Energy Reports 9 (2023) 5977–5991

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Energy Reports
journal homepage: www.elsevier.com/locate/egyr

Research paper

Development of carbonized rice husks briquettes: Synergy between

emissions, combustion, kinetics and thermodynamic characteristics
∗
Vianney Andrew Yiga a,b , , Andrew Nuwamanya a , Agatha Birungi a , Michael Lubwama a,b,c ,
Harriet Nalubega Lubwama b
a
Department of Mechanical Engineering, Makerere University, Kampala, Uganda
b
Department of Research and Development, Yosevi Engineering Services Limited, Kampala, Uganda
c
Africa Center of Excellence in Materials, Product Development and Nanotechnology, Makerere University, Kampala, Uganda

article info a b s t r a c t

Article history: Briquettes uptake continues to be low, despite their ability to offset the negative impacts caused
Received 27 March 2023 by firewood/charcoal. Possible reason for this is lack of literature towards key parameters of the
Received in revised form 2 May 2023 developed briquettes. In the current study, emissions, combustion, kinetics and thermodynamic
Accepted 18 May 2023
characteristics of rice husks agricultural residue carbonized briquettes were obtained. The water
Available online 30 May 2023
boiling test and emissions monitoring system for CO, CO2 and PM2.5 were used to determine fuel
Keywords: and energy consumption, thermal efficiency and emissions while thermogravimetric analysis was
Briquettes utilized in obtaining combustion, kinetic and thermodynamic parameters. The activation energy was
Combustion determined by employing four different model-free methods. Drop strength and particle density of the
Emissions briquettes were 67.8% and 548.15kg/m3 , respectively. Briquettes‘ moisture, volatile matter, ash content
Kinetics and fixed carbon were 7.2%, 16.6%, 47.4% and 28.8% respectively. Average activation energy attained by
Pyrolysis the developed briquettes by Kissinger–Akahira–Sunose, Ozawa–Flynn–Wall, Starink and Tang methods
Rice husks
were 78.3kJ/mol, 83.3kJ/mol, 78.7kJ/mol and 75.0kJ/mol, respectively. Low energy barrier (5.2kJ/mol)
TGA
between activation energy and enthalpy changes indicated that initiation occurs easily. The obtained
thermodynamic parameters indicated that the thermal degradation process was endothermic in nature.
High energetic densities (10,688.9MJ/m3 ) and Fuel Value Indices (255.5MJ/m3 ·%) were attributable to
the higher heating value of the developed briquettes (19.5MJ/kg).
© 2023 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction
Africa’s population at 1.21 billion (or 17% of the world total)
is expected to further rise, indicating a corresponding increase in
demand sources of energy (Oluwafemi‘Femi’Mimiko, 2022). Over
70% of the population in sub-Saharan Africa does not have access
to electricity (Szabó et al., 2016). In Uganda, Uganda Bureau of
Statistics (UBOS) reports that only 20% Ugandans have access
to electricity (Cartland et al., 2022). For homes with access to
electricity, it is majorly used for lighting purposes and an unno-
ticeable composition for cooking. Over 90% of Ugandans depend
on charcoal and firewood as a source of energy for domestic
cooking purposes (Gianvenuti et al., 2022). This has significantly
contributed to high rates of deforestation which is linked to
climate change. With increasing population growth and urban-
ization in Uganda, the demand for firewood/charcoal is expected
to further increase. The demand is projected to more than double
∗ Corresponding author at: Department of Mechanical Engineering, Makerere
University, Kampala, Uganda.
E-mail address: vianney.yiga@mak.ac.ug (V.A. Yiga).
from 48 million tonnes in 2015 to 105 million tonnes per annum
by 2040, which corresponds to an annual wood supply deficit of
72,600 tonnes by 2030 (UBOS, 2020). When firewood/charcoal is
burnt, its combustion reaction produces heat and emissions such
as vapors, gases, and particulates (Yadav and Devi, 2018). The
smoke produced from using firewood/charcoal for domestic cook-
ing applications not only has negative consequences to the envi-
ronment, but also has negative health implications on women and
children especially (Raymer, 2006; Rehfuess and World Health
Organization, 2006). This is mainly because these fuels are often
burnt in poorly ventilated kitchens or traditional cook-stoves
characterized by very low efficiencies or any exhaust-cleaning
mechanisms, thus resulting to high emission of pollutants. Ac-
tually, the smoke emitted during firewood/charcoal combustion
contains toxic components that include a high concentration of
particulate matter (PM), carbon monoxide (CO), nitrogen oxides
(NOX ), sulphur oxides (SOX ), formaldehyde, and polycyclic or-
ganic matter (Sana et al., 2019). Sana et al. (2019) shows many
studies which have highlighted the link between indoor air pol-
lution and the occurrence of various health problems, including
cardiovascular and respiratory diseases in the short and medium

https://doi.org/10.1016/j.egyr.2023.05.066
2352-4847/© 2023 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
V.A. Yiga, A. Nuwamanya, A. Birungi et al. Energy Reports 9 (2023) 5977–5991

term, as well as chronic exposures. Emissions from the com-

bustion of firewood/charcoal are estimated to be responsible for
about 4.6% of the global burden of disease (Lim et al., 2012).
The World Health Organization (WHO) has held emissions from
burning of firewood/charcoal responsible for about 4.3 million of
global premature deaths worldwide (WHO, 2014). The emissions
to the environment from combustion of firewood/charcoal have
led to an upsurge in global warming, causing long-lasting changes
to the climate system, which threatens irreversible consequences
(Gioda, 2019). To curb these challenges, government policy has
been geared towards production of greener fuels for domestic
cooking applications (Mudoko, 2013). One such alternatives is
carbonized agricultural residue briquettes.
Agricultural residue briquettes initially attracted success as
alternatives to firewood/charcoal because of the large of amounts
of agricultural residues generated from agricultural activities. The
theoretical potential production of agriculture residues in Uganda
is approximated to be around 4.4 million metric tons annually
(Miito and Banadda, 2016). Rice husks are one such residues,
whose current production capacity is 136,000 metric tons annu- Fig. 1. Cross-section of step-down kiln for rice husks carbonization.
ally (Buyondo et al., 2020). Their current disposal means include
open burning, a practice which further exacerbates the effects of
climate change. Rice husks agricultural residue briquettes have
been developed but their uptake remains generally very low
(Nakibuuka, 2022; Nakiyinji, 2022; Lubwama et al., 2020a; Yiga
and Lubwama, 2020; Lubwama and Yiga, 2018). One of the major
reasons for this trend could be possible hazardous emissions
produced during their combustion. Additionally, their combus-
tion, kinetics as well as thermodynamic characteristics have not
been reported in the literature, further constraining customers’
perceptions towards utilizing rice husks carbonized briquettes
for domestic cooking applications. Combustion characteristics as
well as kinetic and thermodynamic parameters can be obtained
by thermogravimetric analysis (TGA) (Yiga et al., 2023; Liu et al.,
2021; Li et al., 2019).
In this study therefore, carbonized rice husks briquettes were Fig. 2. Rice husks (a); rice husks biochar (b).
developed using low pressure compaction (≤7MPa) and their
emissions, combustion, kinetics and thermodynamic character-
istics were presented. Additionally, characterizations based on
2.3. Briquette development
SEM/EDX, FTIR, drop strength, particle density, higher heating
value and energetic parameters were also presented.
Briquettes were produced by mixing rice husks biochar
2. Materials and methods (≤600 µm size) with cassava flour peelings binder before low
pressure (≤5 MPa) compaction. To form binder, 100 g of cassava
2.1. Materials flour peelings were mixed in 750 cm3 boiling of water, followed
by stirring to produce a homogeneous starchy paste. 1000 g of
Rice husks (K98 variety) were obtained from Zhong’s Indus- biochar were then mixed with the developed binder to form
tries Limited, Kalungu District, Uganda. Cassava peelings were ob- a homogenous composite material that was compressed into
tained Wandegeya market. The brown outer layer was removed cylindrical briquettes using a mold. The produced briquettes were
so as to obtain a high starch-containing cortex. The peelings were then oven-dried for 16 h at 65 ◦ C.
washed in water and dried for 8 h per day for one week to reach
a < 13% moisture content, before milling into flour.
2.4. Microstructural/EDX studies and FTIR spectrometry
2.2. Carbonization
SEM was used to observe developed briquettes’ networks.
Rice husks were carbonized using a step down kiln (see Fig. 1). Samples were observed under a Tescan Vega 3 scanning electron
To form biochar, rice husks (see Fig. 2a) were placed in saggars microscope, Pleasanton, USA, coupled with energy dispersive X-
of 80L capacity and 0.77 m height. They were then covered with ray (EDX) spectroscopy. They were fixed on double sided adhesive
flat ceramic covers to allow uniform heat flow to the saggars so as
carbon tape, vacuum dried and scanned at an acceleration volt-
to regulate heat transfer. The covers were always smeared using
age of 10 kV. EDX spectra were obtained at an acceleration
mud for pyrolysis to occur gradually from end to another. The
voltage of 20.0 kV and collected for 19 s. The FTIR spectra of
main entrance of the kiln was closed using bricks and mud, such
that the heat generated from burning firewood was maintained the developed briquette samples were collected in the range of
in the combustion area, to allow smooth heat exchange from 4000 to 400 cm−1 using a Jasco FT/IR-6600 type A machine,
the fuel to rice husks. Firing of the fuel was done to provide Cremella, Italy. The resolution was 4 cm−1 , the scanning speed
sufficient heat for carbonization until a temperature range of was 2 mm/sec. The samples were ground to obtain very fine pow-
400–500 ◦ C for 5 h (Guo et al., 2020). The kiln was closed for ders using a mortar and pestle. The presence of free functional
24 h exchanging enough heat to these saggars, thereby forming groups in the samples was determined based on the FTIR spectra
biochar (see Fig. 2b). Obtained biochar was then water-cooled. (Adeleke et al., 2021a).
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V.A. Yiga, A. Nuwamanya, A. Birungi et al.
2.5. Mechanical characterization
To obtain the compaction integrity of the briquettes, they
were elevated up to 2 m and then dropped onto a thick steel
plate. Drop strength was then obtained as the ratio of the weight
after dropping to the weight before dropping (Lubwama and
Yiga, 2017). Drop strength is an extremely important factor in
briquette packaging, storage and transportation (Anggraeni et al.,
2021; Fengmin and Mingquan, 2011). The particle density of
the developed briquettes was obtained by standard procedures
involving ratios of mass and volume (Dao et al., 2022; Lubwama
et al., 2020b). It is an important parameter in understanding if
they will have enough heat for boiling as well as transportation
abilities without crumbling.
2.6. Higher Heating Value (HHV) and Water boiling test (WBT)
Higher heating value of the developed briquettes was obtained
according to Eq. (1) through relationships with ash content, fixed
carbon and moisture content (Lubwama et al., 2020b).
( )
MJ
HHV = 17300 − 117.51AC + 165.551FC − 232.69MC (1)
kg
The Water Boiling Test (WBT) protocol version 4.2.3 was used
to determine pollutant emissions during briquettes combustion
(CCA, 2014). An improved cook-stove was used and performance
analysis was based on the boiling of 5 liters of water in a flat-
bottomed cylindrical cross-section aluminum cooking pan of 7
liters maximum capacity. Tests conducted on the samples simu-
lated normal regular household cooking practices and specifically
determined thermal performance of the fuels and monitored
gaseous emissions namely: carbon monoxide (CO), carbon diox-
ide (CO2 ) and aerosol emissions (Particulate matter, PM2.5 ). Spe-
cific operational parameters measured during a WBT included
thermal efficiency, specific fuel consumption, time to boil, burn-
ing rate, and fire power for all three WBT phases namely: High-
power (cold-start); High power (hot-start) and Low-power (sim-
mering) (Arora et al., 2014; Obeng et al., 2017). During high-
power (cold start), 5 litres of water were brought to a boil in a
7-litre pot using a stove at ambient temperature. For high-power
(hot-start), 5 litres of water were brought to a boil in a 7-litre pot
using a pre-heated stove; and during low-power (simmering), the
water temperature is kept at about 3 ◦ C below boiling point for
62 min (Arora et al., 2014; Obeng et al., 2017).
2.7. Emissions testing
A Laboratory Emissions Measurement System (LEMS) that
measures gaseous emissions carbon monoxide (CO) and carbon
dioxide (CO2 ) was used. In the particulate matter (PM2.5 ) system,
the exhaust is sampled from the duct through an ultra-sharp
cut in the PM2.5 cyclone to remove particles larger than 2.5 µm.
The flow through the cyclone is controlled by a critical precision
orifice. Particles less than 2.5 µm are deposited on a fibre glass
filter using a gravimetric filter system that is humidity condi-
tioned (Kivumbi et al., 2021a; Arora et al., 2014; Obeng et al.,
2017). Weights before and after each experiment are taken on a
calibrated microbalance with the difference in mass of the filter
before and after testing yielding the emission of PM2.5 (Kivumbi
et al., 2021a). Emission factors for CO, CO2 and PM2.5 based on
carbon and on energy were determined (Arora et al., 2014; Obeng
et al., 2017).
2.8. Thermogravimetric analysis
Thermogravimetric analyzer (Eltra Thermostep non isothermal
Thermogravimetric analyzer, Haan, Germany) was used to deter-
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Energy Reports 9 (2023) 5977–5991
mine proximate analysis of raw materials as well as developed
briquettes (Lubwama et al., 2020b). Additionally, TGA was used
to obtain briquettes’ mass loss with increase in temperature
(Lubwama and Yiga, 2017). TGA was carried out according to the
ASTM E1131 standard (ASTM, 2014). The samples were heated
from 40 ◦ C to 600 ◦ C at three different heating rates of 20, 40
and 50 ◦ C/min. High-purity compressed air (Oxygen: Nitrogen =
21:79, > 99.99%) was used for cleaning the crucibles and chamber
prior to TGA experimentation. Nitrogen gas was used as the purge
gas for pyrolysis experimentation. The flow rate was maintained
at 20 mL/min and the sample masses averaged 20 mg. TGA
also provided combustion explanations in terms of differential
thermogravimetry (DTG), peak temperatures and mean reactivity
of the rice husks.
2.8.1. Combustion characteristics parameters
For each heating rate, ignition temperature, Ti is a measure
of difficulty to ignite as low ignition temperature suggests easy
ignition, and vice versa. Burnout temperature, Tf refers to the
temperature of the combustible substances in the completely
burnt state. The ignition and burnout temperatures of the de-
veloped briquettes were determined according to the tangent
method proposed by Liu et al. (2016). The flammability index,
F, reflects the reactivity of the early stages of combustion and is
expressed by Eq. (2).
( dα )
dt max
F = (2)
Ti 2
where, ddtα max is the maximum combustion rate. The larger the
( )
value of flammability index, the more combustible a material is.
The combustion characteristic index, S, reflects how quick the
combustion rate is and is expressed by Eq. (3) (Li et al., 2017).
( dα ) ( dα )
dt dt
max mean
S= (3)
Ti 2 Tf
where, ddtα mean is the average combustion rate. The larger the
( )
combustion characteristic index, the better the combustion char-
acteristics, and the more intense combustion is (Song et al., 2019).
2.8.2. Kinetics modeling
( )
−E
From the Arrhenius equation (k = Ae RT ), the rate constant in
the kinetic equation is closely related to temperature. A is a pre-
exponential factor and T is the absolute temperature. According
to Xiao et al. (2020), a non-isothermal process can be regarded as
an isothermal process within an infinitesimal short time interval.
As such, the kinetic equation for an isothermal homogeneous
phase reaction can be adopted for briquette pyrolysis under a
programmed heating condition by the means of thermal analysis
(see Eq. (4)).
dα
= k × f (α) (4)
dt
where k is the rate constant of the reaction, α is the immediate
weight loss ratio during pyrolysis and is given by Eq. (5), f (α)
is a function that reflects the apparent kinetics of pyrolysis of
substances, which is expressed as shown in Eq. (6).
(m0 − m)
α= ( ) (5)
m0 − mf
Where m0 , m, mf are the initial, instantaneous and final weights
of the sample, respectively.
f (α) = (1 − α)n (6)
Where n is the order of the reaction.
V.A. Yiga, A. Nuwamanya, A. Birungi et al. Energy Reports 9 (2023) 5977–5991
( )
βi 1
Combining Eqs. (4)–(6), we obtain: A plot of ln against for a given value of conversion,
T1.894661 Tαi
dα α (yields )a straight line with slope −1.052Eα
( )
−E
and an intercept
= Ae RT
(1 − α)n (7) R
dt ln R.g (α) + 3.633504 − 1.894661(ln Eα ).
Aα Eα

For a given heating rate, β = dT

dt
, Eq. (8) can be obtained as the
non-isothermal reaction rate. 2.8.3. Thermodynamic analysis
dα dα dt The KAS, OFW, Starink and Tang methods were used to ob-
= × (8) tain thermodynamic characteristics of the developed briquettes
dT dt dT at a given heating rate, including change in Gibbs free energy
Therefore, Substituting Eq. (7) into Eq. (8) gives: (∆G), change in enthalpy (∆H) and change in entropy (∆S) using
dα Eqs. (14)–(16) (Yiga et al., 2023; Saha et al., 2022).
( )
A −E
= e RT
(1 − α)n (9)
β
( )
dT KB T m
∆G = Eα + (RTm ) ln (14)
In the current study, the data obtained from TG/DTG were used hA
to determine the kinetic parameters (activation energy (E) and Eα
( )
β Eα e RTm
pre-exponential factor (A)), based on Arrhenius equation. Fur- Where A =
RTm 2
ther, these kinetic parameters can be estimated graphically by
integrating Eq. (9) and then applying mathematical approxima- ∆H = Eα − (RTm ) (15)
tion for exponential term. Based on previous literatures, five ∆H − ∆G
( )
different approximations were carried out and correspondingly, ∆S = (16)
Tm
four isoconversional (model free) models and a model fitting
method were adopted to calculate the apparent activation energy where KB is the Boltzmann constant, h is the Plank’s constant and
(E) at specific conversion time (α ) (Chandrasekaran et al., 2017; Tm is the peak temperature during combustion.
Das and Tiwari, 2017). Among the above five models, Kissinger–
Akahira–Sunose (KAS), Ozawa–Flynn–Wall (OFW), Starink and 2.9. Energetic characterization
Tang models were used in this study.
The energy per unit volume (energetic density) of developed
(a) Kissinger–Akahira–Sunose (KAS) method
briquettes was obtained by multiplying their particle density with
In the KAS method, mathematical approximation for exponential
their higher heating value (see Eq. (17)). The Fuel Value Index
term is assumed and after approximation and rearrangement, the
(FVI) of the developed briquettes was calculated according to
solution is given by Eq. (10) (Akahira, 1971). Eq. (18) (Yiga et al., 2021; Massuque et al.).
βi
( ) ( )
A α Eα Eα
ln = ln − (10) ED = PD × HHV (17)
Tαi 2 R.g (α) RTαi 3
where ED is Energetic density (MJ/m ), PD is particle density
(kg/m3 ) and HHV is Higher Heating Value (MJ/kg).
( )
βi
A plot of ln against −1
for a given value of conversion, α
Tαi 2 Tαi
( ) ED
−Eα Aα E α FVI = (18)
yields a straight line with slope and an intercept ln R.g (α)
,
R AC
from which Eα can be calculated.
where FVI is Fuel Value Index (MJ/m3 · %), ED is Energetic density
(b) Ozawa–Flynn–Wall (OFW) method
(MJ/m3 ) and AC is Ash content (%).
The OFW method uses the Doyle’s approximation (Doyle, 1965)
and OFW equation is expressed by Eq. (11) (Ozawa, 1965). 3. Results and discussions
( )
A α Eα Eα
ln βi = ln − 5.332 − 1.052 (11) 3.1. Surface morphologies and elemental analysis
R.g (α) RTαi
Where g (α) is constant at a given value of conversion. A plot of The morphology of the developed briquettes is presented in
ln βi against T1 for a given value of conversion, α yields a straight Fig. 3. There were observed structures of granular surface, ir-
αi ( ) regular arrangements and charging effects, possibly due to the
−1.052Eα
line with slope R
and an intercept ln Aα Eα
R.g (α)
− 5.332. high volatility of the developed briquettes (Zhong et al., 2017). A
(c) Starink method porous structure was vivid, which allows more paths for airflow
The Starink method is a non-isothermal model-free method ex- during ignition of briquettes, hence enhancing burning efficiency
pressed by Eq. (12) (Starink, 2003). of the developed briquettes (Kivumbi et al., 2021b; Carnaje et al.,
2018). Moreover, a web of cellulosic fibers that are contained
βi
( )
Eα by an enveloping membrane was observed, which is similar to
ln = Constant − 1.0008 (12)
T 1.92 RTαi the structure of inherent rice husks material (Yiga et al., 2021).
( ) The reason for this observance is because rice husks contain high
βi 1
A plot of ln T1.92
against Tαi
for a given value of conversion, amounts of cellulose (≈30%) (Yiga et al., 2022).
−1.0008Eα Elemental analysis by EDX revealed that the developed bri-
α yields a straight line with slope R
and an intercept
quettes had carbon (64.8%) and oxygen (27.5%) as the main
Constant.
constituents with other elements such as potassium and sili-
(d) Tang method
con having very small percentages (see Table 1). High carbon
The Tang method is a non-isothermal model-free method ex-
composition signals that the developed briquettes will have high
pressed by Eq. (13) (Tang et al., 2003).
fixed carbon compositions, and hence high calorific values (Yiga
βi
( )
and Lubwama, 2020). As expected there was a high carbon–
ln oxygen ratio (2.4:1), which confirms presence of highly thermal
T 1.894661
( ) constituents of rice husks like lignin because it has a higher
Aα Eα Eα
= ln + 3.633504 − 1.894661(ln Eα ) − 1.052 carbon–oxygen ratio compared to cellulose. Similar results were
R.g (α) RTαi reported by Adeleke et al. (2021a). From EDX also, only trace
(13) amounts of Ca, Al and Fe were detected.
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V.A. Yiga, A. Nuwamanya, A. Birungi et al. Energy Reports 9 (2023) 5977–5991

Fig. 3. Surface morphologies of developed briquettes at magnifications of 50 µm (a); 100 µm (b); 200 µm (c).

Table 1
Elemental compositions for EDX of the developed briquettes.
Element C O K Si Ca Al Fe
wt.% 64.8 27.5 3.4 2.3 0.8 0.7 0.6

3.2. Surface functional groups

Fig. 4 shows the FTIR spectra of developed briquettes. Peaks

around 3000 cm−1 and 1100 cm−1 are typical characteristic of
cellulose backbone in rice husks that ascribed to –OH and C–O–C
stretching bands, respectively (Yakaboylu et al., 2021). The broad-
band at around 3300 cm−1 is where moisture content could take
part in the formation of hydrogen bonds is associated with O–H
vibrations in hydroxyl groups due to the presence of pheno-
lic hydroxyl groups (Adeleke et al., 2021a,b). Hydroxyl groups
signal presence of an alcohol, which can contribute to higher
flammability index and hence enhanced combustion character-
istics (Carnaje et al., 2018). Deformation vibration of C–H in
aliphatic carbon (–CH3 ) and –C(CH3 )2 appeared in at around
2800–2975 cm−1 and around 1200 cm−1 . At around 1384 cm−1 , Fig. 4. FTIR spectra of developed briquettes.
the observed band is due to aromatic C==C stretching (Montiano
et al., 2015). The aromatic C==C bonds and characteristic phe-
nolic OH groups were established along with oxygen bridges obtained in the current study, in comparison to those obtained
as strengtheners for briquettes when exposed to curing in inert by Anggraeni et al. (2021) (≥82%), Lubwama et al. (2020b) (>
environment (Adeleke et al., 2021b; Zhong et al., 2017). According 85%), and Obi and Okongwu (2016) (76%–100%), respectively.
to Carnaje et al. (2018), the presence of aliphatic and aromatic This could have been low pressure of ≤5 MPa utilized in the
hydrocarbons in the fuel means that it contains fats and oils that current study. Particle density is extremely important as shows
enhance ignition properties of the developed briquettes. the compactness of a briquette and is directly proportional to
its compressive strength (Granado et al., 2021). Particle densities
3.3. Mechanical characterization reported in this study indicate the briquettes’ ability to burn for
long time thus emitting large quantities of heat during burning.
Drop strength and particle density of the developed briquettes
were 67.8% and 548.15 kg/m3 , respectively. Similar density values 3.4. Proximate analysis
were reported for rice husks briquettes developed by Deshan-
navar et al. (2018) and Arewa et al. (2016) but lower densities Proximate analysis for the raw materials used in making bri-
were obtained by Obi and Okongwu (2016) (333–499 kg/m3 ). quettes as well as accruing briquettes are shown in Fig. 5. Rice
The density obtained by Kipngetich et al. (2023), Suryaningsih husks biochar had the highest moisture content (22.5%), because
et al. (2019a, 2017) for carbonized rice husks briquettes was it was characterized in its moist form as obtained after water
much higher (838–1058 kg/m3 , 873–1158 kg/m3 and 680 kg/m3 cooling from the kiln. The moisture content of cassava peeling
respectively). Drop strength and particle density provide an in- flour (9.1%) is lower than of cassava peelings (10.9%) because
dication of handle-ability, transportation and storage integrity when the peelings are milled its bulk density increases and thus
of the developed carbonized briquettes (Anggraeni et al., 2021; lose moisture to the atmosphere. Cassava peelings flour had the
Deshannavar et al., 2018). It also shows the extent to which highest volatile matter compositions (72.9%) among the sam-
briquettes can be stacked on top of each other during domestic ples. Rice husks biochar obtained the highest ash content (47.1%)
or kiln cooking (Lubwama et al., 2020b). Lower drop strength was due to silica formation during temperature degradation of rice
5981
V.A. Yiga, A. Nuwamanya, A. Birungi et al.
Fig. 5. Proximate analysis.
husks to form biochar (Javed et al., 2022; Chang, 2020). The
least ash contents were obtained in cassava peelings (3.2%) and
cassava peelings flour (3.7%). The highest fixed carbon content
was obtained in rice husks biochar (20.8%) because carbonization
increases carbon formation (Amarasekara et al., 2017). Briquettes‘
moisture, volatile matter, ash content and fixed carbon were 7.2%,
16.6%, 47.4% and 28.8% respectively. These results agree with
previous findings on carbonized rice husks briquettes (Kipngetich
et al., 2023, 2022; Suryaningsih et al., 2019a; Lubwama and
Yiga, 2018; Suryaningsih et al., 2017). Briquettes with such low
moisture contents are feasible for combustion because excessive
energy is needed for drying and higher moisture content is indeed
a challenge while burning (Afsal et al., 2020). Moreover, low
moisture content is synonymous with high calorific values and
easy fuel ignition (Suryaningsih et al., 2019a). The ash contents of
the developed briquettes in the present study were in range with
previous works of Kipngetich et al. (2022) (47.33–51.24%) and
Kipngetich et al. (2023) (38.4–48.7%). The fixed carbon composi-
tions obtained in the briquettes are coherent with the high carbon
content already observed from the EDX results (see Table 1).
It should be noted that the fixed carbon compositions obtained
are much higher than those for firewood (14.6%) but less than
charcoal (56.2%) from the study of Lutaaya et al. (2023).
3.5. Emissions performance results
3.5.1. Ignition properties
Ignition is a rapid transition process by which an exothermic
oxidation reaction and self-supported combustion are initiated
(Chavan et al., 2022). When the briquettes are ignited, their tem-
peratures increase, which makes them decompose into another
solid phase that is less compact. Some of their constituents such
as volatile matter escape during the burning process that occur.
Other constituents such as moisture content turn into vapor
phase gas phase. Corresponding higher heating value (HHV) of
the developed briquettes was 19.5 MJ/kg, which is much higher
than other carbonized rice husks previously developed by Lub-
wama and Yiga (2018) (≈16.5 MJ/kg), Suryaningsih et al. (2018)
(≤13.1 MJ/kg) and Suryaningsih et al. (2017) (≈14 MJ/kg). In
fact, it is also in range than charcoal’s calorific value reported
by Tumutegyereize et al. (2016) (18.3–27.3 MJ/kg). Lutaaya et al.
(2023) reported calorific values of 17.6 MJ/g and 29.4 MJ/kg for
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Energy Reports 9 (2023) 5977–5991
firewood and charcoal, respectively. Clearly, the briquettes devel-
oped in the current study are superior to firewood. Their HHV
are within the ranges of 16.3–22.7 MJ/kg, 16.4–23.7 MJ/kg, 19.9–
23.7 MJ/kg and 13.5–21.5 MJ/kg for carbonized rice husks bri-
quettes developed by Kipngetich et al. (2023, 2022), Suryaningsih
et al. (2019a) and Obi and Okongwu (2016), respectively. Higher
calorific value ranges were obtained by Deshannavar et al. (2018)
(18.6–20.1 MJ/kg) and Elinge et al. (2019) (17.3–34.6 MJ/kg).
HHV of briquettes significantly influences their energy density,
which is an invaluable factor to consider for grouping one or
more residues at the time of briquetting as it allows for stan-
dardization of the briquettes density (de Oliveira et al., 2022).
Fig. 6a shows a stove loaded with briquettes before ignition.
A yellowish bioethanol gel (see Fig. 6b) was used for igniting
briquettes, because it is much thicker than kerosene and produces
smaller blue flames which be sustained for longtime producing a
lot of heat content (Kivumbi et al., 2021a). As heat is exchanged
from the bioethanol gel, the briquettes adjacent to the ash tray
gets heated which later exchanges heat to the other parts of the
briquettes, through Fourier law of conduction (Lubwama et al.,
2020b). It took 5 min to ignite 230 g of rice husks briquettes
and 7 min to ignite 375 g or rice husks briquettes (see Fig. 6c).
Clearly, ignition time depends on the quantity of briquettes as less
amount of fuel is easier to ignite, compared to higher amounts
of fuel. After briquettes have completely burnt, ash remains (see
Fig. 6d) are noticeable because of the high amounts of ash already
noticed from proximate analysis (see Fig. 5).
3.5.2. Emissions in the three phases
The concentrations of CO2 and CO increased during ignition
phase with time, however during this experiment in this experi-
ment three phases have been studied. Maximum emissions of CO2
and CO were obtained during the hot-start phase and less emis-
sions of were obtained during the other phases of cold start, hot
start and simmer phase (see Fig. 7a). CO concentrations remained
non recognizable at the start of the cold-start phase until about
the 20th minute, before exponentially increasing by 55th minute.
The significant increase in CO concentration shows incomplete
combustion, related to evaporation of some moisture from the
briquettes surface (Obeng et al., 2017). Additionally, it is possibly
due to low burning temperature, insufficient oxygen, poor mixing
of fuel with the combustion air and too short residence time of
the combustion gases in the combustion zone (Xiu et al., 2018).
CO2 rate in the first phase is high because significant moisture
content is expelled from the developed briquettes in this phase
(Kpalo et al., 2021). During hot start phase, developed briquettes
lost their volatile matter, fixed carbon, thus easily thus emitting
high emissions. In this phase, CO emissions increased gradually
up. This finding is contrary to findings of Kivumbi et al. (2021a)
who reported that the hot start phase produced less emissions
compared to other cold start and simmer. During the simmer
phase, the CO and CO2 emissions gradually decrease, indicating
a constant dissemination of emissions to the atmosphere. The
emissions of PM2.5 generated ranged between 314.7 ppm and
317.0 ppm (see Fig. 7b). These emissions are related to the inher-
ent ash contents in the developed briquettes (Deng et al., 2019).
Although the trendlines indicated high emission levels for CO
during the test, personal exposure to CO emissions is relatively
low, since the laboratory experiment was conducted under con-
trolled conditions that required placing the stove directly under
the hood which is ideal (Obeng et al., 2017).
3.6. Water Boiling Test (WBT) performance metrics
Table 2 shows the IWA performance metrics as well as the
standard performance measures of the developed briquettes. It
V.A. Yiga, A. Nuwamanya, A. Birungi et al. Energy Reports 9 (2023) 5977–5991

Fig. 6. Burn stove (a); bioethanol gel (b); burning briquettes (c); and burnt briquettes covered with ash (d).. (For interpretation of the references to color in this
figure legend, the reader is referred to the web version of this article.)

Fig. 7. (CO/CO2 ) emissions (a); and PM2.5 emissions (b) produced during the water boiling test.

Table 2
IWA performance metrics and standard performance measures for developed briquettes.
High Power Thermal Efficiency (%) 47.4%
Low Power Specific Consumption (MJ/min/L) 0.003
High Power CO (g/MJd) 10.31
Low Power CO (g/min/L) 0.05
IWA performance metrics
High Power PM (mg/MJd) 60.1
Low Power PM (mg/min/L) 0.36
Indoor Emissions CO (g/min) 0.65
Indoor Emissions PM (mg/min) 3.8
Fuel to Cook 5L (g) 259.0
CO to Cook 5L (g) 29.5
PM to Cook 5L (mg) 184.2
Standard performance measures
Energy to Cook 5L (kJ) 4,749
Time to Boil (min) 56.4
CO2 to Cook 5L (g) 546.5

took 56.4 minutes and 259 g of briquettes at an energy consump-
tion of 4,748.8kJ to boil 5 liters of water, hence emitting 546.5 g,
29.5 g and 184.2mg of CO2 , CO and PM2.5 , respectively. The cor-
responding low power specific consumption rate and high-power
thermal efficiency were 0.003 MJ/min/L and 47.4%, respectively.
The obtained results showed much lower emission dissipation
compared to a study by Obeng et al. (2017) who obtained the
emissions performance of different wood species using different
cook-stoves.
Fig. 8 shows the total emissions and emissions per MJ for PM2.5
(see Fig. 8a), CO (see Fig. 8b) and CO2 (see Fig. 8c) of the developed
briquettes. The highest amount of PM2.5 emissions was gener-
ated during the cold-start phase, since the fuel burned with a
yellow flame accompanied with emission of soot. In the hot-start
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and simmer phases, the soot emission had reduced considerably
(Kivumbi et al., 2021a). The respective total emissions of PM2.5
were 112 mg, 93 mg and 68 mg (see Fig. 8a). Similarly, emissions
and emissions per MJ reduced with change in phase from cold-
start to hot-start and simmer. The total emissions and emissions
per MJ for CO and CO2 during the simmer phase were lower
than those obtained during the cold-start and hot-start phases,
because simmering took less time (Mitchell et al., 2016). These
findings were in contradiction to those obtained by Kivumbi et al.
(2021a) who reported higher emissions and emissions per MJ in
the simmer phase compared to both cold and hot-start phases.
As expected, the emissions per MJ were in line with the total
emissions of CO, CO2 and PM2.5 generated. As such, more CO and
PM2.5 emissions per MJ were generated in the cold-start phases,
V.A. Yiga, A. Nuwamanya, A. Birungi et al.
Fig. 8. Total emissions and emissions per MJ for PM2.5 (a); CO (b); and CO2 (c) for developed briquettes.
compared to the other phases. This is because during the cold-
start phase, a lot of power is focused to evaporating the existing
volatiles in the rice husks briquettes (Lubwama and Yiga, 2018).
Moreover, the incomplete combustion due to inherent moisture
in rice husks briquettes causes formation of high CO emissions.
On the other hand, CO2 emissions per MJ are highest in the
simmer phase (160 g/MJ) possibly due to sufficient time for air to
mix, causing higher CO2 generation (see Fig. 8c). Similar results
were obtained by Kivumbi et al. (2021a).
The basic operational and energy consumption parameters as
well as emission factors for cold-start, hot-start and simmering
operations for the developed briquettes are presented in Ta-
ble 3. It took 55 min to boil water in the cold-start phase as
opposed to the 50 min taken in the hot-start phase. This trend
is due to the fact that less energy is required for the reaction
in the latter. The burning rate was 1.89g/min, 1.93g/min and
0.39g/min for cold-start, hot-start and simmer phases, respec-
tively. Lower rates were reported by Anggraeni et al. (2021)
(≤0.81g/min) while works by Arewa et al. (2016) reported val-
ues in range of the current study (0.7–2.0g/min). Kivumbi et al.
(2021a) obtained higher rates of 3.7–8.2g/min, 2.1–4.2g/min, and
1.1–1.7g/min for cold-start, hot-start and simmer phases, respec-
tively for charcoal fines briquettes while Nwabue et al. (2017)
obtained average burning rates of 1300–3800g/min for bio-coal
briquettes. This implies that the briquettes used in this study burn
slower; thus, the cook-stove does not have to be loaded with fuel
frequently (Kivumbi et al., 2021a). Lutaaya et al. (2023) reported
burning rates of 8g/min and 4g/min for firewood and charcoal
respectively. Thermal efficiencies were 46%, 49% and 65% for
the cold-start, hot-start and simmer phases, respectively. These
were much higher than those obtained for briquettes developed
by Kivumbi et al. (2021a) (21.8%–54.6%) and Lask et al. (2015)
(≈40%) as well as firewood (31%) and charcoal (36%) from Lutaaya
et al. (2023). Specific fuel consumption was 42.8 g/L, 39.7 g/L
and 7.5 g/L for cold-start, hot-start and simmer phases, respec-
tively. Higher specific fuel consumption values were reported by
Anggraeni et al. (2021) (≤560 g/L) in rice husk briquettes as
well as Lutaaya et al. (2023) (80 g/L) in firewood. Corresponding
specific energy consumption rates from the current study were
0.014 MJ/min/L, 0.015 MJ/min/L and 0.003 MJ/min/L, respectively.
The reason for this behavior was the high net calorific value of
the developed briquettes (18.3 MJ/kg) which ensured constant
heat delivery through the briquettes during cooking. Emission
factors are a critical parameter in determining the greenhouse
gas emissions from the combustion of the developed briquettes.
They quantify the magnitude of emission normalized by fuel
or energy consumption (Still et al., 2011). It is clear that CO2
emissions are by far the most dominant emission category in
the determination of the total greenhouse gas emissions while
PM2.5 were least significant. The significance is that more CO2
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Energy Reports 9 (2023) 5977–5991
will be emitted as compared to PM2.5 . However, since rice husks
briquettes are carbon-neutral, the generated emissions during
their combustion can be sustainably absorbed by plants during
photosynthesis (Suryaningsih et al., 2019b; Thao et al., 2012).
3.7. TG and DTG results
Fig. 9 presents the TG, DTG and conversion curves for the
developed briquettes at three different heating rates of 20, 40
and 50 ◦ C/min. The TG curves (see Fig. 9a) show the typical
appearance of pyrolysis of carbonized rice husks briquettes and
from them, the thermal phases for each of the heating rates
can be located (Lubwama and Yiga, 2018; Yiga and Lubwama,
2020). It is evident that the complete pyrolysis process for all the
samples can be divided into three major stages namely; dehydra-
tion, devolatilization and carbonization (Setter and Oliveira, 2022;
Setter et al., 2020). The first stage from 40 to 150 ◦ C causes degra-
dation and hence weight loss (≤8%) of some light components,
including inbound water and light volatile components (Ogwang
et al., 2021; Ojha et al., 2021; Hu et al., 2015)). Corresponding
peaks for water evaporation can be observed in the DTG curves
at this temperature range (see Fig. 9b). Water evaporation formed
a number of slit-shaped cracks on the briquettes’ surface and
these cracks acted as the gateway for pyrolysis gases spilling out
in the subsequent pyrolysis process (Hu et al., 2021). From the
findings of Kuthe et al. (2021), lignocellulosic materials with less
than 15% water content are feasible for making briquettes for
combustion purposes. The reason behind this is that excessive
moisture content poses major issues in grinding and immoderate
strength is required for drying.
The second stage, between 150 and about 400 ◦ C causes the
maximum weight loss during thermal degradation. From Fig. 9a,
it is clear that an increase in heating rate leads to a clear shift
of this phase to the right-hand side, which confirms that higher
temperatures are required to cause decomposition of hemicellu-
lose and cellulose (de Souza et al., 2022; Setter and Oliveira, 2022;
Hu et al., 2021; Kumar et al., 2020; Cao et al., 2014). The shift
is more vivid in the DTG curves as peak temperatures increased
from 354.9 ◦ C to 377.5 ◦ C to 380.7 ◦ C as heating rates increased
from 20 ◦ C/min to 40 ◦ C/min and to 50 ◦ C/min respectively (see
Fig. 9b). The shift is due to the variation in the heat flux within the
rice husks particles caused by the different heating rates (Setter
and Oliveira, 2022; Setter et al., 2020). As such, at the lower
heating rate, sufficient time is available for heating because of the
linear temperature profile between the outer surface and inner
core of the developed briquettes, while at the higher heating rate,
the temperature gradient is sufficient between outer and inner
core of the briquettes (Kumar et al., 2020). The peak temperatures
obtained in the current study are similar to those reported by Hu
et al. (2015) on carbonized rice husks briquettes (358–388 ◦ C).
V.A. Yiga, A. Nuwamanya, A. Birungi et al. Energy Reports 9 (2023) 5977–5991

Table 3
Basic operational and energy consumption parameters as well as emission factors for the developed
briquettes.
Time to boil (min) 55
Burning rate (g/min) 1.89
Basic operation Thermal efficiency (%) 46
Specific fuel consumption (g/L) 42.8
Firepower (W) 577
Net Calorific Value (MJ/kg) 18.3
Energy consumption rate (kJ/min) 35
Specific energy consumption (MJ/min/L) 0.014
Cold-start Energy consumption parameters
Total energy consumed (kJ) 1,923
Energy delivered (MJ) 0.878
Average cooking power (kW) 0.247
CO (g/kg) 115.81
CO2 (g/kg) 1651
PM2.5 (g/kg) 0.68
Emission factors
CO (g/MJ) 4.7
CO2 (g/MJ) 66.4
PM2.5 (mg/MJ) 27.6
Time to boil (min) 50
Burning rate (g/min) 1.93
Basic operation Thermal efficiency (%) 49
Specific fuel consumption (g/L) 39.7
Firepower (W) 589
Net Calorific Value (MJ/kg) 18.3
Energy consumption rate (kJ/min) 35
Specific energy consumption (MJ/min/L) 0.015
Hot-start Energy consumption parameters
Total energy consumed (kJ) 1,787
Energy delivered (MJ) 0.861
Average cooking power (kW) 0.267
CO (g/kg) 109.34
CO2 (g/kg) 1662
PM2.5 (g/kg) 0.63
Emission factors
CO (g/MJ) 5.1
CO2 (g/MJ) 76.8
PM2.5 (mg/MJ) 28.9
Burning rate (g/min) 0.39
Thermal efficiency (%) 65
Basic operation
Specific fuel consumption (g/L) 7.5
Firepower (W) 118
Net Calorific Value (MJ/kg) 18.3
Energy consumption rate (kJ/min) 7
Specific energy consumption (MJ/min/L) 0.003
Energy consumption parameters
Simmer Total energy consumed (kJ) 323
Energy delivered (MJ) 0.209
Average cooking power (kW) 0.078
CO (g/kg) 70.55
CO2 (g/kg) 1722
PM2.5 (g/kg) 0.49
Emission factors
CO (g/MJ) 4.7
CO2 (g/MJ) 114.7
PM2.5 (mg/MJ) 32.3

Fig. 9. TG curves (a); DTG curves (b); and conversion curves (c) for developed briquettes.

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V.A. Yiga, A. Nuwamanya, A. Birungi et al.
Table 4
Combustion characteristics parameters of developed briquettes.
Heating Temperature
rate (◦ C)
(◦ C/min) Ignition Peak Burnout
20 196.7 354.9 439.7
40 219.3 377.5 457.2
50 251.1 380.7 452.8
In third stage, from about 400 to 600 ◦ C, lignin in the devel-
oped briquettes is decomposed off, and the weight loss continues
until char residues are left at the maximum decomposition tem-
perature (Setter and Oliveira, 2022; de Souza et al., 2022; Ogwang
et al., 2021; Setter et al., 2020; Kumar et al., 2020). High amount
of char residues is proportionally linked to high HHV (de Souza
et al., 2022). Increasing char residues were also noted with in-
creasing heating rate due to heat transfer constraints as higher
heating rates reduce the time required to reach the pyrolysis
temperature, and the pyrolysis time thus becomes shorter (Quan
et al., 2009). Similar results were obtained by Liu et al. (2021) for
corn straw briquettes.
The variation in degree of conversion of the developed bri-
quettes as a function of temperature at different heating rates of
20, 40 and 50 ◦ C/min are shown in Fig. 9c. From Eq. (5), when
temperature rises, conversion rates increased due to reduction
in original weight of the briquettes. The trend followed by the
conversion curves is very similar to that presented in TG and
DTG curves, which present a decomposition in original weight
(see Figs. 9a and 9b). Therefore, increase in heating rate gener-
ally shifted the conversion curve to the right, signaling higher
temperatures are required to decompose constituents of devel-
oped briquettes at higher heating rates. Similar observations were
reported by Kumar and Ramesh (2022).
3.8. Combustion characteristics parameters
Table 4 shows the briquettes’ combustion characteristic pa-
rameters. Increase in heating rate generally led to an increase
in ignition, peak and burnout temperatures, which confirmed
the results for thermal stability (see Fig. 9). Similar observations
were noted by Gao et al. (2022) for bamboo briquettes and
Liu et al. (2021) for corn straw briquettes. Increase in heat-
ing rate from 20◦ C/min to 40◦ C/min led to increase in ignition
temperature from 196.7◦ C to 219.3◦ C and further increase in
heating rate to 50◦ C/min increased ignition temperature further
to 251.1 ◦ C. In a similar trend, increasing heating rate from 20
◦ increase in activation energy with increasing conversion rate is
C/min to 40 ◦ C/min led to increase in burnout temperature
from 439.7◦ C to 457.2◦ C while further increase in heating rate to
50◦ C/min decreased burnout temperature by about 1%. Increas-
ing ignition and burnout temperatures with increasing heating
rate is because less time is available for heating combustible
elements in the developed briquettes. Average maximum and av-
erage combustion rates of the developed briquettes were around
0.07 %/min and 0.02 %/min. Average flammability index and com-
bustion characteristic index values were 1.37×10−6 %/min· ◦ C2
and 0.73×10−10 %2 /min2 · ◦ C3 , respectively. Average mean reac-
tivity of the developed briquettes was 0.18×10−3 %/min/◦ C. In-
creasing heating rate led to reducing mean reactivity as well
as flammability and combustion characteristic indices because
less time was available for heating combustible elements in the
developed briquettes.
3.9. Kinetics analysis
Kinetic parameters for pyrolysis of the developed briquettes
including activation energy and pre-exponential factor were de-
Energy Reports 9 (2023) 5977–5991
Combustion rate Flammability Combustion Mean
(%/min) index (10−6 ) characteristic reactivity
index (10−10 ) (10−3 )
Maximum Average (%/ min ·◦ C2 ) (%2 //min2 · ◦ C3 ) (%/min/◦ C)
0.07 0.03 1.78 1.02 0.19
0.06 0.02 1.31 0.70 0.17
0.06 0.02 1.02 0.47 0.17
termined using KAS, OFW, Starink and Tang methods based on the
thermogravimetric analysis data obtained under different heating
rates. In order to compute the kinetic parameters, the same values
of conversion rate (α ) in the range of 0.2–0.8 were considered for
the three heating rates (Pinzi et al., 2020; Buratti et al., 2016).
This range was considered because during the fitting of data using
the KAS, OFW, Starink and Tang methods, the lowest conversion
value (0.1) and the highest conversion value (0.9) did not fit well
because of poor correlation factors (Kaur et al., 2018). In fact, they
may contain errors because at these values thermal degradation
does not reflect the overall pyrolytic behavior of the developed
briquettes (Gan et al., 2018). Figs. 10a, 10b, 10c and 10d show
the KAS, OFW, Starink and Tang linear plots, respectively, for the
conversion values within 0.2–0.8 for the developed briquettes
(Yiga et al., 2023). From their slopes and intercepts, calculated
activation energies and pre-exponential factors from the slopes
and intercepts are listed in Table 5. The average correlation val-
ues of 0.8851, 0.9117, 0.8864 and 0.8868 for KAS, OFW, Starink
and tang methods, respectively, indicated the accuracy of the
individual isoconversional methods and the calculated activation
energies were reliable (Kumar and Ramesh, 2022; Ni et al., 2022).
Corresponding average activation energy values were 78.3 kJ/mol,
83.3 kJ/mol, 78.7 kJ/mol and 75.0 kJ/mol, respectively. The ob-
tained activation energy values for the developed briquettes are
much lower than those for rice husks materials characterized
by Jia et al. (2020) (170.4–326.4 kJ/mol) and Loy et al. (2019)
(153.1–279.9 kJ/mol). This confirms the successful conversion of
rice husks into briquettes with suitable HHV.
The relationship between activation energy and conversion
rate (α ) is shown in Fig. 11, depicting that the activation energy
of the developed briquettes deeply depended on the conversion
rate. It is clear that increase in conversion rate led to increasing
activation energy, due to thermal degradation of different com-
ponents of biomass with increasing temperature. This trend is
synonymous with that obtained by Chen et al. (2021), Jia et al.
(2020) and Kumar et al. (2020) for rice husks materials. The
caused by the decomposition of chars in the developed briquettes
(Liu et al., 2021). It should be noted that OFW method presented
higher activation energy values compared to the KAS, Starink and
OFW methods, but the variations among these methods at each
conversion rate were minimal.
3.10. Thermodynamic parameters
Thermodynamic parameters of the developed briquettes at
the three heating rates of 20, 40 and 50 ◦ C/min were calculated
using the OFW method, as shown in Eqs. (14)–(16) and are
presented in Table 6. Enthalpy of reaction (∆H) and Gibbs free
energy (∆G) increased with increase in conversion rate. The low
energy barrier (5.2 kJ/mol) between the activation energies of the
developed briquettes (see Fig. 11) and their ∆H values for the
process indicated that reaction initiation can occur easily, due
to the fact that the lower difference between ∆H and activation
energy favors the complex formation (Kumar and Ramesh, 2022;
Simões et al., 2022). This is not surprising, since the inherent
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V.A. Yiga, A. Nuwamanya, A. Birungi et al. Energy Reports 9 (2023) 5977–5991

Fig. 10. Kinetic plots for developed briquettes using KAS method (a); OFW method (b); Starink method (c); and Tang method (d).

Table 5
Kinetic parameters of developed briquettes.
Conversion rate Activation energy (kJ/mol) Pre-exponential factor (min−1 ) R2
(α ) KAS OFW Starink Tang KAS OFW Starink Tang KAS OFW Starink Tang
0.2 27.7 32.5 28.0 26.7 6.9E−05 1.4E+04 5.9E−01 2.6E−05 0.9604 0.9734 0.9611 0.9613
0.3 18.5 24.3 18.8 18.0 4.6E−03 1.2E+03 2.8E+00 1.8E−04 0.9325 0.9652 0.9345 0.9351
0.4 31.6 37.9 31.9 30.5 3.1E+01 1.2E+04 7.0E−01 9.8E−06 0.9386 0.9616 0.9398 0.9402
0.5 41.4 49.0 41.8 39.9 3.7E−04 2.5E+04 3.8E−01 9.7E−07 0.4337 0.5424 0.4384 0.4400
0.6 98.8 103.9 99.2 94.5 9.7E−01 5.6E+08 1.0E+01 3.2E−02 0.9844 0.9874 0.9846 0.9846
0.7 114.4 119.0 114.7 109.3 9.5E+00 5.9E+09 1.2E+01 1.7E−01 0.9975 0.998 0.9975 0.9975
0.8 216.0 216.2 216.3 205.9 9.8E+07 7.1E+16 2.9E+01 7.6E+05 0.9487 0.9536 0.9489 0.949
Average 78.3 83.3 78.7 75.0 1.4E+07 1.0E+16 7.9E+00 1.1E+05 0.8851 0.9117 0.8864 0.8868

rice husks also have low energy barriers, which indicate that
rice husk are suitable for pyrolysis (Kumar et al., 2020; Loy
et al., 2019). As observed with previous studies, heating rate
did not significantly affect the briquettes’ enthalpy (Kumar and
Ramesh, 2022). Average ∆H value ranges (depending on heating
rate) were in the ranges of 69.8–78.0 kJ/mol, 69.6–77.9 kJ/mol
and 69.5–77.8 kJ/mol for 20 ◦ C/min, 40 ◦ C/min and 50 ◦ C/min
heating rates, respectively. The obtained positive values for ∆H
values indicated that endothermic reactions were dominant for
the thermal devolatilization of the developed briquettes (Kumar
and Ramesh, 2022; Kali et al., 2022). Additionally, it was clear
that the ∆H values are much lower than those of rice husks
from which the briquettes are made, signaling that less energy is
required to dissociate the complex bonds of briquettes compared
to rice husks for formation of new chemical bonds (Kumar et al.,
2020).
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Gibbs free energy (∆G), which reveals the overall energy
change of the system, was found to decrease with increase in
conversion rate. Lower ∆G values indicates favorable decomposi-
tion which signals that as conversion rate increased, more com-
bustible elements in the developed briquettes were converted
to volatiles. Average ∆G value ranges were 162.7–163.5 kJ/mol,
165.3–166.2 kJ/mol and 165.0–165.9 kJ/mol, for 20 ◦ C/min,
40 ◦ C/min and 50 ◦ C/min heating rates, respectively. Clearly, the
heating rate had a mild effect on ∆G, as is the case in the original
rice husks (Kumar et al., 2020). Previous findings on ∆G of rice
husks showed that they were in the range of 191.8–319.9 kJ/mol.
The corresponding significant drop in ∆G when briquettes are
made implies that less energy was needed to form activated
complex (Loy et al., 2019). These positive values suggested that
the reactions were not spontaneous (Simões et al., 2022). The
V.A. Yiga, A. Nuwamanya, A. Birungi et al. Energy Reports 9 (2023) 5977–5991

Table 6
Thermodynamic parameters of developed briquettes.
∆G ∆H ∆S
Method α
(kJ/mol) (kJ/mol) (kJ/mol.K)
20 ◦ C/min 40 ◦ C/min 50 ◦ C/min 20 ◦ C/min 40 ◦ C/min 50 ◦ C/min 20 ◦ C/min 40 ◦ C/min 50 ◦ C/min
0.2 166.95 169.78 169.48 22.48 22.29 22.27 −0.23 −0.23 −0.23
0.3 169.06 171.96 171.68 13.28 13.09 13.07 −0.25 −0.24 −0.24
0.4 166.26 169.07 168.77 26.38 26.19 26.17 −0.22 −0.22 −0.22
0.5 164.85 167.61 167.30 36.18 35.99 35.97 −0.20 −0.20 −0.20
KAS
0.6 160.31 162.90 162.57 93.58 93.39 93.37 −0.11 −0.11 −0.11
0.7 159.54 162.11 161.78 109.18 108.99 108.97 −0.08 −0.08 −0.08
0.8 156.23 158.67 158.32 210.78 210.59 210.57 0.09 0.08 0.08
Average 163.31 166.02 165.70 73.12 72.93 72.91 −0.14 −0.14 −0.14
0.2 166.11 168.92 168.62 27.28 27.09 27.07 −0.22 −0.22 −0.22
0.3 167.63 170.49 170.20 19.08 18.89 18.87 −0.24 −0.23 −0.23
0.4 165.31 168.09 167.78 32.68 32.49 32.47 −0.21 −0.21 −0.21
0.5 163.97 166.70 166.38 43.78 43.59 43.57 −0.19 −0.19 −0.19
OFW
0.6 160.05 162.63 162.30 98.68 98.49 98.47 −0.10 −0.10 −0.10
0.7 159.34 161.90 161.56 113.78 113.59 113.57 −0.07 −0.07 −0.07
0.8 156.22 158.67 158.32 210.98 210.79 210.77 0.09 0.08 0.08
Average 162.66 165.34 165.02 78.04 77.85 77.82 −0.13 −0.13 −0.13
0.2 166.89 169.72 169.43 22.78 22.59 22.57 −0.23 −0.23 −0.22
0.3 168.97 171.88 171.59 13.58 13.39 13.37 −0.25 −0.24 −0.24
0.4 166.21 169.02 168.72 26.68 26.49 26.47 −0.22 −0.22 −0.22
0.5 164.80 167.56 167.25 36.58 36.39 36.37 −0.20 −0.20 −0.20
Starink
0.6 160.29 162.88 162.55 93.98 93.79 93.77 −0.11 −0.11 −0.11
0.7 159.53 162.10 161.76 109.48 109.29 109.27 −0.08 −0.08 −0.08
0.8 156.22 158.67 158.31 211.08 210.89 210.87 0.09 0.08 0.08
Average 163.27 165.97 165.66 73.45 73.26 73.24 −0.14 −0.14 −0.14
0.2 167.14 169.98 169.68 21.48 21.29 21.27 −0.23 −0.23 −0.23
0.3 169.20 172.11 171.83 12.78 12.59 12.57 −0.25 −0.25 −0.24
0.4 166.45 169.26 168.96 25.28 25.09 25.07 −0.22 −0.22 −0.22
0.5 165.04 167.81 167.50 34.68 34.49 34.47 −0.21 −0.20 −0.20
Tang
0.6 160.54 163.15 162.81 89.28 89.09 89.07 −0.11 −0.11 −0.11
0.7 159.78 162.36 162.02 104.08 103.89 103.87 −0.09 −0.09 −0.09
0.8 156.48 158.93 158.58 200.68 200.49 200.47 0.07 0.06 0.06
Average 163.52 166.23 165.91 69.75 69.56 69.54 −0.15 −0.15 −0.15

(Simões et al., 2022). The low and negative value obtained con-
firmed that extended time is required for thermal decomposition
of active material in the developed briquettes, hence their burn-
ing for long durations. Moreover, these are lower, compared to
those of rice husks, which confirms that there was transforma-
tion of rice husks structure into more complex structures with
briquette formation (Kumar et al., 2020; Naqvi et al., 2019). It
should be noted that increase in heating rate showed no effect
on the ∆S values. This observation is similar to the results of
Kumar and Ramesh (2022). Moreover, variations in entropy con-
firmed existence of complex reactions occurring during thermal
conversion of the developed briquettes.

3.11. Energetic properties

The obtained high values for energetic densities

Fig. 11. Activation energy versus conversion rates for developed briquettes.
relatively high ∆G values indicated unfavorable decomposition
of the developed briquettes.
Change in entropy (∆S), a measure of disorders (Simões et al.,
2022), was recorded as −0.14 kJ/mol.K, −0.13 kJ/mol.K,
−0.14 kJ/mol.K and −0.15 kJ/mol.K for KAS, OFW, Starink and
Tang methods respectively. A negative ∆S value depicts de-
creased disorders of the system, i.e., ordered product formation
5988
(10,688.9 MJ/m3 ) and Fuel Value Indices (255.5 MJ/m3 · %) are
attributable to the high higher heating value of the developed
briquettes (19.5 MJ/kg) (Yiga et al., 2021). Increasing energetic
properties have been reported with densification (Kipngetich
et al., 2023; de Souza et al., 2022). The high energetic densities
are also possibly due to the high carbon contents of the developed
briquettes (Kipngetich et al., 2023). These are noted to facilitate
storage and transport issues (de Oliveira et al., 2022; Hu et al.,
2015)). The high energetic densities provide a greater amount
of heat per unit volume, which is desired for domestic cooking
purposes (de Oliveira et al., 2022; Massuque et al.). Moreover, the
high FVI is due to the high particle density of the developed bri-
quettes (Mierzwa-Hersztek et al., 2019; Marquez-Reynoso et al.,
2017). It should be noted that the high energetic parameters are
also possibly because rice husks themselves inherently have high
ED and FVI (Yiga et al., 2021).
V.A. Yiga, A. Nuwamanya, A. Birungi et al.
4. Conclusions
In this study, a water boiling test and emissions monitoring
system for CO, CO2 and PM2.5 were used to determine emis-
sions released over time while thermogravimetric analysis was
utilized in obtaining combustion, kinetic and thermodynamic
parameters. The high drop strength (67.8%) and particle density
(548.15 kg/m3 ) imply that it is easy to store and transport the
developed briquettes. Moisture, volatile matter, ash content and
fixed carbon were 7.2%, 16.6%, 47.4% and 28.8% respectively. Igni-
tion, peak and burnout temperatures increased with increase in
heating rates. Average maximum and average combustion rates of
the developed briquettes were around 0.07%/min and 0.02%/min.
Average flammability index, combustion characteristic index val-
ues and mean reactivities were 1.37 × 10−6 %/min· ◦ C2 and
0.73 × 10−10 %2 /min 2 · ◦ C3 and 0.18 × 10−3 %/min/◦ C respectively.
Average activation energy attained by the developed briquettes
by Kissinger–Akahira–Sunose, Ozawa–Flynn–Wall, Starink and
Tang methods were 78.3 kJ/mol, 83.3 kJ/mol, 78.7 kJ/mol and
75.0 kJ/mol, respectively. The low energy barrier (5.2 kJ/mol)
between activation energy and enthalpy changes indicated that
initiation occurs easily. The obtained thermodynamic parameters
indicated that the thermal degradation process was endothermic
in nature. High energetic densities (10,688.9 MJ/m3 ) and Fuel
Value Indices (255.5 MJ/m3 · %) were attributable to the high
higher heating value of the developed briquettes (19.5 MJ/kg).
Further works are recommended optimization of the production
process of carbonized rice husks briquettes as well as their life
cycle assessment (LCA) in order to assess their total impact on
the environment.
CRediT authorship contribution statement
Vianney Andrew Yiga: Conceptualization, Methodology, Ex-
perimental design, Formal analysis, Investigation, Writing– origi-
nal draft, Writing – review & editing, Supervision. Andrew Nuwa-
manya: Methodology, Experimental design, Writing– original
draft. Agatha Birungi: Methodology, Experimental design, Writing–
original draft. Michael Lubwama: Conceptualization, Methodol-
ogy, Experimental design, Formal analysis, Investigation, Writing–
original draft, Writing – review & editing, Resources, Supervision.
Harriet Nalubega Lubwama: Methodology, Writing – original
draft, Writing – review & editing.
Declaration of competing interest
The authors declare the following financial interests/personal
relationships which may be considered as potential competing
interests: Agatha Birungi reports fnancial support was provided
by Yosevi Engineering Services.
Data availability
Data will be made available on request
Acknowledgments
This work was financially supported by Yosevi Engineering
Services Limited, Uganda, www.yosevi.com. Technical support
from Mr. Andrew Wabwire from the Department of Mechanical
Engineering, Makerere University, Uganda is gratefully acknowl-
edged.
5989
Energy Reports 9 (2023) 5977–5991
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