Construction and Building Materials 153 (2017) 202–210

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Construction and Building Materials

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Valorization of Dried Olive Pomace as an alternative fuel resource in

cement clinkerization
P.E. Tsakiridis a,⇑, M. Samouhos a, M. Perraki b
a
Laboratory of Physical Metallurgy, School of Mining and Metallurgical Engineering, National Technical University of Athens (NTUA), Heroon Polytechniou 9, 15780 Zografou, Greece
b
Laboratory of Mineralogy, Petrology and Economic Geology, School of Mining and Metallurgical Engineering, National Technical University of Athens (NTUA), Heroon Polytechniou
9, 15780 Zografou, Greece

h i g h l i g h t s

 Dried Olive Pomace (DOP) was examine as alternative fuel in cement clinkerization.
 Different amounts of DOP ashes were introduced in raw meal.
 DOP presence didn’t affect clinkers main mineralogical phases.
 All syntheses satisfied the requirements for the strength class 52.5 as per standard EN 197-1.

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

Article history: The aim of the present investigation is to examine the potential utilization of Dried Olive Pomace (DOP)
Received 6 March 2017 as an alternative fuel in cement clinkerization, determining the effects on the properties of the cement
Received in revised form 5 July 2017 clinker produced, by substituting coal on the burning process for DOP by 50 and 100 wt%. Different
Accepted 10 July 2017
amounts of DOP and coal ashes were introduced in the raw meal before sintering at 1450 °C and the
clinkers produced were characterized by means of chemical analysis, X-ray diffraction (XRD) and scan-
ning electron microscopy (SEM). After co-grinding with suitable amount of gypsum, the produced
Keywords:
cements were evaluated by determining setting times, standard consistency, expansibility and compres-
Dried Olive Pomace
Alternative fuel
sive strength at 2, 7, 28 and 90 days, whereas XRD and TG/DTG analysis were carried out for the hydration
Clinker study evolution. According to the results, DOP presents a promising alternative as a secondary fuel
Cement resource, as the presence of its ash in the raw mixes did not affect negatively neither the clinker miner-
Hydration alogical composition, nor the physico-mechanical properties of the final cements produced.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction
In last decades, the fossil fuel reserves have presented a rapid
decrement, as their consumption degree in industry and transports
has remained almost unchanged. It has been estimated that in the
next twenty to thirty years the consumption will grow exponen-
tially and, as the substitution possibilities will be gradually
exhausted, the coverage of the energy requirements will require
the use of alternatives fuels and the implementation of new tech-
nologies. Today, the need of using alternative and renewable fuels,
over the traditional energy resources, has begun to play a very
important role in the developed world, both for environmental
and economic reasons [1,2].
⇑ Corresponding author.
E-mail address: ptsakiri@central.ntua.gr (P.E. Tsakiridis).
The depletion of high purity natural resources and the urgent
requirement for their preservation, created the imperative need
to explore ways in order to use lower purity materials, mainly min-
erals, agricultural and industrial wastes or by-products. According
to the International Energy Agency, there is an urgent need for a
gradual fossil fuels substitution in combination with the corre-
sponding promotion of alternative fuels, while the European Union
has already proposed the target of producing renewable resources
from 20% by 2020 to 27% by 2030 (renewable energy can be pro-
duced from a wide variety of sources including wind, solar, hydro,
tidal, geothermal, and biomass) [3]. To this effect, different types of
urban, agricultural and industrial waste have been proposed and
used as alternative energy resources for the replacement of the tra-
ditional fossil fuels such as coal, petroleum coke and fuel oil. Much
progress has been reported in designing and developing facilities
for the valorization of waste and by-products such as sewage
sludge, waste oil shale, bituminous sludge, tires, plastic, rice husk

http://dx.doi.org/10.1016/j.conbuildmat.2017.07.102
0950-0618/Ó 2017 Elsevier Ltd. All rights reserved.
 P.E. Tsakiridis et al. / Construction and Building Materials 153 (2017) 202–210
and straw, dust from the bamboo processing (bamboo dust) as sec-
ondary fuels [4].
The alternative of biomass exhibits many advantages, as the
recovery of the contained energy can be carried out by using exist-
ing technologies, thus reducing the dependence on conventional
energy sources and thereby the environmental pollution by CO2
and other emissions. In particular, the biomass and coal co-
combustion, in existing industrial installations, helps both to
extend the life of coal reserves and to overcome the seasonality
problem that characterizes the biomass. On the other hand,
promising is also the case of waste from petroleum, such as heavy
fuel separation waste, oil, tank washings ships, sediment water
that contain hydrocarbons (bilge water), oil from oil slick, heavy
and lighter distillation residue oils, fatty acids etc.
The use of alternative fuels in the cement industry has been
established in many countries in the last 10–15 years [5,6]. How-
ever, only about 10% of the fuel consumed by the cement industry
in Europe is unconventional [7,8]. In rotary kilns, the ground raw
materials (about 75 wt% limestone and 25 wt% aluminium-
silicates) are sintered, using as a source of energy gas, oil, coal, or
alternative fuels. The clinkering temperature is in the range of
1420–1450 °C. It is well known that the limestone decomposition
process, as highly endothermic reaction, is the primary energy con-
sumption of the process, whereas the transformation reactions for
the formation of the final cement clinker mineralogical phases are
predominantly exothermic reactions. As a result, one of the main
cost factors of the cement production is the type of fuel used for
the raw materials sintering, as 4000–4200 MJ are required in order
to produce 1 kg of clinker. Depending on the price of fuel and
because of the coal availability (global coal reserves are much
higher than those of oil) fuel costs in cement production has been
decreased considerably and today its participation in the shaping
of the final factory cost is about 25% [5,7,9].
The production capacity installed in cement industries in
Greece is about 15 million t/year and the total fuel consumption
has been estimated at about 1.5 million tons of coal. Taking into
account that the average calorific value of secondary fuels is about
3000 kcal/kg (1 ton of coal equals to two tons of secondary fuel),
1–2 million tons of alternative fuels could be used in cement
industry, if the traditional energy sources would be replaced by
50–70% [1,5,7]. The main benefits arising from the alternative fuels
valorisation in cement industry are primary related not only with
the cost reduction, but also with environmental reasons, as it
would give solutions to many problems associated with wastes
and by-products disposal.
Certainly, alternative fuels present some disadvantages. One of
the main drawbacks is the lower content of volatile compounds.
The volatile components of the coal are flammable gases (CH4,
H2, CO) and non-combustible, such as CO2, NOx. Obviously higher
volatile content contributes to the easier ignition of the carbon.
The lower content of volatile compounds could lead to the com-
bustion delay and, consequently, to higher flame and tempera-
tures, thus creating products of lower granulometric quality.
Furthermore, their higher moisture content replaces part of the
fuel and reduces the calorific power. Also, the composition of the
combustion solid residue (ash), in relation with the corresponding
of coal, may vary significantly (presence of higher sulphates and
alkalis content) and should be taken into account during the raw
meal design [9,10].
Several investigations have been carried out, burning wastes as
an industrial resource. Most of these studies have been based on
the sintering process simulation in a cement kiln, by designing
the raw meal with different amounts of ashes, produced during
the waste fuels combustion, as only the inorganic constituents
are absorbed in clinker phases, while the organic matter is con-
sumed. Trezza and Scian studied the effect of the addition of small
203
amounts of ashes from used car oils in the clinkering process and
according to the results, their presence in the raw meal did not
seem to alter neither the mechanical nor the hydration character-
istics of final cement clinker [11]. Used oils from different sources
(industrial lubricants, oil sludges etc) have been also tested by
other investigators with very promising results, due to their high
calorific value content (about 32.000 kJ/kg) and to the fact that
they could be used in cement kilns with minimal processing cost
[12,13]. A lot of work has been carried on the utilization of tire
derived fuels (TDF) as supplement fuel in rotary kilns, due to signif-
icant high calorific value of tires (approximately 31.400 kJ/kg)
[14–16]. It has been estimated that the maximum percentage of
TDF during raw meal sintering cannot exceed the 30 wt% of the
fuel, as strong modification in clinker mineralogy and chemistry
have been observed due to the clinker phases enrichment with zinc
[15]. Corresponding work has been carried out with different types
of carbon, such as spent activated carbon from drinking water
treatment plants, or black carbon from pyrolysis process [17,18],
the calorific values of which are in the range of 30.000 kJ/kg (sim-
ilar to those of natural coal). In all cases the results showed that
these types of fuels did not affect the final product quality. Another
interesting alternative fuel resource has been proved the previ-
ously dried sewages sludges, with a calorific value of 8000 kJ/kg,
meeting the corresponding cement industry requirements
[19,20]. It has been estimated that their use in cement kiln as an
alternative fuel could substitute the natural fossil resources by
70%. Finally trials have been accomplished with refuse-derived fuel
(RDF) from shredding and dehydrating municipal solid waste.
Karagiannis et al. have investigated the combinational action of
RDF with cotton stalks, by replacing coal by 100 wt% and conse-
quently introducing the corresponding ashes proportions in the
raw meal before sintering [21]. The results suggested that both
waste materials could be used as an alternative fuel in rotary kilns.
To the authors’ best knowledge little attention has been given to
the utilization of olive pomace as an alternative fuel during the
clinker production in cement rotary kilns. Olive pomace (or olive
cake) is the main by-product obtained during the production of
olive oil in two or three phases centrifugation system and it con-
sists of about 65% of water, added during the olive oil extraction
process, 20 wt% of olive pulp and 15 wt% of crushed olive stones
[10]. It is rich in organic matter, presenting a heating value of about
15–20 MJ/kg and as a result could be used as an alternative fuel for
electrical or thermal production. However, one of its main disad-
vantages is the relatively high amount of ash production (5–8 wt
%) during combustion, which is rich in alkalis (especially potas-
sium). On the other hand, its CO2 emissions excluded from the
greenhouse global gas emissions, as the carbon contained in alter-
native fuels is considered carbon-neutral and do not count to the
Emission Trading System [22].
The aim of the present investigation is to determine the effects
on the properties of the cement clinker produced, by replacing coal
on the burning process by different amounts of Dried Olive Pomace
(DOP). For that reason different amounts of DOP and coal ashes
were introduced in the raw meal before sintering at 1450 °C and
the clinkers produced were studied by means of chemical analyses,
X-ray diffraction, scanning electron microscopy, whereas the cor-
responding cements were tested for water demand, setting times,
soundness and compressive strengths at 2, 7, 28 and 90 days.
2. Experimental
2.1. Materials, raw meal preparation & sintering process
In all cases, one initial Raw Meal (RM) was used, prepared by ordinary natural
raw materials, such as limestone, schist, bauxite and silica sand. Before sintering
process, the raw meal synthesis was modified by adding different amounts of
DOP and coal ashes. The fuels analyses was based on the determination of their
204 P.E. Tsakiridis et al. / Construction and Building Materials 153 (2017) 202–210

Table 1 the produced clinkers storage in order to minimize moisture effects and contamina-
Fuel analyses and determination of calorific value. tion from air. Their characterization was carried out by means of chemical analysis
and X-ray diffraction. A Jeol 6380LV scanning electron microscope was used for
DOP Coal Standard their microstructure observation. Spots analyses of the samples particles were per-
Moisture (wt%) 4.48 3.70 ASTM D-3302 formed by an Oxford INCA Energy Dispersive Spectrometer (EDS) connected to the
Volatile Matter (wt%) 72.60 36.45 ASTM D-3175 SEM.
Ash Content (wt%) 4.28 6.15 ASTM D-3174
Fixed Carbon (wt%) 19.25 88.74 ASTM D-3172 2.3. Cement hydration
Sulfur (wt%) 0.14 0.39 ASTM D-3177
Chlorides (wt%) 0.33 0.12 ASTM D-2361 Suitable amounts of gypsum were added during clinkers grinding to a specific
Gross CV (kcal/kg) 5525 6375 ASTM D-2015 surface area of 3950 ± 50 cm2/g, in a laboratory rotating ball mill, so that the total
soluble SO3 of the produced cements to be about 2.5 wt%. The grinding process
was interrupted at predefined times intervals for specific surface area value deter-
mination, according to the Blaine air permeability method [30]. Mortar specimens
ash content, volatile matter, fixed carbon, sulphur and chlorides according to the (40 mm  40 mm  160 mm) were prepared for compressive strengths determina-
corresponding ASTM standards (Table 1) [23–28], whereas their gross calorific tion according to the European Standard EN 196-1, after 2, 7, 28 and 90 days of cur-
value (CV) determination was carried out according to ASTM D2015 using a LECO ing [31]. Normal consistency and setting times determination according to EN 196-
AC-350 Calorimeter [29]. 3 were performed by using a Vicat apparatus, while the cement pastes expansions
The modification of the raw meal was based on the assumption that about were defined by the Le Chatelier method [32]. The hydration products were miner-
7.5 kg of coal are required for the sintering of 100 kg of raw materials [21]. Taking alogically analysed by X-ray diffraction using a Bruker D8-Focus diffractometer.
into account that the gross calorific value of coal was determined at 6375 kcal/kg They were also thermally analyzed by Thermal Gravimetric Analysis (TGA) using
with an ash content of 6.15 wt%, an additional quantity of about 15 wt% of DOP will a Mettler-Toledo TGA 851 instrument (25–900 °C, 10 °C/min and nitrogen under
be required (8.6 kg of DOP for 100kg of raw meal), as its calorific value reached at static condition). The derivative curves (DTG) were used for the determination of
5525 kcal/kg with an ash content of 4.28 wt%. Therefore, three basic mixtures were the corresponding temperature intervals exact boundaries.
prepared. A reference one, modifying the original raw meal by adding 0.46 wt% of
coal ash (RMC), and two others by adding the corresponding quantities of ashes
for co-combustion with 50 wt% of coal replacement (RMC-DOP) by DOP (i.e. addition 3. Results and discussion
of 0.23 wt% of coal ash and 0.19 wt% of DOP ash) and for 100 wt% of coal replace-
ment (RMDOP) by DOP (i.e.: 0.38 wt% addition of DOP ash). 3.1. Physical, chemical and mineralogical characteristics of coal and
The chemical analyses of both ashes, together with the corresponding of natural
DOP ashes
raw materials were carried out by X-ray Fluorescence (Spectro–Xepos) and atomic
absorption spectrophotometer (Perkin Elmer 4100) and the results are presented in
Table 2. Appropriate proportions of the natural raw materials together with the The particle size distributions of both ashes are shown in Fig. 1,
corresponding quantities of ashes were mixed in a laboratory rotating ball mill. and their 10% (x10) and 90% (x90) cumulative size distributions
The raw meals syntheses are presented in Table 3. The initial raw meal particle with the corresponding mean and median diameters of the PSD
size distributions and the corresponding of both ashes were identified by an
ultrasonic-assisted Mastersizer 2000 (Malvern) particle size analyser (Fig. 1). The
curve are presented in Table 4.
mineralogical phases of both ashes and those of the initial raw meal were According to the results, the DOP ash presented finer grain size,
determined by using a Bruker D8-Focus X-ray diffractometer with nickel-filtered similar to the corresponding of the reference raw meal, whose
CuKa radiation (k = 1.5406 Å), at 40 kV and 40 mA (Fig. 2). 10 wt% consisted of particles with size below 2.65 lm (1.59 lm
in case of DOP Ash) while 50% of it appeared a diameter value
2.2. Sintering process below 25.5 lm (14.22 lm in case of DOP Ash). On the other hand,
coal ash presented coarser grain size, as 50 wt% of its particles pre-
The raw mixes were prepared with the form of small spheres (2 cm in diam- sented a grain size smaller than 46.49 lm, whereas 90 wt% was
eter) after mixing with the appropriate amount of water. Before sintering process below 164.83 lm.
the spheres were left to dry at 110 °C for 24 h and they were placed inside a furnace
at 500 °C. The raw meals were initially heated at 1000 °C for 30 min and then, after
Regarding chemical analysis (Table 1), coal ash, as expected,
gradually increasing temperature, were sintered for 30 min at 1450 °C. During their mainly consisted of Si and Al (about 75 wt%). The bituminous type
removal from the oven, they were rapidly cooled in air. A desiccator was used for of coal used in this study, in contrast with the calcareous ashes

Table 2
Chemical Analysis of Raw Materials.

Oxides Raw Materials Analyses (wt%) Coal Ash

Limestone Schist Bauxite Silica Sand DOP Ash
SiO2 0.23 52.62 17.53 93.22 16.39 51.45
Al2O3 0.09 8.10 42.23 1.33 7.12 23.22
Fe2O3 0.07 6.77 24.12 0.46 2.07 5.12
CaO 55.12 9.21 0.77 0.70 35.82 4.12
MgO 0.11 9.17 0.85 0.10 6.73 1.83
K2O 0.02 0.78 0.68 0.19 19.24 0.75
Na2O 0.01 0.98 0.15 0.10 0.08 0.54
SO3 – – – – 0.12 0.53
TiO2 – 0.47 1.98 0.40 0.18 0.85
LOI1000 43.54 11.10 10.99 2.98 9.82 11.25

Table 3
Raw meals Composition.

Raw Meals Raw Materials (wt%) Coal Ash

Limestone Schist Bauxite Silica Sand DOP Ash
(RM)C 75.30 14.50 4.50 5.70 – 0.46
(RM)C-DOP 75.30 14.50 4.50 5.70 0.23 0.19
(RM)DOP 75.30 14.50 4.50 5.70 0.38 –
 P.E. Tsakiridis et al. / Construction and Building Materials 153 (2017) 202–210 205

100

(RM)Ref
DOP Ash Coal Ash

Cumulative Number of Particles (wt%)

80

60

40

20

0
0 1 10 100 1000
Particle Diameter (μm)

Fig. 1. Particle size distributions of initial raw meal, coal and DOP ashes.

1000
1. CaCO3 - Calcite
1
2. SiO2 - Quartz
3. (Mg,Fe,Al)6 (Si,Al)4 O10 (OH)8 - Chlorite
4. KAl 2 Si3 AlO10 (OH)2 - Muscovite
5. Fe2 O3 - Hematite
800 6. NaAlSi3 O8 - Albite
7. 3Al2 O3 2SiO2 - Mullite
8. CaOf - Free Lime
1
9. (Ca,Na)(Si,Al)4 O8 Anorthite
10. K 2 Ca(CO3 )2 - Fairchildite 2
Arbitrary Units (a.u.)

11.CaSO 4 0.5H2 O - Bassanite 7

600 12. K2 SO4 - Arcanite 1
1
7

7 1
5,7

6,9 7
2 10 7 7
3 9 9 9 1
12 7 8
10,11

400 7 7
3 8 12 7
7 2 7
1 2
10,12

10
8 Coal Ash
3
10 11 10 2 11 10
10 10 10
3 10 10
200 6
10

4 3 3
2 DOP Ash

2 2
6 4 2
2
2 Raw Meal 2
0
5 10 15 20 25 30 35 40 45 50 55
2θ

Fig. 2. Mineralogical phases of initial raw meal, coal and DOP ashes.

Table 4 other hand, CaO was the main constituent of DOP ash, which
Particle Size Distribution Mean Values.
together with K2O (19.24 wt%) account for 55.06 wt% of the initial
Sample PSD ash and are mainly coming from the initial nutritious ingredients
Mean (lm) Median (lm) x10 (lm) x90 (lm) content in olive fruits. It is also characterized and by the relatively
high amount of loss of ignition (9.82 wt%), indicating strong car-
DOP Ash 22.25 14.22 1.59 55.82
Coal Ash 66.35 46.49 4.92 164.83 bonation phenomena during DOP incineration (CaCO3 and K2Ca
Raw Meal 36.25 25.5 2.65 92.04 (CO3)2 formation). Except SiO2, the concentration of which reached
16.50 wt%, other constituents such as Fe2O3, Al2O3 and MgO were
found to be in lower amounts.
(derived from lignite combustion) resulted in the production of a The siliceous type of coal ash was additionally confirmed by the
siliceous coal ash (type F), where silicon, aluminium and iron are corresponding X-ray diffraction pattern (Fig. 2). It is mainly
the predominant elements. The above observation was also con- comprised of silicate phases such as quartz (SiO2), mullite
firmed and by the relatively low content of CaO and SO3. On the (3Al2O3 2SiO2), and anorthite ((Ca,Na)(Si,Al)4O8,) together with an
206 P.E. Tsakiridis et al. / Construction and Building Materials 153 (2017) 202–210

Table 5 hand, and due to the mineralogical phases of the raw materials
Cement Clinkers Chemical Analyses. used for the raw mix synthesis, the initial raw meal mainly consist
Oxides Clinker Analyses (wt%) of calcite, quartz, chlorite, albite, muscovite and hematite.
(PC)C (PC)C-DOP (PC)DOP
SiO2 20.95 20.91 20.85
Al2O3 5.88 5.80 5.78 3.2. Sintering process
Fe2O3 3.37 3.35 3.31
CaO 65.75 65.91 66.05
MgO 1.88 1.93 1.96 Table 5 shows the chemical analyses results of the different sin-
K2O 0.53 0.56 0.63 tered raw mixes, whereas in Table 6 shows the clinker indices
Na2O 0.32 0.30 0.28 along with the potential mineralogical composition according to
SO3 0.33 0.31 0.32 the Bogue equations, assuming that it concerns pure phases in
TiO2 0.25 0.27 0.26
CaOf 1.18 1.21 1.32
thermodynamic equilibrium. According to the results the calcu-
LOI 0.62 0.63 0.66 lated mineralogical phases and the chemical analyses appeared
with insignificant alterations and the additions of different
amounts of DOP and coal ashes did not seem to affect the produced
cement clinkers. The lime saturation factor (LSF) varied in the
Table 6
Clinkers Theoretical Mineralogical Composition & Quality Indexes. range of 96.5–97.5 mainly because of the ashes different nature
(siliceous or calcareous), leading to a relative increment of the
Mineralogical Phases Cement Clinkers Composition (%)
C3S/C2S proportion in case of DOP ash. The silica ratio (SR) and
(PC)C (PC)C-DOP (PC)DOP the alumina ratio (AR) were kept constant at in all cases.
C3S 58.3 59.8 60.5 The confirmation of the above mineralogical composition pre-
C2S 16.2 15.0 14.2 diction was also evaluated and by the clinker X-ray diffraction
C3A 9.9 9.7 9.7
analysis. According to the corresponding patterns of Fig. 3, in all
C4AF 10.2 10.2 10.1
cases the main clinker phases (C3S, C2S, C3A, C4AF) have been well
Quality Indexes
formed and they appeared contiguous.
LSF 96.7 97.2 97.7
AR 1.7 1.7 1.7 The addition of different amounts of ashes do not seem to affect
SR 2.3 2.3 2.3 the degree of crystallization during sintering process, as the cal-
Na2Oeq 0.7 0.7 0.7 cium silicate phases, the triclinic alite (Ca3SiO5) and the monoclinic
belite (b-Ca2SiO4), as well as the cubic C3A and the orthorhombic
C4AF presented similar values intensities at the corresponding 2h
amorphous glassy matrix, which was detected with the form of dif- values. Moreover, similar amounts of free CaO and periclase
fused wide band in the range of 20°–40°, indicating aluminous and (MgO) were also detected. The free lime in all cases, also deter-
silica phases vitrification. In case of DOP ash, calcite (CaCO3) and mined by the ethylene-glycol method, were found to be below
fairchildite (K2CaCO3) were the main detected phases. As calcium 2 wt% (Table 5), indicating well burned clinkers, as CaO has been
and potassium were found to be the main chemical compounds, consumed during the alite formation.
CaCO3 and K2CaCO3 derived from the carbonation reaction of The formation of the main clinker mineralogical phases was
calcium and potassium ions during the incineration process in also confirmed in polished sections by scanning electron micro-
the strong oxidative condition. Quartz (SiO2) and grossular scopy (Fig. 4). The addition of the different amount of DOP and coal
(Ca3Al2Si3O12) were also detected as minor phases. On the other ashes did not result to any modification, during sintering process,

800
1. C3S - Alite 1,2 1,2
1,2
2. C2S - Belite
3. C3A - Calcium Aluminate
4. C4AF - Ferrite
5. CaO f - Free Lime 1
6. MgO - Periclase

1,2
Arbitrary Units (a.u.)

4
3
1 1
400 2
4
1 1,2
1 2 1,2
(PC)DOP 4 1 2 2 5 6

(PC)C-DOP

(PC)C
0
5 10 15 20 25 30 35 40 45

2θ degree

Fig. 3. X-ray Diffraction of produced clinkers.

 P.E. Tsakiridis et al. / Construction and Building Materials 153 (2017) 202–210 207

C3S
C3A/C4AF
C3A/C4AF
C3S C2S

C2S

(PC)C

C3S

C2S
C4AF C4AF
C3A
C3A
C3S
C2S

(PC)C-DOP

C3A

C3S C4AF

C3A
C4AF
C2S C3S
C2S

(PC)DOP

Fig. 4. Clinkers microstructure with different amount of DOP and coal ashes.

Table 7 developed in the presence of free lime excess (CaOf), above

Grindability Test Results. 1250 °C, the addition of calcareous DOP ash led to a slight increase
Sample (PC)C (PC)C-DOP (PC)DOP
of the alite average size and also to its final content (due to higher
LSF). In all cases the clinkerization has proceeded toward C3S for-
Mill Revolutions 4090 4050 4020
mation, as no decomposition reaction at the grains edges was
Specific Surface (Blaine-cm2/g) 3935 3945 3950
Grindability Index (Sblaine/Mill Rev) 0.96 0.97 0.98 observed. Due to the CaOf consumption during the alite formation,
Specific Gravity (g/cm2) 3.22 3.22 3.21 free lime was observed in very low proportion and mainly dis-
wt% SO3 2.40 2.39 2.42 persed among calcium silicate phases. The major configuration of
the belite phase was rounded grains with easily recognised lamel-
las and an average size of 10–20 lm. In some cases smaller
and the solid state clinkerization degree, as well as the final entrapped grains of belite were located within coarser C3S grains,
microstructure appeared to be similar in all cases. a fact that was attributed to the calcium silicate phase’s rapid crys-
Alite was mainly detected in the form of relatively elongated tallization and to their consequent unification. Regarding intersti-
and well-crystallized grains, the size of which was in the range tial phase (C3A and C4AF), the molten phase where the calcium
of 30–50 lm. As the main phase of clinker (Ca3SiO5) can be only silicates have been developed, the calcium aluminates were
208 P.E. Tsakiridis et al. / Construction and Building Materials 153 (2017) 202–210

Table 8
Cements Physical Properties.

Sample Water of Normal Consistency (%wt) Setting Time (min) Le Chatelier Expansion (mm) Flow of Mortar for w/c = 0.5 (%)
Initial Final
(PC)C 26.6 170 225 2.3 100.7
(PC)C-DOP 26.5 170 220 2.1 101.3
(PC)DOP 26.7 180 220 2.2 100.9

The water requirement results and the corresponding of initial

Table 9
Compressive strengths of the cements mixtures produced.
Days of Curing Compressive Strengths (MPa)
(PC)C
2 29.5
7 44.7
28 58.5
90 64.7
observed with the form of rectangular or angular shapes. At the
same time it was relatively difficult to distinguish well-defined
shapes of the ferrite phase (C4AF), indicating a gradually cooled
clinkers.
3.3. Cement hydration
A ball mill with a capacity of 1.5 kg was used for crushing and
co-grinding the sintered clinkers, targeting to a specific surface
area of 3950 cm2/g, with suitable amounts of gypsum (98 wt%
CaSO4
2H2O with 47.5 wt% SO3), in order to produce the final
cement mixtures under investigation. The grindability indexes of
the mixtures (clinker’s ability to resist grinding forces), which have
been determined by the ratio of the ball mill revolution to the cor-
responding specific surface values, are presented in Table 7. No sig-
nificant differences were detected, as in all cases both the
composition of the mineral phases and the clinkers microstructure
were similar.
and final setting times, calculated through Vicat probe and Vicat
needle device, together with the results of Le Chatelier expansion
are shown in Table 8. The presence of DOP or coal ashes slightly
(PC)C-DOP (PC)DOP affected the consistency of the cement mixtures as both the sul-
phate content and the final fineness were kept constant.
29.4 29.4
44.0 44.8
In all cases, the initial setting times, the time at which the paste
58.6 58.8 has begun to stiffen considerably, were similar and above the limit
64.9 65.1 of 45 min, while the final ones, the time where the cement paste
has completely lost its plasticity, were determined in the range
of 220 min. The pastes expansion measured by Le Chatelier rings
were also contiguous and well below the limit of 10 mm [32].
The behaviour observed during compressive strengths determina-
tion after 2, 7, 28 and 90 days of hydration was also similar and the
obtained values were almost identical (Table 9). The mortars com-
pressive strengths after 2 days of curing, were determined in the
range of 30 MPa, while the corresponding value at 28 days reached
60 MPa, satisfying the requirements for the strength class 52.5 as
per standard EN 197-1 [31]. The compressive strength increment
rate was persisted and after 90 days of curing reaching 65 MPa.
The above similarities in compressive strengths development
were also obvious and in the hydration products determination
by XRD analysis at different ages of curing. Fig. 5 shows the X-
ray diffraction patterns of the cement mixtures after 28 days of
hydration.
In all cases the cements reactivity has been evolved similarly
and similar hydration products, in quality and quantity, were
observed. Ca(OH)2 and anhydrated calcium silicate phases (mainly
belite) were detected as the major peaks. Portlandite is the main
product of calcium silicates hydration, with simultaneous

800
1. Ca(OH)2
2. C2 S /C3 S 1
3. C4 AF
4. 2CaO SiO2 2H2 O 1
5. CaSiO4 H2 O
6. Ca6 Al2 (SO4 )3 (OH)2 26H2 O
7. (CaO)x SiO2 2H2 O
600 8. 2CaOSiO2 2H2O
9. MgO 2
2,5
Arbitrary Units (a.u.)

2,8

2
1
6
400 (PC)DOP 2
2,5

2,4

5,8 6 6 6
3 6,9 6
7
2,4

9
2,4

8 8

(PC)C-DOP
200

(PC)C

0
5 10 15 20 25 30 35 40 45
2θ

Fig. 5. X-ray diffraction of cement pastes, hydrated at 28 days.

 P.E. Tsakiridis et al. / Construction and Building Materials 153 (2017) 202–210
100
95
90
Mass Loss (%)
C-S-H
PCC
85
PCDOP
80
75
Ettringite
70
0 100 200 300
Fig. 6. TG/DTG of cement pastes, hydrated at 28 days.
formation of calcium silicates hydrated, and its presence is indica-
tive for the reaction rate of the examined cements, in relation with
the corresponding decrement of clinker phase peaks. On the other
hand, the CSH detection is relatively a difficult task due to their
nature, as the majority of them is with the form of amorphous
gel or semi-crystalline needles. However, the presence of a small
diffused band in the range of 25°–35° is indicative for the forma-
tion of poorly crystallized or CSH gel. Calcium aluminates have
been completed consumed, in the presence of gypsum sulphate
ions, for the development of ettringite, whose attendance was con-
firmed by the characteristics peaks at 8.98°, 15.72° and 22.9°. The
ferrite hydration has not been fully accomplished after 28 days of
curing, as a small peak corresponding to the unreacted C4AF is
detected in all cases at about 12°.
The above outcomes were also validated by the hydration prod-
ucts TG/DTG analysis after 28 days of curing (Fig. 6). The TG curves
comparison and the corresponding derivative ones (DTG) showed
that the addition of different amounts of DOP ashes did not affect
the produced cements hydration evolution, further confirming the
results of physical and mechanical characterization.
The major dehydration peaks observed were attributed to the
calcium silicate hydrated, ettringite and portlandite dehydroxyla-
tion, located at about 120, 460 °C respectively, whereas the carbon-
ates decomposition were detected in the range of 715 °C. Similar
quantities of gelatinous calcium silicates hydrate (CSH), detected
by the characteristic peaks in the range of 100–150 °C, together
with Ca6Al2(SO4)3(OH)12
26H2O (ettringite) seem to have been
formed in all cases, after 28 days of hydration. The decomposition
of (Ca(OH)2), observed at 460 °C, the major hydration compound
derived from the calcium silicate hydration, was indicative for
the identity of the hydration evolution of all mixtures, as almost
equal amounts of portlandite have been produced. The small
endothermic peak at 715 °C was ascribed to the release of CO2 from
calcium carbonate decomposition, previously formed during the
partial Ca(OH)2 carbonation.
Overall, the addition of different amounts of DOP ashes in the
raw mixed did not seem to significantly affect the quality of the
produced clinkers, as the physical and mechanical characteristics,
in relation with hydration development was found to be almost
identical in all cases.
209
0,00
Carbonates
Differential Relative Weight (%/ oC)
-0,02
Ca(OH)2
PCC-DOP -0,04
-0,06
400 500 600 700 800 900
o
Temperature ( C)
4. Conclusions
The potential utilization of Dried Olive Pomace (DOP) as an
alternative fuel in cement clinkerization has been examined,
investigating the effects on the properties of the cement clinker
produced. DOP presented a relatively high calorific value
(5525 kcal/kg) in comparison with the corresponding value of
6375 kcal/kg of a bituminous coal used in the present investiga-
tion, while the ash produced during DOP incineration (4.28 wt%)
was about 45% lower than that of bituminous coal (6.15 wt%). Dif-
ferent amounts of DOP and coal ashes were introduced in the raw
meal before sintering at 1450 °C, substituting coal on the burning
process for DOP by 50 and 100 wt%. The produced cement clinkers
were not negatively affected, as the degree of crystallization during
sintering process was high and the calcium silicate phases, the tri-
clinic alite (Ca3SiO5) and the monoclinic belite (b-Ca2SiO4), as well
as the cubic C3A and the orthorhombic C4AF were well formed. The
cements mixtures physical properties, setting times, water
demand and expansion, were slightly affected and were contigu-
ous in all cases. The mortars compressive strengths after 2 days
of curing, were determined in the range of 30 MPa, while the cor-
responding value at 28 days reached 60 MPa. Due to the produced
cements similarities, regarding mineralogical composition and
finesses, the compressive strengths were almost identical for all
samples, satisfying the requirements for the 52.5 strength class
as per standard EN 197-1.
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