The
change trends of nitrogen content did not have simple linear relation-
ship with the reaction severities. This could be due to the compromise
effect of the increased partitioning of nitrogen into aqueous phase when
operation conditions became severer in certain ranges. The Ref (Yao
et al., 2016a,b) had reported that most of the nitrogen recovered was of
organic form (i.e. Amino acid), and the rest was composed of NH4+ and
NO3 . Nitrogen was one of the plant nutrient elements when the hy-
drochar was used for soil application. However, though the nitrogen
content is small, it also led to serious air pollution as the terms of NOx
when the hydrochar was adopted as fuel.
In general, HTC process mainly includes the process of dehydration,
decarboxylation and demethanation. However, dehydration was
thought be the dominant reaction during HTC. As shown in Fig. 2a,
several kinds of coals, wood, lignin and cellulose position were listed as
a comparison via a van krevelen diagram. The H/C ratio of raw CFP was
higher than cellulose, while the O/C ratio was between wood and
lignin. From 210 °C to 240 °C, H/C and O/C atomic ratios had a large
mutation. It indicated that during 210–240 °C, the hemicellulose and
cellulose in CFP were hydrolyzed, depolymerized and degraded very
rapidly, and almost of them disappeared at the higher temperature.
However, even the lowest obtained values (H/C of 1.47 and O/C of
Z. Yao and X. Ma
Fig. 1. (a) Gross products distributions and (b) gaseous phase composition proportion (%) under different HTC conditions.
0.18) were slightly away from the natural lignite range, namely, H/C of
around 0.8–1.3 and O/C of around 0.2–0.38, as reported in literature
(Escala et al., 2013). Though torr faction can process a large amount of
biomass, without any introduction of medium, the greater coal-like
behavior and increased energy density of hydrochar used as value-
added fuel reflected an important advantage of the HTC process. Fig. 2b
reflects the relationship between the O/C and the N/C by a two-di-
mensional scatter plot, it was can be seen that the hydrochar of
180–100 and 240–100 had the relatively higher N/C ratio of 0.095 and
0.094 among all the hydrochars, revealed the N/C trends didn’t linear
changed with the O/C ratio. The hydrochar of 240–30 revealed that
superior fuel properties through a comprehensive consideration of H/C,
O/C, N/C and HHV.
In addition, the water uptake rate was detected. It was very inter-
esting to see the water uptake rate of raw CFP become constant when
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Bioresource Technology 282 (2019) 28–36
the exposure time is 5 h, and reached a value of 7.29%. However, the
hydrochar of 180–30, 180–100, 210–30 and 240–100 had low stabili-
zation time when the exposure time is 1 h. It revealed that hydrophobic
effect of hydrochar greatly increased. Compared with the hydrochar
180–30, the water uptake rate of hydrochar 180–100 had a slightly
decreased trend. The hydorchar 240–100 had lowest water uptake rate
(∼3.5%). This phenomenon indicated the temperature and residence
time both had effect on enhancing hydrophobicity.
3.3. Structural properties of hydrochar
After HTC, significant changes on the surface morphology can be
found at different reaction severities. These SEM microphotographs
revealed the changes between the raw materials and the upgraded solid
products, showing disruption of physical structures and formation of
Z. Yao and X. Ma Bioresource Technology 282 (2019) 28–36

Table 1 Table 2
Chemical properties of CFP and hydrochars on dry basis. Thermal dynamic properties of CFP and hydrochars.
Sample Ultimate analysis/wt% Proximate analysis/wt% Fuel Sample Atomic HHV LHV CE
ratioc
a b
C H O VM FC Ash H/C O/C N/C (MJ/kg) (MJ/kg) (MJ/kg)

CFP 48.99 7.26 36.06 0.66 77.20 15.78 7.02 0.20 CFP 1.78 0.55 0.0115 20.44 18.84 21.07
180–30 55.20 7.74 32.34 0.55 80.40 15.43 4.17 0.17 180–30 1.69 0.44 0.0085 24.16 22.46 23.23
180–60 55.90 7.62 30.79 0.60 79.94 14.97 5.09 0.19 180–60 1.64 0.41 0.0092 24.23 22.55 23.36
180–100 56.81 7.67 29.42 0.63 79.37 15.17 5.47 0.20 180–100 1.62 0.39 0.0095 24.66 22.98 23.85
210–30 57.27 7.71 28.81 0.55 78.00 16.34 5.66 0.19 210–30 1.62 0.38 0.0082 24.90 23.20 24.10
210–60 58.05 7.75 28.08 0.50 76.66 17.72 5.62 0.23 210–60 1.60 0.36 0.0074 25.30 23.60 24.53
210–100 59.56 8.03 25.36 0.53 75.72 17.77 6.51 0.24 210–100 1.62 0.32 0.0076 26.25 24.49 25.55
240–30 61.91 8.00 23.17 0.57 74.77 18.88 6.35 0.25 240–30 1.55 0.28 0.0079 27.29 25.54 26.70
240–60 64.05 8.02 19.40 0.65 70.84 21.28 7.89 0.30 240–60 1.50 0.23 0.0087 28.13 26.37 27.66
240–100 66.52 8.17 16.31 0.73 68.54 23.19 8.27 0.36 240–100 1.47 0.18 0.0094 29.41 27.61 29.06

a
By difference: O% = 100% − C% − H% − N% − ash%.
b
By difference: Fixed carbon% = 100% − volatile matter% − ash%.
c
Fuel ratio = fixed carbon/volatile matter.
3.4. FTIR analysis of SLF

FTIR analysis was adopted to analyze the functional group char-

individual grains in the products. Apparently, the HTC broke the
structure of the CFP and converted them into smaller uniform particle
products. These changes presented a visual demonstration of sub-
stantial change in intrinsic properties (Kim et al., 2012). Although
considerable microspheres could be clearly seen on the surface of the
hydrochar treated at 240 °C, the hydrochar treated at 180 °C was with
the similar structure to the parent material. The surface morphology of
hydrochar 240–30 differed from that of raw sample, the structure was
partially destructed. There existed obvious structure of pores. Many
microspheres were found on the surface of hydrochar 240–30. The
formation pathway of hydrochar treated at 240 °C may be pre-
dominated by polymerization reaction after hydrolysis due to partial
degradation of the cellulose (Guo et al., 2015). As for the hydrochar
240–100, the cellulose may be almost degraded completely and rough
fragment was left. It is found that most of the lignin was difficult to
dissolve into aqueous phase below 265 °C (Kang et al., 2012). There-
fore, this rough fragment was probably non-dissolved lignin covered
with the phenolics, which called phenolic hydrochar. According to the
Ref (Kambo and Dutta, 2015; Li et al., 2016), due to the porous
structure and the smaller uniform particle, the surface area of the
contact with air and the adsorption performance all increased.
The XRD patterns were shown the peak at 2θ angle = 15.5°, 16.0°
and 22.8° was the 1 0 1, 1 0 1 and 0 0 2 peaks. As the reaction severity
increasing, the crystalline diffraction peaks of cellulose became more
prominent, and then gradually disappeared. Especially, at the 210 °C,
the intensity of 1 0 1 and 1 0 1 peak was exceeded 500 (abs), the 0 0 2
peaks were 1250, which means the amorphous material (hemicellulose,
cellulose and lignin) degraded, leading to crystallinity increased, as the
temperature increased from 180 to 210 °C. However, from 210 to
240 °C, all the crystalline diffraction peaks of cellulose gradually dis-
appeared, which means the high temperature contributed to the de-
gradation of the crystalline cellulose. As for the residence time, it also
had influence on the degradation of cellouse, which had reported. In
addition, the organic compound or metal element existed in the raw
CFP or formed in the HTC process. For instance, the peak at 2θ = 21.37°
was SiO2. However, In the CFP, the metal element existed in the form of
complex crystalline phase, some other crystalline phase also could be
found as the form of natural zeolite (Si/Al = 1). As the reaction in-
creasing the peak at 2θ = 21.37° and 23.7° became more prominent.
Some organic compounds which contains (C, H, O, N, Cu and F) also
founded, the F element existed as the compound of C7H4F4O. In our
previous paper (Yao and Ma, 2018), the fluorinated compounds were
also detected in the pyrolysis products.
acteristics of the SLF. It could be seen that, as the reaction severity
increased, the eOH group had a decreased trend. The relative intensity
of this peak decreased with deeping reaction severity, indicating a great
increase in hydrophobicity of hydrochar compared to raw materials,
this was probably caused by the dehydration process during HTC. It was
interesting to see the peak of 240–30 had opposite trend. The peaks at
2925 cm−1 and 2850 cm−1 revealed asymmetric and symmetric eCH
stretching of methylene groups, respectively. Maybe the formation of
methylene groups came from the fracture of aliphatic side chain, at the
same time with the increase of the temperature. The absorption peak
was very small, suggesting the content of aliphatic side chains was very
low. The peak around 1620 and 1500 cm−1 are attributed to aromatic
C]C stretching and eOCH3 of aromatic groups in lignin. The intensity
of this peak increased with the increased temperature and residence
time, indicating that as other components in the feedstock were de-
graded, lignin did not totally decompose under the hydrothermal con-
ditions. Lignin became relatively more abundant consistent with the
above representations. There was an increase in the relative intensity of
the peak around 1103 cm−1, associated with stretching of eOH group
in alcohol in the lignin. Lignin partially decomposed into phenols
fragments under high temperature. While the phenols monomers
(coniferol, p-coumaryl alcohol and sinapyl alcohol) all contained eOH
groups. Part of the phenolic hydrochar, would locate on the surface of
nondissolved lignin. Due to the partially decomposition of lignin, the
peak of eOH group was more obvious. In conclusion, the HTC of CFP
was a thermal degradation process. Many small molecular substances
such as furans, acids, aldehydes, ketones, alcohols and phenols were
generated. The overall reaction pathway of CFP was shown the reaction
pathway schemes.
3.5. Combustion characteristics of CFP and hydrochar
Fig. 3 presented TG and DTG curves of raw CFP and hydrochars.
Table 3 presented the combustion characteristic parameters of all
samples. The supporting material presented definition of the combus-
tion parameters, such as ignition temperature (Ti), burnout temperature
(Tf), combustibility index (S), and combustion stability index (Rw).
According to Fig. 3b, there existed two weight loss peaks for CFP during
the whole combustion process. These two peaks respectively corre-
sponded to two combustion stages: the volatilization and combustion of
volatile components (271–400 °C), and the combustion of fixed carbon
(400–550 °C). Because of the high volatile matter content in CFP, the
first weight loss peak was centered at 340.85 °C (−15.11%/min) was
more remarkable than the second one at 441.74 °C (−7.87%/min).

32
Z. Yao and X. Ma
Fig. 2. The H/C, N/C and O/C ratio of raw CFP and hydrochar.
After the HTC process, significant differences in the TG and DTG pro-
files were observed for hydrochar. As shown in Table 3, due to the
degradation of cellulose and hemicellulose, the Ti and Tf values of all
hydrochars were higher than CFP (271.45 °C) (Lin et al., 2017b), which
revealed that the HTC process made the combustion process of hydro-
char shift to high temperature. So, HTC prolonged the combustion
process. As displayed in Fig. 3b, the DTG curves of all hydrochars could
be divided into two regions. The DTG curve shapes of the hydrochars
were like that of CFP. Compared to the raw CFP, the first peak tem-
peratures were lower. This result suggested that the volatile compo-
nents contained in CFP would decompose into simpler chemical sub-
stances as the HTC process went deeper. The main components of CFP
consist of cellulose, hemicellulose, and lignin. Previously studies
showed the model compounds broke down into small molecules in the
presence of subcritical water (Hoekman et al., 2011). Meanwhile, the
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Bioresource Technology 282 (2019) 28–36
mass loss rate of the first weight loss peak increased significantly. As
displayed in Table 3, the DTGmax values of hydrochar treated at 180 °C
and 210 °C were much larger than those of CFP. The 210–30 had the
biggest DTGmax value (−26.79%/min). The 180–60 achieved the best
combustion performance, with an index S value of
18.04 × 10−7 min−2 × C−3 and an index Rw value of −15.59 (10−5/
min−1 × C−2), which were much higher than that of lignite and bitu-
minous coal (see the Supporting material). The index S and Rw values
of hydrochar except 240–60 and 240–100 were both greater than those
of CFP, which suggested that the combustion performance of hydrochar
was superior to that of CFP. HTC temperature of 240 °C was not ben-
eficial to combustion for hydrochar. At the same temperature, the hy-
drochars were treated different residence time was similar. Compared
with residence time, the reaction temperature had a dominant effect on
combustion performance.
Z. Yao and X. Ma
Fig. 3. (a) TG curves of raw samples and hydrochars. (b) DTG curves of raw samples and hydrochars.
3.6. The fate of metals in hydrochar
Another important property of a hydrochar is the metal con-
centrations.
Alkali/alkaline earth metals, such as K, Na, Ca and Mg, have a po-
tential fouling and slagging risk for use in combustion purposes. The
CFP, in generally, contained a significant amount of metals, which
34
Bioresource Technology 282 (2019) 28–36
cannot be destroyed and broken-down during HTC process, in contrast
to organic compounds. So, the fates of metal elements during the HTC
process need to be followed. Table 4 presented the content (mg/kg) of
heavy metals, alkali/alkaline earth metals in hydrochar with increasing
temperatures and residence time of the HTC. For the raw CFP, K, Ca and
Mg were the three highest content of the total metal concentrations,
with a value of 3338, 2925 and 702.5 mg/kg, respectively. While the
Z. Yao and X. Ma Bioresource Technology 282 (2019) 28–36

Table 3
The combustion characteristics parameters of CFP and hydrochars at 20 °C/min.
Sample Ti Tf Mf DTG1 T1 DTG2 T2 DTGmean S RW
(°C) (°C) (%) (%/min) (°C) (%/min) (°C) (%/min) (10−7/(min−2 × C−3)) (10−5/(min−1 × C−2))

CFP 271.45 498.72 8.97 −15.11 340.85 −7.87 441.70 −3.45 14.17 −11.16
180–30 309.95 541.59 7.73 −24.61 337.80 −7.44 493.25 −3.53 16.72 −14.66
180–60 307.45 533.29 7.72 −25.56 333.75 −8.64 476.30 −3.56 18.04 −15.59
180–100 310.05 547.35 7.77 −24.78 336.10 −7.47 494.95 −3.54 16.66 −14.60
210–30 313.70 553.52 7.82 −26.79 337.40 −7.61 502.45 −3.54 17.42 −15.43
210–60 312.85 551.92 7.63 −26.29 335.20 −8.14 503.55 −3.55 17.27 −15.23
210–100 312.35 555.33 7.63 −25.32 334.20 −8.14 502.75 −3.54 16.54 −14.59
240–30 309.60 552.57 7.54 −22.55 332.80 −9.19 499.10 −3.54 15.05 −13.18
240–60 302.15 569.51 8.58 −14.29 330.10 −9.63 499.65 −3.46 9.50 −8.30
240–100 297.90 557.78 8.31 −10.87 332.05 −10.85 498.55 −3.45 7.74 −6.54

Ti, the ignition temperature.

Tf, the burnout temperature.
Mf, the combustion residue mass.
DTG1 and DTG2, the weight loss rate according to the peaks.
T1 and T2, the temperature according to the peaks.
DTGmean, the average mass loss rate.

Table 4 of them mainly being enriched in the hydrochars. The fate rate of
The metal elements in the samples by ICP-OES. metals in hydrochars was shown in Fig. 4, it was very interesting to be
Sample Metal elements (mg/kg)
found the temperature and residence time had no significant effect on
the metal removal unlike as imagined beforehand, but HTC process of
K Ca Na Mg Cu Zn Fe Al itself played dominant role. The Fe (∼14.34–88.43%), Cu
(∼25–108.33%) and Al (∼24.63–113.28%) showed an increased ac-
CFP 3333.8 2925.0 276.3 702.5 6.0 21.3 313.8 253.8
180–30 295.0 1403.8 213.8 66.3 7.5 15.0 358.8 316.3
cumulation in hydrochar as the reaction was more severe during HTC
180–60 160.0 1527.5 210.0 82.5 9.5 15.0 427.5 321.3 process. While the alkali/alkaline earth metals (Ca, Na, K and Mg) had
180–100 193.8 1455.0 171.3 62.5 9.5 11.3 330.0 297.5 good removal efficiency. Especially the removal rate of K and Mg were
210–30 201.3 1571.3 137.5 70.0 7.5 12.5 316.3 366.3 higher than 88%. Because the alkali/alkaline earth metals exist mainly
210–60 176.3 1248.8 152.5 60.0 8.8 20.0 362.5 406.3
in the form of ions present in the CFP. Meanwhile, K, Na, and Mg were
210–100 146.3 1165.0 216.3 61.3 8.8 15.0 380.0 350.0
240–30 167.5 937.5 161.3 52.5 10.0 16.3 416.3 351.3 well soluble in subcritical water.
240–60 130.0 1128.8 210.0 58.8 10.0 16.3 433.8 363.8 Compared with K, Na and Mg, Zn was more difficult to dissolve in
240–100 163.8 1222.5 231.3 63.8 12.5 18.8 591.3 541.3 water. So, the MR of Zn (∼11.73–29.58%) was relatively lower than K,
Ca and Mg. After HTC, Cu, Zn, Fe and Al were still the major compo-
nents of heavy metals in the hydrochar samples, of which the con-
total concentrations of Zn and Cu were in a relative low level, with a centrations reached up to 12.5, 18.8, 591.3 and 606.3 mg/kg, respec-
low value of 21.3 and 6 mg/kg. Due to these heavy metals in hydro- tively, at the HTC temperature of 240 °C for 100 min. Due to the
chars with a low water solubility and cation exchange capacity in enrichment of heavy metals, they all showed enrichment phenomenon
generally, then may suffer from dissolution and precipitation under in hydrochars.
subcritical condition during the coupled HTC process, resulting in most

Fig. 4. The fate of the metal elements of hydrochar during the HTC process.

35
Z. Yao and X. Ma
4. Conclusions
The HHV and chemical exergy increased gradually as temperature
and residence time increased. The water uptake rate also decreased as
the reaction severities (7.29%−3.5%), which revealed a good hydro-
phobic characteristic. After HTC, Cu, Fe and Al were still the major
components of heavy metals in the hydrochar samples, of which the
concentrations reached up to 12.5, 591.3 and 606.3 mg/kg, respec-
tively. HTC didn’t had effect on the removal of the heavy metals. The
180–60 achieved the best combustion performance, with an index S
value of 18.04 × 10−7 min−2 × C−3.
Acknowledgements
National Natural Science Foundation of China (51476060,
51676074); Natural Science Foundation of Guangdong Province, China
(2016A030310424, 2018A030313228).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.biortech.2019.02.130.
References
Benavente, V., Calabuig, E., Fullana, A., 2015. Upgrading of moist agro-industrial wastes
by hydrothermal carbonization. J. Anal. Appl. Pyrolysis 113, 89–98.
Channiwala, S.A., Parikh, P.P., 2002. A unified correlation for estimating HHV of solid,
liquid and gaseous fuels. Fuel 81 (8), 1051–1063.
Escala, M., Zumbühl, T., Koller, C., Junge, R., Krebs, R., 2013. Hydrothermal carboni-
zation as an energy-efficient alternative to established drying technologies for sewage
sludge: a feasibility study on a laboratory scale. Energy Fuels 27 (1), 454–460.
Guo, S., Dong, X., Wu, T., Shi, F., Zhu, C., 2015. Characteristic evolution of hydrochar
from hydrothermal carbonization of corn stalk. J. Anal. Appl. Pyrolysis 116, 1–9.
Guo, S., Dong, X., Zhu, C., Han, Y., Ma, F., Wu, T., 2017. Pyrolysis behaviors and ther-
modynamics properties of hydrochar from bamboo (Phyllostachys heterocycla cv.
pubescens) shoot shell. Bioresour. Technol. 233, 92–98.
He, C., Giannis, A., Wang, J.-Y., 2013. Conversion of sewage sludge to clean solid fuel
using hydrothermal carbonization: hydrochar fuel characteristics and combustion
behavior. Appl. Energy 111, 257–266.
He, C., Tang, C., Li, C., Yuan, J., Tran, K.-Q., Bach, Q.-V., Qiu, R., Yang, Y., 2018. Wet
torrefaction of biomass for high quality solid fuel production: a review. Renew.
Sustain. Energy Rev. 91, 259–271.
Hoekman, S.K., Broch, A., Robbins, C., 2011. Hydrothermal carbonization (HTC) of lig-
nocellulosic biomass. Energy Fuels 25 (4), 1802–1810.
Huang, H.-J., Yuan, X.-Z., 2016. The migration and transformation behaviors of heavy
metals during the hydrothermal treatment of sewage sludge. Bioresour. Technol. 200,
991–998.
Jain, A., Balasubramanian, R., Srinivasan, M.P., 2016. Hydrothermal conversion of bio-
mass waste to activated carbon with high porosity: a review. Chem. Eng. J. 283,
789–805.
Kambo, H.S., Dutta, A., 2015. A comparative review of biochar and hydrochar in terms of
production, physico-chemical properties and applications. Renew. Sustain. Energy
Rev. 45, 359–378.
Kang, S., Li, X., Fan, J., Chang, J., 2012. Characterization of hydrochars produced by
hydrothermal carbonization of lignin, cellulose, d-xylose, and wood meal. Ind. Eng.
Chem. Res. 51 (26), 9023–9031.
36
Bioresource Technology 282 (2019) 28–36
Kim, D., Prawisudha, P., Yoshikawa, K., 2012. Hydrothermal upgrading of Korean MSW
for solid fuel production: effect of MSW composition. J. Combust. 2012, 1–8.
Kumar, M., Olajire Oyedun, A., Kumar, A., 2018. A review on the current status of various
hydrothermal technologies on biomass feedstock. Renew. Sustain. Energy Rev. 81,
1742–1770.
Laginhas, C., Nabais, J.M.V., Titirici, M.M., 2016. Activated carbons with high nitrogen
content by a combination of hydrothermal carbonization with activation.
Microporous Mesoporous Mater. 226, 125–132.
Li, Y., Meas, A., Shan, S., Yang, R., Gai, X., 2016. Production and optimization of bamboo
hydrochars for adsorption of Congo red and 2-naphthol. Bioresour. Technol. 207,
379–386.
Lin, Y., Ma, X., Peng, X., Hu, S., Yu, Z., Fang, S., 2015. Effect of hydrothermal carboni-
zation temperature on combustion behavior of hydrochar fuel from paper sludge.
Appl. Therm. Eng. 91, 574–582.
Lin, Y., Ma, X., Peng, X., Yu, Z., 2017a. Forecasting the byproducts generated by hy-
drothermal carbonisation of municipal solid wastes. Waste Manage. Res. 35 (1),
92–100.
Lin, Y., Ma, X., Peng, X., Yu, Z., 2017b. Hydrothermal carbonization of typical compo-
nents of municipal solid waste for deriving hydrochars and their combustion beha-
vior. Bioresour. Technol. 243, 539–547.
Lin, Y., Ma, X., Peng, X., Yu, Z., 2016. A mechanism study on hydrothermal carbonization
of waste textile. Energy Fuels 30 (9), 7746–7754.
Liu, L., Chang, H.M., Jameel, H., Park, S., 2018. Furfural production from biomass pre-
treatment hydrolysate using vapor-releasing reactor system. Bioresour. Technol. 252,
165–171.
Liu, Z., Quek, A., Kent Hoekman, S., Balasubramanian, R., 2013. Production of solid
biochar fuel from waste biomass by hydrothermal carbonization. Fuel 103, 943–949.
Lu, L., Namioka, T., Yoshikawa, K., 2011. Effects of hydrothermal treatment on char-
acteristics and combustion behaviors of municipal solid wastes. Appl. Energy 88 (11),
3659–3664.
Mau, V., Quance, J., Posmanik, R., Gross, A., 2016. Phases' characteristics of poultry litter
hydrothermal carbonization under a range of process parameters. Bioresour. Technol.
219, 632–642.
Mazar, A., Jemaa, N., Wafa Al Dajani, W., Marinova, M., Perrier, M., 2018. Comparative
study: furfural production from two types of pre-hydrolysates produced using aspen
and maple chips. Biomass Bioenergy 111, 103–113.
Parshetti, G.K., Liu, Z., Jain, A., Srinivasan, M.P., Balasubramanian, R., 2013.
Hydrothermal carbonization of sewage sludge for energy production with coal. Fuel
111, 201–210.
Peduzzi, E., Boissonnet, G., Maréchal, F., 2016. Biomass modelling: estimating thermo-
dynamic properties from the elemental composition. Fuel 181, 207–217.
Song, G., Xiao, J., Zhao, H., Shen, L., 2012. A unified correlation for estimating specific
chemical exergy of solid and liquid fuels. Energy 40 (1), 164–173.
Yao, C., Pan, Y., Lu, H., Wu, P., Meng, Y., Cao, X., Xue, S., 2016a. Utilization of recovered
nitrogen from hydrothermal carbonization process by Arthrospira platensis.
Bioresour. Technol. 212, 26–34.
Yao, C., Wu, P., Pan, Y., Lu, H., Chi, L., Meng, Y., Cao, X., Xue, S., Yang, X., 2016b.
Evaluation of the integrated hydrothermal carbonization-algal cultivation process for
enhanced nitrogen utilization in Arthrospira platensis production. Bioresour.
Technol. 216, 381–390.
Yao, Z., Ma, X., 2018. Effects of hydrothermal treatment on the pyrolysis behavior of
Chinese fan palm. Bioresour. Technol. 247, 504–512.
Yao, Z., Ma, X., Lin, Y., 2016c. Effects of hydrothermal treatment temperature and re-
sidence time on characteristics and combustion behaviors of green waste. Appl.
Therm. Eng. 104, 678–686.
Yao, Z., Ma, X., Wang, Z., Chen, L., 2017. Characteristics of co-combustion and kinetic
study on hydrochar with oil shale: a thermogravimetric analysis. Appl. Therm. Eng.
110, 1420–1427.
Zhai, Y., Liu, X., Zhu, Y., Peng, C., Wang, T., Zhu, L., Li, C., Zeng, G., 2016. Hydrothermal
carbonization of sewage sludge: the effect of feed-water pH on fate and risk of heavy
metals in hydrochars. Bioresour. Technol. 218, 183–188.
Zhang, Y., Wang, Q., Li, B., Li, H., Zhao, W., 2018. Is there a general relationship between
the exergy and HHV for rice residues? Renew. Energy 117, 37–45.