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ICTWESDA-2022 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1178 (2023) 012019 doi:10.1088/1755-1315/1178/1/012019

Development of refractories for the pyro-processing (heat-

based) industry in Nigeria through the evaluation of mixtures
of Enugu Iva-Pottery clay, Nsu-clay and palm kernel shell
waste
Sunday C Agbo1,2* Olufemi A Odewole3,4, Francis K Ojo5, Ogechi L Alum3, Kovo
G Akpomie3,4, Anthony C Ofomatah6, Helen O Chukwuemeka-Okorie7, Julius U
Ani3. and Caius C Onu1

1
Ceramics Research and Production Department, Projects Development Institute (PRODA),
Enugu State, Nigeria.
2
Department of Pure and Industrial Chemistry, Nnamdi Azikiwe University, Awka Anambra
State, Nigeria
3
Department of Pure & Industrial Chemistry, University of Nigeria, Nsukka, Nigeria
4
Department of Chemistry, University of the Free State, Bloemfontein, South Africa
5
Department of Chemical Sciences, Bingham University, Karu, Nassarawa State, Nigeria
6
National Centre for Energy Research and Development, University of Nigeria, Nsukka,
Nigeria
7
Department of Chemistry, Michael Okpara University of Agriculture, Umudike, Abia State,
Nigeria

*Corresponding author: sc.agbo@stu.unizik.edu.ng

Abstract. The energy demand is on the global increase as the world economy is increasing
steadily. Hence, the need to develop energy-saving technology with local raw materials and
abundant waste materials becomes paramount. The mixtures of Enugu Iva-pottery clay, Nsu
clay and PKS were evaluated to improve the quality of locally produced refractory for pyro-
processing industries. The chemical and mineralogical composition of the PKS and the clay
were determined. Eight recipes were made by varying PKS with quartz from 5 to 35% and
produced by the wet pressing technique, then fired to 1200 oC and 1300oC respectively. The
mechanical properties were determined by the Modulus of Rupture test, also, the bulk density,
linear shrinkage, total shrinkage, apparent porosity, water absorption and thermal efficiency
tests of the produced refractories were ascertained.
The recipe with 15% PKS sintered well at 1300oC and gave the best optimum results of
1.76g/cm3 bulk density, 6.49% linear shrinkage, 21.384% apparent porosity, 20 cycles of
spalling tests at 1300 oC. The results comply well with the standards of refractory properties.
The PKS additives have shown significant improvement in the properties of the locally
produced refractories and waste control; hence, can promote sustainable development of the
local pyro-processing industry.

1. Introduction
The need to develop energy-saving technology with local raw materials and abundant waste materials
could be a potential means to technological advancement and industrial revolution in developing
countries like Nigeria. Nigeria is blessed with abundant natural resources among which are solid
minerals in inestimable quantities in different parts of the country yet local content is still negligible

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IOP Conf. Series: Earth and Environmental Science 1178 (2023) 012019 doi:10.1088/1755-1315/1178/1/012019

[1]. The Inadequate research on our indigenous minerals and lack of pyro-processing technology has
impeded the development of our local and indigenous industries such as ceramics, metallurgy and oil
and gas which has consequently led to total dependence on imported things from the developed world
among which are ceramic and petrochemical products. With a record of more than 40 minerals with
known reserves, Nigeria in sub-Saharan Africa (surface area 923.768 Km2) is a country with
significant riches in natural resources. [2-4].
Pyro-processing industries include ferrous, as well as industries involve in non-ferrous metals
(copper, lead, zinc, etc.), cement, chemicals, pulp and paper, and anything linked to food production
that involves high temperatures applications. The pyro-processing industries use refractories; the
major constituent of refractory is clay, which is known to be found in every part of Nigeria. Clay is an
important material used in metallurgical pyro-processing industries such as mould casting, furnace
linings and binders [5-8]. Refractory can be expressed as a non-metallic, inorganic material made from
crystalline minerals used for the construction of high-temperature equipment e.g. furnaces, kilns and
crucibles. They are used to construct high-temperature equipment because they can withstand high
temperatures [9]. Refractories can endure fast temperature changes, corrosion from molten metal,
glass melt, slag, and hot gas, as well as heat and mechanical abrasion. For a refractory to be accepted
in service, it needs to have a few particular characteristics. However, these specifications differ
depending on the type of refractory application, which often includes; Resistance to extreme
temperatures, bearing loads, fluxes, corrosive fluids like slag, thermal shocks caused by abrupt thermal
effects, and so on. Strength, specific gravity, and thermal and electrical conductivity are further
characteristics. [10]. Some of the properties are listed below; crushing strength, apparent porosity,
linear shrinkage, modulus of rupture and bulk density. Refineries in Nigeria between 1997 and 2002
were recorded to have spent about $850 million on their turnaround maintenance in which the fluid
catalytic cracking, which is lined with an enormous quantity of different refractory linings remained
the critical unit in the maintenance [11]. In oil and gas refineries, about 70% of heat energy is
conveyed with furnaces [5, 12].
Grog is calcined clay, which is added to affect the microstructure and chemical properties of
the refractories, hence, contributing to an enhancement in the physical characteristics of the
refractories such as reduced shrinkage, and reduced density with better abrasion resistance and thermal
shock resistance. Grog is an alumina precursor/ rich, which brings about an increase in mullite
formation during sintering [12-15].
Palm kernel shell (PKS) is an agricultural waste that causes environmental issues because of
its nature, the disposal by burning could cause serious adverse effects on our ozone layer through the
intense release of smoke [16]. Nigeria is recorded to be the third-largest producer of palm oil in the
world and as such, palm kernel shell waste generation and disposal have proven to be a major
environmental problem [16, 17]. The pks can serve as a filler and flux in refractory composition
because of their high-quality silica composition as well as Calcium oxide content, when judiciously
applied it could improve the quality of refractory and also serves as an alternative disposal means of
the palm kernel shells in Nigeria. Adding value to Nigeria's abundant ceramic resources through pyro
processing will, over time, lead to economic empowerment, the creation of jobs, and technological
advancement, and thus, will strengthen the country and bring it closer to the world's economically and
technologically advanced nations. The study involves the use of palm kernel wastes generated, and
some local clay deposits for the development of refractories for the pyro-processing (heat-based)
industry in Nigeria.

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ICTWESDA-2022 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1178 (2023) 012019 doi:10.1088/1755-1315/1178/1/012019

2. Materials and Methods

2.1 Materials
The Enugu Iva-pottery clay was collected from its deposit at Iva-pottery, Onyeama Coal mine sections
located at Iva-valley, Enugu North local government area in Enugu state of Nigeria while the Nsu-clay
was got at Nsu at Ehime-Mba Ano in Imo state Nigeria. Palm kernel shell was collected at a palm oil
mill at Emene Enugu-East in Enugu Nigeria. Other materials and equipment used were grogs, silica
sand, water, a kiln, a graduated cylinder, a weighing scale (ek530) X-ray fluorescence (XRF) and an x-
ray diffractometer (XRD).

2.2 Methods
2.2.1 Sample Collections and Preparation
The collected clay samples were crushed in a pan mill and put in a container with excess water and
there was vigorous stirring to ensure better dissolution. The clay solution was sieved with 100 mesh
and after 24 hours, it was settled and the water was removed. The grog used is the fired Enugu Iva-
pottery and Nsu clay composition in a ratio of 50:50. The clay was then sundried, pulverized ready for
formulation. The palm kernel shell was milled with a pan-milling machine and sieved with a 100 mesh
sieve size.

2.2.2 Physical analyses of formulated refractory Bodies

Eight compounded bodies which involve Enugu Iva-pottery clay, Nsu clay as a binder and grog were
made by varying palm kernel shells with silica sand from 5 to 35% as shown in Table 1 and were
produced by the wet pressing technique, then fired to 1200oC and 1300oC.
Table 1. The proportion of Quartz, EV-clay, PKS, Nsu clay and grog composition for refractory
bodies
code Quartz EV-clay PKS Nsu Grog
A 30 20 0 10 40
B 25 20 5 10 40
C 20 20 10 10 40
D 15 20 15 10 40
E 10 20 20 10 40
F 5 20 25 10 40
G 0 20 30 10 40
H 20 20 15 10 40
EV= Enugu Iva-pottery Clay.
2.2.3. The physical analysis of the compounded refractory bodies
The refractories’ physical Properties such as apparent porosity, apparent density, apparent porosity,
rupture modulus, spalling resistance and refractoriness were determined [18].

2.2.3.1. Determination of linear shrinkage, water absorption, apparent porosity and bulk density.
The linear shrinkage, water absorption, apparent porosity and bulk density were calculated using
similar procedures by Ekpunobi et al, Agbo et al and Etukudoh et al [19,20 &26] the formulae are
shown below;
Linear Shrinkage (%) = 100[Ld - Lf]
Ld [1]
Where the Ld is the dried length while Lf is the fired length
Water of Absorption (%) = 100 [M2 – M1]
M1 [2]
Where the M1 (g) is the dry weight while the M2 (g) is the soaked weight

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ICTWESDA-2022 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1178 (2023) 012019 doi:10.1088/1755-1315/1178/1/012019

Apparent Porosity (%) = 100 [M2- M1]

M 2 – M3 [3]

Apparent Density = M1/[M1 – M3] [4]

Bulk Density = M1/[M2 – M3] [5]

Where the M1 (g) is the dry weight the M2 (g) is the soaked weight while the M3 is the suspended
weight

2.2.3.2. Thermal shock resistance

The compounded Eight samples were tested for spalling resistance by inserting each in a furnace with
a constant temperature of 1300oC for ten minutes in and ten minutes out until a crack is developing.
Each sample's thermal shock resistance was noted and recorded as the number of heating and cooling
cycles before cracking.
2.2.4 Chemical and Mineralogical Characterizations
The constituents of the crystalline phase (minerals) and the elements that make up the clay and the
palm kernel shell were studied. Under a wide-angle range using XRD GBC EMMA powdered
diffractometer with monochromatic CuKα radiation (k = 1.541 Å) voltage of 40 kV and 40 mA. From
5° to 65°, 2θ at a step size of 0.05° and the rate of 3.57°/min, the diffraction angle was scanned.

3. Results and Discussion

3.1. Raw Materials Characterisations

The result of the chemical composition of all the raw materials used is shown in Table 2
Table2. Chemical Analysis of raw materials
Component EV-Clay Nsu-clay Nsude sand PKS Grog
(%)

SiO2 64.0 53.6 99.15 50.30 21.0

Al2O3 21.0 25.4 0.73 13.80 67.0
Fe2O3 1.0 2.3 0.005 9.94 1.5
MgO 0.031 0.3 ND 2.4 2.3
K2O 0.75 0.3 ND 0.15 1.2
TiO2 0.9 1.4 ND 1.27 2.4
LOI 11.34 12.62 0.61 ND 2.45
EV= Enugu Iva-pottery Clay
Table 2 displays the outcomes of the raw materials' chemical analyses. Based on the outcomes shown
in Table 2 it is observed that Enugu Iva-pottery clay has a very high content of silica (64%) which is
within the requirements for manufacturing high-duty heat refractories (55-73%),[20] however the
Alumina content of (21%) is moderate and may make the clay unsuitable for some refractory
applications. It can be deduced from the analysis that Enugu Iva-pottery clay falls within the fire clay
type of Al2O3 (20 -40%) and SiO2 (55 – 74%) [21], and so has limited application when used alone
because of low alumina concentrations, Therefore the need for a chemical reaction between an
alumina-rich material and the bulk of the silica present will promote the creation of mullite. [12-15,
22].
The silica content of PKS is large, compared to the other oxides, it has a significant amount of
calcite (CaO) which acts as a flux and may bring an increase in the rate of mullite formations as a
result of the eutectic effect of the calcium oxide of PKS as shown in table 2 above, the alumina content

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ICTWESDA-2022 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1178 (2023) 012019 doi:10.1088/1755-1315/1178/1/012019

of the PKS is high when compared with any other organic materials which play a role in the formation
of alumina mullite, especially in clay or bodies that have relatively low alumina. It is also observed,
that grog is very rich in alumina, thus the name “aluminosilicate”, with an alumina-silica ratio of 3:1
and could be used to improve the refractory of Enugu Iva-pottery fire clay. The Nsu-clay has less
silica content and higher alumina when compared with the Enugu Iva-pottery clay, hence more plastic
and was used mainly as a binder because of its plastic nature. The Analyses of the raw materials'
results reveal that they include components appropriate for producing high-quality alumina refractory
bodies [13, 23]. High alumina refractory has a wider application in pyro-processing industries.
According to Kingery, Fire clays combined with alumina-rich minerals and a decrease in the amount
of free silica (consumed in the creation of mullite) can be used to create high alumina refractories,
which can be used at higher temperatures than fire clay refractories only, up to 1800°C. [12,24]. The
higher the alumina mullite content of refractories the more improved creep resistance and better
corrosion behaviour, this is due to the decrease in volume thermal expansion as well as the anisotropy
thermal expansions caused by alumina increase. For steel industry applications that required refractory
materials with higher performance levels than fireclay, high alumina refractories were created [12-13,
25].

3.2. Mineralogical analysis of raw materials

The XRD diffractogram of Enugu Iva-potter clay is shown in Fig1. It is observed that the pattern has
prominent peaks at angle 2θ of 20.80 and around 28.3 which correspond to quartz and muscovite
mineral peaks. Hence, it falls under the mica structure sub-group type of clay where muscovite
belongs. Fire clay is muscovite clay and has a mica structure clay [23]. The interpretation agrees well
with the XRF analysis of low alumina and high concentration of silica of the Enugu Iva-pottery clay.
According to Harbison, Fireclays have Al2O3 contents that range from 20 to 45 wt%, with silica being
the other major constituent [22]. The SEM (fig2) showed the microstructure of the Nsu-clay to have
fine grain shapes and sizes. Image J software was used to determine the pore size distribution, and it
revealed an average range of 0.75 μm. This is in an agreement with the reported literature [22], that
ball clay ranges in size from (0.1–2μm). Because of the fine size particle, it is known to be highly
plastic when mixed with other clay types, hence acts as a binder and gives the body both green and
fired strength. The Nsu-clay served as a ball clay in the refractory formulations, hence bonding and
strengthening the refractory.

Fig1:.XRD diffractogram of Enugu Iva-pottery clay

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ICTWESDA-2022 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1178 (2023) 012019 doi:10.1088/1755-1315/1178/1/012019

Fig2. SEM microgram of the Nsu sample

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ICTWESDA-2022 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1178 (2023) 012019 doi:10.1088/1755-1315/1178/1/012019

Linear shrinkage (%)

14
12
10
8
6
4
2
0

1200oC 1300oC

Fig3: The linear shrinkage of the sintered refractory samples at 1200oC and 1300oC
The linear shrinkage which is known as dry-fired shrinkage determines the dimensions of the
refractory products. The shrinkage of the samples is generally low between (4 -13%) and within the
standard required for refractory materials of < 14% (17). It is observed that the samples’ dried fired
shrinkage increases with temperature increase from 1200 oC to 1300oC. The shrinkage (fig3) increases
with an increase in PKS and a decrease in the silica additions. This is a result of PKS being burnt out
and converted to oxides, thereby creating pores that further compress together as the vitrification
occurs. The highest linear shrinkage as shown in Fig 3 is recorded at sample G with 0% silica and 30%
PKS.
The fig4 shows the samples' apparent porosity. The greater the percentage rise of PKS and reduction
in the quantity of silica brought about the apparent porosity increase. In addition, from 1200°C to
1300°C, the samples' apparent porosity reduces as the temperature rises. This is explained by the fact
that the body shrank more as the firing temperature increased, which caused some pores to close or
diminish in size. The apparent porosity is proportional to water absorption.

Apparent porosity (%)

160
140
120
100
80
60
40
20
0

1200oC 1200oC

Fig4: The apparent porosity of the sintered refractory samples at 1200oC and 1300oC

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ICTWESDA-2022 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1178 (2023) 012019 doi:10.1088/1755-1315/1178/1/012019

Bulk Density(g/cm3)
1.8
1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0

1200oC 1200oC

Fig5. The bulk density of the sintered refractory samples at 1200oC and 1300oC

Figure 5 shows the bulk density of the samples. The results show that the bulk density decreases with
PKS increase. 15% PKS, and 20% Quartz (H) fired at 1300oC exhibited the maximum bulk density
value of 1.86g/cm3. Which is within the required specification of 1.6 to 2.0 g/cm3 for good refractory
materials [26].
The result of the thermal shock resistance showed that sample G with 0% silica and 35% PKS
gave the highest number of cycles of 23 cycles followed by 15% of PKS which produced 20 cycles.
This could be attributed to the PKS being able to create pores in the refractory body also the thermal
shock resistance which depends mainly on the mineralogy content of the body, the PKS has a
significant amount of alumina and amorphous silica which exhibits poor spalling attacks so increase in
PKS additions increases the thermal shock resistance.

4. Conclusions
The Enugu Iva-pottery fire clay has been improved to meet the refractory standards for the pyro-
processing industry. The samples produced showed very good refractory qualities. These were
attributed to the incorporation of PKS, the PKS replacement of quartz resulted in improved thermal
shock resistance of the refractory while the grog which contains a higher concentration of alumina
brings about the thermal stability of the refractory, hence wider application in pyro-processing, also
the grog as a non-shrinking materials control the shrinkage of the refractory. The Nsu-clay as a binder
contributed to both dried and fired strength. The recipe with 15% PKS sintered well at 1300oC and
gave the best optimum results of 1.76g/cm3 bulk density, 6.49% Linear shrinkage, 21.384% apparent
porosity, 20 cycles of spalling tests at 1300 oC. The results comply well with the standards of
refractory properties. The PKS additives have shown significant improvement in the properties of the
locally produced refractories and waste control; hence, can promote sustainable development of the
local pyro-processing industry

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ICTWESDA-2022 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1178 (2023) 012019 doi:10.1088/1755-1315/1178/1/012019

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