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Using oil shales for production of low-carbon Portland cement

Conference Paper · June 2019

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Using oil shales for production of low-carbon Portland cement
Goncharov A1*, Zhutovsky S1

ABSTRACT
Oil shales with low organic content can be potentially used for the production of Portland cement. The presence of oil in them
can significantly reduce the consumption of fuel in clinker production. In addition, oil shale added to the kiln feed reduce the
temperature of clinkerization. In this study, Israeli oil shales with low organic content were investigated as a raw material for
kiln feed in the production of cement. It was found, that Israeli oil shale can replace up to 76% of the typical raw materials in
the production of belite-rich cement. The clinkerization temperature required to obtain the necessary compounds was 1250 °C.
The resulting clinker was analyzed with respect to the mineral composition, density, and hydration rate. The results of the
current research indicate that the use of oil shale for cement production may result in significant energy saving and reduction
of carbon dioxide emissions.
Keywords: Clinker production; Portland cement; Oil shale.

1| INTRODUCTION mainly contains calcium oxide in its mineral composition,

Cement is a product that ranks first in terms of production
volume. In combination with water, cement forms a glue
that connects mineral aggregates to form concrete, which is
the second most used material after water [1]. Accordingly,
cement is one of the most important materials in the
construction industry and its consumption is constantly
growing, especially in developing countries. Cement
production requires a large amount of energy. Between
12% and 15% of all industrial energy is consumed by the
cement manufacturing sector. The cement industry
accounts for 6-8% of anthropomorphic carbon dioxide
emissions [2]. With the increase of cement production
volume, it is important to find new ways to improve the
sustainability of cement production and reduce its carbon
footprint [3]. Solving this problem, it is important to consider
the local capabilities of each country and its region
separately, taking into account the availability of natural
resources and economic opportunities. A possible solution
can be finding an alternative natural local raw material for
low carbon cement production that is able not only to
reduce carbon dioxide emissions but also meet the
requirements in terms of economy, production volume and
sustainability is a difficult task.
The scientific community has long been engaged in the
search for the optimal solution to reduce greenhouse gases
(GHG) emissions in the process of cement production, a lot
of research efforts have been devoted to this topic and a
large number of scientific papers have been published. The
proposed solutions included the replacement of the fuel for
the rotary kiln from oil to coal, the partial replacement of
clinker in cement with pozzolanic materials, such as fly ash
[4–6], coal gangue (CG) [7–12], or other industrial wastes.
Currently, significant research efforts are focused on finding
alternative fuels [13,14] and raw materials for clinker
production [15,16], as well as on the development of
alternative low-carbon non-clinker binders [17,18]. The
replacement of clinker with low-carbon supplementary
cementitious materials (SCM) in concrete is still attracting a
significant research interest, but it is apparent now that the
availability of SCMs gradually becomes limited [19]. In
many countries, oil shales can represent a great alternative
to the traditional raw materials in Portland cement
production.
The properties of oil shale are highly dependent on its
origin. In case of siliceous oil shale, which mainly contains
silica in its mineral composition, the ash after combustion
can be used as a pozzolanic material [20], that is as an
SCM partially replacing the clinker in cement. But if oil shale
then it can become a part of a kiln feed for clinker
production. The production of clinker from oil shale has
already been considered [21–23]. The use of oil shale in a
kiln feed can be considered beneficial if their energy value
is relatively small and the energy released during
combustion is not sufficient to economically produce
electricity or extract oil [24–26]. In previous studies, it was
confirmed that Israeli oil shales belong to this group and
have a lower calorific value range of 1000-1800 cal/gr [27].
The present study will consider the use of Israeli oil shale
as a kiln feed, which has a dual benefit both as a partial
energy source for the rotary kiln and as a source of
minerals for clinker formation. To further reduce energy
consumption and carbon dioxide emissions, the production
of a cement reach in belite rather than alite was considered.
A raw meal was formed from oil shale, limestone, and
siliceous sand and a trial clinker batch was produced in a
laboratory furnace. The processed of calcination and
clinkerization were studied by means of thermogravimetric
analysis and differential scanning calorimetry. The mineral
composition was studied using X-ray diffractometry. The
grinding time and gypsum content were optimized using
laser diffractometer and isothermal calorimeter,
respectively. The presented study demonstrated the great
potential of using oil shale simultaneously as an energy and
mineral source, for the production of low-carbon belite-
reach cement in order Improve sustainability and carbon
footprint of concrete.
2| MATERIAL AND METHODS
2.1 Materials
In this research, shales collected from Maastricht, Ghareb
Formation age, mined from quarry Mishor Rotem, Northern
Negev, Israel were used. Oil shales contained 59.8%
calcite, 15.7% gypsum, 2.2% quartz, 2.2% pyrite, and 1.8%
apatite as determined by XRD. Amorphous phase
comprised 16.3% and the calorific value was 3.616 MJ/kg.
Oil shales were used at the rate of 76% of clinker raw meal
in addition to 6% of silica sand and 18% of limestone to
complement the chemical composition of clinker. The
chemical composition determined by Inductive Coupled
Plasma (ICP) spectrometry and loss on ignition (LOI) of oil
shale, limestone, silica sand, as well as a raw meal are
given in Table 1. For the oil shale LOI due to organic and
mineral parts was 15.4% and 25%, respectively. More
detailed characterization of oil shale is given in [28]. For
cement preparation, reagent quality calcium sulfate

(1) Department of Civil and Environmental Engineering, Technion – Israel Institute of Technology, Haifa, Israel.
* Corresponding author(s): gantonina@technion.ac.il

JUNE 2019 | LONDON, UNITED KINGDOM | 1

hemihydrate was used. The calculated lime saturation
factor (LSF), silica ratio (SR) and alumina ratio (AR) were
Table 1 | Chemical composition of the raw materials [28]
CaO SiO2 Al2O3 Fe2O3 MgO
Oil shale 37.42 9.01 3.31 1.85 0.57
Limestone 55.12 1.16 0.27 0.09 0.25
Silica sand < 0.01 96.34 2.04 0.97 0.18
Raw meal 38.36 12.84 2.56 1.42 0.48
2.2 Methods
Before producing the clinker raw meal for the laboratory
furnace, the oil shale was burned at a temperature of 650
°C for 2 hours to remove the organic component. The
clinker raw meal was powdered in a ball mill and intermixed
with water to prepare a thick paste. Spherical nodules of
approximately 10 mm in diameter were formed from the
paste and dried at a temperature of 105 °C for 24 hours.
After that, the nodules were placed in Pt/Rh crucible and
calcined at the temperature of 900 °C for one hour, followed
by the burning of clinker at a temperature of 1250 °C for 30
minutes with subsequent cooling at the rate of 20 °C/min.
The mineral composition was determined using X-ray
diffraction (XRD). XRD scan was performed using a
Malvern PANAlytical EMPYREAN X-ray diffractometer with
the following configuration: an X-ray source was CuKα1,2
(λ= 1.5408 Å) with X-Ray generator operated at a voltage of
45 kV and a current of 40 mA; a Goniometer radius was
240 mm; the incident beam optics included 10 mm mask,
0.04 rad Soller slit along with ¼° divergence and 1° anti-
scatter fixed slits; the diffracted beam optics consisted of 8
mm anti-scatter fixed slit and 0.04 rad Soller slit. The
detector was PIXcel 3D detector used in 1D continuous
scan mode. The scan was performed using Brag-Brentano
− geometry, between 10 and 70 °2θ. Time step of 80.32 s
with a step size of 0.013 º2θ were used resulting in a total
measurement time of 25.22 s. The quantitative analysis was
performed by means of Rietveld refinement using
HighScore Plus software.
Differential Scanning Calorimetry (DSC) and thermo-
gravimetric analysis (TGA) were performed using a Netzsch
STA 449 F5 Jupiter instrument at a heating rate of 10°C/min
in platinum crucibles. Samples were subjected to heating
from 25°C to 1500°C under dry air atmosphere purged at
the rate of 100 ml/min in order to test the organic and
inorganic decomposition and clinkerization processes. The
experiments were replicated 3 times and a consistent result
was obtained.
Grinding process was performed using a vibratory ball mill.
Grinding media was stainless steel cylindrical grinding
elements with a total mass of 5800 g. One charge of the mill
was 800g of clinker. The tested milling times were: 30, 60,
120 and 180 minutes. Determination of the particle size
distribution was carried out by means of Malvern
Mastersizer 3000 laser diffraction particle size analyzer.
The analysis was carried out in isopropanol media.
The optimum content of gypsum in cement was determined
using Isothermal calorimeter TAM AIR by measuring the
evolved heat of the hydration. The samples for analysis
heat of the hydration were prepared as follows: 5 grams of
ground clinker were mixed with 2.5 grams of distilled water
(water-cement ratio of 0.5), and gypsum in form of
hemihydrate. The tested contents of hemihydrate were 0%,
4%, 5%, and 6%, by weight of the clinker. Each test was
duplicated and the average of 2 samples is presented. A
standard CEM I Portland cement paste with a water-cement
ratio of 0.5 was tested for a reference. The density of
2 | LONDON, UNITED KINGDOM | JUNE 2019
0.96, 3.22, and 1.80, respectively, which is in the range of
normal values for Portland cement.
TiO2 K2O Na2O P2O5 Mn2O3 SO3 LOI 950
0.14 0.38 0.15 2.61 < 0.01 4.60 40.40
0.01 0.07 < 0.01 0.02 < 0.01 0.08 43.28
0.20 0.42 < 0.01 0.01 0.03 < 0.01 0.69
0.11 0.30 0.11 1.99 0.00 3.51 38.49
clinker and cement was determined using Helium
Pycnometer Quantachrome Ultrapyc 1200e. The density
test was replicated 5 times and an average result is
presented.
The compressive strength was determined on the
40×40×160 mm beams at the age of 28 days in accordance
with European standard EN 196-1:2016.
3| RESULTS DI SCUSSI ON
3.1 Thermal analysis
The results of thermal analysis of raw meal are presented in
Fig.1. As seen in Fig. 1, four main stages in the process of
heating raw clinker meal in the range from 30 °C to 1500°C
can be recognized:
(1) Dehydration takes place in the range between 30 and
150 °C. Below 100 °C, the mass loss occurs mainly due to
evaporation of free moisture. At a temperature of about 140
°C, a small endothermic peak is detected due to by the
water loss by gypsum.
(2) In a temperature range from 200 °C to 600 °C, the
major mass loss is due to the decomposition of organic
components of oil shale. This reaction is exothermic for the
air atmosphere. The two exothermic peaks at 326 and 447
°C are associated with the burning of kerogen and bitumen
contained in oil shales. The calorific value of these two
peaks is equal to of 3.6 MJ/kg and can be potentially used
for the heating of the raw meal materials in a preheater or a
precalciner.
(3) In a temperature range from 650 °C to 900 °C, there is
the highest mass loss, which is mainly due to the
decomposition of calcium carbonate (calcination). This
reaction is endothermic. The corresponding endothermic
peak is observed at 793 °C. The amount of absorbed
energy at this temperature is about 6 times less than the
amount of energy released in the previous temperature
interval.
(4) Above 900 °C is the most important stage for the
formation of clinker minerals. As can be seen in Fig. 1, in
order to synthesize belite, a temperature of 1250 °C is
sufficient. However, after this temperature, there is an
additional mass loss, which is associated with the release of
sulfur oxide from the anhydride. As can be seen in Fig. 1.
The decomposition of anhydride and further formation of
alite results in additional consumption of energy.
3.2 Mineral composition
Based on the thermal analysis of the raw meal, the
temperature of 1250 °C was selected for the trial clinker
burning. The XRD diffractogram of obtained clinker is given
in Fig. 2. The difference plot, Rwp, and the phase
composition obtained from Rietveld refinement are also
shown in Fig. 2. As can be seen, the main mineral phase in
the resulting clinker is the belite - 62%, the next is apatite
18%, approximately the similar amounts of perovskite and
brownmillerite of 6.9% and 6.6%, respectively. There are
also present a small amount of alite 3.9%, langbeinite 1.6%
and ye’elimite 0.9% in the resulting clinker. The chemical
composition was estimated using the XRD software based
on the mineral phase composition. The following content of
major oxides was obtained: CaO 57.04%, SiO2 24.79%,
Fe2O3 3.91%, Al2O3 2.94%. It should be noted that because
of the high content of apatite in the mineral composition, the
content of phosphorus oxide in the obtained clinker was
relatively high at 7.55%. It was reported in some studies
that by increasing the content of P2O5 in the clinker, the
content of alite decreases, and the content of belite
increases. Moreover, it may critically affect the compressive
strength and heat of hydration, which can be detrimental to
the quality of cement.
Fig. 1 TGA and DSC curves of raw clinker meal in a dry air
atmosphere.
Fig. 2 XRD diffractogram and calculate mineral phase composition
of clinker.
3.3 Grinding time optimization
Particle size distributions of clinker at different time intervals
of grinding in the ball mill are presented in Fig. 3. As can be
seen in the graph, with increasing grinding time, the
distribution shifts towards smaller particles. In order to
increase the reactivity of belite cement, its particle size has
to be smaller than that of ordinary Portland cement. In
accordance with the results shown in Fig. 3, the grinding
time of 180 minutes was selected as an optimal. The further
increase in grinding time did not significantly reduce the
particle size. The mean particle size (D50) at the selected
grinding time reached 4.74 µm. D90 and D10 were 24.5 µm
and 0.971 µm, respectively. The density of clinker as
measured by helium pycnometry was 3.3318 g/cc.
Fig. 3 Particle size distribution after 30, 60, 120, 180 minutes of
grinding.
3.3 Gypsum content optimization and rate of hydration
The curves of the heat flow and the total evolved heat
measured during the hydration of cement prepared with the
addition of calcium sulfate hemihydrate at the rates of 0, 4,
5 and 6% by weight of clinker are presented in Fig.4 and
Fig. 5, respectively. It can be seen that the rate of heat
evolution of belite cement is significantly lower than original
cement regardless of gypsum concentration. However, it
should be noted the enthalpy of complete hydration for
belite (262 J/g) is almost twice lower than that of alite (517
J/g) [30]. However, the belite heat peak is wider, and as can
be seen in Fig. 5 the heat release continues almost linearly
increasing over time, reaching 71% of CEM I Portland
cement at the hemihydrate content of 5%.
Fig. 4 Thermal power of hydration for belite cements with 0%, 4%,
5%, 6% and original cement (water-cement ratio of 0.5).
The mixture containing 5% gypsum resulted in the highest
heat release. For this reason, it was chosen for further
analysis. The density of the produced cement was 3.2773
g/cc. The average compressive strength determined at 28
days was 48.3 MPa with the standard deviation of 1.66 MPa
that complies with requirements for CEMI 42.5N.
5| CONCLUSIONS
In this study, Israel oil shale was investigated as a potential
raw material for the production of low-carbon cement. It was
demonstrated to oil shale can replace up to 76% of raw
materials for clinker manufacturing. This amount of oil shale
is sufficient to supply energy for the preheating and
calcination, which means that the fuel consumption at this
stage can be reduced.
The mineral composition of the obtained clinker was studied
and it was found to be reach in belite and contained also
JUNE 2019 | LONDON, UNITED KINGDOM | 3
apatite, perovskite, brownmillerite, alite, langbeinite, and
ye’elimite. The optimal grinding time of 180 minutes in a
laboratory ball mill produced a mean particle size of 4.74
m, which in combination with 5% of calcium sulfate
hemihydrate resulted in a good rate of hydration with
reduced heat of hydration. In spite of the high content of
apatite and perovskite, the tested cement complied with the
compressive strength requirements at 28 days for CEMI
42.5N. The mixture containing 5% gypsum resulted in the
highest heat release. For this reason, it was chosen for
further analysis. The density of the produced cement was
3.2773 g/cc. The average compressive strength determined
at 28 days was 48.3 MPa with the standard deviation of
1.66 MPa that complies with requirements for CEMI 42.5N.
Fig. 5 Heat of hydration for belite cements with 0%, 4%, 5%, 6%
and original cement (water-cement ratio of 0.5).
The production of such type of low-carbon cement seems
very prospective for improving the sustainability and carbon
footprint of concrete. However, high levels of phosphorus
oxide can affect the quality of the cement. A further detailed
study is needed to test the long-term properties such as
degree of hydration, compressive and tensile strength of the
resulting cement. Further research also is planned to
include: (i) Life cycle analysis to evaluate the amount of
energy and carbon dioxide emissions that can be reduced
in the process of cement production using this technology,
(ii) Evaluation of mechanical and durability properties of the
obtained cement, (iii) The compliance to standard
specifications for Portland cement, and (iv) compatibility
with concrete admixtures used in market today.
ACKNOWLEDGMENTS
This study was supported by the Ministry of National
Infrastructures, Energy and Water Resources, Israel.
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