Waste Management 48 (2016) 323–333

Contents lists available at ScienceDirect

Waste Management
journal homepage: www.elsevier.com/locate/wasman

Use of bottom ash from olive pomace combustion in the production

of eco-friendly fired clay bricks
D. Eliche-Quesada a,⇑, J. Leite-Costa b
a
Department of Chemical, Environmental, and Materials Engineering, Higher Polytechnic School of Jaén, University of Jaen, Campus Las Lagunillas s/n, 23071 Jaén, Spain
b
Department of Chemical, Environmental, and Materials Engineering, Higher Polytechnic School of Linares, University of Jaen, 23700 Linares (Jaen), Spain

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

Article history: Olive pomace bottom ash was used to replace different amounts (10–50 wt%) of clay in brick manufac-
Received 14 August 2015 turing. The aim of this study is both studying bricks properties and showing a new way of olive pomace
Revised 4 November 2015 bottom ash recycling. Properties of waste bricks were compared to conventional products following stan-
Accepted 26 November 2015
dard procedures in order to determine the maximum waste percentage. The amount of olive pomace bot-
Available online 2 December 2015
tom ash is limited to 20 wt%, obtaining bricks with superior engineering properties when 10 wt% of waste
is added. Adding higher amount of waste (30–50 wt%) resulted in bricks with water absorption and com-
Keywords:
pressive strength values on the edge of meeting those established by standards. Therefore, the addition of
Bottom ash
Olive pomace
10 and 20 wt% of olive pomace bottom ash produced bricks with a bulk density of 1635 and 1527 kg/m3
Recycling and a compressive strength of 33.9 MPa and 14.2 MPa, respectively. Fired bricks fulfil standards require-
Eco-friendly bricks ments for clay masonry units, offering, at the same time, better thermal insulation of buildings due to a
Sustainability reduction in thermal conductivity of 14.4% and 16.8% respectively, compared to control bricks (only clay).
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction sources, biomass is defined as: ‘‘The biodegradable fraction of

products, waste and residues of biological activities from agricul-
The evolution of oil prices and the geographical distribution of ture (including vegetal and animal substances), forestry and
energy reserves have conditioned the energy options in developed related industries, including fishing and aquaculture, as well as
countries for more than three decades. Securing supply, respecting the biodegradable fraction of industrial and municipal waste”.
the environment and economic competitiveness are the corner- Using biomass energy allows the replacement of fossil fuels, a
stones of the European and Spanish energy policy. Spain now greater self-sufficiency and energy diversification, and contributes
boasts a solid normative framework in support of renewable to the maintenance of activities in rural areas. Biomass potential
energy. Energy from biomass for use in thermal and electrical detected in Andalusia amounts to 3958 ktep. Considering that con-
applications is having more growth prospects thanks to the Span- sumption of primary energy in Andalusia in 2011 was of
ish Development Plan Renewable Energies. In Spain, biomass con- 19053.3 ktep, the potential of biomass represents 20% of the
sumption has been rising in recent years, being in 2010 of energy needs in Andalusia.
4751 ktep GW h, 8.0% higher than the previous year according to In Andalusia, during 2011, a total surface of 1,500,000 Ha of
the data from the European Observatory for Renewable Energy, olive groves was reached, what in an average campaign produced
EurObserv’ER. Among the Spanish autonomous communities, about 4,650,000 tons of olive. Of these, approximately
Andalusia, Galicia and Castilla-Leon recorded higher consumption. 4,300,000 tons/year are intended to obtain olive oil and the
Almost 40% of all the energy from biomass in Spain can be found in remaining 350,000 tons/year will be used in dressing table olive
Andalusia, Spain’s southermost region. Therefore, Andalusia boasts industry. The average quantity of oil produced is 900,000 tons/
an important wealth of biomass, largely coming from the cultiva- year. For each ton of processed olives yield, 0.73 Tm of pomace
tion of olive and its derived industries. According to the directive (73%) is produced. Once dried and submitted to the oil extraction
2009/28/EC of the European Parliament and of the Council of 23 process, 27% (0.197 Tm) of pomace is transformed into dry olive
April 2009 on the promotion of the use of energy from renewable cake or orujillo, which can be used as fuel. Orujillo is a by-product
with humidity around 10% which has good properties as fuel, with
a calorific value of around 4200 kcal/kg on a dry basis, and it can be
⇑ Corresponding author. used for both energy and heat generation in industries. A part of
E-mail address: deliche@ujaen.es (D. Eliche-Quesada).

http://dx.doi.org/10.1016/j.wasman.2015.11.042
0956-053X/Ó 2015 Elsevier Ltd. All rights reserved.
324 D. Eliche-Quesada, J. Leite-Costa / Waste Management 48 (2016) 323–333

Nomenclature list

ktep kilotonnes equivalent to petroleum LOI loss on ignition

GW h Gigawatt hour OPBA olive pomace bottom ash
Ha hectare or square hectometer
Tm tonnes
MW Megawatt

orujillo in the cooker hoods consumes itself in the installation, both 2. Experimental
during pomace drying process and steam generation in boilers.
Olive pomace and dry olive cake are rich in organic matter and 2.1. Materials
potassium (Alburquerque et al., 2004). At present, there are 18 sta-
tions of electric biomass and cogeneration with biomass in Andalu- Clay was supplied by a clay pit located in Bailen, Jaen (Spain). It
sia with a total installed capacity of 25,748 MW, and newer plants was obtained by mixing three types of raw clay in equal parts: red,
are planned. Ash produced by combustion process can be classified yellow and black clay. Waste used was bottom ash, a by-product of
into bottom and fly ash (cyclone and filter fly ash). Bottom ash is combustion in a steam boiler from the biomass power plant La
produced on the grate in the first combustion chamber of the boiler Loma in Villanueva del Arzovispo, Jaen (Spain). The biomass power
and they consist of totally or partially burnt biomass. Fly ash are plant used olive pomace as fuel.
particles carried outwards the combustion chamber by the flow
of gases. Using dry pomace as fuel generates a large amount of 2.2. Experimental method
ash (between 4% and 8% of the burnt waste). Biomass plays a fun-
damental role in an energy framework in which sustainability, The moisture content of olive pomace bottom ash (OPBA) and
diversification and a high degree of self-sufficiency prime. There- organic content was measured according to ASTM D-2974, Stan-
fore, various administrations, both at regional, national and Euro- dard Test Method for Moisture, Ash, Organic Matter of Peat and
pean level are determinedly betting on this renewable energy. Other Organic Soils (ASTM D-2974, 1987) and their pH using a
Common disposal of biomass ash is landfilling next to power PCE-PH20S pH-meter.
plants, but this alternative is the least attractive in an environmen- Particle size distribution was performed using sieve granulom-
tal management. Consequently, the volume of biomass ash gener- etry following EN 933-1:2012 (EN 933-1, 2012).
ated will be important and will grow in the upcoming years, Carbonate content (expressed as calcium carbonate) was deter-
ensuring enough biomass ash for recovery is available. Dry olive mined by calcimetry in a Bernard calcimeter.
pomace ash is used mainly as fertilizer due to its high content in Qualitative determination of major crystalline phases in clay
potassium (Nogales et al., 2011). Other studies describe potential and OPBA was achieved using the Philips X’Pert Pro automated
use of olive pomace ash as soil amendment (Nogales et al., 2006), diffractometer equipped with a Ge (1 1 1) primary monochromator.
as adsorbent to remove copper (Cu2+) ions from aqueous solutions Chemical composition was determined by X-ray fluorescence (XRF)
(Bouzid et al., 2008), as raw materials for cement based products using the Philips Magix Pro (PW-2440). Thermal behaviour was
(Cuenca et al., 2013; Cruz-Yusta et al., 2011) and as building mate- determined by thermogravimetric and differential thermal analy-
rial (De la Casa and Castro, 2014; Fernández-Pereira et al., 2011; sis (TGA–DTA) with a Mettler Toledo 851e device in oxygen. The
García Calvo et al., 2010). So, even though only few studies have total content of carbon, hydrogen, nitrogen, and sulphur was deter-
assessed olive pomace ashes, many authors have described the mined by combustion of samples in O2 atmosphere using the
recovery of biomass ashes as raw material for building materials CHNS-O Thermo Finnigan Elementary Analyzer Flash EA 1112.
(Cabrera et al., 2014; Carrasco-Hurtado et al., 2014; Hinojosa The higher heating value (HHV) was determined using a Parr
et al., 2014; Kalembkiewicz and Chmielarz, 2012; Maschio et al., 1341 Plain Oxygen Bomb Calorimeter.
2011; Pavšič et al., 2014; Pérez-Villarejo et al., 2012; Rajamma After characterization of the clay and the bottom ash, the appro-
et al., 2009; Sua-Iam and Makul, 2015; Vassilev et al., 2013b) in priate mixtures for samples were designed. To obtain a uniform
recent years. For environmental protection and sustainable devel- particle size, clay was crushed and ground to yield a powder with
opment, many authors have studied the utilization of industrial a particle size suitable to pass through a 150 lm sieve. The waste,
waste materials as additive of clay bricks. Some different inorganic olive pomace bottom ash, was dried in an oven at 105 °C and
waste materials such as ferrochromium slag, pumice, marble, gal- milled in a ball mill until homogeneous particle size was obtained.
vanic sludge, waste glass, and construction and demolition waste Particles were sieved throught a 150 lm mesh prior to their incor-
have been used (Gencel, 2015; Gencel et al., 2013; Muñoz- poration into clay bricks in order to reduce agglomeration. The
Velasco et al., 2014; Neves Monteiro and Fontes Vieira, 2014; OPBA was added to clay in different amounts (0–50 wt%) and it
Pérez-Villarejo et al., 2015; Phonphuak et al., 2015; Sutcu et al., was mixed to obtain good homogenization. To enable comparative
2015; Xu et al., 2014; Zhang, 2013). Mineralogical and composition results, ten samples per series were prepared for testing. The nec-
content of industrial inorganic wastes are well-matched with the essary amount of water (7–10 wt% moisture) was added to the
of brick structure. samples to obtain adequate plasticity and absence of defects,
This research work tries to deepen the characterization and pos- mainly cracks, during the semi-dry compression moulding stage
sible use of olive pomace bottom ash, focusing on determining, by under 54.5 MPa of pressure, using a uniaxial laboratory-type press-
means of laboratory scale tests, the technological properties of raw ing Mega KCK-30 A. Waste-free mixtures were also made as a ref-
materials in the preparation of clay bricks, optimizing the quantity erence. Solid bricks with 30  10 mm cross sections and a length of
of residue to be added, checking physical, mechanical and thermal 60 mm were obtained. Samples were fired in a laboratory furnace
properties of the new materials, compared to those obtained by at a rate of 3 °C/min up to 950 °C for 4 h. Samples were then cooled
using only clay (control bricks). to room temperature by natural convection inside the furnace.
 D. Eliche-Quesada, J. Leite-Costa / Waste Management 48 (2016) 323–333 325

Shaped samples were designated as C for the bricks without waste The concentrations in the filtrate were measured with an
and C-xOPBA for mixtures with olive pomace bottom ash, where x Inductively Coupled Plasma-Atomic Emission Spectrometer
denotes the content (wt%) in the clay matrix. (ICP–AES Agilent 7500).

2.3. Testing methods for the bricks 3. Results and discussion

Linear shrinkage was obtained by measuring the length of sam- 3.1. Analysis of materials
ples before and after the firing stage, using a caliper with a preci-
sion of ±0.01 mm, according to ASTM standard C326 (ASTM 3.1.1. Olive pomace bottom ash
C326, 1997). Water absorption values were determined from Particle size distribution of olive pomace bottom ash is shown
weight difference between the as-fired and water-saturated sam- in Fig. 1. A significant percentage of large particles were observed,
ples (immersed in boiling water for 2 h), according to ASTM stan- so that grinding and particle separation process are considered
dard C373 (ASTM C373, 1994a). Open porosity (in vol.%) were necessary before compaction. Out of total samples tested, 32.5%
determined from weight difference between saturated mass and was characterized as fine mode (passed tough a sieve of 400 lm).
dry mass with respect to exterior volume and closed porosity (in The sample was composed of well-graduated material with pre-
vol.%) was calculated from weight difference between dry mass dominantly sand sized particles (61.5%). It was thus necessary to
and suspended mass in water with respect to exterior volume homogenize particle size to obtain particles of 150 lm by sieving
according to ASTM standard C373 (ASTM C373, 1994a). Bulk den- process.
sity was determined by the Archimedes method (ASTM C373, Olive pomace bottom ash had a moisture content of 4.15%.
1994a). Water suction of a brick is the volume of water absorbed Weight loss was also investigated by calcination of samples of
during a short partial immersion. Tests to determine water suction grain size <150 lm at 950 °C. The high amount of unburnt matter
was implemented according to standard procedure UNE-EN 772-1 content in ash is also noteworthy. The weight loss measured was
(UNE-EN 772-1, 2001). 25.5%. The result indicated that incorporating ash into clay mate-
Compressive strength of bricks is their bulk unit charge against rial can incur in a reduction in volume that would result in pieces
breakage under axial compressive strength. For this trial, six fired deformation or breakage during sintering, if heat treatment is
samples were studied. Tests on compressive strength were per- implemented at a non-adequate heating rate. Alkalinity of bottom
formed according to standard UNE-EN 772-1 ((UNE-EN 772-1, ash pH = 9.5 is mainly due to its carbonate, bicarbonate and
2002) on a Suzpecar CME 200 SDC laboratory press. The area of hydroxide content (Nogales et al., 2011). The CNHS analysis of olive
both bearing surfaces was measured and the average taken. All pomace bottom ash (Table 1) showed that ash is composed mainly
samples were submitted to a progressively increasing normal of carbon (3.4%), hydrogen (0.97%) and a small quantity of nitrogen
strength, with the load applied centered on the upper surface of (0.13%). It also contains a small amount of sulphur. Carbon content
the sample until breakage. The compressive strength of each sam- in ash usually depends on the efficiency of combustion technology.
ple was obtained by dividing the maximum load by the average Large amounts of organic carbon in ash indicate incomplete com-
surface of both bearing surfaces, expressed in MPa with 0.1 MPa bustion of olive pomace, which suggests inefficient fuel use
accuracy. (Demirbas, 2005). The carbon content is medium and ash pre-
Development of porosity in samples was also evaluated by sented high loss on ignition, indicating that, in addition to the
means of a scanning electron microscope (SEM), using the high- elimination of organic matter and carbonates, moisture, sulphates
resolution transmission electron microscope JEOL SM 840. Samples and phosphates are removed. Chemical components of ceramic
were placed on an aluminium grate and coated with carbon using bodies can be classified into three groups: (1) skeleton compo-
the ion sputtering device JEOL JFC 1100. nents, which form the framework and surface of ceramic bodies,
Thermal conductivity of samples was evaluated with a C-Therm mainly consisting of SiO2 and Al2O3; (2) flux materials, which low-
TCi Analyzer with a universal sensor from Mathis Instruments Ltd. ered the melting point, mainly containing alkaline metal oxide and
This equipment uses the modified transient plane source tech-
Table 1
nique, applying a momentary, constant heat source produced by Chemical composition of the fired clays and olive pomace bottom ash.
a one-sided, interfacial heat reflectance sensor to the sample.
Oxide content Red Yellow Black Mixture of OPBA
Finally, leachability of heavy metals in the samples was studied
(%) clay clay clay clays
using the toxicity characteristic leaching procedure (TCLP) accord-
SiO2 53.94 53.54 45.50 47.17 10.88
ing to EPA method 1311 (Environmental Protection Agency, 1992).
Al2O3 15.93 11.78 11.55 12.51 1.68
Fe2O3 14.22 7.02 5.82 6.49 1.38
CaO 3.84 13.67 21.45 13.52 13.07
MgO 1.81 2.20 2.10 2.11 1.92
Cumulative Weight Percentage (%)

100 MnO 0.032 0.063 0.10 0.05 0.03

Na2O 0.22 1.72 1.40 0.31 0.13
90
K2O 7.95 4.17 3.43 3.61 38.01
80 TiO2 1.54 1.56 1.21 0.78 0.13
70 P2O5 0.21 0.10 0.10 0.14 3.67
60 SO3 – – 2.91 1.58 1.40
50 NiO – – – 0.0086 0.0075
CuO – – – 0.0017 0.037
40
ZnO – – – 0.0082 0.0074
30 Ga2O3 – – – 0.0027 –
20 Rb2O – – – 0.017 0.016
10 SrO 0.035 0.096 0.22 0.043 0.048
0 ZrO2 – 0.059 0.141 0.035 0.0071
10 100 1.000 10.000 Nb2O5 – – – 0.0021 –
BaO – – – 0.047 –
Particle size (μm)
Cl – – – – 2.01
LOI – – – 10.6 25.53
Fig. 1. Particle size distribution of olive pomace bottom ash.
326 D. Eliche-Quesada, J. Leite-Costa / Waste Management 48 (2016) 323–333

alkaline-earth metal oxides such as CaO, Na2O, K2O and MgO; (3) 6000 * KHCO3
gaseous components, which generate gases and bloat ceramic bod- + K3CaH(PO4)2

ies during sintering at high temperature (Hongtao et al., 2012; Qi K8(SO4)4

5000
♦Ca8Mg(SiO4)4Cl2
et al., 2009). Results of chemical analysis of bottom ash obtained
K1.25Al1.25Si0.75O4

Intensity (a.u.)
by XRF data are shown in Table 2. K2O and CaO are the major oxi- 4000
K3CaH(PO4)2
♦
des (>10 wt%) present, in decreasing order of abundance. High con- *
*
* • Fe1O4P1
3000 **
tent in K2O is due to the oxide being a major component of the • ++
pomace used as fuel. Oxides SiO2, P2O5, Fe2O3, MgO and Al2O3, in ♦ + •
2000 + *
similar order, are present in a 1–10 wt% proportion, whereas +
*
* +
Na2O is a minor oxide (0.1–1 wt%). Chloride content is also high 1000
* *
+
• +
1.76 wt%. As indicated in Table 2, the total content of Si and Al
(estimated as oxides) is lower than the level obtained in other bot- 0
tom ash due to their low level in the feeding fuel. High contents of 10 15 20 25 30 35 40 45 50 55 60 65 70
fluxing oxides (K2O) and auxiliary fluxing oxides (CaO, MgO) in 2 theta (º)
waste are suitable to the low temperature firing process for brick Fig. 2. XRD patterns of olive pomace bottom ash used as raw materials in the
preparation. Loss on ignition at 950 °C indicates a high content in preparation of bricks.
organic matter (13.5%), carbonates (35.2%) or hydrated phases, as
well as the decomposition of inorganic compounds, with a 1.3%
value of SO3. The higher LOI value could be due to a less effective 0,5
combustion or thermal decomposition of inorganic species. Miner- 44 TGA 0
alogical characterization of olive pomace bottom ash (Fig. 2)
42
showed the presence of an alkaline carbonate kalicinite (KHCO3), DTA -0,5

Weight loss ( mg)

a potassium sulphate (K8(SO4)4), a calcium chlorosilica mineral 40
-1

ΔT (ºC)
containing magnesium, rondorfite (Ca8Mg)(SiO4)4Cl2, a potassium
38
aluminosilicato (K1.25Al1.25Si0.75O4), a potassium calcium -1,5
hydrophosphate (K3CaH(PO4)2) and an iron phosphate (Fe1O4P1). 36 ↑ exothermic -2
The bottom of the diffractogramm and the looping indicate as well
the presence of a significant amount of amorphous phase. Accord- 34 ↓ endothermic -2,5
ing to its chemical composition, OPBA is classified as ‘‘C” type, -3
32
commonly comprising carbonates, oxyhydroxides, glass, silicates
and some phosphates and sulphates (Vassilev et al., 2013a). 30 -3,5
Thermo-gravimetric study (TGA–DTA) of olive pomace bottom 50 150 250 350 450 550 650 750 850 950
ash (Fig. 3) showed an soft endothermic peak at approximately Temperature (ºC)
90 °C with a weight loss of 2.3% between 50 and 100 °C, corre-
Fig. 3. TGA–DTA analysis of olive pomace bottom ash (OPBA).
sponding to the elimination of hydration water. From 100 to
250 °C, a strong endothermic peak centered at 170 °C is observed
due to the elimination of structural water, producing 7.4% of
weight loss. Between 250 and 590 °C, weight loss was 5.6%, result- and alumina content. Red clay is not plastic enough for shaping
ing from the combustion of organic matter and remaining unburnt resistant unfired pieces. Regarding traditional mixture described
matter. An exothermic reaction is observed in DTA curve with a in Table 2, used as reference raw material in the present work,
maximum centered at 400 °C. From 590 to 950 °C, weight loss the addition of red clay allows modifying the technological beha-
observed was high (8.5%), consequently to various thermal effects. viour of yellow and black clays. Due to the proportions of clays
At 600 °C, residue presents an endothermic peak due to the elimi- used, clay mixture has appropriate plasticity (plasticity index:
nation of structural water from hydroxide ions, whereas a strong 9.6%) for shaping. Clay mixture shows the expected typical compo-
exothermic peak is shown at 800 °C, resulting from decarbonation sition: high amounts of SiO2 (55.82%), as predominant oxide, and
reactions. Bernard calcimetry revealed the existence of calcite and Al2O3 (12.13%) mainly due to silicates present in clay. The signifi-
FRX the presence of CaO, one of the major components in ash apart cant content of CaO (13.52%) is related to the abundance of carbon-
from K2O. Total weight loss was 21.4%. ates, which explain the loss on ignition observed. Clay is
considered calcareous if CaO > 6 (Gökhan and Simsek, 2013). This
3.1.2. Clay information is very important for manufacturers so they can adapt
Three types of clay were used in this work. Chemical composi- drying and firing processes to avoid cracking. During firing, carbon-
tion of raw yellow, red and black clay after firing at 950 °C was ates acts as pore-forming agents and generate crystalline phases,
determined by XRF (Table 2). Yellow and black clays are rich in cal- which enhance mechanical strength (García-Ten et al., 2010). Clay
cium oxide, showing very high levels in black clay. The decrease in mixture also contains a small amount of K2O and MgO (minor com-
calcium oxide content is correlated to an increase in SiO2 content, ponents of Ti and Na oxides), accompanied by a significant amount
reaching values of 54% SiO2 in the case of yellow clay. Red clay is of iron oxide (6.49 wt%), a high temperature fluxing agent, which is
characterized by a low calcium oxide content with higher ferrite responsible for dark colour in fired pieces.

Table 2
Carbonate content and CNHS analysis of raw materials.

Sample Organic matter content (%) Carbonate contenta (%) %C %H %N %S

Clay 3.50 ± 0.37 11.67 ± 0.24 2.30 ± 0.004 0.50 ± 0.004 0.05 ± 0.00 0.03 ± 0.008
OPBA 13.54 ± 0.08 42.28 ± 0.56 4.21 ± 0.007 0.96 ± 0.021 0.13 ± 0.00 0.08 ± 0.006
a
Determined according ASTM D-2974.
 D. Eliche-Quesada, J. Leite-Costa / Waste Management 48 (2016) 323–333 327

Quartz 3.2. Characterization of the bricks

Calcite
Gehlenite No defects such as cracks, bloating nor efflorescence were
• Hematite observed after firing. Colour of fired samples probes is reddish in
Intensity (a.u.)

ο Albite
control bricks. Instead, bricks tend to go reddish-orange when
∗ Microcline
+
Dolomite ash is added. Bricks lightness increased with increasing olive
pomace ash content (Fig. 6).
Tests for linear shrinkage, mass loss on ignition, bulk density,
water absorption capacity, water suction and compressive strength
were performed, in order to verify whether the resulting fired brick
∗ ο samples fulfilled the building standards. Experimental tests were
+ * • ο ∗ •
ο carried out with mixtures of different proportions of OPBA (0–
10 20 30 40 50 60 70 50 wt%) and clay to study their engineering properties.
2 theta (º) Linear shrinkage (Table 3) reflects expansion/contraction beha-
viour during thermal treatment, being a key parameter for fired
Fig. 4. XRD pattern of fired clay.
bricks. Linear shrinkage of bricks after sintering depends on flux
materials, or on the amount of liquid phase generated during firing
XRD pattern of fired clay (Fig. 4) showed quartz as main compo- and the decomposition of gaseous components. Flux materials
nent, as well as lower amounts of various silicates such as albite, could produce molten materials to compress interspaces, whereas,
microcline and gehlenite. Carbonates as calcite and dolomite, and in the second case, gases could be released to expand the pores.
possible iron oxide-hydroxides and hematites, are also present in Linear shrinkage of reference ceramics (clay without industrial
small quantities. Comparing the mineralogical composition of clay waste) was 0.10%. Clay bricks showed a contraction at this sinter-
mixture with the overall composition of common raw materials for ing temperature. As shown in Table 2, SiO2 and Al2O3 weight per-
ceramic products (Dondi et al., 1992) reveals that clay mixture centage in clay was about 47.2% and 12.6%, respectively, which
contains the appropriated phyllosilicates, carbonate and quartz meant that 60% of clay weight was made of skeleton components.
contents to be considered potentially suitable for structural cera- Flux materials (19.5%) and gaseous components all were found
mic products. (6.5% Fe2O3, 11.7% CaCO3 and 3.5% organic matter). When temper-
In order to investigate the reactions taking place during the fir- ature grew from room temperature to 950 °C, hematite and calcite
ing process, clay was studied by DTA–TGA. TGA curve of clay decomposed at 800 °C, and organic matter at 550 °C, generating O2
(Fig. 5) showed a total weight loss of 12.0%. Water evaporation and CO2. However, the volume of O2 was very small due to the low
and carbonate decomposition are the most significant weight loss mass fraction of Fe2O3, which meant CO2 was the main gas during
processes in brick manufacturing. Water evaporation mainly
occurs at temperatures below 100 °C, although the process is
extended up to 150 °C (Yariv, 2003). Other minors thermal pro-
cesses occur between 150 and 650 °C, related to the combustion
of organic matter and dehydration and dehydroxilation of laminar
silicates present in clay (Arsenovic et al., 2014; Dweck, 2008; Wang
et al., 2000). Up to 650 °C, gradual loss may be observed but, after C
650 °C, it diminished abruptly due to the breakdown of carbonates,
releasing high levels of CO2. Calcium carbonate decomposition
takes place in the range between 600 and 800 °C (Dollimore
et al., 1996). DTA curve showed that dehydration, release of OH C-10OPBA
(dehydroxilation reactions) and decarbonation reactions are
endothermic processes, with peaks centered at 76 °C, 557 °C and
750 °C, respectively, while decomposition of organic matter is an
exothermic process, with peaks centered at about 350 °C and C-20OPBA
425 °C.

33,5 0,5 C-30OPBA

32,5 0
TGA
Weight loss (mg)

31,5 DTA -0,5 C-40OPBA

ΔT (ºC)

30,5 ↑ exothermic -1

↓ endothermic
29,5 -1,5 C-50OPBA

28,5 -2
50 150 250 350 450 550 650 750 850 950
Temperature (ºC)

Fig. 5. TGA–DTA analyisis of raw clay. Fig. 6. Photo of clay bricks and OPBA-clay bricks containing (10–50 wt%) of waste.
328 D. Eliche-Quesada, J. Leite-Costa / Waste Management 48 (2016) 323–333

Table 3
Technological properties of construction bricks made from clay, olive pomace bottom ash.

Sample Waste content (wt%) Bulk density (kg/m3) Linear shrinkage (%) Loss on ignition (%) Suction water (kg/m2 min)
C 0 1.757 ± 25 0.10 ± 0.08 10.99 ± 0.15 2.38 ± 0.21
C-10OPBA 10 1.635 ± 24 0.07 ± .093 11.25 ± 0.24 2.20 ± 0.14
C-20OPBA 20 1.527 ± 13 0.32 ± 0.14 13.43 ± 0.22 2.86 ± 0.15
C-30OPBA 30 1.481 ± 18 0.51 ± 0.12 14.26 ± 0.13 3.13 ± 0.07
C-40OPBA 40 1.377 ± 28 0.60 ± 0.07 16.77 ± 0.22 3.77 ± 0.20
C-50OPBA 50 1.278 ± 9 0.63 ± 0.11 20.61 ± 0.12 4.38 ± 0.11

sintering. This indicated that many little interspaces were present carbonates. The lowest value of water suction is obtained when
inside the dried specimens before sintering, and that the volume 10 wt% of residue is added, lower than the value of control bricks.
fraction of such interspaces would be slightly increased, corre- However, the particular technical specifications will set the limit to
sponding to the removal of adsorbed water and crystal water dur- water suction in bricks. In any case, water suction must not be
ing sintering. When the temperature reached 950 °C, molten greater than 4.5 kg/m2 min (RL-88 2004), meaning that all the
materials would fill these little interspaces and cause shrinkage, waste-containing bricks comply with this criterion.
being the flux effect predominant over the decomposition of gas- Apparent porosity and water absorption increased with OPBA
eous components. Adding olive pomace bottom ash changed linear content (Fig. 7). Adding OPBA waste caused apparent porosity
shrinkage from contraction to expansion. The OPBA waste was increase from 28.3%, in the case of control bricks, until 39.0%, for
formed by a 9.8% of SiO2 and Al2O3, a 51.5% of flux materials and the brick containing the maximum amount of residue, 50 wt%.
some content in Fe2O3, carbonate and organic matter of 1.6%, Water absorption data act the same way. Water absorption of
35.2% and 13.5%, respectively. Therefore, clay samples containing bricks is classified in accordance to the different grades of weath-
residue expanded slightly when fired at 950 °C, resulting in a typ- ering exposure condition according to ASTMC67–07a:2003
ical behaviour of porous materials. The proportions of OPBA had a (ASTMC67–07a, 2003). For severe weathering resistance bricks,
weak effect on linear shrinkage, increasing slightly by adding lar- water absorption may not be higher than 17%. For moderate
ger amount of residue. The addition of OPBA produced liquid phase weathering resistance bricks, water absorption will not be higher
at lower temperature and a decrease in temperature at sintering than 22% and no limit is set for negligible weathering resistance
onset. However, at firing temperature of 950 °C, liquid phase bricks. Results of water absorption ranged from 16.3% to 31.0%
allowed gas trapping, an increase in gas pressure inside the closed for bricks with 0 wt% and 50 wt% of OPBA, respectively. Adding
pores, resulting from the decomposition of Fe2O3, organic matter more than 20 wt% of OPBA resulted in bricks with very high water
and CaCO3, which tends to expand the pores. As a result, bulk den- absorption values that do not fall within the standards of conven-
sity decreased rapidly. Such behaviour reflects that the effect of tional bricks, mainly due to the increase of bottom ash content.
porosity formed in the material with high OPBA content is greater Bottom ash is a water-absorbent material that increased water
than the effect provided by the melting capacity of waste. absorption capacity of the hardened matrix when added to it.
Loss on ignition of clay samples at 950 °C was 10.99%. The addi- Other authors have found similar results for fly ash
tion of OPBA increased loss on ignition to values varying from (Ahmaruzzaman, 2010; Paki, 2010; Shakir et al., 2013). Relation-
11.25% to 20.61%. According to the thermal analysis of raw materi- ship between water absorption and OPBA content is reported in
als, weight loss could be due to the elimination of water content Fig. 7. Water absorption is observed to increase almost linearly
from clay mineral due to dehydroxylation reactions, to the elimi- with bottom ash content (R2 = 0.98), reaching its maximum for
nation of the organic matter by means of combustion and to the 50 wt% OPBA. High water absorption capacity is attributed to
decomposition of carbonate from clay and waste. All these pro- higher open porosity.
cesses were almost completed below 950 °C. Therefore, loss on Bottom ash in the clay matrix can reduce the firing tempera-
ignition of fired bricks is expected to increase (Table 3) by increas- ture, since the fluxing capacity of the residue lowers the melting
ing the proportion of OPBA. point of the material. The higher amount of OPBA in the clayey
Adding OPBA obviously reduced bulk density of fired bricks
(Table 3), which exhibited values ranging from 1278 to 1635 kg/
m3, i.e., lower than the values for clay bricks of 1757 kg/m3. Bulk 40 35
density of fired bricks decreased by increasing the proportion of
residue. Bulk density decreased by 6.9% and by 27.3%, when 38 30
10 wt% and 50 wt% of OPBA was added, respectively. y = 0,298x + 16,031
R² = 0,9863
Water absorption (%)
Apparent porosity (%)

Water suction refers to the amount of water absorbed in 1 min 36 25

through the bed surface of the brick. Water suction can affect the
quality of the final material and its durability significantly. Low 34 20
water infiltration into the bricks contributes to having good dura-
bility, and, consequently, higher resistance to natural environment. 32 15
Therefore, higher values should be avoided since they can cause
bricks with defects and lower durability. As detailed in Table 3, 30 10
adding 20 wt% of waste, or more, produced a significant increase
in suction water. Control bricks showed water suction values of 28 5
2.38 kg/m2 min, whereas C-20OPBA and C-50OPBA samples
26 0
showed values of 2.86 kg/m2 min and 4.38 kg/m2 min, respec-
0 10 20 30 40 50
tively. Therefore, incorporating 20 wt% or more of olive pomace
OPBA waste content (wt%)
bottom ash into the clay produced an increase in the intercon-
nected surface porosity, possibly due to a growth in pores, both Fig. 7. Apparent porosity and water absorption as a function of OPBA addition (0–
in size and in number, caused by the organic waste content and 50 wt%) of the clay.
 D. Eliche-Quesada, J. Leite-Costa / Waste Management 48 (2016) 323–333 329

matrix can result in the formation of liquid phase at lower temper- strength of fired products is shown in Fig. 10. Compressive strength
ature and can have suitable viscosity at firing temperature 950 °C, decreased with increasing ratio of bottom ash in bricks, especially
avoiding the release of gases resulting from the decomposition of when the ratio is equal or higher than 20 wt%. The highest value
Fe2O3, organic matter and CaCO3 which may be trapped inside obtained corresponds to the control bricks (47.96 MPa). Compres-
the clay matrix, causing open porosity. As shown in Fig. 8, open sive strength values decreased by 29.4%, down to 33.9 MPa, when
porosity (in vol.%) increased from 5.6%, for control brick containing 10 wt% OPBA was added. Adding 20 wt% reduced compressive
only clay, up to 9.5% for the brick containing 50 wt% of OPBA. How- strength to 14.2 MPa and major additions, 30–50 wt%, decreased
ever, closed porosity (in vol.%) remained constant, varying between the value by approximately 78%, down to 10.9–10.2 MPa. Results
14.2% and 14.9% for 0 wt% and 50 wt% waste. These results are in are in accordance with data for bulk density and water absorption.
accordance with SEM micrographs. The microstructure of fired Bulk density of bricks has been reduced as the amount of the bot-
bricks has been studied by SEM on fracture surface. Fig. 9 shows tom ash increased to reach 1278 compared to 1757 kg/m3 for con-
SEM micrographs and EDAX analysis for control bricks and OPBA trol bricks. At high OPBA dosages (20 wt% or more), waste bricks of
bricks containing 10, 20 and 50 wt%. The surface of all samples higher porosity, lower compressive strength and higher water
showed a low grade of densification with important open porosity. absorption were produced. Open pores may concentrate pressure
Clay porosity is due mainly to open porosity, which is formed by and decrease compressive strength in bricks (Carty and Senapati,
fine, interconnected, irregularly-shaped pores and a lower propor- 1998) due to their irregular shape and microscopic imperfections.
tion of small-sized and closed pores. The composition analyzed by Despite OPBA additions providing a decrease in mechanical
EDS was typical of clays, with several areas that constituted parts properties of waste bricks, the addition of bottom ash may help
of original silicates (Si, Al, Mg, Ca, K and Fe, among others), and strong thermal isolation in building bricks, thus thermal conductiv-
Ca, as part of the original calcite (Fig. 9). The addition of OPBA ity is highly influenced by porosity and bulk density (Carty and
changed clay porosity. Clay-waste micrographs showed some tiny Senapati, 1998; García-Ten et al., 2010; Gualtieri et al., 2010;
sphere known as cenospheres, perfectly round smooth and intact. Rhee, 1975; Shakir et al., 2013; Sutcu and Akkurt, 2009). Pores
High amounts of OPBA, 20 wt% or more, produced the formation incorporate convection to the brick heat transfer and thermal trans-
of lots of open porosity, as well as, larger macropores and small mittance of the pieces is therefore reduced (Gon et al., 2013).
particles that become isolated and nearly spherical, characteristic Fig. 11a shows thermal conductivity versus percentage of OPBA
of the viscous flow sintering mechanism. The joint of pores and residue added up to 20 wt%. Values ranged from 0.99 W/mK, for
their size increase in samples with high waste content indicated bricks without additive, to 0.82 W/mK, when 20 wt% of OPBA was
the beginning of a coalescence process. Together with the semi- added. The addition of 10 wt% of OPBA resulted in bricks with a
spherical big pores, additional tiny pores sized below 2–6 lm are thermal conductivity value of 0.85 W/mK. Therefore, this repre-
observed. The formation of these pores might be related to the sented 14.1% and 17.2% improvement in the thermal conductivity
crystallization carried out during sintering. As indicated by water when 10 and 20 wt% of OPBA is incorporated to the clay, respec-
absorption analysis, SEM results confirmed the formation of a high tively. Therefore, as bottom ash is substituted by clay, thermal con-
porosity structure, which is responsible for the obvious decrease in ductivity decreases since it is associated with a progressive
compressive strength. Adding low amounts of OPBA (10 wt%) decrease in bulk density. Low density samples tend to have higher
changed clay microstructure to a lesser extent, showing a high proportions of air volume filling the voids that act as useful insula-
level of open porosity, essentially interconnected in agreement tors, decreasing thermal conductivity of the entire solid matrix.
with the water absorption, and closed porosity in a similar propor- Pores, created by the combustion of OPBA during brick firing, pro-
tion to that of pure clay. EDAX microanalysis showed a homoge- vide this insulating quality. Fig. 11b shows thermal conductivity
neous distribution of ash in clay, locating areas where the same (in terms of Lnk) versus bulk density of fired clay bricks. The rela-
elements were present though in different proportions. tion between these two parameters has been described elsewhere
Compressive strength is the most critical index for building (Wallace and Criss, 1986). In fact, considering the data, there seems
materials. According to RL-88, the general specification for the to be a correlation between both factors R2 = 0.88, though other
reception of ceramic in construction (RL-88, 2004), compressive factors as mineralogical composition, bricks microstructure in
strength of fired bricks must be at least 9.8 MPa. Compressive terms of kind of porosity (open or closed porosity) and pore size,
are important factors governing thermal conductivity (García-Ten
et al., 2010; Gualtieri et al., 2010; Dondi et al., 2004).
The environmental study carried out on the conformed bricks
12 containing 0, 10 and 20 wt% of OPBA has been studied to assess
14 the degree of metal immobilization achieved in brick manufactur-
10 ing processes. TCLP leaching tests (USEPA, TCLP leaching test,
12
1992) were applied to pulverized brick samples. Leachate concen-
trations have been compared with the US Environmental Protec-
Closed Porosity (%)

8 10
Open Porosity (%)

tion Agency (USEPA) limits (Table 4). In general, as shown by the

8 present results, fired clay bricks with OPBA (10 and 20 wt%) met
6
the USEPA regulatory TCLP limits and Spanish legislation on haz-
6
ardous waste disposal (Ministerio de Agricultura, Alimentación y
4
Open Porosity 4 Medio Ambiente, 2013). According to these results, these fired clay
Closed Porosity bricks can be classified as acceptable at landfills for inert and non-
2 2 hazardous waste. Since the leaching test indicated a degree of
immobilization of heavy metals, incorporating OPBA into ceramic
0 0
products is an efficient inertization method. Therefore, no serious
0 10 20 30 40 50
environmental problems are expected for the use of bricks devel-
OPBA waste content (wt %)
oped in this study, at least not from the point of view of heavy
Fig. 8. (a) Open porosity and closed porosity (vol.%) of the fired bricks at as a metals.
function of OPBA addition (0–50 wt%) of the clay.
330 D. Eliche-Quesada, J. Leite-Costa / Waste Management 48 (2016) 323–333

C
3μm
2

2
1

μm
10μ C-10OPBA

1
3 2

1 2

Fig. 9. SEM micrographs and EDAX analysis of bricks without residues added; with 10, 20 and 50 wt% of OPBA.
 D. Eliche-Quesada, J. Leite-Costa / Waste Management 48 (2016) 323–333 331

C-20OPBA

10μm

1 2

30μm C-50OPBA

1 2

Fig. 9 (continued)

4. Conclusions materials and decreasing pollution. OPBA is the main residue from
olive pomace incineration plants. Based on the experimental
This study has demonstrated a feasible way for using olive results obtained in this study, the following conclusions can be
pomace bottom ash (up to 20 wt%) as a clay substitute to produce underlined:
good quality bricks, becoming an effective measure for saving raw
332 D. Eliche-Quesada, J. Leite-Costa / Waste Management 48 (2016) 323–333

50 Table 4
USEPA TCLP test results (ppm) and the maximum concentration of contaminants for
45 toxicity characteristics.

40 Component (ppm) Sample USEPA regulated

Compressive strength (MPa)

TCLP limits (ppm)

35 C C-10OPBA C-20OPBA
As 0.025 0.0007 0.0025 5
30
Ba 0.230 0.364 0.247 100
25 Cd 0.001 0.0008 0.0010 1
Co 0.050 0.060 0.029 –
20 Cr 0.259 0.057 0.060 5
Cu 0.022 0.009 0.017 5
15 Ni 0.139 0.142 0.066 –
Pb 0.266 4.534 0.2889 5
10 Sb 0.0014 0.0009 0.0006 –
Se 0.0046 0.0049 0.0003 1
5 Sn 0.0003 0.0002 0.0002 –
V 0.013 0.038 0.109 –
0
Hg 0.00009 0.00005 0.00007 0.2
0 10 20 30 40 50
Zn 0.561 265.99 24.13 300
OPBA waste content (wt%)

Fig. 10. Compressive strength of the fired bricks as function of waste addition.

(2) The maximum amount of OPBA to be added is limited to

1 20 wt%, higher proportions of waste (30–50 wt%) resulted
a in bricks with very high water absorption values and low
compressive strength that do not fall within the limits for
standards of conventional bricks.
Thermal conductivity (W/mK)

0.9 (3) Test results indicated that bulk density decreased by 7–13%
with the addition of 10 and 20 wt% of waste, respectively,
and up to 27% with the addition of 50 wt% of OPBA. The
reduction in compressive strength is more pronounced,
0.8 decreasing by 29% when 10 wt% of waste is added and up
to 70–79% in the case of 20–50 wt% of waste, due to the
increase in water absorption. Water absorption increased
by 13% with the addition of 10 wt% of OPBA and by 40 and
0.7 90% with the addition of older content in ash 20–50 wt%.
(4) OPBA-clay bricks featured a decrease in thermal conductiv-
ity (0.143–0.166 W/mK) when adding 10–20 wt% of OPBA,
if compared to the control brick, due to the increase in
0.6
0 5 10 15 20
porosity.
(5) TCLP leaching concentrations for heavy metals in clay bricks
OPBA waste content (wt%)
and OPBA-clay bricks met the USEPA regulated TCLP and
0
current regulatory thresholds and Spanish legislation on
b hazardous waste disposal.
(6) The optimum amount of OPBA was 10 wt%, confirming a
ln (Thermal conductivity) (W/mK)

good balance between the effect provided by the melting

capacity of waste and the role of OPBA as pore forming
agent. Waste-clay bricks presented optimal technological
-0.1
properties that meet more than the brick quality standards.

y = 0.0008x - 1.4486
R² = 0.8831
Acknowledgments
-0.2
This work has been funded by the Project ‘‘Valorización de dis-
tintos tipos de cenizas para la obtención de nuevos materiales
cerámicos sostenibles” (UJA2014/06/13), Own Plan University of
Jaen, sponsored by Caja Rural of Jaen. The authors thank ‘‘La Loma”
-0.3 Power Biomass Plant located in Villanueva del Arzovispo, Jaen
1400 1500 1600 1700 1800 (Spain) for supplying the waste and the Technical Research Ser-
Bulk density (kg/m3) vices of the UJA for help in determining some properties.

Fig. 11. (a) Thermal conductivity versus the percentage of added OPBA residue up
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