Journal of Cleaner Production 277 (2020) 124295

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Journal of Cleaner Production

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

Binderless fuel pellets from hydrothermal carbonization of municipal

yard waste: Effect of severity factor on the hydrochar pellets
properties
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 s

Article history: It has become crucial to understand the combined effect of temperature and time on hydrochar pellets
Received 11 February 2020 quality if large scale pellets production is envisaged. This study investigated the effect of hydrothermal
Received in revised form carbonization (HTC) of yard waste at different severity factor (SF) based on the Arrhenius equation on the
15 September 2020
fuel, mechanical, storage, transport and combustion characteristics of the hydrochar pellets. No addi-
Accepted 16 September 2020
Available online 20 September 2020
tional binder was used. The increasing SF level during HTC has a direct effect on the calorific value and
energy density of the hydrochar pellets. Tensile strength of the hydrochar pellets increased from
^as de
Handling Editor: Cecilia Maria Villas Bo 1.53 MPa to 4.80 MPa for lowest and highest SF level respectively. The natural length expansion of
Almeida hydrochar pellets was maximum (21%) for lower SF, and was minimum (7%) for higher SF level pellets.
Higher SF level increased the mass (1662 kg/m3) and energy (42 MJ/m3) density of pellets as compared to
Keywords: lower SF level (1473 kg/m3 and 27 MJ/m3 respectively). The result of hydrophobicity, impact resistance
Hydrothermal carbonization and length expansion revealed that the lower SF level hydrochar pellets has lower durability as
Hydrochar pellets compared to higher SF level hydrochar pellets. Higher SF level improved combustion performance of
Solid waste
hydrochar pellets which was evident from the improved burnout and ignition temperature. The study
Pelletization
revealed that densified, durable, energy-rich fuel pellets could be produced from municipal yard waste
Biofuel
Renewable energy using HTC at a higher SF level without using any binders thus identifying itself as a valuable renewable
energy source.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction
Ever increasing energy demand has necessitated the need for
the transition towards renewable energy system. In order to in-
crease the share of renewable energy sources, waste materials/
biomass is increasingly being used as a fuel or as a feedstock for fuel
production (Stancin et al., 2020). Despite its increasing utility, use of
traditional biomass with inferior fuel properties should be
discouraged, instead focus should shift toward used and production
of enhanced biofuels (Stancin et al., 2020). The production of bio-
fuel pellets from organic waste and biomass as an enhanced biofuel
is being studied extensively for last several years (Mostafa et al.,
2019). The global wood pellets production has increased steadily
from 7 Mt in 2006 to more than 26 Mt in 2015. The expanding
* Corresponding author.
E-mail address: bkdubey@civil.iitkgp.ac.in (B.K. Dubey).
global wood pellets market demand is being met globally from
expanding supplier such as Asia, Latin America, and Australia
(Thr€ an et al., 2017). Pellets has more market value as compared to
the chips and powder mainly due to its higher mass and energy
density. Pellets are easy to handle, store and transport as compared
to powder and chips.
Research regarding biomass pelletization using range of feed-
stock has attracted great attention in academia due to enormous
potential in the market recently (Kang et al., 2019); however,
without any pre-treatment raw biomass pellets present technical
challenges during co-firing (Gao et al., 2019). Raw biomass has a
lower heating value and higher oxygen content, which increases
the fuel reactivity thereby, limiting the amount of biomass that
could be blended with coal. The raw biomass pellet also has higher
bulk volume due to its fibrous clinging nature which increases the
natural rebound effect of pellets after pelletization causing high
length expansion. The ambiguity over using raw biomass pellets
still prevails which are mainly due to its poor durability and strong

https://doi.org/10.1016/j.jclepro.2020.124295
0959-6526/© 2020 Elsevier Ltd. All rights reserved.
H.B. Sharma and B.K. Dubey
affinity for moisture which becomes very critical if its long-term
storage is envisaged under ambient weather conditions (Liu et al.,
2014). Hygroscopic fuel pellets absorbs free moisture from the
ambient environment and opens the pores by swelling which ul-
timately leads to its disintegration. The absorbed moisture also
provides a conducive environment for bacterial and fungal activity
which promotes biodegradation of fuel during the storage. The
microbial activity generates heat and gas which create a high risk of
fire hazard during storage and transportation. Pellets with high
durability and low moisture uptake (hydrophobic) would be
preferred for repetitive loading, unloading and for long distance
transport. Pellets prepared from the untreated raw biomass have
weak mechanical strength, lower mass and energy density. Me-
chanical and the fuel properties of the pellets also depend on the
component of feedstock and as well on the pellets preparing
conditions.
In a growing area of research moisture-laden organic waste like
Yard waste (henceforth YW), food waste (Saqib et al., 2019), agri-
cultural residues (Zhu et al., 2018) and other waste biomass (Zhu
et al., 2019) is being treated in a process called as hydrothermal
carbonization (HTC). The HTC treatment doesn’t needs pre-drying
of moisture laden feedstock to produce carbon-rich char; which
mean aforementioned challenges of raw biomass could be handled.
The HTC is a thermochemical treatment process which uses sub-
critical liquid water as the reaction medium to convert moist
waste into carbon rich hydrochars (Sharma et al., 2020). The HTC
process mostly rely on the chemical dehydration, decarboxylation
and demethanation reaction to convert organic waste into carbon-
rich hydrochar (Funke and Ziegler, 2010). Reaction mechanism
mentioned above mostly lowers atomic H/C and O/C ratio, thus
making hydrochar properties similar to that of the lignite coal.
Hydrochar have demonstrated higher mass and energy densities,
improved hydrophobicity and grindability and higher carbon con-
tents as compared to the product of other treatment processes
(Sharma et al., 2019).
The hydrochar produced is then pelletized to produce hydrochar
pellets. Integration of hydrothermal pretreatment and pelletization
presents a promising method to produce carbon-neutral, solid
biofuel from waste biomass (Theppitak et al., 2020;
Ruksathamcharoen et al., 2019). The major factors that influences
hydrochar pellet quality include feedstock properties, particle size,
processing conditions. Extend of mechanical durability of pellets
also depend on different types of binder used. Most commonly
used binder for the production of the mechanically durable pellets
are starch, crude glycerin, protein and molasses (Hu et al., 2015).
Utilization of binder depends on the cost-effectiveness and envi-
ronmental impacts that it incurs (Whittaker and Shield, 2017).
Apart from different types of commercial binding agent, Equilib-
rium Moisture Content (EMC) in the sample can also act as binder/
lubricant by establishing liquid bridging with adjacent particles
(Kaliyan and Morey, 2010). Lignin, which is the component of
lignocellulosic waste also can act as a natural binder above its glass
transition temperature (lignin softens at the glass transition tem-
perature) (Reza et al., 2012). The soften lignin above its glass
transition temperature has a viscous flow which engulfs the nearby
particle. When the temperature falls below the glass transition
temperature softened lignin gets solidify with the engulfed particle
and creates a solid bridge. The established solid bridge increases
the mechanical durability of the pellets produced.
The study by Liu et al. (2014) using different woody biomass to
produced fuel pellets was limited to only single temperature; effect
of different hydrochar production temperature on the quality of the
hydrochar pellets was not carried out. The study by Yan et al. (2014)
using Loblolly pine at two different temperature was limited only to
density and water immersion test. The comprehensive study on the
2
Journal of Cleaner Production 277 (2020) 124295
mechanical, storage and combustion properties was not carried
out. In our previous study (Sharma et al., 2019a) it was found that
the higher reaction severity produces YW hydrochar powder with a
poor flowability. The YW hydrochar powder with poor flowability is
mostly appropriate for making fuel pellets and briquettes rather
than using it in a fluidized combustion bed (Sharma et al., 2019a).
Aforementioned conclusion with respect to pellets production from
YW was based on the flowability parameter and not on actual
pelletization study. This study is a follow up to the same study to
investigate the theoretical conclusion made in the previous study
by conducting actual comprehensive pelletization study using
severity factor approach. The unknown reaction orders, in-
teractions, and intensities has delayed the commercialization of
HTC (Heidari et al., 2019). To characterize HTC reaction processes in
which both temperature and time are important parameters, it is
useful to combine these parameters into a single factor that defines
overall reaction severity (Hoekman et al., 2017). To understand the
combined effect of HTC reaction time and temperature, concept of
severity factor (SF) has been introduced Hoekman et al. (2017). The
dearth of knowledge on the introduction of concept of severity
factor for the production of fuel pellets from municipal solid waste
like municipal yard waste has necessitated this study. It becomes
crucial to understand hydrochar pellets quality on the different
severity condition if large scale pellets production is envisaged.
Yard waste constitutes a significant fraction of MSW in devel-
oping nations. Due to limited technological options and knowledge,
YW is mainly burned or left to decompose (which cause GHGs
emission) in the designated dumpsite in the developing countries.
Due to its high moisture content in YW, the quality of the pellets
gets affected. Properties like; elongation, moisture absorption, hy-
drophobicity and strength (compressive and tensile) become very
critical in view of long term storage and transportation of YW
pellets. Finding of this study would help policymaker to identify the
abundant YW generated in municipality as a valuable renewable
energy sources and eliminate its indiscriminate disposal related
problem. The objectives of this study were to (1) hydrothermally
carbonized municipal yard waste and evaluate its fuel properties
under different HTC severity condition (2) preparation of hydrochar
pellets using self-designed pelletizer and subsequently assess its
mechanical, storage and combustion properties while taking
severity factor into consideration and thereby, shed light on the
binding mechanism.
2. Material and methods
2.1. Material
Municipal YW as feedstock was collected from the Indian
Institute of Technology Kharagpur (IIT), West Bengal, India.
Municipal YW mostly consisted of fallen leaves, grass trimming,
and twigs, etc., which were mixed homogeneously using a blender.
The detail of municipal YW collection procedure, composition and
grinding procedure can be found in our previous study (Sharma
et al., 2019a). The prepared municipal YW simple was stored in
an airtight vessel for further analysis.
2.2. Hydrothermal carbonization
In the present study, HTC of municipal YW was conducted in a
750 mL stainless steel reactor (Chemito India). The detail of the
reactor is shown in the schematic diagram as shown in Fig. 1. Solid
to liquid ratio (YW: Water) used in this study was 1:20 for each
experiment. The nitrogen was purged into the reactor for 5 min to
expel all the oxygen from the reactor while keeping external
release valve open. After the purging was concluded, the reactor
H.B. Sharma and B.K. Dubey Journal of Cleaner Production 277 (2020) 124295

Fig. 1. Schematics of the HTC reactor used in the study.

was sealed and programmed with a heating ramp of 13 ± 4 C/min

at the motor stirring rate of 100 RPM. The reaction severity (shown
in Table 1) was chosen based on the findings of our previous study
(Sharma et al., 2019a). After the reaction was completed, the reactor
was turned off and immersed in a cold ice bath to quench the re-
action beyond the desired reaction time. Once the temperature
dropped below 100 C the pressure valve was immediately released
and rector was opened. Step by step procedure was followed to
mimic the exact same HTC experimental procedure as in our earlier
study (Sharma et al., 2019a) with non-stirring reactor. The dark
coffee-scented slurry was vacuum filtered using the cellulose ni-
trate membrane filter (0.45 mm) and was washed with distilled
water. The hydrochar was dried at 105 C for more than 16 h and
was stored in a zip lock bag until further analysis.
To have a better sense of how the temperature and the residence
time during HTC together can affect pellets properties, severity
factor (SF) based on the Arrhenius equation (Eq. (1)) and (Eq. (2))
were used.
T 100=14:76
Ro ¼ te
SF ¼ log Ro (2)
Where, Ro ¼ reaction ordinates (min); t ¼ Reaction time (min);
T ¼ Reaction temperature (oC). The nomenclature of the sample
was based on the severity factor and the same is presented in
Table 1.
The extend of the coalification and delineation of the reaction
mechanism during HTC for stirred and non-stirred case (pervious
study using the smaller reactor) under exact same reaction condi-
tions (Sharma et al., 2019a) was also compared to understand the
need for the stirring condition during HTC of the grounded
municipal YW sample.
3. Preparation and characterization of the pellet
3.1. Pelletization
Prior to the pelletization experiment, raw YW, and hydrochar
samples prepared at the different severity factor level was groun-
(1)
ded using a ball mill (NSAW, TM, and India). In each run 5 g of the
sample was grounded for 20 min at 100 RPM. Sieve of different size

Table 1
Sample nomenclature on the basis of severity factor. ̊
Reaction Temperature (o C) Raw 160 180 200 200 200 200 200

Reaction time (h) Raw 2 2 2 4 8 12 24

Severity Factor (SF) e 2.7 2.8 2.9 3.2 3.5 3.7 4
Sample Name YW SF2.7 SF2.8 SF2.9 SF3.2 SF3.5 SF3.7 SF4

̊ 3
H.B. Sharma and B.K. Dubey
(75 mme425 mm) was used to analyze the particle size distribution
of the grounded samples. The ground sample was used for pellet-
ization experiment. The densification experiments were performed
using self-designed hydraulic hand pellets press used in our pre-
vious study (Sharma and Dubey, 2020(fortcoming)). Briefly, pellet
press consists of a piston of 10 mm diameter and 110 mm length,
and a cylinder die slightly more than 10 mm internal diameter and
90 mm length. Image of fabricated pelletizer with detail parts and
process of pelletization in the form of schematics diagram is shown
in Fig. 2. The material of construction was hardened stainless steel
(SS 316). Band heater was attached to the pellet die to heat the
sample to the desired temperature during pelletization. Thermo-
couple and temperature controller was attached to the heating
band and the temperature was set to 100  C. The small aount of
moisture content in the sample acts as a natural lubricant and
binder during pelletization (Kaliyan and Morey, 2010). To bring the
sample into EMC both the raw and hydrochar samples were
exposed to the open environment conditions with relative hu-
midity between 60 and 70% for at least 24 h before the pelletization.
EMC of the sample was calculated using the gravimetric method.
The EMC of the sample YW, SF2.7, SF2.8, SF2.9, SF3.2, SF3.5, SF3.7
and SF4 were around 5%, 4%, and 3.5%, 2.7%, 2.3%, 1.5%, 1.3% and
0.40% respectively.
For each pelletization experiment top of the cylindrical hole was
manually filled with 1.2 g of sample. The die was heated to more
90  C (mainly it being a glass transition temperature of lignin which
helps form a natural binder within the pellets (Reza et al., 2012)).
Fig. 2. Schematic of the fabricated self-designed hand pelletizer at laboratory, and process of pelletization (Phase wise, 1e3).
4
Journal of Cleaner Production 277 (2020) 124295
The bottom of the die was closed using a removable backstop plate.
For each pelletization experiment, sample was compressed with
pressure of 250 MPa using a lever attached to the hydraulic hand
pellet press. The compressed sample was then held under the
applied pressure for 30 s, and thereafter it was released and back
stop was removed. Once the backstop was removed, the pellets
were extruded out by reapplying the pressure on the same die
channel without the backstop. The extruded pellets were left un-
disturbed for 1e2 min, after which its mass, length and diameter
were measured. The pellets was then kept in a sealed container at
4  C for one week to find out its natural length expansion.
3.2. Length expansion of the pellets
A digital vernier caliper (Advance, Tm No. 1348969) was used to
measure the dimensions of the pellets (as conducted in the previ-
ous study (Sharma and Dubey, 2020(fortcoming))). The length
expansion of the pellets were calculated using the following
equation:
Li L0
L¼ (3)
L0
Where Lo is the length of the initial pellets immediately after the
pelletization and Li is pellets length at the end of one week (after its
natural length expansion due to rebound effect).
H.B. Sharma and B.K. Dubey
3.3. Mass and energy density measurements
The density of each pellet was calculated based on the mea-
surement of dimensions (i.e. length and diameter for cylindrical
pellets and expressed as the ratio of the mass to volume). The
volume of the pellet was determined by using a digital caliper
(Advance, Tm No. 1348969). The mass was measured using an
analytical balance (Afcoset Balances e ER200A). Each pellet was
weighed to the nearest value of 0.0001 g. By multiplying the mass
density of the pellet with the HHV (Higher Heating Value) of the
pellet its volumetric energy density was calculated.
3.4. Tensile strength measurements
The internal bonding strength or the maximum force that pellet
can withstand can be found out using compressive or tensile
strength of pellets (Zhu et al., 2018). The formula given in the
equation below was used to calculate the tensile strength of fuel
pellets.
2f
Tp ¼ (4)
pld
Where “f” is maximum force; “d” is the diameter of pellets and
length of pellets is denoted as “l”. Each pellets were placed hori-
zontally between the two anvils of the universal testing machine
(UTM) (H50KS, Tinius Olsen United Kingdom), and the compressive
force was given to it until the pellets were broken and maximum
force was recorded. The compression rate of 1 mm/min was pro-
grammed in the UTM. The UTM was immediately stopped when the
fractured in the pellet was observed and the graph started to
recede.
3.5. Durability assessments
The impact resistance, the drop resistance or the shattering
resistance test was conducted to simulate the pellets durability
during transportation and handling as describe by Kaliyan and
Morey (2009). Impact Resistance (IR) of the samples was evalu-
ated by dropping the hydrochar pellets from the height of 1.83 m
onto the steel surface four times. The weight retained as the per-
centage of the initial weight was taken as the pellet durability
(Kaliyan and Morey, 2009).
4. Hydrophobicity
4.1. Equilibrium moisture content (EMC)
The moisture content of the sample in the thermodynamic
equilibrium with the moisture in the ambient environment is
defined as Equilibrium Moisture Content (EMC). The EMC test was
tested for understanding the hydrophobicity of the pellets. The
controlled environment (Humidity test chamber: Carelab Tech-
nology, India) with a relative humidity: 48e52% was used to
determine the EMC of raw YW and the hydrochar pellets samples
(Kambo and Dutta, 2014). The test was conducted at 22e25  C for
24 h. The exposed raw YW and hydrochar samples were dried in an
oven at 103  C for 16 h. The EMC was expressed as the change in the
weight before and after drying.
4.2. Moisture absorption
4.2.1. Water immersion test
Water immersion test (Pimchuai et al., 2010) was conducted to
demonstrate the water resistance capacity of the hydrochar pellets,.
5
Journal of Cleaner Production 277 (2020) 124295
Briefly, experiments were conducted by immersing the pellets in
water for 2 h. Later the pellets were removed and the excess water
was drained using adsorbent paper. The pellets were then exposed
to a controlled environment (relative humidity: 45e60% at
35e38  C) for 4 h (natural condition). The final weight of the
sample was recorded after 4 h exposure to the controlled envi-
ronment. The change in the initial and final weight was expressed
as the moisture content.
4.2.2. Moisture absorption kinetics
In another set of experiment, pellets were exposed to a relative
humidity of 45e60% at 35e38 C using humidity test chamber
(Carelab Technology, India) and its weight was recorded at the in-
terval of 5 min for first 1 h. After 1h, pellets weight was recorded at
the interval of 60 min up to 8 h. Final weight of the pellets sample
was recorded after 12 h. The raw and hydrochar pellets sample
were dried at 105 C for 24 h in a hot air oven before the moisture
uptake test. The moisture absorption kinetic was studied using thin
layer model using Equation (Eq. (5)).
M Meq kt
¼e (5)
Mo Meq
Where, M, Meq, and M are moisture at time t, equilibrium moisture,
and initial moisture content in dry basis respectively. The coeffi-
cient k is moisture absorption constant (min 1) and ‘t’ is the
exposure time (min).
5. Thermal analysis and characteristic combustion
parameters
Thermal analysis of the sample was conducted using TG-DTG
analyzer (PerkinElmer Pyris Diamond). All the combustion exper-
iments were carried out in a temperature range of 50e850  C. The
heating rate during the experiment was 15  C/min. The air was
purged at the flow rate of 100 mL/min.
̊ The tangent intersection
method was used to determined ignition temperature (Ti), burnout
temperature (Tf). Thermal gravimetric analysis (TGA) and Differ-
ential Thermogravimetric analysis (DTG) are used to measure the
weight loss and rate of weight loss of the sample respectively under
high-temperature̊ conditions in a controlled atmosphere. The
combustion stability index (Rw) by using Eq. (6) (Chen et al., 2018).
DTGm
Rw ¼ 8:5875  107  (6)
Ti  Tm
Here, DTGm is maximum weight loss rate and Tm represent the
peak temperature at the maximum loss weight loss rate. Com-
bustion stability index was used to understand the combustion
stability of hydrochar combustion, and its higher value indicates
improved combustion stability (Xie et al., 2018).
6. Results and discussion
6.1. Basic fuel analysis
The proximate and ultimate analyses of the raw municipal YW
and hydrochar prepared at different severity factor (SF) level are
presented in Fig. 3. It is evident that with the increase in the SF
level, fixed carbon content increased but at the same time the
volatile matter content decreased. High volatile matter content in
the municipal YW, and hydrochar prepared at low SF is a proof that
it would burn violently with high reactivity, exhibiting lower en-
thalpies of combustion when directly combusted (Gao et al., 2019).
Municipal YW has around 85% volatile matter content and
H.B. Sharma and B.K. Dubey
Fig. 3. Ultimate and Proximate analysis of raw municipal YW and Hydrochar sample prepared at the different HTC severity factor. [C: Carbon; H: Hydrogen; N: Nitrogen; H:
Hydrogen; O: Oxygen; A: Ash content; VS: Volatile Solid; FC: Fixed Carbon].
approximately 7% fixed carbon content. Hydrochar prepared at
highest SF has the least volatile matter content while fixed carbon
content was highest. Volatile matter content in the hydrochar
sample SF4 was approximately 63% and fixed carbon content was
around 28%.
The increase in the elemental carbon and fixed carbon content,
and decrease in the oxygen and volatile matter content with an
increase in HTC reaction severity is evident from the table
(Table A1). The carbon content of the raw municipal YW was 44%
which got substantially increased to 60% upon increasing the HTC
reaction severity to 4.
With decreased O/CeH/C atomic ratio with increasing HTC re-
action severity, hydrochar fuel properties became more like lignite.
The O/CeH/C atomic ratio for the hydrochar SF4 was 0.40e1.03,
which was similar to lignite coal. Increasing reaction severity also
reduced the oxygen content. Raw municipal YW has around 50%
oxygen content, which upon increasing the reaction severity from
SF2.7 to SF4 got decreased to 49 to 32% respectively. Form the data
presented in Table A1, it is clear that increasing the reaction severity
during HTC improved the percent fixed carbon and elemental
carbon content; however, decreased volatile mater content and
oxygen content. The reason for which is mainly due to the fact
higher severity during HTC promotes more ionization of water
which in turn promoted dehydration and decarboxylation reaction
by means of bond cleavage (Kambo and Dutta, 2015a). The extend
of the coalification process and delineation of the reaction mech-
anism using Van Krevelen diagram during HTC for stirred and non-
stirred case (pervious study using smaller reactor) however, under
same reaction condition (Sharma et al., 2019a) was compared and
shown in (Fig. 4). No substantial different in the coalification extend
was achieved in the present study as compared to the previous
study (non-stirred case). For a well grinded sample, having stirring
condition makes not much of a different with respect to fuel quality
if stirrer is not used in the reactor. Well grinded feedstock would
6
Journal of Cleaner Production 277 (2020) 124295
naturally be able to mix well during high temperature HTC;
therefore, for the feedstock with smaller particle size, and having
less heterogeneity, the reactor with stirrer might not be needed.
Despite less significant changes stirred condition facilitated more
decarboxylation reaction as compared to prevailing demethanation
reaction for the non-stirred case (as shown by the arrows for each
samples in Fig. 4). Dehydration reaction was major reaction in both
the case as it is evident from the Van Krevelen diagram Fig. 4 (A).It
is apparent that for a well grinded and finer particle size feedstock a
non-stirred reactor could be designed during upscaling of the HTC
technology.
The particle size distributions of all the grounded raw and
hydrochar samples are presented in Fig. 4. Higher grindability was
observed for the hydrochar produced from the HTC of higher SF
level. The HTC at higher severity factor level significantly improved
grindability of municipal YW waste by changing its lignocellulosic
microstructure which lowers its fibrous nature. Degradation, de-
polymerization followed by softening of lignocellulosic compo-
nent (hemicellulose, cellulose and lignin) also helps in the wrecking
of the municipal YW thereby improving its grindability (Sharma
et al., 2019a). The durability of the hydrochar pellets gets signifi-
cantly affected by its particle size. The finer particle size accepts
moisture which helps in the conditioning the fibers (Kaliyan and
Morey, 2009). The fine particles with moisture will promote
liquid bridge formation apart from inducing attractive molecular
force due to its ability to develop more contacts points during
pelletization pressure. Besides, large hydrochar particles in the
pellets cause cracks and fractures in pellets.
6.2. Mechanical properties
6.2.1. Mass and energy density
Pellet density which is an important parameter determines the
energy density per volume and the hardness of the pellets. The
H.B. Sharma and B.K. Dubey Journal of Cleaner Production 277 (2020) 124295

Fig. 4. Coalification and delineation of reaction pathway during hydrothermal carbonization showed in Van Krevelen diagram (A). The effect of HTC severity factor on the particle
size distribution is shown in B.

information about the energy and mass density of hydrochar pel-
lets are crucial in the transportation and handling economics to
reduce inefficiency in logistics. The fuel pellets with high bulk and
energy density occupy less space during storage and trans-
portation, thereby minimizies the expenses incur with it. Since
carbon content is directly related to calorific value (HHV) (Sharma
et al., 2019a) therefore, improvement of its value improves overall
density (as energy density is directly related to HHV). The mass and
the energy density are presented in Table 2. The minimum value of
the bulk density set for solid biofuel pellets set by ISO is 600 kg/m3
(Mostafa et al., 2019). Likewise, European guideline has set
accepted standard range of density for single pellets density to be
around 1000e1400 kg/m3 (Emadi et al., 2017). The result presented
in Table 2 is self-explanatory about the fact that with an increase in
the reaction severity level the mass density of the hydrochar pellets
produced increased.
The municipal YW pellets have the least mass density (around
1445 kg/m3) and energy density (about 23 MJ/kg). Hydrochar pel-
lets SF4 has around 41 MJ/kg of energy density as compared to
approximately 23 MJ/kg for the hydrochar pellets SF2.7. During the
pelletization process the sample was heated at 90  C to soften the
lignin which helped to bind the hydrochar particle together.
Hydrochar produced at higher reaction severity generally has
higher lignin content (Kambo and Dutta, 2015b); therefore, for the
same pelletizing pressure we observed different mass and energy
density of pellets. Increased in the lignin content not only helps in
binding the hydrochar particle together during pelletization but it
also improves calorific value (mainly due to the higher carbon
content in the lignin as compared to the other components). The
density of the produced hydrochar in this study is within the
guideline of the ISO standard. Likewise, pellets produced at higher
SF level (>SF3.2) exceeded the minimum value set by the European
standard and meets the export quality.
6.2.2. Surface morphology
The photographic surface appearance of raw municipal YW and
its hydrochar pellets prepared at different reaction severity is
shown in Fig. 5. Hydrochar prepared from the higher reaction
severity (SF3.5, SF3.7 and SF4) when pelletized produced smooth
surface pellet in comparison to pellets prepared from hydrochar
prepared at low reaction severity (SF2.7, SF2.8, SF2.9 and SF3.2). As
can be seen from Fig. 5, the pellet from the raw municipal YW has a
very rough surface while glossiness seems apparent for the SF3.5,
SF3.7 and SF4.0. The increase in the darkness (often related with
carbon/charcoal) of the hydrochar pellets with the rise in the HTC
reaction severity was clearly visible (Fig. 5). The enhanced darkness
was due to enhanced carbonization and restructured lignin with
the increase in HTC reaction severity level. Lignin, which itself is a
natural binder is squeezed out of the matrix during pelletization
process and formed a dark glassy coating. The dark glassy coating
can act as solid bridges which bind the hydrochar particles together
(Kalyani and Pandey, 2014).
The surface morphology of the pellet surface was also recorded
using the optical analyzer Microscope (Leica DMLM, Germany) to
understand bonding mechanism of the pellets better. It is clear
from the micrograph (Fig. 5) that surface of hydrochar pellets

Table 2
Mass and energy densities, tensile and compressive strength, the calorific value of raw yard waste and hydrochars pellets prepared at the different severity factor level.

Sample Maximum compressive Tensile strength Length Expansion HHVb(MJ/ Mass Density (Kg/ Energy Density Modulus (N/ a
IR Ultimate stress (N/
force (N) (MPa) (%) Kg) m3) (MJ/m3) mm2) (%) mm2)

YW 124.60 0.79 23.09 15.78 1444.86 22.80 21.20 95.04 1.58

SF2.7 240.00 1.53 20.91 18.23 1472.70 26.85 36.70 95.90 3.05
SF2.8 269.00 1.71 20.6 18.94 1485.58 28.14 36.90 95.90 3.42
SF2.9 465.00 2.96 15.81 20.09 1497.22 30.08 83.80 95.90 5.91
SF3.2 676.00 4.31 15.68 20.70 1531.73 31.71 151.20 96.69 8.60
SF3.5 854.00 5.44 12.04 20.89 1558.27 32.55 223.00 97.52 10.87
SF3.7 628.00 4.00 7.73 23.99 1580.83 37.92 167.00 98.35 7.99
SF4.0 754.00 4.80 6.74 25.54 1661.59 42.44 227.00 99.17 9.60
a
Impact Resistance (IR).
b
HHV ¼ 0.3383  C þ 1.422  (HeO/8) (Xiao et al., 2012).

7
H.B. Sharma and B.K. Dubey
Fig. 5. Microscopic and photographic image of pellets and surface priced at different severity level (100X).
(SF3.5, SF3.7 and SF4) was very smooth and uniform without any
apparent voids and cracks. On the other hand, hydrochar pellets
(SF2.7, SF2.8, SF2.9 and SF3.2) although was devoid of any apparent
crack yet small voids and gaps/surface undulation (surface rough-
ness) existed on the surface. In contrast, raw municipal YW pellets
surface revealed substantial voids/surface undulation which could
even be felt by touching the surface by hand. The presence of a gap
indicated poor adhesion. These voids and undulation can reduce
the pellet stiffness to the deformation during load application
(during storage and transportation) which may promote the
movement of particles within the matrix of the pellets thereby
making pellets mechanically less durable. The presence of voids/
gaps and undulation implies not so strong between hydrochar
particles.
8
Journal of Cleaner Production 277 (2020) 124295
6.2.3. Compressive strength and durability
Fig. 6 shows stressestrain curves under compressive loading of
the raw municipal YW pellets and hydrochar pellets produced at
different HTC reaction severity. The maximum compressive forces
tensile strengths, young’s modulus and ultimate stress for all the
pellets are presented in Table 2. Stress strain curve show the
complete picture of mechanical behaviour of the material. Strain is
the physical deformation response of a material to stress. With the
help of such curves we can understand how the material deforms
with increasing loads. Under the applied compressive loads, some
materials fracture at their compressive strength limit while others
deform irreversibly; therefore, compressive strength is a key value
to understand the mechanical properties of pellets. Compressive
strength/Tensile strength (N/MPa) of raw biomass pellets and
H.B. Sharma and B.K. Dubey
Fig. 6. Stress-Strain curves of the yard waste and hydrochar pellets showing the deformation mechanism. Sharp fall of the graph depicts the brittle nature of the pellets (up).
Photographic image of fractured hydrochar pellets after compressive strength test depicting the nature of fracture (down).
hydrochar was in the following order: S3.5 (854/5.44) > S4.0 (754/
4.8) > S3.2 (676/4.31) > S3.7 (628/4) S2.9 (465/2.96) > S2.8 (269/
1.71) > S2.7 (240/1.53) >YW (124.6/0.79). The broken pellets image
after compressive strength test using a universal testing machine is
shown in the figure (Fig. 6). The bottom images (Fig. 6) showed that
the deformation of the YW hydrochar pellets (SF2.7, SF2.8, SF2.9
and SF3.2) under steady compression rate was mainly in the axial
direction. On the contrary, deformation of the pellets prepared
from hydrochar prepared at higher reaction severity (SF3.5, SF3.7
and SF4) was in its radial direction at ultimate compressive force.
Moreover, these pellets broke into two halves with a sharp cracking
sound. The deforming/breaking pattern of raw municipal YW pel-
lets and pellets of hydrochar prepared at low reaction severity
(SF2.7, SF2.8, SF2.9 and SF3.2) show weak bonding within hydro-
char pellets matrix. On the other hand hydrochar pellets (SF3.5,
SF3.7 and SF4) deforming pattern revels strong bonding within
hydrochar particles.
The sudden rupture of hydrochar (SF3.5, SF3.7 and SF4) pellets
9
Journal of Cleaner Production 277 (2020) 124295
into a two half at the maximum applied load revealed its brittle
nature. Hoekman et al., in their study (Hoekman et al., 2014) have
concluded that the pellets prepared from the hydrochar prepared at
higher temperature are brittle. The phenomenon is possibly
because at the high reaction severity HTC, lignin gets degraded and
loses the glass transition behaviour. The brittle nature of the
municipal YW pellets was possibly also due to weakening of
hydrogen bond between cellulose and lignin, and the covalent bond
between cellulose fibres due to high-temperature HTC (Wang et al.,
2017). However, for brittle pellets, ultimate applied load far
exceeded the ultimate load applied for other pellets, and therefore
is much stronger and durable for mechanical loading, unloading
and transportation.
It is clear that the increase in the severity factor during the HTC
increased tensile strength; however, it was only accurate up to a
certain limit. There was a sharp decrease in tensile strength value
after certain limit (Table 2). During compression test, pellets pro-
duced from raw municipal YW and lower SF hydrochar sample
H.B. Sharma and B.K. Dubey
(SF2.7, SF2.8, SF2.9 and SF3.2) showed barreling tendency and
deformed slowly. Pellets produced from higher SF hydrochar (SF3.5,
SF3.7 and SF4) showed no barreling tendency and quickly fractured
with a snapped sound. The deformation and fracture trend of raw
YW and its hydrochar pellets is clear from the stress strain plot. The
sharp fall of graph for pellets (SF3.5, SF3.7 and SF4) is proof that the
hydrochar produced at higher reaction severity produces a pellet
with a brittle nature. Hydrochar pellets SF3.2 showed maximum
tensile strength of 4.31 MPa at 676 N compression loading without
showing any brittle nature. Brittle material breaks under subjected
load without significant plastic deformation as it absorb relatively
little energy before fracture; it’s true for even high strength mate-
rial. Hydrochar pellets (SF3.5, SF3.7 and SF4) are characterized as a
brittle by the fact that rupture occurs without any notice prior
change in the rate of elongation during compressive strength test.
Among all hydrochar pellets, SF3.5 showed maximum tensile
strength 5.44 MPa at compression load of 854 N. The SF3.5 pellet
was able to withstand the maximum ultimate stress of 10.87 N/
mm2; it also had a maximum modulus value (223.00 N/mm2).
Young’s modulus measures the resistance of a material to elastic
(recoverable) deformation under load. A stiff material has a high
Young’s modulus. A flexible material has a low Young’s modulus
and changes its shape considerably.
6.2.4. Durability
Drop test (Kaliyan and Morey, 2009) was conducted to investi-
gate the impact resistance of the pellets. Impact resistance dura-
bility of the raw and hydrochar pellets (IRS) is presented in Table 2.
It can be observed from the table that the improvement in the IRD
of the pellets is directly related to the increases in the HTC reaction
severity level. Hydrochar produced at higher reaction severity
when pelletized improved pellets durability. The IRD of raw
municipal YW pellets was around 95%, and it increased with an
increase in HTC reaction severity (i.e. from SF 2.7 to SF4). IRD for
SF2.7 was 95%, and for SF4.0 it was 99%. Fine particles of the
hydrochar pellets tend to shatter into powder when dropped in a
metal plate from the height of 1.83 m (Kambo and Dutta, 2014). The
higher pelletization pressure helps bridge the hydrochar particles
by reducing the voids and space between them. A strong bonding
force between hydrochar particles makes hydrochar pellets devoid
of such fissure and voids. The reduced voids and spaces enhance
contact between hydrochar particles which leads to the improve-
ment in the bonding mechanism of hydrochar pellets. Besides with
the increase in the HTC reaction severity, the lignin percentage gets
improved (Kambo and Dutta, 2014). The hydrochar with higher
lignin percentage when pelletized with high pressure bind the
hydrochar particles together. Lignin gets squeezed out during high
pressure heated pelletization forming dark glassy coating which act
as solid bridges (Kaliyan and Morey, 2010). This is the reason in the
improvement in the IR value of the pellets with high SF. The pri-
mary bonding mechanism for pellets is predominantly due to the
attractive force like hydrogen bonding, van der Waals force and
mechanical interlocking. However, extractives in raw municipal
YW prevents close contact between two bonding sites which leads
to a weak hydrogen bonding and van der Waals force (Liu et al.,
2014). The reduced hydrogen bonding, Vander wall force and me-
chanical interlocking between raw municipal YW particles make its
pellets less durable against impact loading as compared to hydro-
char pellets.
6.3. Storage properties
6.3.1. Length expansion
Length expansion of the raw municipal YW and hydrochar
pellets were recorded to understand spring back effect, also called
10
Journal of Cleaner Production 277 (2020) 124295
an elastic recovery effect after two week of storage. Fig. 7 shows the
detailed length expansion of the pellets. The pellets produced from
the hydrochar of higher SF HTC showed only limited expansion,
exhibiting consistent dimensional stability compared to the raw
YW pellets. As shown in the figure, raw municipal YW pellets
showed maximum length expansion (23%) over 2 weeks time. This
is most likely to be caused by the elastic recovery of raw YW par-
ticles which further indicates its weak bonding within the pellet
matrix. It is clear from the graph that the length expansion of the
pellets is the direct function of HTC reaction severity. Pellets pre-
pared from the hydrochar produced from the higher HTC reaction
severity (SF3.5, SF3.7 and SF4) has lower length expansion as
compared to pellets made from hydrochar of lower reaction
severity (SF2.7, SF2.8, SF2.9 and SF3.2).
Notable length expansion was observed within the initial two
days after which no apparent expansion was observed even after
the four days of storage for the hydrochar pellets SF3.7 and SF4. For
raw municipal YW pellets, expansion was noticed until 7 days. The
narrow length expansions of the hydrochar pellets of higher SF
value confirmed the strong bonding between hydrochar particles
and the excellent durability of hydrochar pellets (Liu et al., 2014). It
also confirmed that the strong bonding between hydrochar parti-
cles and the excellent durability is directly related to HTC reaction
severity. Hydrochar of higher SF have higher lignin content; lignin
softens during pelletization at the glass transition temperature
(sample was heated at 90  C during pelletization) and exhibits its
thermosetting properties which was responsible for particle
binding and dimensional contraction.
Furthermore, higher length expansion of raw municipal YW
pellets indicated the existence of pore spaces and gaps within the
pellet matrix. The pores and gaps reduces the pellet resistance to
relative movement (Jiang et al., 2016b). In other words, higher re-
action severity HTC reduces the spring back effect of municipal YW
pellets. Higher reaction severity HTC degrades hemicellulose which
has viscoelastic properties within the YW fiber matrix; its degra-
dation 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. 7. Length expansions of the raw yard waste pellets sample and pellets produced
from hydrochar prepared at different severity factor level.
H.B. Sharma and B.K. Dubey
6.3.2. Hydrophobicity analysis
The moistures uptake profile of the raw municipal YW and
hydrochar pellets against the exposure time are presented in Fig. 8.
The raw municipal YW pellets revealed greater moisture uptake as
compared to the hydrochar pellets, and no observable moisture
adsorption was observed even after 300 min of exposure of raw
municipal YW pellets, and 80e200 min for hydrochar pellets. For
the SF4.0 hydrochar pellets, EMC was observed within 80 min. It is
clear from the figure that the saturated moisture content for the
raw municipal YW pellets was around 5%. With the increase in the
SF level during HTC, saturated moisture content decreased and was
lowest for the SF4.0 hydrochar pellets. The trend in the decrease of
the saturated moisture content with the increasing reaction
severity was attributed to the hydrophobicity of the hydrochar
samples which increased with an increase in reaction severity.
Due to the improved hydrophobicity, the hydrochar samples
showed strong resistance against water immersion. The raw
municipal YW pellets and its hydrochar pellets were immersed in
the water and its moisture content and swelling evaluated using
the method described in the methodology section. Fig. 9 shows the
appearance of pellets after 2 h water immersion test. Water im-
mersion test result for the raw yard waste pellets, and pellets
produced from hydrochar prepared at different severity factor level
is shown as percentage moisture absorption (PMA) (Table 3).
Following observations were made immediately after the pellets
were dropped/immersed in a beaker full of water.
1. The raw municipal YW pellet immediately started to disinte-
grate and completely crumbled within 1 min after water
immersion.
2. Pellets made from lower severity hydrochar (SF2.7, SF2.8) when
dropped in the beaker full of water started floating however, it
immediately started swelling and disintegrating. The disinte-
gration however was relativity slower as compare to the raw
municipal YW pellets. The SF2.7 hydrochar pellets swelled and
disintegrated within the 4 min of water immersion. The SF2.8
pellets started to elongate after the 4 min of water immersion
to almost four times its initial size. The elongation took place
for 4 min before it completely disintegrated. The fate of raw
YW and hydrochar pellets after water emersion test is shown in
Fig. 9.
Fig. 8. Moisture uptakes profile of raw YW and hydrochar pellets.
11
Journal of Cleaner Production 277 (2020) 124295
3. Pellets made from higher severity hydrochar (SF2.9, SF3.2, SF3.5,
SF3.7 and SF4) when dropped in the beaker full of water,
immediately sank to the bottom (Fig. S1).
4. Among the pellets that sank, pellets SF2.9 and SF3.2 started
swelling after 9 min. Pellets SF3.5 developed bubbles at its
surface (Fig. S1) after 9 min; however, its swelling rate was
lower.
5. Hydrochar pellets SF3.5, SF3.7 and SF4 retained its complete
shape with minimum swelling even after 2 h of water immer-
sion. The hydrochar pellets SF3.2 and SF3.5 got swollen and
elongated 2 to 4 times its initial size however without getting
disintegrated (Fig. 9 and Fig. S1).
6. Hydrochar pellets SF4 showed complete repellent property and
robustness, as no visible bubble and swelling was noticed even
at the end of the 2h experiment.
Table 3 shows the percentage of moisture absorption after the
water immersion test. The trend in the reduction of the moisture
absorb with increasing severity factor is clear from the table. It is
clear the PMA for SF4.0 hydrochar pellets is least (1.67%) and for
municipal YW pellets it was around 55%. The result of PMA, and the
behaviour of pellets during the water immersion test indicated that
the pellets produced from the YW hydrochar at higher SF (mainly
SF3.7 and SF4) are highly hydrophobic and therefore can be stored
and transported without being decomposed by bacterial or fungal
activity. The shipping/transporting of such hydrophobic pellets will
be less costly as less water content (moisture content) would be
carried along with it as compared to raw hygroscopic municipal YW
pellets. In order to compare mechanical properties of municipal YW
hydrochar pellets prepared from hydrochar produced at different
severity factor with other studies, Table A.2 was summarized.
6.3.3. Discussion on the hydrophobicity analysis of hydrochar
pellets
The robustness of the hydrochar pellets due to the inability of
water to soak in inside the surface of the hydrochar pellets owing to
its hydrophobic nature likely results from the removal of hydro-
philic hydroxyl ( OH) groups from the municipal YW and the in-
crease of hydrophobic carbon content (Zhu et al., 2018). The
saturated moisture content of municipal YW pellets mainly
depended on the HTC condition. The hydrophobic behaviour of the
hydrochar is directly linked with the chemical composition of
feedstock and the chemical composition is greatly altered by HTC
condition. The HTC condition can change the hydrophobicity of the
hydrochar pellets. For example, among lignocellulosic component,
hemicelluloses have the greatest capacity of water adsorption
whereas, lignin shows the least tendency for water sorption
(Acharjee et al., 2011). Higher reaction severity HTC removes
hemicellulose, which fractionally increases the lignin content. The
reduction in the hygroscopic hemicellulose and the increase in the
hydrophobic lignin content (comparatively) improved the overall
hydrophobicity of hydrochar pellets made from hydrochar of
higher reaction severity HTC. Raw municipal YW tends to absorb
moisture from the atmosphere even after drying. Presence of such
moisture promotes fungal and bacterial growth which makes
stored feedstock likely to rot with time. The chemical composition
of raw municipal YW has a strong influence on hydrophobic
behaviour. Untreated raw biomass can self-ignited or/and release
harmful toxic gaseous during storage and transportation due to
sufficient heat release by microbial activity or chemical oxidization
reaction promoted by absorbed moisture. Therefore, hydropho-
bicity is a critical property as moisture absorbed can affect not only
the durability but also the energy density and the combustibility of
the pellet (Jiang et al., 2016a; Peng et al., 2013). Lignocellulosic
waste like municipal YW can adsorb moisture in three different
H.B. Sharma and B.K. Dubey Journal of Cleaner Production 277 (2020) 124295

Fig. 9. Fate of raw yard waste and hydrochar pellets after 2 h water emersion test.

Table 3
Water immersion test result for raw yard waste pellets sample and pellets produced
from hydrochar prepared at different severity factor level.
a b 1
Sample PMA (%) k (min )

YW 55.18 0.0180
SF2.7 53.26 0.0198
SF2.8 52.60 0.0186
SF2.9 44.72 0.0140
SF3.2 33.67 0.0163
SF3.5 13.48 0.0179
SF3.7 9.85 0.0153
SF4.0 1.67 0.0285
a
Percentage moisture absorption after water immersion test.
b
Moisture absorption constant.

ways: (a) free water (b) non-freezing bounded water, and (c)
freezing bounded water. Hydrogen-bonding to the hydroxyl groups
of the cell wall is the characteristic of the both non-freezing and
freezing bounded water. Relative humidity and the non-bounded
moisture are directly related with each other (Kambo and Dutta,
2014). Raw biomass is difficult to store in either indoor or out-
door conditions. All this results in expensive handling and storage
of raw municipal YW pellets mainly incur in terms of energy spent
in evaporating the water before combustion or gasification for
power generation. The aforementioned findings clearly support the
reason behind the high hydrophobicity of the HTC pellets as
compared to raw YW pellets.

6.4. Combustion properties

The hydrochar and raw municipal YW combustion profiles using

thermogravimetric (TG) and Differential Thermogravimetric (DTG)
process are shown in Fig. 10. Due to the exact HTC condition (except
the slow stirring condition of 100 RPM in this case) of the grinded
municipal YW sample as our previous study (Sharma et al., 2019a),
the combustion profile of the sample in this study got precisely
replicated. The replicated combustion profile proves the reliability
of the experiment conducted for the production of hydrochar. Fig. 10. TG (above) and DTG (below) of the pellets prepared from the hydrochar
Furthermore, the replication of the combustion profile also shows prepared at different severity factor level.
that the stirring condition of the already grinded municipal YW
sample was insignificant. The likelihood of replication of the
combustion profile is strongly supported by the fact that the municipal YW pellets are summarized in Table 4. The ignition
proximate analysis result was insignificantly different from the temperature and burnout temperature was found out using inter-
previous study [For comparison data is available at Table A.1 and section methods as followed in the previous study (Sharma et al.,
(Sharma et al., 2019a)]. The combustion characteristic temperatures 2019b). As depicted in the DTG (Fig. 10), the combustion of the
and different peak points during combustion of hydrochar and raw hydrochar pellets and raw municipal YW pellets took place at three

12
H.B. Sharma and B.K. Dubey Journal of Cleaner Production 277 (2020) 124295

Table 4 7. Overall discussion on the municipal yard waste

The combustion properties of the pellets prepared from yard waste and their cor- pelletization and binding mechanism
responding hydrochars prepared at the different severity factor level.

Sample Rw (10 5) Dehydration phase Devolatilization Ti Tf The primary process by which the fuel pellets becomes resilient
phase involves compaction, flow, and binding of solid particles. The pro-
Tmax DTGmax (%/s) Tmax DTGmax (%/s) cess that takes during and before compaction is illustrated in the
YW 0.0177 80.04 0.08 336.5 0.45 272.3 385.6 figure (Fig. 11, motivated from (Kang et al., 2019)). During the
SF2.7 0.0243 71.39 0.07 359.6 0.63 312.1 387.5 heated pelletization process high pressure transmitted by plunger
SF2.8 0.0254 71.39 0.07 363.5 0.66 312.5 390.1 may help develop solid bridge mainly due to diffusion of molecules
SF2.9 0.0241 71.39 0.07 366.5 0.63 313.5 410
between two particles at the contact point. The solid bridge may
SF3.2 0.0270 71.39 0.04 375 0.71 315.3 410.6
SF3.5 0.0154 71.39 0.03 373 0.41 318.4 440.1 also get developed due to crystallization of some ingredients,
SF3.7 0.0114 68.44 0.02 375.8 0.29 318 475.2 chemical reaction, hardening of binders, and solidification of mel-
SF4.0 0.0060 101.97 0.01 420.5 0.23 320.5 490.5 ted components (Kalyani and Pandey, 2014). The primary binding
Ti, Tf, DTGmax and Tmax represents; Ignition temperature, Burnout temperature, mechanism in a pelletized hydrochar is due to solid bridge for-
Maximum weight loss rate, Temperature at maximum weight loss rate respectively. mation. In the absence of solid bridge formation when high pres-
sure causes the particle to come together forces such as molecular
stages viz: dehydration phase (until 150  C), volatilization phase hydrogen bridges, van der Waals’ forces, magnetic forces and
(200  Ce500  C) and char combustion/burnout phase electrostatic could cause solid particles to stick to each other. The
(500  Ce700  C). The stages are also represented by yellow boxed EMC present in the hydrochar particles will help to form liquid
in a DTG plot. From DTG profile it is clear that initial mass loss bridge that would help hold particles together by capillary and
(dehydration phase) occurred below 150  C. The DTG max viscous forces. The increase in the HTC reaction severity increases
(maximum weight loss rate) during dehydration phase was only the lignin percentage (Kambo and Dutta, 2014). When hydrochar
observed for YW sample (0.08%/s) which was mostly due to higher with higher lignin percentage is pelletized (heated pelletization)
moisture value as compared to the hydrochar sample. Hydrochar with high pressure lignin gets squeezed out of the matrix and forms
are hydrophobic in nature due to the elimination of oxygenated dark glassy coating. The glossy dark coating of soften lignin acts as a
function groups during HTC; therefore, they have less moisture solid bridge that binds hydrochar particles together (Kaliyan and
content and have less weight loss rate during the dehydration Morey, 2010). The removal of hydrophilic hydroxyl ( OH) groups
phase. The reaction mechanism like hydrolysis, dehydration and from the YW and the increase of hydrophobic carbon content
decarboxylation are responsible for the removal of oxygenated caused by higher severity HTC (Zhu et al., 2018) are the main reason
function group. Pellets experienced mass losses in two steps after for the improved robustness of the hydrochar pellets. The improved
the dehydration phase as shown in figure (indicated by the bigger robustness of the hydrochar pellets is mostly attributed to the
and smaller yellow boxes). It is clear from DTG profile that the main inability of water to soak inside the hydrochar pellets owing to
mass loss occurred in the second mass loss stage (larger yellow box) improved hydrophobic nature of YWH. The higher severity HTC
for all the pellets. The main reason for the maximum mass loss at improves grindability of hydrochar. The hydrochar with high
the second stage is due to the release of the volatile matter. grindability leads to formation of finer hydrochar particles when
Hydrochar pellets demonstrated lower reactivity as compared to grinded (Fig. 4 (B)). Finer hydrochar particle gets easily pelletized
the raw biomass pellets which is evident from the inversely related which causes the reduction in the voids and spaces thereby
temperature value at the maximum weight loss rate. The increased enhance contact between hydrochar particles which leads to the
Ti and the decreased DTG max of the hydrochar pellets made from improvement in the bonding mechanism of hydrochar pellets. The
higher SF hydrochar (SF3.5, SF3.7 and SF4) indicated stable com- finding presented above is scientifically valid; as for the pellets, the
bustion of the hydrochar pellets as compared to low SF hydrochar major bonding mechanism is predominantly due to the attractive
pellets (SF2.7, SF2.8, SF2.9 and SF3.2). The higher thermal efficient force like hydrogen bonding, van der Waals force and mechanical
hydrochar pellets can be achieved as suggested by the increased interlocking.
final temperatures and the continuous and elevated combustion At higher reaction severity HTC, most of the hemicellulose and
temperature ranges. The elevated combustion temperature ranges some cellulose get degraded from YW, while very less lignin get
of hydrochar pellets (especially of higher SF value: SF3.5, SF3.7 and degraded (concentrating the lignin per unit mass). The lignin gets
SF4) on comparison to raw YW suggests reduced emissions during soften during high-temperature pelletization which promotes the
combustion. YW pellets have lowest Ti (272.3  C) and Tf (385.6  C) formation of solid bridges between particles when soften lignin
value. The narrow combustion range of raw municipal YW pellets gets harden once the pellets gets cooled (solidification of melted
suggested high reactivity due to high volatile matter content (refer components) (Kalyani and Pandey, 2014). The HTC at higher reac-
table of ultimate and proximate analysis: Table A.1). tion severity leads to the formation of polar organic compounds
With the increase in the severity, both Ti and Tf value increased. like furan and phenolic resins. The intermediate products like de-
Ti and Tf value for pellets SF4 were 320.5  C and 490.5  C respec- rivatives of furan and other chemicals react with each other during
tively, as compared to 312.1  C and 387.5  C respectively for SF2.7. complex HTC reaction to form cross-linked oligomers and polymers
High reactivity of the raw municipal YW pellets and as well of known as furan resins (Hoekman et al., 2014). The furan acts as an
pellets of low severity hydrochar (SF2.7, SF2.8, SF2.9 and SF3.2) can adhesive by creating liquid bridge which helps in the binding the
also be described using high maximum weight loss rate (DTGmax) of hydrochar particles together during pelletization which result in
raw municipal YW pellets and low SF value pellets. The DTGmax pellets with high compressive strength. The HTC also improves
value for raw YW pellets was 0.45 and its value for hydrochar friability/grindability of YW hydrochar which promotes formation
pellets SF4 was 0.23. The DTGmax occurred at 336.5  C for raw YW of smaller hydrochar particles (Sharma et al., 2019a). The smaller
pellets. The significant rise of DTGmax temperature was seen for hydrochar particles during pelletization promotes the formation of
hydrochar pellets SF4 (420.5  C). The increased Ti and Tf value and strong electrostatic attraction such as H-bonding and Vander
increased DTGmax temperature with the rise in severity factor are Waal’s force (Kalyani and Pandey, 2014) due to improved surface
mainly ascribed to improved fixed carbon value and reduced vol- contacts which overall improves durability of pellets.
atile matter content by high SF HTC.
13
H.B. Sharma and B.K. Dubey
Fig. 11. Mechanism of yard waste hydrochar pelletization (phase wise) and binding mechanism.
8. Conclusion
Through this study, we successfully demonstrated that fuel
qualities, along with mechanical storage and combustion charac-
teristics of municipal yard waste hydrochar pellets gets affected by
HTC severity factor (SF). It was found out that the increasing SF level
has direct correlation with the calorific value; the calorific value of
the hydrochar increased from 18.23 MJ/kg at SF2.7e25.54 MJ/kg at
SF 4.0. Tensile strength of the hydrochar pellets were directly
affected by the SF level, as its value increased from 1.53 MPa to
4.80 MPa for SF2.7 and SF4.0 respectively. Pellets produced from
the higher SF level (SF3.5, SF3.7, SF4) showed brittle nature; how-
ever, the breakage point of the brittle pellets was much higher than
other pellets, asserting that it was able to withstand more
compressive force. The increase in the SF level improved hydro-
phobicity of the pellets and decrease length expansion. The
14
Journal of Cleaner Production 277 (2020) 124295
combustion performance for higher SF level pellets showed uni-
form and stable combustion profiles, which would be mostly suited
for utilization in standard furnaces. The improved mechanical,
storage, transport and combustion properties of hydrochar pellets
were correlated with the alteration of lignocellulosic components
during higher SF level HTC, which lowers the hemicelluloses con-
tent and improved lignin content. The increased moisture resis-
tance of the pellets along with improved tensile strength, and
reduced length expansion showed that hydrochar produced at
higher SF level is better suited than lower SF level for the produc-
tion of solid biofuel pellets. The study concludes that pelletization
without any addition of commercial binder for municipal yard
waste hydrochar is possible. The HTC helps in concentrating the
lignin from yard waste, which acts as a natural binder by forming
the solid bridge between hydrochar particles during heated
pelletization. Further study should focus on effect of varying
H.B. Sharma and B.K. Dubey
stirring condition (rpm) during HTC, and varying particle size on
the properties of hydrochar pellets. In spite of promising result of
solid fuel pellets from municipal yard waste, the question of
techno-economic feasibility still needs to be answered. Future work
should investigate the economic, social, and environmental feasi-
bility of pellets production using detail life cycle assessment (LCA)
and techno-economic analysis.
CRediT authorship contribution statement
Hari Bhakta Sharma: Conceptualization, Writing - original
draft, conceived the presented idea, did all the experiments and
prepared the first draft of the manuscript. Brajesh K. Dubey: Data
curation, Methodology, Writing - review & editing, verified the
analytical methods, data analysis and reviewed the writing of the
manuscript.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgement
The Authors highly acknowledge the grant of PhD Research
Scholarship to Mr. Hari Bhakta Sharma by the Indian Institute of
Technology Kharagpur. Mr. Rajesh Kola is acknowledged for his
assistance during elemental analysis.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jclepro.2020.124295.
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