Egyptian Journal of Petroleum xxx (2017) xxxxxx

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Egyptian Journal of Petroleum

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The impact of cooling water types on the cement clinker properties

Ahmed M. Shafeek a,, Hamdy Salah b, Nabila Shehata b, A.B. Saddek c
a
Minia White Cement Plant, Heidelberg Cement Group, Minia, Egypt
b
Department of Environmental Science, Industrial Development, Faculty of Postgraduates for Advanced Sciences, Beni-Suef University, Egypt
c
Civil Engineering Department, Faculty of Engineering, Beni-Suef University, Egypt

a r t i c l e i n f o a b s t r a c t

Article history: This paper studied the influence of the different water types on clinker properties. It concern with cement
Received 16 January 2017 plants which are using the water for cooling the clinker (El-Minia white cement plant). The water types
Revised 16 March 2017 are Nile, ground and deionized water. The cooling was mad suddenly for clinker by three water types at
Accepted 3 April 2017
the same time. The paper discusses the physical and chemical analysis and algal detection of all water
Available online xxxx
types. It also discusses the chemical and physical analysis for kiln feed, clinker. The analysis of water
showed that the concentration of dissolved salts in groundwater is higher than Nile water. The concen-
Keywords:
tration of algae gave opposite direction; the algae concentration in Nile water is higher than groundwa-
Cement
Nile River
ter. While the deionized is completely free from dissolved salts and algae. The cement tests for clinker
Groundwater which treated by the different water types showed that the cement strength was reducing when used
Clinker the Nile water with high algae count. From another side, the high concentration of dissolved salts in
Compressive strength groundwater does not affect on strength. The water contained the algae prevent the complete crystalliza-
tion of calcium silicate for clinker. The results also showed that the best type of water, which improved
cement compressive strength ranged according to algae count by the sequence deionized
water > groundwater > Nile water.
2017 Egyptian Petroleum Research Institute. Production and hosting by Elsevier B.V. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction
River Nile is always an important fresh water resource, for
Egypt. It is a natural potential source of irrigation, drinking and
industry [1]. Groundwater will be an important source of future
water supply. The concentrations of anions and cations in the sur-
face Nile water are fit with the standards limits, while they are
above the permissible levels in groundwater and are not suitable
for drinking and domestic purposes [1,2]. Cement considers the
second most consumed substance on the earth after water; each
person uses around three tons per year from the concrete. Cement
is very important for construction activities, so it is tightly related
to the global economy [3]. Cement is a binder, a substance that sets
and hardens independently, and can bind other materials together
[4].
Portland cement (OPC, Ordinary Portland Cement) is the most
common type of cement. It is a basic ingredient of concrete, mortar,
stucco and most non-specialty grout. The raw materials for cement
Peer review under responsibility of Egyptian Petroleum Research Institute.
Corresponding author.
E-mail addresses: A.shafik@suezcem.com (A.M. Shafeek), nabila@psas.bsu.edu.eg
(N. Shehata).
production are the mixture (as fine powder in the Dry process) of
minerals containing calcium oxide, aluminum oxide, silicon oxide,
ferric oxide, and magnesium oxide [5]. Clinker is a multiphase mix-
ture and, so far, more than 30 constituent phases have been iden-
tified [6]. After high temperature calcinations in a cement rotary
kiln, cement clinkers are cooled, the cooling was made by water
or air [7]. Portland cement clinker is a hydraulic material which
shall consist of at least two-thirds by mass of calcium silicates
(3CaO
SiO2 and 2CaO
SiO2), the remainder consisting of aluminum
and iron-containing clinker phases and other compounds [5].
Consider
C2S Ca2 SiO4
C3S Ca3 SiO5
C3A Ca3 Al2 O6
C4AF Ca4 Al2 Fe2 O10
White cement is special cements differ from conventional Port-
land cements in their phase composition and chemical as well as in
their properties. Their properties can be achieved by using a mod-
ified raw mix, a grinding admixture or by adjusting the grinding

http://dx.doi.org/10.1016/j.ejpe.2017.04.003
1110-0621/ 2017 Egyptian Petroleum Research Institute. Production and hosting by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Please cite this article in press as: A.M. Shafeek et al., The impact of cooling water types on the cement clinker properties, Egypt. J. Petrol. (2017), http://dx.
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2 A.M. Shafeek et al. / Egyptian Journal of Petroleum xxx (2017) xxxxxx
fineness of the cement. The whiteness is understandably one of the
most important properties of white cement. In view of its low iron
content the raw material melts at higher temperatures, at 1420
1450 C [8]. Concrete is one of the major building materials use
in modern day construction. It is a composite construction material
composed of cement and other cementitious materials such as fly
ash and slag cement. Concretes compressive strength is generally
used as a measure of overall concrete quality [911]. Water added
during cement industry in three stages which are cooling clinker,
grinding and during mixing water for making concrete. Most pre-
vious studies concerned only with mixing water. Almost the water
used as mixing for making concrete should be pure as natural
water that is drinkable and has no odor or pronounced taste. High
concentration of impurities in mixing water not only effect on con-
crete strength and setting time, but also may cause corrosion of
reinforcement, staining, volume instability, efflorescence, and
reduced durability. Therefore, certain optional limits should be
set on these impurities especially sulfates, chlorides [12]. Water
containing impurities with less than 2000 parts per million
(ppm) of total dissolved solids can generally be used without prob-
lem for making concrete. The impurities such as alkali carbonate
and bicarbonate, chloride, iron salts, tin, manganese, copper, zinc,
lead, sulfate, calcium and magnesium carbonates and industrial
waste water [1216]. When pH values are less than 3.0 for acid
waters this may create handling problems so should be avoided
if possible. Organic acids, for example, Tannic acid, with higher
concentration can cause a significant effect on strength [17]. The
algae have a high effect on strength where it reduces the strength
so the water containing algae is unsuited for making concrete.
The study is aiming to improve the physical properties of
cement. By introducing a proposal for using an alternative source
for Nile water.
2. Material and methods
2.1. The experimental area
The area under study is El-Minia white cement plant which
locates at Bani Khaled, Samalout, El-Minia Governorate. The plant
includes industrial processes related to the production of white
cement. It is using Nile water at different processes such as cooling
clinker in the rotary cooler and at grinding cement through a ball
mill. The plant has industrial water treatment unit which is a sand
filter.
Fig. 1. Nontraditional methods for clinker sampling.
Please cite this article in press as: A.M. Shafeek et al., The impact of cooling water types on the cement clinker properties, Egypt. J. Petrol. (2017), http://dx.
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2.2. Sample collection
The water samples were manually collected during January
2016 (drought period for the Nile) from three different areas which
are a Nile water before and after treating for plant under study b
Groundwater before and after treating from nearby well owned
for another cement plant far from the Nile c deionized water pro-
duced from water distillation unit, double distillation (GFL Water-
distilling Apparatus 2108).
The water samples were collected in plastic bottles (3.0 L) for
chemical analysis. While the samples for algal detection were col-
lected in sterile brown bottles (1 L), fitted with Iodine. The chemi-
cal analysis was measured at the laboratory of National Research
Centre, water pollution control department. The algal detection
were measured at El-Minia laboratory of The Holding Company
for Potable Water and Sanitary Drainage.
Clinker samples were manually collected by nontraditional
method before rotary cooler as shown in Fig. 1. Every clinker sam-
ple divided into three identical samples in order to standardize the
samples and to avoid any changes. The three samples will be
cooled suddenly at the same time by three different water types
separately. The amount of water which used for clinker cooling
are equal amounts for all samples, it around 600 ml of water for
each kg from clinker. The sampling repeated three times every
time clinker treated with the different water types.
2.3. Analysis
2.3.1. Water analysis
2.3.1.1. In situ measurements. The temperature (C) was measured
by using an ordinary dry mercury thermometer.
2.3.1.2. Laboratory measurements.
2.3.1.2.1. The algal detection. Enumeration of phytoplankton con-
centration was measured by Microscope, (Model Leica CM-E).
The analysis was carried out according to APHA [18].
2.3.1.2.2. Physico-chemical analysis and heavy metals. The hydrogen
ion concentration (pH) was measured by using pH meter, (Model
Jenway 3510). Total solids (TS), volatile suspended solids (VSS),
total dissolved solids (TDS), total suspended solids (TSS) and oil
& grease were measured by gravimetric methods. Conductivity
(EC) was measured by using Conductivity meter, (Model Jenway
3110). Turbidity was measured by using turbidity meter, (Model
Turbo Direct). The color was measured by using UVVIS
 A.M. Shafeek et al. / Egyptian Journal of Petroleum xxx (2017) xxxxxx 3

spectrophotometer, (Model Gary 100 UVVis). The analysis of
CO3

and HCO 3 was measured by titrimetric methods. Analysis
of Cl, SO  2+ 2+ + +  
4 , Ca , Mg , Na , K , NO2 , NO3 , total phosphorus (TP)
-
and F were measured by using Ion chromatography, (Model
Dionex-ICS-5000). Analysis of Mn, Zn, Al, Fe, Cu, Pb, Cd, As, Co,
Cr, Ni, Sn, Hg, Ti and B were measured by using inductively coupled
plasma optical emission spectrometry (ICP), (Model Agilent
ICP-OES 5100). Analysis of N-NH4 was carried out by using
Gerhardt Digestion and Distillation apparatus, (Model Vapodest
20S). All the analysis were carried out according to the American
Public Health Association for the Examination of Water and Waste
water APHA [18].
Nabertherm more than heat 303000 C) according to (EN 196/2)
[20]. The chemical analysis was measured by X-ray fluorescence
apparatus, (Model Axios mAX by PANalytical) according to (EN
196 2.2:2005) [21] and (ASTMC 114) [22]. A quantitative phase
analysis was performed using X-ray powder diffraction (X Ray
diffractometer, Panalytical Embryean, Model No.: 202964). Deter-
mination of expansion (soundness) was carried out by Le Chatelier
method (Model LD-50) according to (ES 2421-3) [23] and (UNIEN
196-3) [24]. Setting time was measured by VICAT apparatus
according to (ES 2421-3) [23] and (UNIEN 196-3) [24]. The com-
pressive strength was measured by compression and bend test
apparatus, (Model Toni/Technik) according to (UNIEN 196-1) [25].

2.3.2. Cement analysis

The free lime in clinker was measured by titrimetric methods 3. Results and discussion
according to (ES 474 1994) [19]. The whiteness of clinker was
measured by Color measurement apparatus, (Model colorFlex The physical and chemical analysis and the algal detection of
EZ). Loss of ignition (LOI) was measured by Muffle furnace, (Model groundwater and Nile water (raw water & treated water) given

Table 1
Detection of algal presence in ground and Nile water samples (raw and treated).

Parameters Units Groundwater Nile water

Raw water Treated water Raw water Treated water
Air temp C 8 8 8 8
Water temp C 9 12 7 10
Diatoms Cell/ml 56 4 1850 650
Green Algae Cell/ml 4 1 120 40
Blue green Algae Cell/ml 2 0 99 20
Total Algal Count Cell/ml 61 5 2069 710

Table 2
Physical and chemical analysis of groundwater and Nile water.

Parameters Units Groundwater Nile Water

Raw water Treated water Raw water Treated water
Air temp C 8 8 8 8
Water temp C 8 12 7 10
TDS mg/L 610 600 244 239
Carbonate mg/L 186 146 120 114
Bio-carbonate mg/L 114 89 40 40
Chloride mg/L 120 117.19 66 66
Fe mg/L 0.05 0.05 0.05 0.05
F- mg/L 0.34 0.28 0.48 0.43
T.P mg/L 0.52 0.33 0.35 0.35
SO4 mg/L 34.7 34.8 32.9 33
Ca mg/L 45 42 30 30
Mg mg/L 56 51 38.6 38.6
pH 7.8 8 7.6 8.1
TSS mg/L 1.5 13 12 3
VSS mg/L 1 5 10 2
NO2 mg/L N.D N.D N.D N.D
NO3 mg/L 8.55 9.6 0.2 0.2
NH4 mg/L N.D N.D N.D N.D
Color Pt/Co 1 1.3 6 1.2
Oil& grease mg/L 1.5 3 3.8 3.5
Na mg/L 78 89 41.8 41.8
K mg/L 5 5 5 5
Cr mg/L <0.01 <0.01 <0.01 <0.01
Ti mg/L <0.01 <0.01 <0.01 <0.01
Mn mg/L <0.01 <0.01 <0.01 <0.01
Sn mg/L <0.01 <0.01 <0.01 <0.01
Zn mg/L <0.01 <0.01 <0.01 <0.01
Cu mg/L <0.01 <0.01 <0.01 <0.01
Pb mg/L <0.01 <0.01 <0.01 <0.01
B mg/L <0.01 <0.01 <0.01 <0.01
Co mg/L <0.01 <0.01 <0.01 <0.01
Ni mg/L <0.01 <0.01 <0.01 <0.01
Cd mg/L <0.01 <0.01 <0.01 <0.01
Hg mg/L <0.005 <0.005 <0.005 <0.005
AS mg/L <0.005 <0.005 <0.005 <0.005
Tannic acid mg/L N.D N.D N.D N.D

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4 A.M. Shafeek et al. / Egyptian Journal of Petroleum xxx (2017) xxxxxx

Fig. 2. Concentration of TDS and algae in different water types.

Table 3A
Physical and chemical analysis of Kiln feed.

Parameters Units 1st sample 2nd sample 3rd sample

XRF for K.F SiO2 % 15.37 15.36 15.41
Al2O3 % 2.44 2.34 2.51
Fe2O3 % 0.11 0.09 0.10
CaO % 44.39 44.46 44.30
MgO % 0.01 0.01 0.01
SO3 % 0.19 0.18 0.21
Cl % 0.04 0.02 0.04
LOI % 35.5 35.6 35.4
LSF 96.53 97.02 95.94
SM 6.03 6.32 5.90
C3A 9.74 9.39 10.03
AM 22.18 26.00 25.10
Na2O % 0.00 0.00 0.00
K2O % 0.01 0.01 0.01
Residue on 90 m % 2.4 2.3 1.8
Residue on 63 m % 7.3 7.0 5.5

LSF = Lime saturation factor & SM = Silica modules & AM = Alumina modules & LOI = Loss of ignition. K.F = Kiln feed & XRF = X-ray fluorescence.

Table 3B
Physical and chemical analysis for clinker samples by using different water types.

Parameters Units 1st sample 2nd sample 3rd sample

Ck + Nile Ck Ck + de- Ck Ck Ck + de- Ck Ck Ck + de-
Water + groundwater ionized + Nile + groundwater ionized + Nile + groundwater Ionized
water water water water water
XRF for SiO2 % 24.94 24.92 25.02 24.04 24.54 24.32 23.59 23.81 23.73
clinker Al2O3 % 4.12 4.12 4.11 3.72 3.75 3.72 4.12 4.12 4.12
Fe2O3 % 0.16 0.16 0.16 0.15 0.15 0.15 0.16 0.16 0.16
CaO % 68.8 68.95 68.78 68.55 68.78 68.58 68.09 68.7 68.47
MgO % 0.05 0.05 0.05 0.04 0.04 0.04 0.05 0.05 0.05
SO3 % 0.2 0.2 0.2 0.2 0.18 0.2 0.2 0.2 0.2
Cl % 0.01 0.01 0.01 0.01 0.05 0.01 0.01 0.01 0.01
L.S.F 91.99 92.24 91.69 95.46 95.29 94.47 95.8 95.9 95.9
S.M 5.83 5.82 5.86 6.2 6.3 6.3 5.5 5.5 5.54
C3A 10.64 10.65 10.62 9.6 9.69 9.6 10.6 10.6 10.6
C3S 62.59 63.29 62.3 71.1 72.11 69.04 69.94 70.8 70.44
C2S 30.49 29 31.85 23.1 26.7 25.4 26.6 24.46 26.3
AM 25.58 25.66 25.96 24.5 25.7 24.5 25.9 25.18 25.94
Free lime % 2 1.7 2.2 2.5 2.4 2.5 3.8 3.1 3.7
Whiteness % 84.6 84.3 83.8 87 86.7 86.3 84.5 84.3 84
LOI % 0.5 0.4 0.5 0.4 0.5 0.4 0.3 0.4 0.5
Soundness mm 3.0 2.0 3.0 3.0 3.0 3.0 4.0 3.0 4.0
Setting Initial min 120 120 115 115 110 110 125 120 125
time Final min 150 150 150 145 140 140 160 150 160
Strength 2 Days N/ 28.95 37.54 38.14 24.85 30.8 31.3 28.19 32.4 33.8
mm2
7 N/ 45.12 48.86 50.15 45.78 49.34 48.42 43.65 48.99 50.95
mm2
28 N/ 60.59 64.58 65.76 62.66 63.2 63.2 58.85 63 64.25
mm2

Ck = clinker.

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 A.M. Shafeek et al. / Egyptian Journal of Petroleum xxx (2017) xxxxxx 5

in (Tables 1 and 2). The deionized water is completely free from
any inorganic salts or algae.
The analysis of the groundwater showed that the concentration
of inorganic salts or TDS in groundwater is higher than Nile water
whether in raw or treated water (Table 2). The TDS for treated
ground and Nile water was 600 mg/L and 239 mg/L respectively.
The comparison results were agreed with that finding by El-
Sayed and Salem [1]. While the concentration of algae gave oppo-
site direction; the algae concentration in Nile water is higher than
groundwater whether in raw water or treated water (Table 1). The

Fig. 3. (AC) the relation between strength (2, 7, and 28 days) and different types of water.

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6 A.M. Shafeek et al. / Egyptian Journal of Petroleum xxx (2017) xxxxxx
algae concentration for treated ground and Nile water was
5  103 cell/l and 7.10  105 cell/l respectively The third type of
water was deionized is completely free from dissolved salts and
algae Fig. 2. The algal count results for Nile River were agreed with
that finding by Salwa A. Shehata [26] at drought period. While the
physical and chemical results for Nile River were agreed with that
finding by many authors (Gupta and Paul, Niles and Mohammed,
Rawway and Abdulraouf, Goher, Hassanein, Ollivier and Radako-
vitch, Ali, Salem and Zaky, Abdo) [2735].
The chemical and physical analysis for kiln feed was done
before burning process at the kiln. While the analysis and mea-
surements related to clinker and cement were done after burning
process and exposing the clinker samples for all kinds of water. It
was happened by sudden cooling for the clinker samples under kiln
directly at the same time. The clinker samples have the same Kiln
feed or mix design, the test duplicated for three-times (Tables 3A
and 3B).
The clinker cooled by different types of water showed variation
at the strength in all three samples as shown in Fig. 3. The com-
pressive strength of clinker samples which were cooled by deion-
ized water was slightly higher than clinker samples which were
cooled by using treated groundwater. And the strength of both of
them was strongly higher than the strength of samples which were
cooled by treated Nile water especially at the early ages (<28 days).
The difference in values of cement compressive strength of 2, 7,
and 28 days for clinker samples, which were cooled by using
deionized and groundwater were 2.42%, 1.56% and 1.26% respec-
tively. The difference in values of the compressive strength of 2,
7, and 28 days for clinker samples, which was cooled by using
deionized and treated Nile water were 20.63%, 10.01%, and 5.75%
respectively Fig. 3.
The present results showed that the presence of algal in Nile
water can impair or decrease the cement strength at early ages
(<28 days). These results give a full right to say the cement
strength was reduced when the algae present in treated Nile water.
From the other hand, algae concentration in groundwater is very
few compared to the Nile waters. While the concentration of inor-
ganic impurities in groundwater was very high but does not affect
on strength. The concentration of algae and inorganic impurities in
groundwater under the permissible limit according to (Kucche and
Sadgir, Taryal and Yousef, Komastka and Panarese) [15,36,12]. They
mentioned that the permissible limit of inorganic salts or total dis-
solved solids (TDS) is 2000 mg per liter, Organic is 200 mg per liter,
Fig. 4. XRD analysis for different clinker samples.
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Sulfate is 400 mg per liter and Chloride is 500 mg per liter. The
results also showed that the deionized water gave high compres-
sive strength compared with the other types of water. The main
reason referred to the purity of deionized water from chemical
and biological impurities. The best type of water which improved
cement compressive strength ranged according to algae count by
the sequence deionized water > groundwater > Nile water.
All previous studies were concerned with mixing water which
added to cement for making concrete. They proofed that the algae
can cause an excessive reduction in strength this was agreed with
(Olugbenga, Kucche and Sadgir, Joshi) [37,15,38]. Komastka and
Panarese mentioned that the algae in water lead to lower strengths
either by influencing cement hydration or by causing a large
amount of air to be entrained in the concrete [12].
The present study takes care with water using for cooling clin-
ker according to the design of cement plant (El-Minia white
cement plant). The study showed that, the algae affected on the
clinker and lead to decreasing the strength of cement especially
at early ages (<28 days). It was clear that strongly when applied
XRD analysis for three different clinker samples according to water
types.
Portland cement (PC) is a mixture of clinker and ground gypsum
(controller plug). Portland cement clinker mainly consists of CaO,
SiO2, Al2O3 and Fe2O3. In clinker, they are not present oxide, but
exist as compounds formed by two or more oxides. The mineral
phases are very fine, usually 3060 mm and consist mainly of alite
(C3S), belite (C2S), calcium aluminate (C3A) and aluminoferrite
(C4AF) [39]. The white clinker contains three major constituents:
alite (C3S = Ca3SiO5 = 3CaO-SiO2), belite (C2S = Ca2SiO4 = 2CaO-
SiO2), tricalcium aluminate (C3A = Ca3Al2O6 = 3CaO-Al2O3) [40].
The formation of alite is very complex. Alite is only formed in the
presence of excess CaO, that is, at CaO/SiO2 > 1 and is thermody-
namically stable above 1250 C [41]. This mineral is found in all
the samples in a distinctive crystalline form. The crystallized
phases of alite C3S present different morphologies and crystal sizes
[42]. Alite C3S has seven polymorphic phases in industrial clinker:
three triclinic, three monoclinic, and a rhombohedral one [43,44].
The XRD data showed all clinker samples have proximately the
same phases Fig. 4. The phases of cement presenting in eight of
strongest diffraction 2h values and relative intensities. The Alite
forms the bulk of the clinker and is important for strength develop-
ment at early ages (<28 days) [43]. The present study focused on
the alite phases according to its responsibility about early strength.
 A.M. Shafeek et al. / Egyptian Journal of Petroleum xxx (2017) xxxxxx
Fig. 5. (AB) alite peaks at two positions for clinker samples.
The peaks of C3S that are generally resolvable (not too highly over-
lapped with other phases), unique and commonly is distinguished
by the profile of the diffraction line occurring around 51.0 to 52.0
and 30.0 2h [43,45]. By zooming on this two position of C3S peaks
at last graph as shown at Fig. 5(A and B).
It is clear the sample was treated by Nile water give less intense
than those of clinker samples were treated by deionized and
groundwater. This indicated that the incomplete crystallization of
the calcium silicate [46], for clinker sample which treated with Nile
water.
From the previous results, we can say that the defect in clinker
sample which was treated by Nile water meanly referred to the
presence of algae. The algae prevented the complete crystallization
of calcium silicate, and lead to the poor formation of mineralogical
phases.
4. Conclusion and recommendation
From the previous discussion mentioned, we can conclude that
1- The groundwater has TDS concentration higher than Nile
water. While the Nile water has algae concentration higher
than groundwater.
2- The best type of water used for clinker cooling ranged
according to algae count as the following order; 1 deion-
ized water 2 groundwater 3 Nile water. From other
hand the groundwater gave approximating results such as
that obtained when using deionized water for cooling the
clinker, so it is advisable to use the groundwater for cooling
the clinker because it more commercial than deionized
water.
3- The presence of algae in water prevented the complete crys-
tallization of calcium silicate for clinker. It also, lead to the
poor formation of mineralogical phases for clinker.
Acknowledgements
We are grateful to the National Research Centre, water pollu-
tion control department and El-Minia laboratory of The Holding
Company for Potable Water and Sanitary Drainage for useful
suggestions. Also, we are grateful to Mr. Magdy M. Taha, quality
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7
manager of El-Minia white cement plant and his team for support,
cooperation and facilities.
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