ISSN 1068-364X, Coke and Chemistry, 2021, Vol. 64, No. 11, pp. 496–507. © Allerton Press, Inc.

, 2021.

COAL

Physiochemical, Mineralogical, Thermal and Kinetic

Characterisation of Selected Coals from the Benue Trough
and Anambra Basin, Nigeria
Bemgba B. Nyakumaa, b, *, Segun A. Akinyemic, Syie L. Wongd,
Olagoke Oladokune, Aliyu Jaurof, and Tuan Amran T. Abdullahb
a Research
Initiative for Sustainable Energy Technologies, North-Bank, Makurdi, Benue State, Nigeria
b
School of Chemical and Energy Engineering, Faculty of Engineering,
Universiti Teknologi Malaysia, Skudai, Johor, Malaysia
c
Department of Geology, Faculty of Science, Ekiti State University, Ado Ekiti, Ekiti State, Nigeria
d
Dpto. Matemática Aplicada, Ciencia Ingeniería Materiales Tecnología Electronica,
Universidad Rey Juan Carlos, Madrid, Spain
e Department of Chemical Engineering, Covenant University, Canaan Land, Ota, Ogun State, Nigeria
f National Centre for Petroleum Research and Development, Abubakar Tafawa Balewa University, Bauchi State, Nigeria

*e-mail: [email protected]
Received May 1, 2021; revised May 1, 2021; accepted July 15, 2021

Abstract—This study examined the physiochemical, mineralogical, thermal, and kinetic characteristics of
selected Nigerian coals, namely; Chikila (CHK), Lafia Obi (LFB) and Okaba (OKB) from the Benue Trough
and Anambra Basin. Physicochemical analyses revealed significant carbon, volatile matter, fixed carbon, and
higher heating values (~25–30 MJ/kg) along with low contents of moisture and ash. The deduced properties
indicate subbituminous to bituminous rank coals. The morphological, microstructure and elemental analyses
revealed heterogeneous sized coal particles with a glassy lustre, which are ascribed to quartz, alumina, kaolin-
ite, hematite, and other clay or aluminosilicate minerals. Thermal analysis under oxidative conditions indi-
cated the coal samples are highly reactive, which resulted in significant degradation as evident in the high
mass losses (ML = 91.59–94.04)% and low residual masses (RM = 5.96–8.41)%, which occurred in the order
LFB > OKB > CHK for ML whereas RM was CHK > OKB > LFB. Kinetic analysis values of activation energy
(Ea) from 30.07 to 43.91 kJ/mol, frequency factor (A) from 1.16 × 10–02 to 6.73 × 10–02 min–1 and R2 from
0.98–0.99 based on the Coats–Redfern model. The kinetic analysis indicated the coals are highly reactive
and suitable for energy recovery.

Keywords: coal energy conversion, thermokinetics, Benue Trough basin, Nigeria

DOI: 10.3103/S1068364X21110065

1. INTRODUCTION compared to oil (19%) and natural gas [5]. The most
significant deposits located in the United States, Rus-
Coal is a high carbon content, brown-to-black sia, Australia, China, India, Indonesia, Germany,
coloured, organic sedimentary rock formed from the Poland and Ukraine collectively account for ~90% of
high temperature and pressure reactions on tectoni- the total global reserves [6]. However, energy data
cally buried plant materials in the earth’s crust [1, 2]. indicates that commercial coal mining is projected at
The formation of coal historically commenced about 6.9 billion tonnes and occurs in over 50 countries
290 million to 360 million years ago due to the physi- worldwide [4].
cochemical changes, which transformed vegetation In general, coal is utilised for the production of
into peat and eventually into the various ranks of coal. iron, steel, cement, chemicals, fuels, and fertilisers [7].
Hence, coal is a solid fossil-based fuel formed from the The primary utilisation of coal is for power generation,
remnants of antediluvian plant life collected in peat where it accounts for ~40% or about 8200 terawatt-
bogs or coal forming swamps [3, 4]. Over the years, hours (TWh) of electricity generated annually [8].
coal has become an integral part of the global energy Coal-fired power generation provides cheap and reli-
mix due to its abundance and accessibility worldwide. able electricity required to provide the heat and power
Currently, coal accounts for 64% of globally econom- needs of domestic and industrial locations [8, 9].
ically recoverable fossil fuels (~1 trillion tonnes) when Therefore, the utilisation of coal in developing coun-

496
 PHYSIOCHEMICAL, MINERALOGICAL, THERMAL 497

tries is critical for infrastructural development, socio- State, which is located in the Anambra Basin. The
economic growth, and poverty alleviation [10]. rock sized coal samples were dry milled in a grinder
According to the IEA, coal-fired power generation (Panasonic Mixer MX-AC400, Malaysia) before siev-
could also address energy poverty [8], which currently ing using the analytical sieve (RetschTM, Germany,
affects 1.3–3.5 billion people or 50% of humanity who Mesh size 60 or 250 μm) for further characterisation.
either have limited or zero access to electricity [11, 12].
The lack of electricity and related energy crises is prev-
alent in Africa’s largest economy and most populous 2.2. Methods
nation, Nigeria. Over the years, the country has expe-
rienced persistent low voltage, load shedding, inter- 2.2.1. Physicochemical Analyses. The physico-
mittent power outages and extended blackouts [12, 13]. chemical analysis of the coal samples was examined by
These challenges are ascribed to poor power generation ultimate, proximate, and calorific analyses. The ulti-
and distribution along with dilapidated power infra- mate analysis deduced the carbon (C), hydrogen (H),
structure, which has caused transmission losses and nitrogen (N), and sulphur (S) composition using an
system failures in the national electricity grid [14, 15]. elemental analyser (vario MACRO Cube, Germany),
whereas the oxygen content was computed by differ-
According to energy analysts, the diversification of ence from the sum of C, H, N and S. The proximate
Nigeria’s energy mix currently dominated by hydro- analysis was performed through thermogravimetric
power and gas-fired electricity could address the cur- analysis (TGA) (Shimadzu TG-50, Japan) to deter-
rent issues associated with power generation in Nigeria mine moisture (M), volatile matter (VM), and ash
[16, 17]. Hence, the adoption of coal-fired electricity (AC) compositions. The fixed carbon (FC) was then
based on the vast coal reserves in Nigeria could serve computed by difference from the sum of the M, VM,
as a practical panacea to the nation’s energy crises [18, and AC. The calorific analysis was performed using a
19]. The nation’s reserves of coal are estimated at bomb calorimeter (IKA C2000, USA) based on
640 million proven and 2.75 billion tonnes of provi- ASTM standard D-2015 to determine the higher heat-
sional tonnes, which are located across the six geopo- ing value (HHV).
litical regions of Nigeria [20, 21]. Despite the vast
reserves, wide accessibility, and availability, the utili- 2.2.2. Morphological and Microstructural Analy-
zation of coal for electricity generation is non-existent ses. The morphologic and microstructure properties
in Nigeria [22, 23]. One of the widely reported reasons were determined by scanning electron microscopy
for zero coal utilisation is the lack of comprehensive (SEM) and energy dispersive X-ray (EDX) spectros-
data on the fuel and energetic properties of the various copy. SEM analysis was performed using the JEOL
coal deposits in the country [18, 24]. The limited tech- JSM IT 300 LV (Germany) analyser at the voltage of
nical expertise and scientific knowledge along with the 20 kV and the working distance of 5 mm. For each test,
energy, economic, and environmental ramifications of the selected coal sample was spray deposited on car-
coal utilisation also need to be addressed in detail. bon epoxy tape placed on grain mounts. Next, the
Therefore, this paper seeks to examine the physico- sample was sputter-coated with gold (Au) using the
chemical, mineralogical, thermal, and kinetic fuel thin film automatic sputter coater (Quorum Q150R S,
properties of selected Nigerian coal samples from UK) fitted with 57 mm diameter disc-style targets and
Chikila (CHK), Lafia Obi (LFB) and Okaba (OKB) operating at the pressure of 2 × 10–03 mbar. The sam-
in the Benue Trough and Anambra Basin. ples were sputter-coated to avert the impacts of
charging, damage to the electron beam, and increase
the clarity of the images during the analysis. On com-
2. EXPERIMENTAL pletion, the grain mounts containing the samples were
transferred to the SEM analyzer for morphology and
2.1. Materials and Sampling microstructure analysis. The SEM micrographs were
The dark brown to black rock coal samples, subsequently captured at a magnification of ×2000.
namely; Chikila (CHK), Lafia Obi (LFB), and Okaba Lastly, EDX analyzer was performed on the analyser
(OKB) were obtained from mines or seams located in (JEOL JSM IT 300 LV, Germany) based on the point
the Benue Trough and Anambra Basin of Nigeria. ID technique, which detects the elements present in
Sampling was carried out by direct excavation from the mapped zones of SEM micrographs. The average
coal bed mines distributed across various locations in composition in weight per cent (wt %) of each element
each seam to guarantee representative channel sam- was determined by charge balance and computed by
ples. The CHK coal was acquired from Chikila village point ID using the software (AZTEC, Oxford Instru-
in Guyuk town of Guyuk local government area ments, England).
(LGA) of Adamawa state, which is situated in the 2.2.3. Mineralogical Analysis. The mineral compo-
Upper Benue Trough of Nigeria. The LFB coal sam- sition of the coal samples was examined by wavelength
ple was acquired from Lafia-Obi LGA of Nasarawa dispersive X-ray fluorescence (WDXRF) spectros-
state situated in the Middle Benue Trough of Nigeria. copy. The tests were performed using the WDXRF
The OKB coal was acquired from Ankpa LGA in Kogi analyser (Rigaku, ZXS Primus II WDXRF, Japan),

COKE AND CHEMISTRY Vol. 64 No. 11 2021

498 NYAKUMA et al.

which used rhodium (Rh) target end-window based the final) thermally degraded during TGA. The reac-
X-ray tubes. The device is equipped with a smart sam- tion model term for n order of the reaction is given as;
ple loading system and a mapping feature for deter-
f ( x ) = (1 − x ) .
n
mining the topography and distribution of sample ele- (3)
ments. Based on the pellet method, each sample was
weighed, pelletized, and transferred to the WDXRF Therefore, the decomposition rate and tempera-
sample holder. The sample preparation process ture dependence of the coal degradation process can
ensured the sensitivity, calibration, and reliability of be described by the Arrhenius equation given as;
the results. The sample test was then initiated for a run
k (T ) = A exp  − a  .
E
time of one minute after which the metal and non- (4)
metallic composition of each coal sample was com-  RT 
puted by the WDXRF analyser. The oxides of each The term A denotes the frequency factor (min–1);
metal and non-metallic element for each coal sample Ea is the reaction activation energy (kJ/mol); R is the
were then computed after automatic corrections using molar gas constant (J/mol K); and lastly, T is the
the Rigaku XRF EZ-scan (Japan) software combined absolute temperature (K). When the oxidative thermal
with the SQX fundamental parameters. decomposition process occurs at a fixed heating rate,
2.2.4. Thermal Analysis. The thermal properties
the term β = dT is introduced and substituted into
were examined by thermogravimetric analysis (TGA) dt
under oxidative and non-isothermal conditions using Eq. 1 to derive the relation;
the TG Analyser (Shimadzu TG-50, Japan). During
dx = A exp  − Ea  1 − x n .
each TG run, 13 mg of each coal sample was weighed  ( ) (5)
in an alumina crucible before ramping the furnace dT β  RT 
temperature from 27 to 1000°C based on the heating
rate of 20°C/min under airflow at the rate of 20 mL/min. After separation of variables, Eq. 4 can be rear-
On completion, the TG furnace was cooled to ambient ranged to consider the decomposition of the coal at a
temperature using an automatic air blower. Next, the fixed heating rate during TGA, which subsequently
raw thermogram data were recovered for analysis results in the relation;
using the Shimadzu Workstation (TA-60WS) thermal dx = A exp  − Ea  dT .
analysis software. The mass loss (TG, %) and deriva-   (6)
tive of mass loss (DTG, %/min) data were subse- (1 − x )n β  RT 
quently plotted against temperature (°C) in Microsoft Next, Eq. 6 can be integrated to derive the integral
Excel (2013). Next, the temperature profile character- function for the reaction model that describes the
istics (TPCs) of each coal sample was deduced based thermal decomposition of the coal samples as given by
on the plots using the thermal analysis software. In the the relation;
current study, the TPCs determined were the onset
temperature (Tons), midpoint temperature (Tmid), x T

g ( x) = dx = A exp  − Ea  dT
maximum peak decomposition temperature (Tmax),
offset temperature (Toff), mass loss (ML, %) and resid-

0 (1 − x )
n
β T0 
 RT 
(7)

ual mass (RM, %). The TPCs provide critical insights The term g(x) in Eq. 7 represents the integral func-
into thermal degradation, potential decomposition tion of the reaction model that can be used to apply the
yield, and product distribution during thermochemi- Coats–Redfern model. Based on the approximate
cal conversion [25, 26]. method of the CRM, Eq. 7 can be re-written as;
2.2.5. Kinetic Analysis. The kinetic analysis was
 g ( x )    E
performed based on the integral graphical method of ln  2  = ln  AR 1 − 2RT  − a . (8)
the Coats–Redfern Model (CRM). According to the T  β Ea  Ea  RT
model, the thermal decomposition of the coals under
  
oxidative conditions can be represented as [27]; The terms ln  AR 1 − 2RT  in Eq. 8 can be
β Ea  Ea 
( )
dx = kf x , (1)  AR   2RT 
 since 1 − E  equate to unity.
dt reduced to ln 
m − mt β Ea   a 
x= 0 . (2) Hence, Eq. 8 becomes;
m0 − mf
 g ( x )   E
ln  2  = ln  AR  − a . (9)
The terms; dx represent the rate of reaction; k is T  β Ea  RT
dt
the rate of reaction constant; f(x) is the mechanism of In this study, the first-order reaction model was
the reaction model, and x is the ratio of the sample selected due to high sample conversion rates during
masses (m0 is the initial; mt is the fixed time; and mf is TG analysis. Hence, Eq. 9 is modified as;

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 PHYSIOCHEMICAL, MINERALOGICAL, THERMAL 499

Table 1. Physicochemical fuel properties of selected nigerian coals

Coal Symbol Chikila Lafia Obi Okaba
Property (Units) (CHK) (LFB) (OKB)
Carbon C, wt % 73.55 61.22 61.40
Hydrogen H, wt % 5.95 6.45 5.59
Nitrogen N, wt % 1.67 1.13 1.44
Sulphur S, wt % 0.57 1.54 0.66
Oxygen O, wt % 18.26 29.65 30.92
Moisture M, wt % 3.07 11.59 8.63
Volatile matter VM, wt % 35.27 46.04 40.03
Ash A, wt % 7.86 7.21 7.69
Fixed carbon FC, wt % 53.80 35.16 43.65
Higher heating value HHV, MJ/kg 30.83 26.05 24.86

− ln (1 − x )   E The rank classification of each coal was predicted

ln   = ln  AR  − a . (10) according to the ASTM standard D388 [28]. Typically,
  β Ea  RT
2
T
the standard is employed to predict the rank, classifi-
The kinetic parameters Ea and A can be derived cation, and potential application of coal samples based
E   on the HHV, particularly in the absence of petro-
from the slope − a and intercept ln  AR  of the graphic and vitrinite analysis. According to the stan-
R β
 a
E
dard, coals with volatile matter above 31 wt % can be
 − ln(1 − x)
straight-line plots of ln against 1 which ranked or classified accordingly [3]. Based on the
 T 2  T
is based on the governing reaction mechanism of ther- standard, CHK (HHV = 30.83 MJ/kg) is classified as
mal degradation. The values of Ea and A describe the high-volatile B bituminous coal with HHV values typ-
rate of the thermal reactions, which are dependent on ically from 30.20 to 32.60 MJ/kg. The findings for
the degree of conversion (x), temperature (T, K), and CHK are in excellent agreement with several authors
time (t, min) during the TG analysis. based on the vitrinite reflectance of %Rmax ≈ 0.70 in the lit-
erature [29, 30]. In contrast, LFB (HHV = 26.05 MJ/kg)
is classified as high-volatile C bituminous and
3. RESULTS AND DISCUSSION
agglomerating coal with HHV values typically from
3.1. Physicochemical Properties 30.20 to 32.60 MJ/kg. However, Akinyemi et al. [31]
reported that LFB coal is subbituminous based on its
Table 1 shows the physicochemical properties of vitrinite reflectance of %Rmax ≈ 0.39, which contrasts
the selected Nigerian coals examined in this study.
The results indicate that the coals contain high pro- markedly with [19, 29, 30, 32, 33] who have reported a
portions of carbon ranging from 61.22% (LFB) to similar classification (bituminous coal and %Rmax ≈
73.55% (CHK) and oxygen from 18.26% (CHK) to 1.0) as reported in this study. Lastly, OKB (HHV =
30.92% (OKB). As observed in Table 1, the higher 24.86 MJ/kg) is classified as Subbituminous A and
heating value (HHV) occurred between 24.86 MJ/kg non-agglomerating coal with HHV typically from
and 30.83 MJ/kg as observed for OKB and CHK 24.40 to 26.70 MJ/kg [3]. The subbituminous nature
coals, respectively. The highest HHV observed for
CHK is explained by its high carbon but low oxygen of OKB in this study is corroborated by the findings of
and moisture contents. In comparison, the OKB coal Adeleke et al. [34] and Oboirien et al. [19] in the liter-
has the highest oxygen contents among the samples, ature. Based on the above criteria, CHK and LFB are
which implies it will exhibit higher thermal reactivity considered high-ranked coals, whereas OKB is con-
and oxidative degradation compared to LFB and sidered low ranked coal. In addition to the potential
CHK. However, LFB exhibited the highest moisture applications earlier proposed, CHK and LFB could be
and volatile matter but low ash contents, which makes also utilised for value-added applications such as the
it the most suitable coal sample for gasification into
syngas and fuel gases. Likewise, the thermal conver- production of metallurgical coke, iron or steel. OKB
sion of LFB could potentially yield higher volumes of could be utilised for producing thermal coal or for
condensable and non-condensable gases compared to industrial thermal processes, power generation, or
CHK and OKB coals. cement production.

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500 NYAKUMA et al.

3.2. Morphological and Microstructural Properties

The surface morphology and microstructure of the
coal samples were examined by SEM spectroscopy.
Figures 1–3 present the high-resolution SEM micro-
graphs of CHK, LFB, and CHK coals examined at a
magnification of ×2000. The morphological and
microstructural analysis using SEM presents valuable
insights into the chemical composition, pore struc-
ture, orientation of particles, and surface composition
of solid materials [35, 36]. It also provides an indica-
tion of the mineral components present in the struc-
ture of coals examined during the process [37]. The
morphology of each coal is characterised by a rough, ×2.000 10 m
contoured, and compact (or sintered) surface with no
evident macro- or micro-pores despite the heteroge-
neous sized and shaped particles randomly dispersed Fig. 1. HR-SEM images of Chikila Coal.
on the surfaces.
The coal particles observed in the SEM micro-
graphs also exhibited a glassy sheen at the edges and
contours, which indicates the presence of mineral or
metallic constituents in their structure. The glassy or
reflective nature of the surface particles observed on
the coal surfaces could be due to the presence of alu-
minosilicate and iron-containing minerals such as
quartz, kaolinite, calcite, and pyrite [38–40]. The
mineralogical analysis of coals in previous studies have
also detected gypsum, Jarosite, montmorillonite and
compounds like sodium chlorate [30, 41, 42]. The
metallic elements Ti, Mn, and Fe along with the min-
erals present in elemental and fused forms are also
considered major determinants of surface morphol- ×2.000 10 m
ogy, thermochemical properties, and quality of the
coal [43]. To examine this, the elemental composition Fig. 2. HR-SEM images of Lafia-Obi Coal.
of CHK, LFB, and OKB was examined by EDX spec-
troscopy as presented in the next section of the paper.
Table 2 shows the micro-elemental composition of the
CHK, LFB, and OKB examined by energy-dispersive
X-ray (EDX) spectroscopy. The elements detected
were; carbon, oxygen, aluminium, silicon, sulphur,
calcium, and iron in various quantities.
As observed, a total of seven elements (namely; C,
O, Al, Si, S, Ca, Fe) were detected in the CHK and
LFB coals, although Ca was not detected (ND) in the
OKB coal. In this study, the major elements defined as
elements with weight per cent (wt %) above 1.00 wt %
are carbon (C) and oxygen (O), whereas the minor
(trace wt % < 1.00) elements detected were Al, Si, S,
Ca, Fe, and Ca. The metallic elements detected in
coal are typically associated with the presence of salts, ×2.000 10 m
clay or substituted porphines (or porphyrin rings) [3].
The metallic element Al indicates the presence of alu- Fig. 3. HR-SEM images of Okaba (OKB) Coal.
mina (Al2O3); whereas Si is ascribed to quartz (SiO2),
which is considered the most abundant mineral on the
earth’s crust. The presence of Ca, Si, and O in com- The presence of limestone (termed coal balls) in coal
bined form could indicate the presence of the calcium beds is widely reported in the literature [44, 45]. The
ino-silicate (or metasilicate) mineral (CaSiO3) other- presence of Al and Si could also be ascribed to the clay
wise called Wollastonite, whereas Ca, C and O may be (silicate) mineral kaolinite [Al2Si2O5(OH)4]. The ele-
due to limestone (calcite) or gypsum (CaSO4⋅2H2O). ments Fe and S indicate the presence of the sulphide

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 PHYSIOCHEMICAL, MINERALOGICAL, THERMAL 501

Table 2. EDX elemental composition of selected nigerian coals

Chikila Coal Lafia-Obi Coal Okaba Coal
Element Symbol
(CHK, wt %) (LFB, wt %) (OKB, wt %)
Carbon C 86.37 79.83 76.04
Oxygen O 12.81 19.24 21.77
Aluminium Al 0.10 0.11 0.87
Silicon Si 0.10 0.29 0.80
Sulphur S 0.43 0.42 0.43
Calcium Ca 0.09 0.05 ND
Iron Fe 0.10 0.07 0.08

mineral pyrite in the coal structure. In general, EDX commonly detected minerals in soils and sedimentary
analyses revealed the CHK, LFB and OKB coals con- rocks (such as shale and coal) formed from weathering
tain clay and metal-based minerals such as quartz, processes. The oxide of titanium (TiO2) detected in
kaolinite, Wollastonite, gypsum, calcite, kaolinite, the coal samples may be largely due to ilmenite
and other silicates, which denotes the high abundance (manaccanite, FeTiO3) and the naturally occurring
of clay minerals in the coal samples examined in this minerals including rutile and anatase [57, 58].
study. Other studies have similarly detected the pres- According to Vassilev and Vassileva [59], TiO2 could
ence of these minerals in coal and coal fly [46, 47]. also originate from aragonite, brockite, calcite, iron
According to Barwood et al. [48], the accurate identi- sulphides, gypsum, mica, oxy-hydroxides and other
fication of clay minerals in coals is critical to utilisa- organic or clay minerals. Lastly, the oxides of carbon
tion during thermochemical conversion such as coal (CO2) and sulphur (SO3) denote the organic nature or
liquefaction. The findings of the study also indicated history of the coals.
that the abundance of clay minerals presents crucial
information on the environment of coal deposition. In contrast, about 22 oxides of selected metals were
Furthermore, the chemical species found in coal are detected in minor quantities in the coal samples. Most
also considered an indication of chemical weathering notably, the OKB coal contains the oxides Ga2O3,
[49, 50]. It also serves as a measure of the degree of Y2O3, Rb2O, Ar2O3, Nb2O5, BaO, La2O3, CeO2,
coalification, rank, and the source of mineral matter Nd2O3, Gd2O3, Er2O3, and WO3, which were either
in coal [43, 51, 52]. detected in trace amounts in LFB or undetected in
CHK. The findings indicate that OKB contains higher
concentrations of oxides of alkaline earth (Ba), transi-
3.3. Mineralogical Properties tion (Nb), rare earth (Ce, La, Nd, Gd, Er,) metals and
The mineralogical properties of CHK, LFB and the toxic oxides of the metalloid (Ar). The oxides of
OKB were examined by X-ray fluorescence (XRF) the rare earth elements (REE) indicate minerals of
spectroscopy. Table 3 presents the computed miner- organic origins particularly apatite, calcite, feldspars,
alogical (metal oxides and non-metallic) composi- iron sulphides, mica, monazite, siderite, xenotime,
tions of each coal sample in this study. The XRF anal- and zircon [59]. The higher concentrations of the REE
ysis revealed the presence of 23 major oxides and detected in the study also reveals the level of weather-
traces in the CHK and LFB coals, whereas a total of 30 ing, maturity, rank and classification of the coals.
were detected in OKB coal. The major oxides com- Based on the findings, the rank of the coals is in the
monly detected in all the coal samples were; SiO2, order CHK > LFB > OKB, which is in good agree-
Al2O3, Fe2O3, CO2, MgO, CaO, TiO2, K2O, Na2O and ment with earlier submission based on ASMT D388.
SO3 corresponding to the oxides of silicon, alumin- The concentrations of the REE and other elements in
ium, iron, carbon, magnesium, calcium, titanium, OKB conforms to its low-rank status compared to
potassium, sodium and sulphur. The highest compo- LFB and CHK, which suggests higher thermal reac-
sition of the oxides in the coal samples is due to silicon tivity or degradation during thermal conversion pro-
oxide (SiO2) along with the alkali/alkali earth metal cesses. Hence, the thermal degradation behaviour,
decomposition pathways, and temperature profile
oxides (CaO, Al2O3, MgO, Na2O, and K2O). The characteristics of the coals were also examined in this
presence of silicon oxide (SiO2) and aluminium oxide study.
(Al2O3) indicate the presence of quartz and alumina
formed from the SiO2–Al2O3 system [53, 54] along
with kaolinite minerals in the structure of the coals 3.4. Thermal Properties
[55, 56]. Furthermore, iron oxide (Fe2O3) may be due Figures 4 and 5 show the thermogravimetric (TG)
to the presence of hematite, which is one of the most and derivative (DTG) plots for the CHK, LFB, and

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502 NYAKUMA et al.

Table 3. XRF compositions of nigerian coals

Metal Chikila Coal Lafia-Obi Coal Okaba Coal
Oxide (CHK, wt %) (LFB, wt %) (OKB, wt %)
CO2 6.05 4.94 6.46
Na2O 0.41 0.14 0.09
MgO 1.86 3.83 0.22
Al2O3 20.61 10.88 27.41
SiO2 55.41 31.33 58.42
P2O5 0.06 0.06 0.09
SO3 0.14 9.45 0.01
K2O 1.23 0.23 0.30
CaO 1.48 14.41 1.32
TiO2 1.24 1.65 2.85
V2O5 0.04 0.00 0.00
Cr2O3 0.03 0.03 0.03
Fe2O3 11.30 22.87 1.95
Co2O3 0.01 0.04 0.04
NiO 0.02 0.04 0.06
CuO 0.02 0.03 0.02
ZnO 0.03 0.01 0.21
Ga2O3 0.00 0.01 0.01
Ar2O3 0.00 0.01 0.00
GeO2 0.02 0.00 0.00
Rb2O 0.00 0.00 0.00
SrO 0.01 0.05 0.01
Y2O3 0.00 0.01 0.03
ZrO2 0.01 0.01 0.02
Nb2O5 0.00 0.00 0.00
BaO 0.00 0.00 0.08
La2O3 0.00 0.00 0.06
CeO2 0.00 0.00 0.15
Nd2O3 0.00 0.00 0.10
Gd2O3 0.00 0.00 0.03
Er2O3 0.00 0.00 0.01
WO3 0.00 0.00 0.01

OKB. The findings indicate that the oxidative and liptinite groups [3]. Based on the rank, classification,
non-isothermal heating TGA process resulted in the and source of the coal the proportion of each organic
rapid thermal degradation of the coal samples as evi- components can range from 5–10% for liptinite, 50–
dent in the downward Z shape curves, significant mass 90% for vitrinite, and 50–70% for inertinite. The ther-
loss (ML > 90%) but low residual masses (RM). The mochemical reactivity along with the yield and distri-
mass loss during TGA could be ascribed to the loss of bution of products from coal conversion is largely
volatile organic components or macerals in the struc- influenced by the proportion of macerals [60, 61], par-
ture of the coals. The organic components of coal are ticularly vitrinite and inertinite fractions [62]. The loss
typically comprised of inertinite, vitrinite, and of mass during coal degradation could also be

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 PHYSIOCHEMICAL, MINERALOGICAL, THERMAL 503

110
Chikila
100 Lafia-Obi
90 Okaba

80

Mass loss TG, %

70
60
50
40
30
20
10

0 100 200 300 400 500 600 700 800 900 1000 1100
Temperature, °C

Fig. 4. TG plots for oxidative TG coal analysis.

–0.025
Chikila
Lafia-Obi
Okaba
–0.020
Deriv. mass loss, %/min

–0.015

–0.010

–0.005

0 100 200 300 400 500 600 700 800 900 1000 1100
Temperature, °C

Fig. 5. DTG plots for oxidative TG coal analysis.

attributed to the degradation of lignocellulosic materi- whereas the residual mass (RM, %) was from 5.96–
als (resins, cellulose, lignin) originating from plants 8.41% for the coals. The ML is in the order LFB >
during the coalification process [63, 64]. OKB > CHK, whereas the RM is in the reverse order
The effect of the thermal degradation process on CHK > OKB > LFB. Based on the findings, LFB
the mass loss (ML), residual mass (RM) and the corre- experienced the highest mass loss (ML, %) along with
sponding temperature profile characteristics of the the lowest residual mass (RM, %), which indicates it is
coals are presented in Table 4. The TPCs deduced in more thermally reactive when compared to OKB and
this study are; the onset (Tons), midpoint (Tmid), and CHK. In contrast, CHK was the least thermally reac-
offset (Toff) temperatures. The results indicate that the tive as it experienced the lowest mass loss (ML, %) but
mass loss (ML, %) was in the range 91.59–94.04%, the highest residual mass (RM, %). The findings indi-

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504 NYAKUMA et al.

Table 4. Coal characteristic temperature and mass loss profiles

Coal Onset temp. (Tons, Midpoint temp. Offset temp. Mass loss Residual mass
Code
sample °C) (Tmid, °C) (Toff, °C) (ML, %) (RM, %)
Chikila CHK 394.94 530.54 657.27 91.59 8.41
Lafia-Obi LFB 336.19 460.58 576.91 94.04 5.96
Okaba OKB 321.70 436.77 548.58 92.35 7.65

Table 5. Characteristic coal TPCs for DTG plots and mass loss rates
Coal Dry peak temp. Drying Devolatilization peak Devolatilization.
Code
sample (Tdry, °C) rate, %/min temp. (Tdev, °C) rate, %/min
Chikila CHK 60.40 1.04 517.61 7.17
Lafia-Obi LFB 88.40 2.88 428.46 7.70
Okaba OKB 89.51 2.62 436.14 7.89

cate that LFB and OKB are lower in rank compared to from RT to 200°C for all the coal samples. Based on
CHK due to their higher reactivity during TGA. the mass losses; CHK (3.483 wt %), LFB (11.732 wt %)
Typically, low ranked coals exhibit high thermal and OKB (9.587 wt %) or ML < 12 wt % during this
reactivity due to the presence of inert components and stage, the thermal degradation could be ascribed to the
non-coking properties [65]. Furthermore, the struc- loss of moisture and low molecular weight volatile coal
ture of low ranked coals contains highly reactive func- components. The second stage is characterised by a
tional groups, higher contents of H and O, along with larger set of asymmetric peaks compared to the first
higher pores and surface area compared to coals of stage and was observed between 200 and 650°C for
higher ranks [66]. Hence, the higher contents of rare OKB and LFB whereas it was 700°C for CHK. The
earth and alkali/alkali earth metals of LFB and OKB mass loss during this stage is due to the thermal degra-
(as earlier surmised in Table 3) may account for the dation of macerals notably the inertinite and vitrinite
higher mass loss of the coals. The high reactivity of fractions of the coals [62]. Based on the findings CHK
low-rank coals particularly at low temperatures can requires a higher temperature range for thermal degra-
result in spontaneous combustion, thereby posing dation compared to LFB and OKB, which further
human safety and environmental risks during storage emphasises it is a higher-ranked coal. Table 5 presents
[66]. Hence, the TGA results also provide valuable the characteristic of coal TPCs for DTG plots and
insights into the health and safety of coal storage and mass-loss rates.
utilization.
The characteristic coal TPCs deduced from the
The TPCs also showed that thermal degradation DTG peaks showed that the maximum temperatures
revealed distinct values of onset (Tons), midpoint for drying occurred between 60.40°C (CHK) and
(Tmid), and offset (Toff) temperatures for each coal 89.51°C (OKB), whereas the drying rates (%/min)
examined. The analysis indicated that the onset (Tons) were observed from 1.04 to 2.88%/min. The results
ranged from 321.70 to 394.94°C, whereas the mid- further indicate the drying rate of LFB was the highest
point (Tmid), was from 436.77 to 530.54°C and the off- of the coals examined in this study, which could be
set (Toff) was from 548.58 to 657.27°C. The findings ascribed to its high moisture content (11.59 wt %)
indicate that the CHK exhibited the highest onset compared to OKB and CHK. As earlier surmised, the
(Tons), midpoint (Tmid), and offset (Toff) values of second stage of the TGA process was characterised by
394.94, 530.54, and 657.27°C, respectively, whereas a larger asymmetric peak culminating in a maximum
the lowest values were observed for OKB. This obser- value termed the devolatilization peak temperature
vation confirms that CHK is more thermally stable (Tdev, °C). In this study, the Tdev was observed from
compared to the lower-ranked OKB and LFB coals 428.46°C (LFB) to the highest value of 517.61°C
examined in this study. Further studies to examine the (CHK). The high Tdev is related to the effect of volatile
thermal reactivity of the coal samples through deriva- matter (VM), which accounts for the thermal ignition
tive thermal analysis (DTG). and reactivity of carbonaceous materials [67]. As
The DTG against temperature plots for CHK, reported in Table 1, the volatile matter of CHK
LFB, and OKB are presented in Fig. 5. The plots show (35.27 wt %) is much lower than LFB (46.04 wt %),
several endothermic peaks of various sizes and shapes and OKB (40.03 wt %). Hence, the high Tdev value of
resulting from the thermal degradation process. The CHK is explained by its comparatively lower VM,
first set of small yet symmetric peaks can be observed which accounts for its higher ignition temperature

COKE AND CHEMISTRY Vol. 64 No. 11 2021

 PHYSIOCHEMICAL, MINERALOGICAL, THERMAL 505

–12.0
Chikila

–12.5 Lafia-Obi

Okaba
–13.0
Linear
ln ((g(x)/T2))

–133.5 (Chikila)

–14.0

–14.5

–15.0

–15.5
1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8
1000/T

Fig. 6. CRM kinetic plots for thermal degradation of benue trough coals.

(Tons = 394.94°C) reported in Table 4. Likewise, CHK the findings confirm that LFB is more thermally reac-
has the lowest reactivity (due to its low VM and high tive when compared to the OKB and CHK in decreas-
ranked nature) as evident in its low devolatilization ing order. In comparison, Sonibare et al. [68] reported
rate of 7.17%/min compared to 7.70%/min for LFB that the oxidative thermal analysis of selected coals
and 7.89%/min for OKB. The thermal reactivity of the from Nigeria are; Ea of 68.50 kJ/mol–90.90 kJ/mol,
coals can be further examined by kinetic analysis. A of 4.3 × 1001 min–1–6.7 × 1002 min–1, and R2 of
0.980–0.994. Hence, the values of CHK, LFB, and
OKB in this study differ markedly from the findings
3.5. Kinetic Properties from Sonibare et al. [68]. The differences could be
The kinetic parameters; activation energy (Ea, kJ/mol) ascribed to the variable physicochemical, macerals
and frequency factor (A, min–1) was computed based composition, rank classification, and reactivity of the
on the governing equations of the Coats–Redfern coals.
model. The Ea and A were calculated from the slope
and intercept of the downward sloping kinetic plots in
Fig. 6. 4. CONCLUSIONS
For the coal samples examined in this study, the The physiochemical, mineralogical, thermal and
value was computed as presented in Table 6. The Ea kinetic fuel properties of selected coal samples from
values range from 30.07 to 43.91 kJ/mol, whereas A is the Benue Trough and Anambra Basins of Nigeria
from 1.16 × 10–02 min–1 to 6.73 × 10–02 min–1 with the were examined in this study. The physicochemical
minima and maxima ascribed to LFB and CHK, characterisation revealed high compositions of car-
respectively. The results indicate that the thermal deg- bon, volatile matter, fixed carbon but relatively low
radation of the coals is highly reactive as evident in the moisture, and ash. The calorific analysis revealed high
low values of Ea and A in Table 6, which were com- heating values indicating mid-to-high ranked subbitu-
puted at high R2 values of 0.98–0.99. Furthermore, minous and bituminous coals. The surface morphol-

Table 6. Calculated kinetic properties of coals based on Coats–Redfern model

Coal Temperature Regression
Code Ea, kJ/mol A, min–1
Sample range, °C Coefficient (R2)
Chikila CHK 394.94–657.27 0.998 43.91 6.73 ×10–02
Lafia-Obi LFB 336.19–576.91 0.988 30.07 1.16 ×10–02
Okaba OKB 321.70 –548.58 0.996 32.48 2.41 × 10–02

COKE AND CHEMISTRY Vol. 64 No. 11 2021

506 NYAKUMA et al.

ogy and microstructure revealed randomly dispersed 8. Global coal demand by forecast for 2000–2024, in
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The authors wish to acknowledge the Hydrogen Fuel 19. Oboirien, B., North, B.C., Obayopo, S., Odusote, J.,
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Cell at Universiti Teknologi Malaysia (UTM) for the TGA pp. 64–70.
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