Waste Management 118 (2020) 521–533

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

Co-hydrothermal carbonization of food waste with yard waste for solid

biofuel production: Hydrochar characterization and its pelletization
Hari Bhakta Sharma, Brajesh K. Dubey ⇑
Environmental Engineering and Management, Department of Civil Engineering, Indian Institute of Technology Kharagpur, Kharagpur, West Bengal 721302, India

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

Article history: In this study, Co-HTC of food waste with yard waste was conducted for biofuel pellets production, and
Received 5 April 2020 also to understand any possible synergy between two feedstock types. The calorific value of blended
Revised 6 August 2020 raw feedstock was 13.5 MJ/kg which increased to 27.6 MJ/kg after Co-HTC at 220 °C for 1 h. Energy yield
Accepted 3 September 2020
and fuel ratio calculated was 45% and 0.65 respectively. Hydrochar produced demonstrated a stable com-
bustion profile as compared to reactive combustion profile for raw samples. The blend of food and yard
waste hydrochar was easily pelletized, and its pellets showed improvement in mechanical properties as
Keywords:
compared to pellets made from mono-substrate((food waste) hydrochar. Pellets produced from the blend
Food waste
Co-hydrothermal carbonization
of food and yard waste hydrochar showed higher energy (46.4 MJ/m3) and mass density (1679 kg/m3) as
Biofuel pellets compare to the pellet produced from food waste hydrochar alone. Tensile strength obtained for the
Coal replacement blended hydrochar pellet was 2.64 MPa while same for the pellets produced from food waste hydrochar
Pelletization alone was 1.30 MPa. In addition to improving hydrophobicity, soften lignin from yard waste also helped
in binding the food waste hydrochar particles together within the pellets matrix during heated pelletiza-
tion. The results presented in the study indicated that in the presence of all favorable conditions, there is
a potential that approximately 11% of the global coal consumption could be replaced by the combustion
of hydrochar produced from food and yard waste globally.
Ó 2020 Elsevier Ltd. All rights reserved.

o1. Introduction
It has become important than ever to address the growing con-
cern of mismanaged Municipal Solid Waste (MSW) in developing
nations. The issue has become even more imperative for the
organic fraction of MSW (food and other green waste), generation
of which is inevitable and is ever increasing. Nearly 3 billion tonnes
of food is wasted every year of which an estimated 1.3 billion ton-
nes ends up rotting in the bins of consumers and retailers due to
poor transportation and harvesting practices (Kaza et al., 2018).
Furthermore, unmanaged food waste disposal have negative envi-
ronmental impacts at the end of its life, as it is mostly associated
with greenhouse gas emission (mostly methane), which has a glo-
bal warming potential of 25 times greater than carbon dioxide on a
100-year time scale (Kaza et al., 2018). If we adopt a market based
approach to tackle the aforementioned issue, the MSW (including
organic fractions) recycling and resource recovery approach could
generate estimated US $410 billion annually (Nizami et al., 2017).
In a resource recovery and market based approach for the organic
fraction of MSW, biofuel production is most preferred lately.
⇑ Corresponding author.
E-mail address: bkdubey@civil.iitkgp.ac.in (B.K. Dubey).
Despite liquid and gaseous biofuel production approach being fol-
lowed predominantly, lately, production of solid biofuel pellets has
gain tremendous attention (Wang et al., 2018a; Yilmaz and Akçay,
2018; Zhai et al., 2018; Zhao et al., 2014). As compared to the chips
and powder, pellets has more commercial value mainly due to
higher mass and energy density, apart from being easy to handle,
store and transport. However, moisture laden, high volatile organic
waste creates considerable challenges during pellet production.
Moisture and high volatile matter not only deteriorate pellets qual-
ity but also increase the risk of fire hazard during storage and
transportation due to microbial activity promoted by the presence
of moisture.
To overcome aforementioned challenge, organic waste in often
treated using the treatment techniques like pyrolysis and torrefac-
tion. These treatment methods requires waste condition to be dry;
moisture laden waste is not suitable, hence requires energy inten-
sive pre-drying step (Sharma et al., 2019a). Hydrothermal car-
bonization (HTC), which is a wet waste conversion technique is
being widely used/studied to tackle moisture laden waste in a
recent time (Kambo and Dutta, 2014; Funke et al., 2010; Saqib
et al., 2019a). The HTC takes advantage of high moisture in the
waste and converts it into a carbon rich hydrochar by the series
of reaction such as; hydrolysis, dehydration, de-carboxylation,

https://doi.org/10.1016/j.wasman.2020.09.009
0956-053X/Ó 2020 Elsevier Ltd. All rights reserved.
H.B. Sharma, B.K. Dubey
aromatization, condensation & polymerization (Hoekman et al.,
2011;Libra et al., 2011). Due to high adaptability to the wet waste,
HTC have been extensively used for production of hydrochar using
range of high moisture containing feedstocks like; MSW, specific
lignocellulosic biomass including specific fruits waste and peels,
micro algae, sewage and paper mill sludge and non-
lignocellulosic waste (Berge et al., 2011;Chen et al., 2017;
Heilmann et al., 2010; Mäkelä and Yoshikawa, 2016; Zhai et al.,
2016). Apart from advantageously utilizing water during HTC,
hydrochar produced has improved grindability, improved mass
and energy density, and hydrophobicity (Sharma et al., 2019a;
Kambo and Dutta, 2014). The qulity of the hydrochar and its pellets
is dictated by HTC operation conditions like type of feedstock,
operation temperature and time (Saqib et al., 2019a). The hydro-
char pellets quality depends on the type of feedstock; lignin rich
material like lignocellulosic yard waste (YW) promotes solid
bridge-type bonding within the hydrochar pellets matrix thus
increasing its mechanical durability.
Major componenet of OFMSW MMlignocellulosic The food and
yard waste are the major fraction of MSW. Yard waste(YW) is lig-
nocellulosic in nature, and the lignin, cellulose and hemicellulose
are its major component. Ligin softens and start to flow above its
glass transition temperature during the heated peleltizatiom. The
food and yard waste are the major fraction of MSW. YW is lignocel-
lulosic in nature; the lignin, cellulose and hemicellulose are its
major component. Flowing lignin engulfs nearby hydrochar parti-
cles. When temperature falls back soften lignin solidifies and forms
a solid bridge along with engulfed hydrochar particle. Which
means, feedstock with higher lignin content could be easily pel-
letized into durable and robust pellets. Typical lignin percentage
in YW and other similar green waste sample ranges between 19%
and 25% (based on total solid of the sample). Panigrahi et al
(Panigrahi et al., 2019) reported and average percentage lignin
for the YW used in their study to be around 19%. Brown et al.
(2012) reported around 22% lignin content in YW sample used in
their study. Brown and Li (2013) reported around 23% of lignin
content in the YW sample used in their study. It is worth to men-
tion that the structural composition of lignocellulosic biomass may
vary as per the compositional mix in the representative sample,
season of collection and locality (Panigrahi et al., 2019; Sharma
et al., 2020). Apart from lignin, Equilibrium Moisture Content
(EMC) in the feedstock could also acts as a binder by promoting liq-
uid bridging (Kaliyan and Morey, 2010). In the absence of lignin or
for the feedstock with low lignin content, binders like starch, crude
glycerin and molasses have been extensively used for the produc-
tion of the mechanically durable pellets in the past (Hu et al., 2015;
Kaliyan and Morey, 2009; Zhai et al., 2018). However, utilization of
binder should also be looked upon from the point of cost effective-
ness and its environmental impacts (Whittaker and Shield, 2017).
The knowledge achieved hitherto on pellet durability is mainly
for lignocellulosic waste (which is rich in lignin content), and for
non-lignocellulosic waste like food waste, the knowledge achieved
is limited. Food waste has limited lignin content (main compo-
nents in food waste are protein and carbohydrate like starch and
glucose), as a result it has been rarely considered for making fuel
pellets after hydrothermal carbonization processing. Few studies
that has attempted to make food waste based hydrochar pellets
has used additional binder like molasses to increase mechanical
durability (Zhai et al., 2018). Apart from the advantage of lignin
acting as natural binder, the additional advantage that Co- HTC
of FW (non- lignocellulosic waste) with YW (lignocellulosic waste)
brings along with it is, the possibility of solving the problem
related to solid waste management especially, the organic fraction.
Of the total waste estimated 2.01 billion, metric ton of MSW gen-
erated, green (yard waste) and organic waste comprises approxi-
mately 44% (Kaza et al., 2018). This study is an attempt to use
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Waste Management 118 (2020) 521–533
both this waste type for hydrochar pellets production and there-
fore establish it as a valuable renewable source of energy. Likewise,
the knowledge achieved in this study could be utilized for the
development of the decentralized/in-situ Co-HTC based treatment
technology for food and yard waste in the residential campus,
gated communities, and food processing industries.
In this study, food waste was blended with YW for Co-HTC to
produce hydrochar at its maximum utility (1:1, i.e. 50% each),
which was then subsequently pelletized using self-designed labo-
ratory pelletizer. The chosen 1:1 food to YW ratio will help us
understand the behaviour of solid biofuel prepared when both
the waste type would be utilized at its highest weighted percent-
age in the real life scenario. Hydrochar produced from Co-HTC con-
dition was characterized for any possible synergetic effect;
physiochemical, structural and combustion kinetic using range of
techniques. The fundamental fuel properties of hydrochar like;
ultimate and proximate analysis, energy densification, fuel ratio
and calorific value were also evaluated. The study also investigated
mechanical, storage and combustion properties of hydrochar pel-
lets. Based on hydrochar energy yield and the present global coal
consumption, the fraction of coal replacement by hydrochar pellets
combustion produced from food and YW globally was also esti-
mated in this study using method described by Mau and Gross
(Mau and Gross, 2018).
2. Material methods
2.1. Material acquisition and hydrothermal carbonization
The yard waste (YW) used in this study was collected from the
campus of Indian Institute of Technology Kharagpur. The YW con-
sists of tree leave (65%), grasses and garden trimmings (33%), fallen
sticks and flowers (2%). The details about YW composition, collec-
tion, grinding and storage methods could be found in the previous
study (Sharma et al., 2019a). Food waste (FW) used in this study
was collected from the food and vegetables processing section of
boys hostel mess. The mix food waste consist of following compo-
nent in equal propotion: onion peel, cabbage, carrot peel, banana
peel, capsicum, bread, rice, chapattis (flatten wheat bread) and
cucumber peel. Equal proportion of all component of collected food
waste was taken and was homogenously mixed with a mixer blen-
der as previously done by Komilis and Ham (2006). Both the YW
and FW were mixed thoroughly in equal proportion before HTC
to simulate maximum utilization of both type of waste for pellets
production at its highest weighted percentage. The motivation for
using equal proportion was also derived from the study by Wang
et al, which concluded that for practical applications Co-HTC of
food waste-woody biomass with FW ratio from 50% to 75% at
220 °C was more suitable for pelletization (Wang et al., 2018a).
HTC was conducted using 750 mL stainless steel reactor by Che-
mito India. For every 20 g of waste sample, 400 mL of de-ionized
water was used, the ratio was based on our previous study
(Sharma et al., 2019a). Nitrogen was purged into the reactor for
5 min to expel all the oxygen from the reactor while keeping exter-
nal pressure release valve open. Series of HTC reaction condition
was run for the food waste between 220 °C and 260 °C for 60 to
240 min, and the condition with maximum energy yield percent-
age was chosen for further experiment (supplementary section
(A.1)). The food waste gets easily degraded and transformation to
an aqueous fraction (Berge et al., 2011) at high temperature HTC
which results in low solid yield. The transformation of food waste
and low solid yield was also characterized by high chemical oxygen
demand (COD) and high total organic carbon (TOC) in HTC process
water (Tradler et al., 2018). Due to the aforementioned reason, the
Co-HTC condition was based on food waste HTC condition which
H.B. Sharma, B.K. Dubey Waste Management 118 (2020) 521–533

resulted in high energy and solid yield (Table A.1). After the nitro- hydrochar sample and differential weight loss rate (DTG) were
gen purging was concluded, the reactor was sealed and pro- found using TG/DTG Perkin Elmer Pyris Diamond. The air flow rate
grammed for 220 °C for 1 h with heating ramp of 13 ± 4 °C/min. used was 100 mL/min and samples were heated between 50 and
The stiller mounted with the reactor was set to 100 RPM in accor- 850 °C. The comprehensive combustion index (CCI), combustion
dance to our previous study. The auto generated pressure inside stability index (Rw) and Ignition index (Di) were determined by
the reactor for each experiment was between 4 and 5 MPa. After using Eq. (5), Eq. (6) and Eq. (7) respectively (Xie et al., 2018).
the reaction time got elapsed, the HTC reactor was turned off, pres-
DTGm  DTGmean
sure valve was released and the vessel was immersed into the ice CCI ¼ ð5Þ
cold water to quench the reaction further. The dark coffee scented T 2i  Tb
slurry was vacuum filtered using the cellulose nitrate membrane
filter (0.45 mm). Process liquid was stored separately for another DTGm
Rw ¼ 8:5875  107  ð6Þ
study to understand its anaerobic bio-degradability while, for this Ti  Tm
study, the solid fraction, i.e. hydrochar was dried at 105 °C for 24 h
and was then stored in a zip lock bag for further analysis. DTGmax
Di ¼ ð7Þ
TiTm
2.2. Characterization of hydrochar Here, DTGm, DTGmean, indicates the maximum and average weight
loss rate, respectively. Ti, Tb and Tm are the ignition temperature,
Proximate analysis (moisture content, volatile matter and ash) the burnout temperature and the peak temperature at maximum
of the samples were investigated using ASTM standard methods weight loss rate respectively (Lang et al., 2019; Xie et al., 2018).
(ASTM-E871, ASTM-E1755, and ASTM-E872). Elemental carbon, CCI, Rw and Di were calculated to understand the combustion stabil-
nitrogen, hydrogen and oxygen were determined by EURO EA ele- ity of hydrochar during its combustion (Xie et al., 2018). CCI con-
mental analyzer using tin capsule. The equilibrium moisture con- tains comprehensive factors of the combustion behavior
tent (EMC) of the hydrochar was measured using a humidity test including: the ignition temperature, burnout temperature, maxi-
chamber (Carelab Technology, India) at 25 °C with 60% relative mum DTG reaction rate and mean DTG reaction rate. A larger CCI
humidity. The higher heating value (HHV)was calculated using indicates that the sample burns more vigorously and rapidly (Ma
empirical approach using Dulong’s formula as mentioned in previ- et al., 2019).
ous study (Sharma et al., 2019b). Fuel ratio, solid yield (%), energy
densification (ED) and energy yield were calculated using follow- 2.4. Combustion kinetic analysis of hydrochar
ing formulae.
Arrhenius kinetic parameters of the combustion process were
Fuel ratio ¼ ðFixed carbonÞ= ðVolatile matterÞ ð1Þ
calculated and summarized using following equation in order to
determine the amount of weight loss for raw and hydrochar sam-
Hydrochar yield ð%Þ ¼ ðHydrochar weightÞ= ðFeedstock weightÞ
ple. The change in mass vs. temperature can be defined as given in
 100 Eq. (8)
ð2Þ da Ea
¼ AeðRT Þ ð1  aÞn ð8Þ
dt
Energy densification ¼ ðHHV of hydrocharÞ= ðHHV of feedstockÞ
where, ‘A’ stands for pre-exponential factor, ‘E’ represents the acti-
ð3Þ vation energy and ‘n’ stands for reaction order. Using the kinetic
parameter for non- isothermal combustion as given by Coats-
Energy yield ð%Þ ¼ Hydrochar yield Redfern (Coats and Redfern, 1964) and then rearranging the above
 Energy densification ð4Þ equation (Sharma et al., 2019a), we get following form of the equa-
tion (Eq. (9)).
The surface morphology of the sample were analyzed using

 
field emission scanning electron microscopy (FESEM), Merlin. Bru- lnð1  aÞ AR 2RT Ea 1
ln ¼ ln 1   ð9Þ
ker D2 Phaser X-Ray diffraction (XRD) was used to analyze the T2 bEa Ea R T
crystalline properties of the samples by using scattering angle 2h h i
lnð1aÞ 1
10° to 80° at 30 kV having 10 mA of Cu Ka radiation. The surface The plot of ln T2
and T
result into a straight line with the
Ea
functionality of sample were was investigated using PerkinElmer slope as .
The activation energy ‘E’ and pre-exponential factor ‘A’
R
Fourier-transform infrared spectroscopy (FTIR). The objective of were calculated using the slope and intercept obtained from Eq.
the study was to explore an opportunity of the usage of YW lignin (7).
binding properties during pelletization of blended food and yard
waste hydrochar. Food waste and its hydrochar possess low lignin 2.5. Hydrochar pelletization
content as proteins and carbohydrates are the main components of
food waste (Zhai et al., 2018). Therefore, the focus has been on the The pelletization experiments were performed using self-
cellulose, hemicellulose and lignin content for YW and its hydro- designed hydraulic hand pellets press. The pellet press as shown
char sample in this study. Therefore, the compositional analysis in the Fig. S1(Supplementary) was fabricated at the local workshop
(Lignin, Cellulose and Hemicellulose) for lignocellulosic YWR and The pellet press consists of varying load cell, a piston of 10 mm in
YWH were only measured in this using the procedure explained diameter and 110 mm length, and a cylindrical die with 10 mm
in our previous study for yard waste (Panigrahi et al., 2020). internal diameter and 90 mm length. For each pellet production,
1.2 g of the sample was manually filled and tapped into the cylin-
2.3. Thermal analysis and characteristic combustion parameters drical die. After which die was heated up-to 90 °C to soften the lig-
nin (glass transition temperature of lignin), as it helps to form
The percentage weight loss and rate of weight loss under high- natural binder within the pellets (Reza et al., 2012). The bottom
temperature, air controlled atmosphere were investigated using of the die was closed using a removable backstop plate. For each
thermal gravimetric analysis (TGA). The weight loss of raw and pelletization experiment, sample was compressed with pressure
523
H.B. Sharma, B.K. Dubey Waste Management 118 (2020) 521–533

of 250 MPa using a lever attached to hydraulic press. The pressure
of 250 MPa was the highest attainable pressure using a hand lever
attached hydraulic hand press. The sample was held under the
applied pressure for 30 s and after that pressure was released. After
each compression, the backstop plate was removed from the die
and the pellet was extruded out of the die channel using the same
piston that was used for compression. The pellet samples were left
undisturbed for 1–2 min after which it’s mass, length and diameter
were measured. After the dimensional measurement of pellet it
was kept in a sealed container at 4 °C for two week to find out
undisturbed natural length expansion. A digital Vernier caliper
(Advance, Tm No. 1348969) was used to record the dimensions
of the pellets and length expansion was measured using Eq. (10).
Li  L0
L¼
L0
where, Li represents the initial pellet length and Lo represents the
length of the expanded pellet after one week.
Pellets were also tested for its tensile strength. The tensile
strength of the pellets was measured using Universal Testing
Machine (UTM) (H50KS, Tinius Olsen, United Kingdom). The pellets
were placed horizontally between the anvils and compressive force
applied by the loading ram until the pellet failed. The tensile
strength was calculated using the equation (Eq. (11)) (Liu et al.,
2014)
2f
Tp ¼
pld
where, ‘f’ represents the maximum compressive force applied,
while ‘l’ and ‘d’ are the length and diameter of the pellets,
respectively.
Mass and energy density of the pellets were calculated using
stereometric method. Method is based on the measurement of
dimensions for cylindrical pellets and expressing it as the ratio of
the mass to volume. The energy density of the pellets was calcu-
lated by multiplying the mass density of the pellet with the calori-
fic value of the pellet. For hydrophobicity experiment, 2 h water
immersion test and humidity chamber test for two week at relative
humidity 60% and 40 °C was conducted as described by (Pimchuai
et al., 2010). The brief explanation of the hydrophobicity experi-
ment is presented in the Supplementary section (A.3).
3. Results and discussion
3.1. Physiochemical and fuel properties
Ultimate and proximate analysis is an important characteriza-
tion tool to know the elemental constituent of the sample (pre-
sented in the Table 1). The HTC of individual feedstock resulted
in the increased in percentage carbon content, and decreased in
percentage hydrogen, oxygen and nitrogen contents. Average ele-
mental percentage carbon in the raw food waste (FWR), raw yard
waste (YWR) and the mix food and yard (YWR + FWR) waste sam-
ple was found out to be 37%, 45% and 42% respectively, whereas,
for its hydrochar sample (FWH, YWH and YWH + FWH) it was
found out to be 59%, 65% and 68%, respectively (Table 1).Table 1:
Ultimate, proximate and fuel properties of raw and hydrochar sam-
ple. The blend of FW and YW showed better carbonization poten-
tial as compare to FW alone, which suggested some synergetic
effect between lignocellulosic (YW) and non lignocellulosic (FW)
portion during HTC. Lower values of nitrogen in hydrochar sample
was mainly attributed to the fact that it may leach into the liquid
ð10Þ phase and nitrogen is unlikely to get detected in the gas phase as
reported in study by (Hoekman et al., 2011). It is self-evident from
Table 1 that HTC of food and yard waste decreased volatile matter
content and increased fixed carbon content. The decrease in vola-
tile matter and increase in fixed carbon is mainly due to the con-
densation and polymerization reaction that takes place during
HTC (Sharma et al., 2020). The increasing trend of percentage car-
bon content after HTC agrees with the outcome of the study using
yard waste as feedstock (Akbari et al., 2019).
The values of ultimate and proximate analysis reported here is
significantly higher than those reported for the other types of feed-
stock for different experimental set, example for MSW (Berge et al.,
ð11Þ 2011). Berge et al. (Berge et al., 2011) reported lower fixed carbon
content of the hydrochars resulting from the HTC of MSW feed-
stocks. However, Liu et al. (2010) reported a fixed carbon content
of carbonized pinewood to be around 43%, which is comparable
to this study. Berge et al conclude that the fixed carbon yield is
influenced by HTC process conditions and that larger fixed carbon
yields may result at different temperatures, reaction times, and/or
solids concentrations (Berge et al., 2011). HTC results in the
decrease of percentage ash content as compared to raw feedstock,
as evident from Table 1. The decrease in ash content was attributed
to high temperature HTC which caused inorganic components in
raw feedstock to dissolve in the liquid phase (Liu et al., 2014).
The lower the ash content of hydrochar potentially mitigated
ash-related problems by the use of hydrochar.
The molar atomic ratios of H/C and O/C of raw sample along
with its hydrochar are illustrated by the Van Krevelen diagram in
Fig. 1. The Van Krevelen diagram displays the evolution of H/C
and O/C molar atomic ratios and also illustrates the coalification
degree after HTC. Points near to the origin of the Van Krevelen dia-
gram suggested better coalification and far from origin show less
coalification. Furthermore, Van Krevelen diagram also delineates
the reaction mechanism as showed by the arrows in Fig. 1. The

Table 1
Ultimate, proximate and fuel properties of raw and hydrochar sample.

Sample YWR FWR YWR + FWR YWH FWH YWH + FWH

Elemental Analysis C (%) 44.2 ± 0.63 35.16 ± 3.36 42.41 ± 1.13 65.2 ± 0.83 59 ± 1 68.26 ± 0.96
H (%) 6.24 ± 0.99 4.9 ± 0.12 5.78 ± 0.25 5.83 ± 0.2 5.43 ± 0.08 6.02 ± 0.13
N (%) 0.84 ± 0.35 1.01 ± 0.02 0.99 ± 0.01 0.88 ± 0.03 1.56 ± 0.19 1 ± 0.07
O (%) 48.21 ± 1.69 56.8 ± 2.48 50.8 ± 1 28.05 ± 1.01 34 ± 0.85 24.4 ± 0.88
Proximate Analysis FC (%) 6.98 ± 0.47 15.75 ± 0.90 14.33 ± 0.57 40.64 ± 0.77 32.68 ± 0.75 37.56 ± 1.62
VM (%) 84.75 ± 2.46 76.62 ± -0.85 78.71 ± 0.84 55.54 ± 0.82 62.87 ± 0.32 57.4 ± 1.14
A (%) 8.30 ± 0.15 5.39 ± 0.35 7.05 ± 0.08 4.34 ± 0.12 4.14 ± 0.16 4.32 ± 0.02
@
HHV (MJ/kg) 15.43 ± 0.40 9.48 ± 1.40 13.54 ± 0.45 24.37 ± 0.75 21.64 ± 0.43 27.64 ± 0.48
Yield (%) 59.83 ± 1.75 13.64 ± 0.43 45.27 ± 1.28
*ED 1 ± 0.02 1 ± 0.02 1 ± 0.01
1
EY (%) 59.98 ± 0.50 13.64 ± 0.68 45.29 ± 2.01
Fuel ratio 0.07 ± 0.19 0.20 ± 1 0.18 ± 0.69 0.73 ± 0.93 0.51 ± 2.3 0.65 ± 1.41
@
Higher heating value: (HHV = 0.3383 * %C + 1.422 * (%H – %O/8).
#
Based on mean value*Energy Densification, 1Energy Yield.

524
H.B. Sharma, B.K. Dubey
Fig. 1. Van Krevelen diagram displays the evolution of H/C and O/C atomic ratios.
major reactions involved are decarboxylation, dehydration and
demethanation reaction which is suggested by the evolution of
the hydrochar samples following the diagonal line (Fig. 1).
According to the reaction vectors displayed in the diagram,
decarboxylation and dehydration were the main reaction during
HTC at 240 °C for all the sample type. A shift in the O/C ratio sug-
gests that decarboxylation also occurs (Berge et al., 2011). The
claim is well supported by the fact that HTC significantly decreased
H/C and O/C atomic ratios along the reaction vector displayed. It
can be observed that the raw sample showed higher atomic O/C
and H/C ratios, ranging from 0.81 to 1.61 (FWR), 1.15 to 1.60
(YWR) and 0.89 to 1.63 (YWR + FWR) whereas its respective hydro-
char moved towards origin. From the Fig. 1 it can be well argued
that that the dehydration was essential reaction pathway. The ratio
of O/C and H/C decreases in hydrochar compared with raw YW and
FW which was attributed to the dehydration reaction which causes
the elimination of H2O and CO2; the trend was similar to study on
YW by Akbari et al. (2019). In similar trend, the HTC of lignocellu-
losic biomass resulted in O/C–H/C ratios comparable to lignite
(Kambo and Dutta, 2014). The carbonization trend described above
could be due to the fact that the HTC process increased the carbon
content and reduced the oxygen content. It can be well inferred
from the decreased value of H/C ratio that substitution reaction
occurred in the reaction process and breakage of C-C chain
occurred, indicating increased instauration of the product (Soler
et al., 2018). The main reason behind the strong carbonization in
HTC is due to the presence of water as a reacting medium
(Kambo and Dutta, 2014). The values for HHV (Higher Heating
Value), fuel ratio, energy yield, and energy densification (ED) of
the samples were calculated and summarized in the Table 1. The
mean calorific values for the raw samples: YWR, FWR, and
YWR + FWR were 15.43 MJ/kg, 9.48 MJ/kg and 13.54 MJ/kg, respec-
tively. The calorific value of hydrochar: YWH, FWH, and
YWH + FWH were 24.37 MJ/kg, 21.64 MJ/kg and 27.64 MJ/kg
respectively. HHV increased upto100% by the HTC process on com-
525
Waste Management 118 (2020) 521–533
parison to the HHV of raw feedstock. In a similar trend, the HHV of
24.8 MJ/kg in the same range as bituminous coal was reported for
the type of YW sample used in the study of Akbari et al. (2019). The
improvement in HHV is linked with the increase in the carbon con-
tent. Berge et al, reported in their study that the HHVs directly cor-
relates well with carbon content of the organic solids (Berge et al.,
2011). The blend of food and yard waste hydrochar has higher HHV
as compared to individual feedstock. This is most likely due to
increased carbon content influenced by synergic effect of lignocel-
lulosic and non-lignocellulosic portion. The HTC process water has
been showed to have significant amount of organic acid like acetic,
levulinic acid and formic acid (Stemann et al., 2013). The acid
would help initiate hydrolysis reaction of food waste and improved
overall carbonization process, this explains why YWH + FWH
showed improved carbonization potential.
Results presented in the Table 1 indicates that the hydrochar
solid yield was minimum for FW. Percentage mass yield of food
waste significantly decreased as compared to yard waste and its
blend. The decrease can mostly be attributed to primary and sec-
ondary decomposition of FW during HTC. Mostly, polymer of FW
undergo dehydration and decarboxylation reaction to constitute
into gaseous and liquid product (Pińkowska et al., 2011; Reza
et al., 2014). Moreover, FW mostly contains easily degradable poly-
mer like cellulose, carbohydrate, lipids etc., as compared to YW
which are lignocellulosic is nature. These lignocellulosic compo-
nents (hemicellulose and lignin) are complex polymer of sugar
and phenols, which are not easily degraded and solubilized there-
fore resulting in lesser yield. As reported in the Table 1, ED (energy
densification) value improved after Co-HTC (equal or greater than
1 for all the sample type). The improved ED value is due to
decreases in solid mass due to dehydration and decarboxylation
reactions during HTC which causes energy densification (Berge
et al., 2011). It can be well understood from Table 2 that after
HTC the degradation of hemicellulose was almost complete. During
HTC process the initial hydrolysis reaction promoted by the pres-
H.B. Sharma, B.K. Dubey
Table 2
Fiber analysis of raw yard waste and yard waste hydrochar samples.
YWR YWH
Cellulose (%) 38.8 45.3
Hemicellulose (%) 25.2 3.3
Lignin (%) 19.1 28.8
ence of hot compressed water results in the cleavage of ether and
ester bonds between monomeric sugars which causes more degra-
dation of hemicellulose (Kambo and Dutta, 2015). The degradation
of hemicellulose results in the increase percentage concentration
per unit mass of lignin and cellulose. The trend could be seen in
Table 2, the percentage lignin for YWR was around 19% which after
HTC at 220 °C for 1 h increased to around 28%. The lignin trend for
YWH (with C: 65%, HHV: 24 MJ/kg and Mass yield (%) was ‘close
enough’ with the proposed model with lignin content 20% at sever-
ity factor 4.432 (with HHV: 24.9 MJ/kg, C: 59.30% and mass yield:
65.24% (Heidari et al., 2019).
Since, hemicellulose have the greatest capacity of water adsorp-
tion, while lignin shows little tendency for water sorption. There-
fore, the removal of hemicellulose which would cause fractional
increase in the lignin content will improve the hydrophobicity of
hydrochar (Kambo and Dutta, 2015). In terms of the HHVs of ligno-
cellulosic waste like YW, lignin has the highest heating value and is
in the range of 23.3–26.6 MJ/kg, followed by cellulose and hemicel-
luloses with about 17.6–17.9 MJ/kg (Demirbasß, 2005). The thermal
stability of lignocellulosic waste like YW from least to most follows
the order: Hemicellulose < Cellulose < Lignin (Grønli et al., 2002;
Kambo and Dutta, 2015). All the trend support the finding that
HTC significantly improved lignin content in the hydrochar which
in turn played a role of binder during FWH + YWH waste
pelletization.
3.2. Combustion behavior
The raw and hydrochar combustion behaviour is presentedin
Fig. 2(A) and (B) in the form of TG and DTG curve between 30
and 700 °C. The combustion parameter like ignition temperature
(Ti), burnout temperature (Tb), peak temperature at maximum
weight loss rate (Tm) were calculated using tangent intersection
method as described in our previous study (Sharma et al.,
2019b). Likewise, DTGm and DTGmean, indicating the maximum
and average weight loss rate respectively, were also calculated to
better understand the combustion profile of the sample. It is clear
from TG curve (Fig. 2(A)), that mass loss occurred mainly between
220 °C and 550 °C in two zones (zone 1 and zone 2) also known as
de-volatilization phase. Sandwiched between two zones in the
sharp DTG profile (Fig. 2(B)) of YWH depicts early onset of char
combustion which resulted in its reactive burnout and more final
residue.
The initial ‘‘bump” (DP zone) below 150 °C is ascribed to weight
loss (also seen below in the DTG curve) and is mainly associated as
dehydration phase during hydrochar combustion. The combustion
of FWR and YWR + FWR occurred in two stage (between the tem-
perature ranges of 220550 °C). The main mass loss which was
observed at the lower temperature was mainly caused by the
degradation of oxygenated functional groups carbon motif and
furan rings (Zhao et al., 2016). Apart from aforementioned reason
for mass loss, partial combustion and volatile matter release must
have happened which resulted in such mass loss trend. Likewise,
mass loss at higher temperature range may be attributed to the
conjugated carbon atoms oxidation (Zhao et al., 2016). The data
for the combustion parameters is presented in the Table 3. It is
clear from the table that HTC increased the ignition temperature
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Waste Management 118 (2020) 521–533
and extend the overall combustion zone of the hydrochar sample;
extended combustion zone depicts the stable thermal nature of
hydrochar and is more suitable for using it as a biofuel
The increase in the ignition temperature (Ti) means that hydro-
char was less volatile which was mostly due to decreased volatile
matter content as explained in the proximate analysis result. The
increased Ti value means that the storage and transportation of
hydrochar pellets would be less likely for fire hazard. Increased
Tm value for hydrochar depicts the improvement in the thermal
stability. The increased value of Tf which is ascribed to the
improvement in the fixed carbon content means, that hydrochar
has a longer combustion temperature range and is generally an
attribute of a thermally stable biofuel (Lucian et al., 2018). The
main sharp peak of YWH at 360 °C was due to the degradation of
lignocellulosic constituent of yard waste like cellulose and lignin.
The smaller shoulder peak of YWH around 250 °C is due to the
degradation of hemicellulose. The shoulder peak of hemicellulose
at 250 °C (Sharma et al., 2019a) was seen only for raw yard waste
(YWR) and was not seen on its hydrochar sample, which is ascribed
to its possible decomposition during HTC. The sharp DTG peak at
250 °C for food waste was due to rapid volatilization of volatile
matter content; the peak shifted to higher temperature range after
the HTC. The shifted peak at higher temperature was attributed to
the combustion of increased amount of fixed carbon content after
HTC (which is in the agreement with the proximate analysis
result). The improvement in lignin content could also be under-
stood by the fact that HTC improved calorific value of resulting
hydrochar and significantly improved combustion profile of TGA
(seen mostly due to improved value of burnout temperature (Tf)).
3.3. Combustion kinetics of hydrochar
The computation of kinetic parameters such as activation
energy is of paramount importance when industrial expansion of
HTC process is envisaged. The reaction collision frequency while
taking into account reactant orientation and contact surface of
solid fuel is represented by the pre exponential factor whilst,
energy barriers involved in the combustion stage is estimated by
the activation energy. As described in Section 2.4, the kinetic
h i
parameter was calculate using linear fit plot of ln lnð1aÞ
T2
and T1
using Coats–Redfern method. The kinetic parameters along with
the comprehensive combustion index (CCI), combustion stability
index (Rw) and Ignition index (Di) is presented in the Table 4.
The kinetic plot of the raw and hydrochar sample is shown in the
Fig. 2(C). Least square correlation value was greater than 0.85
indicting reasonable degree of fit. After HTC, both the activation
energy (Ea) and the pre-exponential facto (A) increased. It was
clear from the table that, ‘Ea’ and ‘A’ value increased after HTC.
The apparent values of Ea for YWH, FWH and YW + FWH were
2.39, 2.71 and 2.90 kJ/mol respectively. The increase in the activa-
tion energy as presented appears to contradict with the results pre-
sent in most of the literature. However, the results suggested
oxidative resistance at the commencement of hydrochar combus-
tion which was likely due to modification of char after HTC; most
likely due to formation of secondary char or re-polymerized char
on hydrochar surface (Gao et al., 2019). High temperature HTC is
also successful in components configuration of hydrochar which
result in higher resistance to oxidation, apart from forming the car-
bonaceous structures with greater energy content. Such compo-
nent demands higher initial energy to break energy barriers
during the combustion. Zhao et al. (2016) in their study concluded
that HTC could remove reactive species from the raw samples
which would possibly increase minimum energy required to fur-
ther carbonize the sample during combustion. Furthermore, hydro-
char structure is mainly aromatic in nature and elimination of
H.B. Sharma, B.K. Dubey Waste Management 118 (2020) 521–533

hFig. 2. iTGA profile showing different zones of degradation[DP = Dehydration Phase](A); DTG profile showing different rates of degradation (B); and linear fitted plot of ln
lnð1aÞ
T2
and 1T for determination of activation using Coats–Redfern method (C).

Table 3
Combustion parameters of raw sample and its respective hydrochar sample.

Sample DP (°C) DTGmax (%/s) DTGmean (%/s) Stage 1 Stage 2

Ti Tf Tmax Ti Tf Tmax
YWR 30–140 9.95 1.04 260 480 310 – – –
FWR 30–140 8.33 0.97 250 320 290 410 500 430
YWR + FWR 30–140 11.16 1.16 220 310 285 410 490 455
YWH 30–140 15.97 0.88 270 600 360 – – –
FWH 30–140 7.89 1.17 310 500 435 – – –
YWH + FWH 30–140 9.01 1.06 305 498 400 – – –

Table 4
Combustion kinetic parameters of raw and its respective hydrochar samples.

Sample CCI (107 min2 °C3) Di  10-5 (mg/(min°C2) Rw (105) A E (kJ/mol) R2

YWR 3.19 12 1.06 14.35 2.38 0.99
FWR 2.59 7.7 0.67 15.01 2.47 0.85
YWR + FWR 5.46 11 0.96 14.63 2.14 0.90
YWH 3.21 16 1.42 14.54 2.39 0.86
FWH 1.92 5.9 0.50 15.16 2.71 0.98
YWH + FWH 2.06 7.4 0.63 15.20 2.90 0.99

527
H.B. Sharma, B.K. Dubey
reactive species from sample will certainly increase energy barrier
thus increasing overall activation energy. These observations are in
logical agreement with the fact that post-carbonization preferen-
tially removed more reactive species from the samples thus
increasing the energy required for further carbonization as the
bond in the remaining structures would be increasingly aromatic.
Higher CCI, Di and RW imply combustion stability, which was evi-
dent from YWH sample (Table 4). However, for blend hydrochar,
its CCI, Di and RW got decreased and is likely due to higher reactive
component in food waste based hydrochar. However, YWH + FWH
was expected to have better combustion performance than
YWR + FWR and the contradictory result could be explained using
same argument used for the explanation of activation energy.
3.4. Structural properties of hydrochar
Functional group analysis using FTIR spectra of raw and hydro-
char sample is present in the Fig. 3(A). The spectra revealed abun-
dant availability of functional groups in both raw and hydrochar
sample. It is also clear that CAH, CAO and AOH function groups
were mostly present, which is mostly due to the cellulose, hemicel-
lulose and lignin present in the lignocellulosic feedstock. The peak
within the cyan shaded area (shown in Fig. 3(A)) centered at
3400 cm1 is mostly due to vibrational stretching of AOH groups
and amino groups present in phenols and alcohols (Wang et al.,
2018b). The decrease in the intensity of AOH for the hydrochar
sample is mostly due to dehydration reaction during HTC. As com-
pared to YWH, FWH showed greater extend of dehydration reac-
tion during HTC which is evident from the lowest intensity of
AOH stretching. The decrease in the intensity of the oxygenated
functional group (AOH) also mean increased hydrophobicity of
the hydrochar sample.
The FTIR band between 3000 and 2700 cm1 is ascribed to
ACHn group stretching and are mostly of aliphatic and aromatic
nature. The absorbance peak between 1700 and 800 cm1 are
mostly due to vibrational stretching of C@O, CAC and CAOAC
groups of esters, carboxylic acids or aldehyde from cellulose or lig-
nin and are indicative of CO2 generation (Gao et al., 2013). The raw
feedstock (FWR and YWR) contained obvious characteristics peaks
related to lignocellulosic component, including the AC@C stretch-
ing (1650 cm1) of benzene ring in lignin, the ACAO (1200–
1000 cm1) of hydroxyl group in cellulose, the AC@O
(1705 cm1) and AOAH stretching (890 cm1) of carboxyl groups
in hemicellulose (Zhuang et al., 2019). The particular band around
1700 cm1 was attributed to C@O stretching in hemicellulose. The
presence of ester, carboxyl and carbonyl ground in hydrochar sam-
ples indicates the domination of oxygenated functional groups on
the hydrochar surface (Sevilla and Fuertes, 2009). The overall trend
in the decrease of the intensity of band between 300 and
3800 cm1 suggested that the major reaction that occurs during
HTC of food waste and yard waste were dehydration and decar-
boxylation reaction (Sharma et al., 2019a; Elaigwu and
Greenway, 2016). After HTC, the oxygen containing functional
groups decreased via the reaction of dehydration and decarboxyla-
tion. Meanwhile, the characteristic peaks of lignin and cellulose
ranged from 1650 to 1450 cm1 becoming stronger and broader
in response to the high temperature HTC suggest the development
of single aromatics to polyaromatics (Fu et al., 2009).
The surface morphology of the raw and hydrochar sample is
presented in the SEM micrographs (Fig. 3(B). The modification
and breakdown of the surface of raw sample due to HTC process
is clearly visible in the respective SEM images of hydrochar. The
surfaces of raw sample were predominantly flakey in nature, while
its physical structure was intact. FW hydrochar surface was cov-
ered with numerous small independent carbon spheres while;
some were crossed linked into larger microsphere. The cross link-
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Waste Management 118 (2020) 521–533
ing of the smaller carbon sphere to form larger microsphere sug-
gest the polymerization and condensation reaction occurred
during HTC (Sevilla and Fuertes, 2009). The formation of micro-
sphere is a consequence of HTC reaction condition and the type
of feedstock used. The FW have abundant saccharide (glucose,
starch and sucrose) in it, as a result, more microsphere formation
take place after HTC. The variation in the microsphere formation
in YW and FW was due to the variation in the decomposition of
saccharides (starch and sucrose) which, obviously is greater in
FW (Sevilla and Fuertes, 2009). On the other hand YW exhibited
porous structure and no visible microsphere was observed. The for-
mation of the porous structure is related with volatilization of
organic matter during HTC. In the YWH + FWH sample, small
microspheres were dispersed along the hydrochar surface, which
may be due to localized condensation and aromatization reaction
of the sugars from the aqueous phase. The mixed feedstock
(YWH + FWH) showed different hydrochar formation pathway as
evident from SEM images. The result suggested that the hydrochar
from mixed feedstock (Co-HTC) showed different hydrochar for-
mation pathway as compared to single substrate HTC. The differ-
ence is due to the fact that during Co-HTC, FW provides
carbohydrates and nitrogen resources which behaves differently
during HTC (Wang et al., 2018b) as compared to single substrate
HTC where lignocellulosic component (lignin, hemicellulose and
cellulose) are carbonized in absence of carbohydrates source and
therefore behaves differently hence demonstrating different
hydrochar structure (Wang et al., 2018b).
The XRD pattern (Fig. S3) of raw and hydrochar sample
showed a broad diffraction peak at a 2h range of 12–28° which
is the indication of non-graphitic carbon (Wang et al., 2011).
The microcrystalline structure of raw FW disappeared after HTC
as evident from the disappearance of 2h peak at 20° for FWH
sample. The interlayer reflection due to the asymmetrical poly-
cyclic aromatic sheets of amorphous carbon could be attributed
to the appearance of broad peak in the hydrochar sample (Sun
et al., 2013). The Co-HTC of FW and YW produced the hydrochar
with distinct XRD pattern which suggested that carbonization
was affected by presence of food waste. However, localized
graphitization was seen in the YW and YW + FW hydrochar
which was evident from the peak at 2h at 23° and 26° for both
the samples type, respectively. The localized graphitization
means, that during HTC, crystalline cellulose was preserved which
was mainly due to presence of protective layer of lignin in ligno-
cellulosic waste like YW (Wang et al., 2011).
4. Pelletization
4.1. Mass and energy density
Energy density of the pellets depends on the mass density and
the calorific value. The mass density was measured using method
explained earlier while energy density was calculated by multipli-
cation of mass density with HHV. The values of the mass and
energy densities of the raw and hydrochar sample are presented
in the Table 5. The mass density of the all the hydrochar sample
increased and was maximum (1678 Kg/m3) for the YWH + FWH
sample. Likewise, FWH pellets showed around 46% increase in
the mass density after HTC. Possibly, such drastic increase in the
mass density of FWH (1445 Kg/m3) pellets was due to the fact that
the hollow microspheres as seen in SEM images crumbled during
pelletization pressure which led to the agglomeration (easy com-
paction) of more mass per unit volume. Despite FWH showing
highest increase in the mass density, YWH + FWH showed highest
energy density which was due to the higher lignin content (higher
HHV of lignin) in YWH.
H.B. Sharma, B.K. Dubey Waste Management 118 (2020) 521–533

Fig. 3. FTIR spectra of raw and hydrochar sample (A); and SEM images of raw and hydrochar sample (B).

Table 5
Mechanical properties of fuel pellets along with their mass and energy density.

Sample Maximum compressive force (N) Tensile strength (MPa) Length Expansion (%) Mass Density (kg/m3) Energy Density (MJ/m3)
YWR 302 1.91 23.09 1597.40 24.49
FWR 79.6 0.51 11.52 990.71 9.39
YWR + FWR 202 1.29 10.64 1595.68 21.61
YWH 959 6.11 0.84 1621.06 39.51
FWH 188.3 1.20 8.31 1444.86 31.27
YWH + FWH 414 2.64 6.91 1678.00 46.38

4.2. Mechanical and morphological properties of pellets Eq. (11) to find out its tensile strength. The value of the tensile
strength and compressive force applied are presented in the
For mechanical strength, the pellet samples were tested for ten- Table 3. It is clear that maximum tensile strength was observed
sile strength using UTM. Applied compressive force was used in the for YWH pellet followed by its blend pellets hydrochar pellets

529
H.B. Sharma, B.K. Dubey
(YWH + FWH). Least compressive force was observed for FWR pel-
let and followed by FWH. The stress-strain graph (Fig. 4) also
revealed poor performance by both FWR and FWH pellets. The
poor mechanical strength of the FWH and FWR pellets was due
low lignin content as the main components of the FW are mainly
carbohydrates, protein, glucose and lipid, which are incapable to
form strong bridging between particles to improve mechanical
strength. It is clear from the SEM images of FWH (Fig. 4(A)) and
its pellets that the possible limited mechanical strength was
mainly due to carbon-microspheres which relies much on the
attraction forces without a solid bridge formation between the
Fig. 4. Surface morphology of the raw pellets sample and their respective hydrochar pellets (A); and image showing the fractured pellets under compressive force and its
stress-strain profile (B).
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Waste Management 118 (2020) 521–533
adjacent particles. The absence of solid bridge formation between
the food waste hydrochar particles resulted in weak tensile
strength of the resulting pellets.
On the other hand, when the blend of yard waste and food
waste hydrochar was pelletized, resulting pellets showed improve-
ment in its tensile strength. The tensile strength of YWH + FWH
was 2.64 MPa which was comparable to tensile strength
(2.70 MPa) of food waste hydrochar (prepared at 230 °C) pellets
produced using 15% molasses as binder by Wang et al (Wang
et al., 2019). Furthermore, hydrochar produced at 240 °C and 15%
molasses binder showed less tensile strength (2.02 MPa) as com-
H.B. Sharma, B.K. Dubey Waste Management 118 (2020) 521–533

pared YWH + FWH. Likewise, food waste hydrochar pellets pro-

duced at 200 °C and using 20% molasses as binder by Saqib et al.
(2019b) showed comparable tensile strength (2.8 MPa) with
YWH + FWH. The solid bridge formed by YWH hold the hydrochar
particle together in a pellets matrix. Moreover, soften lignin from
YW (during heated pelletization temperature (>90°, glass transi-
tion temperature)) acts as a binder thus helps in improving the
tensile strength. The high temperature HTC results in decomposi-
tion of hemicellulose and cellulose and improves percentage lignin
content per unit mass of hydrochar. The lignin enriched hydrochar
from YW is responsible for increasing tensile strength of the
pellets.
The brittle nature of YW hydrochar pellets was clear from the
sudden drop in stress-strain graph (Fig. 4(B)); however, YWH
was still durable as compared to FWH. The brittle nature of the
YW and YWH + FWH pellets was possibly due to weakening of
hydrogen bond between cellulose and lignin, and covalent bond
between cellulose fibers due to high temperature HTC (Wang
et al., 2017). From the stress-strain graph, it is also clear that
YWH + FWH pellets showed improved resiliency to the compres-
sive loading and didn’t followed fate of FWH; rather,
YWH + FWH pellets showed multiple breaking peaks. The fracture
of YWH + FWH pellets in multiple breaking peaks rather than brak-
ing in ductile manner similarly to FWH pellets is due to the rein-
forcement provided by lignin rich YWH. The plausible
explanation for the improvement of the durability of YWH infused
FWH pellets is due to the interpenetration of the soften lignin from
YWH into its particle matrix during heated pelletization. During
the high pressure pelletization, lignin enhanced YWH will release
lignin (after getting crushed) from its retained cellular structure.
During heated pelletization (T > 90 °C) lignin softens and starts
to flow and engulf adjacent FWH particles. When the pellets cools
down, softened (sticky) lignin gets converted into glossy solidified
lignin thus developing solid bridge between YWH and FWH
particles.

4.3. Storage properties

The economic prospects of biofuel pellets production is greatly
affected by transportation, handling and storage of pellets. Durable
pellets are easy to handle, store and transport. The raw biomass
sample when pelletized has a natural tendency to spring back
due to elastic recovery effect which causes pellets to undergo nat-
ural length expansion. The pellets which exhibit higher length
expansion are more susceptible to disintegration and are likely to
reduce its durability. Likewise, raw biomass also has tendency to
absorb moisture; pellets made as such is likely to promote fungal
and bacterial growth during storage and transportation. Therefore,
it becomes very important that pellets produced have high density
(mass and energy) and are hydrophobic. The natural length expan-
sion of undisturbed pellet over a two weeks shown in Fig. 5(B).
It is clear from graph (Fig. 5(B)) that YWH showed minimum
length expansion (around 3%) and FWR showed maximum length
expansion (around 32%). Food waste hydrochar showed maximum
length expansion of about 11%, followed by blend (YWH + FWH)
(around 7.5%) and YWH (around 2.5%). The trend for higher length
expansion for FWH is most likely to be caused by the elastic recov-
ery of raw FW particles which also indicates its poor bonding
within the pellet matrix. The length expansion of more than 30%
for raw FW means that food waste was unable to hold pellets
matrix together and would be easily disintegrated. The blend of
FW and YW pellets demonstrated less length expansion as com-
pared to FW pellets, which is most likely due to interaction effect
of YW presence in pellet matrix. The lignin from YW softens during
pelletization at the glass transition temperature (sample was
heated at 90 °C during pelletization) thereby demonstration ther-
531
Fig. 5. Moisture absorption profile of the pellets samples in humidity test chamber
(A); and length elongation profile of pellet samples (B).
mosetting properties; this thermosetting properties are responsi-
ble for particle binding and dimensional contraction, and for
holding the pellets matrix together (Kashaninejad and Tabil,
2011). However, higher length expansion of raw YW pellets as
compared to its hydrochar pellets indicate the possibility of pore
spaces and gaps in the pellet matrix, which reduces the pellet resis-
tance to relative movement during storage and transportation
(Jiang et al., 2016).
It is also confirmed that the strong bonding between hydrochar
particles and the excellent durability is directly related to HTC
reaction severity. Hydrochar of higher severity condition have
higher lignin content. In other words, higher reaction severity
HTC reduces the spring back effect of raw YW pellets. Higher reac-
tion severity HTC degrades hemicellulose which has viscoelastic
properties within the YW fiber matrix; its degradation reduces
the stress relaxation of the component and lowers the spring back
effect (Zaini et al., 2017). The higher length expansion decreases
pellets density, mechanical hardness and pellets resistance to
impact loading during storage and transportation.
Fig. 5(A) presents the moisture absorption profile of pellets sub-
jected to relative humidity 60% at 40 °C. The YWH showed least
moisture absorption capacity (around 3%) proving its hydrophobic
nature. FWH was the worst performer as it showed maximum
moisture absorption (approx. 10%). The YWH + FWH pellets
showed less absorption capacity as compared to FWH asserting
H.B. Sharma, B.K. Dubey
its hydrophobic nature. It becomes clear that the YWH addition in
blend (YWH + FWH) not only improved mechanical durability, also
enhanced hydrophobicity. The improvement in hydrophobicity is
attributed to the reduction in oxygenated functional (AOH) in
hydrochar during high temperature HTC which makes resulting
pellets less hygroscopic (Kambo and Dutta, 2014).
5. Estimation of coal replacement potential
The hydrochar sample YWH + FWH was chosen for energy cal-
culation based on the idea that both the organic fraction of MSW
will be equally utilized for hydrochar production.
Electricity generation from hydrochar production was calcu-
lated as below (Eq. (12)).
ðGJÞ ¼ W  Y  DHc g
 ð12Þ
where, W is the total annual organic waste produced in the world
(8.85 * 1011 kg) (taken from world bank report, i.e. 44% of total
waste generated is green and food waste (Kaza et al., 2018)), g
 is
the efficiency of coal-fired power plants 0.33 (Mau and Gross,
2018), Y is Hydrochar yield (0.48) and calorific value is denoted
by DHc.
Electricity from coal was found using equation (Eq. (13)):
ðGJÞ ¼ 3600 E ð13Þ
where, E is a worldwide electricity production from coal in GWh
and is equal to 9,707,489 GWh (Mau and Gross, 2018). A fraction
of coal replaced by hydrochar was found out using Equation (Eq.
(14)).
Electricity from hydrochar production
F¼  100% ð14Þ
Electricity from coal
F is fraction of coal replaced by hydrochar combustion.
According to the World Bank report, an estimated 2.01 billion
metric ton of solid waste is generated annually worldwide (Kaza
et al., 2018). Of the total waste generated, green and organic waste
comprises approximately 44%. If green and organic waste is
hydrothermally converted into hydrochar; about 424 million met-
ric tons (hydrochar yield) of hydrochar could be generated. If all
the OFMSW derived hydrochar derived is combusted, up-to 3.8 bil-
lion GJ of renewable energy could be generated, which is equiva-
lent to approximately 11% of electricity generated worldwide by
coal (Eq. (14)). Hence, it becomes evident that hydrochar derived
from the organic fraction of MSW like yard and food waste could
be a potential renewable energy source to substitute coal.
The detail mechanism of pellets production under Co-HTC con-
dition is explained in the supplementary section (Supplementary;
A.1). It should be noted that, although as calculated above, there
is a coal replacement potential of 11% by YWH + FWH hydrochar
combustion which would only be possible if an ideal conditions
are achieved in terms of these combustion facilities. A detailed
technical and economic analysis is needed supported by compara-
tive techno-economic and life cycle assessment tools to ascertain
real coal replacement potential during field scale applications.
6. Conclusion
Carbon rich hydrochar with a calorific value up to 27.64 MJ/kg
was derived from the Co-HTC of food waste with lignocellulosic
yard waste. Food waste when carbonized and pelletized along with
yard waste produced a durable and hydrophobic pellets with a ten-
sile strength of 2.64 MPa. Above glass transition temperature,
soften lignin of lignocellulosic yard waste hydrochar played a role
of binder, and therefore eliminated the need of additional binder.
Hydrochar showed stable combustion profile with improved com-
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Waste Management 118 (2020) 521–533
bustion parameters as compared to raw feedstock. Worldwide
combustion of food and yard waste hydrochar has a potential to
replace 11% of global coal consumption in an ideal setting thus,
identifying itself as a new renewable energy feedstock.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgement
The grant of PhD Research Scholarship to Mr. Hari Bhakta
Sharma by the Indian Institute of Technology Kharagpur is highly
acknowledged by the authors. Mr. Rajesh Kola is acknowledged
for his assistance during elemental analysis. Likewise, Venkata
Sai Praneeth is acknowledged for his help during analysis of coal
replacement potential.
Appendix A. Supplementary material
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.wasman.2020.09.009.
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