Available online at www.sciencedirect.

com

CERAMICS
INTERNATIONAL

Ceramics International 40 (2014) 1667716687

www.elsevier.com/locate/ceramint

Utilisation of spent ltration earth or spent bleaching earth from the oil
renery industry in clay products
D. Eliche-Quesadaa,b,n, F.A. Corpas-Iglesiasb
a

Department of Chemical, Environmental, and Materials Engineering, Higher Polytechnic School of Jan, University of Jan, Campus Las Lagunillas s/n,
23071 Jan, Spain
b
Department of Chemical, Environmental, and Materials Engineering, Higher Polytechnic School of Linares, University of Jan, 23700 Linares (Jan), Spain
Received 13 July 2014; received in revised form 7 August 2014; accepted 7 August 2014
Available online 15 August 2014

Abstract
In this work, the feasibility of using spent ltration earth (SFE) and spent bleaching earth (SBE), as both pore-forming agent and silica
precursor in bricks was reported. Raw materials, clay, SFE and SBE discarded during ltration and bleaching stages in the rening process of
vegetable oils and fats, were analysed by X-ray diffraction, uorescence and thermal analysis. Samples containing (030 wt%) SFE or SBE waste
were compressed and sintered in air inside an electric furnace (950 1C, for 4 h). The results obtained (ring shrinkage, bulk density, water
absorption, mechanical strength and thermal conductivity) show that adding increasing amounts of SFE or SBE waste produced both positive
effects (weight loss, bulk density and thermal conductivity decreased and porosity increase) and negative ones (increase of water absorption and
mechanical strength decrease). The equilibrium could be reached with the addition of 10 wt% of SFE or SBE waste, reducing the mechanical
strength (10% and 24%, respectively), a bulk density reduction of 6.2% and 9.5%, and a decrease in thermal conductivity of 14.1% and 17.7%,
respectively to the standard one, due to the good balance between the effect of pore forming and the melting effect of waste, which increases nal
vitrication in bricks, as indicated by SEM micrographs. The addition of higher amounts of waste, 20 wt% SFE or SBE, shows a predominant
effect in pore forming, leading to higher water absorption values with compressive strength around 3025 MPa, which fall within the range
specied by brick standards, and thermal conductivity of 0.770.75 W/mK. Therefore, SFE or SBE waste can be used to obtain bricks with
insulating and high mechanical properties using a pore-forming and silica carrier alternative raw material, reducing ceramic raw material
consumption and energy, but also production and landll cost as waste disposal area requirements.
& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Keywords: Spent ltration earth; Spent bleaching earth; Clay ceramics; Recycling; Sustainability

1. Introduction
Rening process is an essential step for the production of
vegetable oils and fats. Filtration earth and bleaching earth are
usually used for rening vegetable oils and the product is
known as spent ltration earth (SFE) and spent bleaching earth
(SBE). SFE and SBE contain 2040 wt% of residual oil,
metallic impurities and other organic compounds [1]. Residual
oil can rapidly oxidise to the point of spontaneous ignition as a
consequence of clay-catalysed auto-oxidation reactions [2].
n

Corresponding author. Tel.: 34 95 3211861; fax: 34 95 3212141.

E-mail address: deliche@ujaen.es (D. Eliche-Quesada).

http://dx.doi.org/10.1016/j.ceramint.2014.08.030
0272-8842/& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Disposal of waste is an important environmental and economic

problem for the oil rening industry. SFE and SBE are a type
of waste material with difcult handling and management,
both by nature and volume generated, due to the current lack
of real alternatives for recovery. For many years, the conventional route for the disposal of these wastes has been direct
landll. However, current changes in environmental legislation
have done this method of disposal unacceptable due to the
potential environmental hazards [3]. The environmental problems related to SFE and SBE disposal could be largely solved
by removing the oil and ltrated or colouring materials
absorbed on the clay. The residual oil can be extracted and
can be used as raw material for the production of biodiesel or

16678

D. Eliche-Quesada, F.A. Corpas-Iglesias / Ceramics International 40 (2014) 1667716687

as concentrate in animal feed applications [4]. At present, a

major effort to nd alternatives to the use of de-oiled clay is
being made, resulting in some very promising solutions. But
even general preparation techniques are not applicable with
sufcient guarantee, product quality and protability. Therefore, the most feasible solution at this time is focused on
collection, segregation and disposal to authorized agents or as
raw material for companies that can serve them in their
activities for example, clay substitute in bricks (building
materials, lled quarries...), and can be reused as an adsorbent
in wastewater treatment [59].
Considering the high volume of processed materials, the ceramic
industry is one of the largest consumers of natural raw materials
and presents manufacture processes especially suitable for waste
valuation [1013]. Clay-based materials show a natural forgiveness
towards the incorporation of a variety of materials, including
potentially hazardous industrial wastes or sub-products. Traditional
clay-based materials are heterogeneous products that can accommodate different wastes or sub-products without modication of its
production process or the nal product properties [1416]. There
are two groups of wastes: organic waste or biomass and inorganic
wastes. Organic wastes release their caloric value during combustion produced in the ring process to manufacture ceramics,
producing a porous microstructure, diminishing their density and
likely, improving their ability for thermal insulation [8,1731]. In
addition, combustion of organic waste arises lower energetic cost
during manufacturing process. Inorganic wastes have a composition similar to ceramic raw materials. Therefore, these wastes can
be incorporated in the matrix of ceramic materials due to the
formation of crystalline phases or to vitrication during the ring
process and, thus, giving rise to inertization of the waste.
Valorization of inorganic waste allows raw material saving and a
decrease in ring temperature, being, therefore, energy-saving.
Consequently, some industrial wastes are not only compatible with
raw ceramic materials but also benecial in the fabrication of
ceramics [3241]. In addition, different initiatives are considering
to increase the energetic efciency of buildings, which is required
to improve the thermal insulation capacity of bricks. Thermal
conductivity can be reduced by adding pore-forming agents, waste
material to the bricks before ring that generated porosity or
reduced bulk density.
The work proposed to obtain sustainable clay bricks by using
spent ltration earth or spent bleaching earth, inorganicorganic
wastes, as alternative raw materials of ceramic bricks. The effect of
the incorporation of different amounts of SFE or SBE waste has
been evaluated by physical, mechanical and thermal properties
determination in red bricks, together with microstructural characterization. Such application would ameliorate the environmental
impact of these waste cover disposal.
2. Experimental
2.1. Materials
Clay was supplied by a clay pit located in Bailen, Jaen (Spain).
It was obtained by mixing three types of raw clay in equal parts:
red, yellow and black clay. The wastes, spent ltration earth

(SFE) and spent bleaching earth (SBE) from the oil rening
industry, were supplied by the company Coosur S.A.Oils from
the South at Vilches, Jan (Spain).
2.2. Processing method
To obtain uniform particle size, the clay was crushed and
ground to yield a powder with a particle size suitable to pass
through a 150 m sieve. The wastes, SFE or SBE, were added
to the clay in different amounts (030 wt%) and mixed to
obtain good homogenization. To enable comparative results,
ten samples per series were prepared for testing. The wastes
have enough oil amount to obtain adequate plasticity and
absence of defects, mainly cracks, during the semi-dry
compression moulding stage under 54.5 MPa pressure, using
a uniaxial laboratory-type pressing Mega KCK-30A. Wastefree mixtures were also made as a reference. Solid bricks with
30  10 mm cross sections and a length of 60 mm were
obtained. Samples were red in a laboratory furnace at a rate
of 3 1C/min up to 950 1C for 4 h. Samples were then cooled to
room temperature by natural convection inside the furnace.
The shaped samples were designated as C for the bricks
without waste and C-xSFE for the mixtures with spent
ltration earth and C-xSBE, where x denotes the content (%)
in the clay matrix.
2.3. Techniques of characterization
Qualitative determination of major crystalline phases in clay
and ash waste was achieved using the Philips XPert Pro
automated diffractometer equipped with a Ge (1 1 1) primary
monochromator. Chemical composition was determined by
X-ray uorescence (XRF) using the Philips Magix Pro (PW2440). The thermal behavior was determined by thermogravimetric and differential thermal analysis (TGADTA) with a
Mettler Toledo 851e device in oxygen. Determination of
organic content was performed according to ASTM D-2974,
Standard Test Method for Moisture, Ash, Organic Matter of
Peat and Other Organic Soils [42]. Ignition temperature was
440 1C. The content of carbonates from clay and waste was
determined by calcimetry. The total content of carbon, hydrogen, nitrogen and sulphur was determined by combustion of
samples in O2 atmosphere using the CHNS-O Thermo
Finnigan Elementary Analyzer Flash EA 1112. The higher
heating value (HHV) was determined using a Parr 1341 Plain
Oxygen Bomb Calorimeter.
2.4. Properties of red samples
Linear shrinkage was obtained by measuring the length of
samples before and after the ring stage, using a caliper with a
precision of 7 0.01 mm, according to ASTM standard C326
[43]. Water absorption values were determined from weight
difference between the as-red and water-saturated samples
(immersed in boiling water for 2 h), according to ASTM
standard C373 [44]. Bulk density was determined by the
Archimedes method [44]. Water suction of a brick is the

D. Eliche-Quesada, F.A. Corpas-Iglesias / Ceramics International 40 (2014) 1667716687

volume of water absorbed during a short partial immersion.

The test to determine water suction was implemented according to standard procedure UNE 67-031 [45].
The compressive strength of bricks is their bulk unit charge
against breakage under axial compressive strength. For this
trial, six red samples were studied. Tests on compressive
strength were performed according to standard UNE-EN 772-1
[46] on a Suzpecar CME 200 SDC laboratory press. The area
of both bearing surfaces was measured and the average taken.
All samples were submitted to a progressively increasing
normal strength, with the load applied centered on the upper
surface of the sample until breakage. The compressive strength
of each sample was obtained by dividing the maximum load by
the average surface of both bearing surfaces, expressed in MPa
with 0.1 MPa accuracy.
The development of porosity in samples was also evaluated
by means of a scanning electron microscope (SEM), using the
high-resolution transmission electron microscope JEOL SM
840. The samples were placed on an aluminium grate and
coated with gold using the ion sputtering device JEOL
JFC 1100.
Thermal conductivity of the samples was evaluated with a
C-Therm TCi Analyzer with a universal sensor from Mathis
Instruments Ltd. This equipment uses the modied transient
plane source technique, applying a momentary, constant heat
source produced by a one-sided, interfacial heat reectance
sensor to the sample.
Finally, the leachability of heavy metals in the samples was
studied using the toxicity characteristic leaching procedure
(TCLP) according to EPA method 1311. The concentrations in
the ltrate were measured with an Inductively Coupled PlasmaAtomic Emission Spectrometer (ICP-AES Agilent 7500).
3. Results and discussion
3.1. Characterization of raw materials
The chemical composition of clay, SFE and SBE wastes,
obtained by XRF, is given in Table 1. Before XRF analysis,
samples were red at 950 1C for 4 h. The clay mixture shows
the expected typical composition: rich in silica, alumina and
calcium oxide with a small amount of K2O and MgO (minor
components of Ti and Na oxides), accompanied by a signicant amount of iron oxide (6.49 wt%), a high temperature
uxing agent, which is responsible for dark colour in the red
pieces. The SFE waste contains large amount of silica (64.2 wt
%), manganese oxide (16.7 wt%) and alumina (8.27 wt%) and
lower amount of Fe2O3 (2.6 wt%), calcium oxide (1.2 wt%) as
well as low amount of uxes such as alkaline oxides, Na2O
and K2O. The SBE waste contains mainly silica (82.2 wt%)
with lower amounts of alumina (2.8 wt%), sodium oxide
(2.5 wt%) and ferric oxide (2.2 wt%). Minority elements are
in very low proportion, some heavy metal oxides, such as
Cr2O3 (0.02 wt%) in SFE and SBE wastes. SBE waste also
contains PbO (0.02 wt%). Thus, leaching tests should be
performed to identify the environmental impacts of red
bricks, especially by adding SFE or SBE waste.

16679

Table 1
Chemical composition of the clay ash, spent ltration earth (SFE) ash and
spent bleaching earth (SBE) ash.
Oxide content (%)

Clay

SFE ash

SBE ash

SiO2
Al2O3
Fe2O3
CaO
MgO
MnO
Na2O
K2O
TiO2
P2O5
SO3
Cr2O3
NiO
CuO
ZnO
Ga2O3
Rb2O
SrO
ZrO2
Nb2O5
BaO
PbO
Cl
V2O5
LOI

47.17
12.51
6.49
13.52
2.11
0.05
0.31
3.61
0.78
0.14
1.58

0.0086
0.0017
0.0082
0.0027
0.017
0.043
0.035
0.0021
0.047
0.07

10.6

64.18
8.27
2.58
1.15
16.62
0.04
0.43
1.06
0.26
0.43
0.15
0.016
0.003
0.002
0.005

0.006
0.009
0.022

0.022

82.16
2.84
2.19
0.63
0.25
0.03
2.47
0.29
0.54
0.34
0.06
0.018
0.009
0.001
0.004

0.001
0.01
0.009

0.015
0.17

53.5

27.0

Fig. 1 shows X-ray diffraction patterns of raw materials,

which agree with the results obtained by XRF. The XRD
pattern of red clay (Fig. 1a) shows quartz as main component,
lower amounts of various silicates such as albite, microcline
and gehlenite. Calcite and possible iron oxide-hydroxides and
hematite are also present. The XRD pattern of red SFE waste
(Fig. 1b) only reveals the presence of quartz, aluminosilicate:
anorthite sodian, and the magnesium silicate (enstatite), as
crystalline phases. Fired SBE waste contains mainly cristobalite low together with anorthite, dolomite and muscovite, in
lower proportion.
The elemental analysis of raw materials (Table 2) indicated
relative large amounts of carbon and hydrogen in wastes, and
minor sulphur content, as compared with the clay. SBE
contains higher amount of carbon and hydrogen content and
it does not contain sulphur. It is associated to carbonates and
mainly organic matter present in samples. Then, the weight
loss of SFE (27.00 wt%) and SBE (53.5 wt%) can be due to
decomposition of oil contamination, organic matter (21.2 wt%
for SFE and 54.4 wt% for SBE) and calcite.
The incorporation of these wastes with high carbonaceous
content might provide a sensible energetic contribution to the
ceramic process. The HHW for SFE and SBE wastes is
6117 kJ/kg and 17,824 kcal/kg, respectively (Table 2). Brick
manufacturing usually includes some materials with variable
organic matter content like olive pomace or coke [47]. For
example, in the case of olive pomace, with an average higher
heating value of 18,000 kJ/kg, the addition of 1% by weight to
the clay body represents 180 kJ/kg, equivalent to 6.018% of

16680

D. Eliche-Quesada, F.A. Corpas-Iglesias / Ceramics International 40 (2014) 1667716687

the heating requirements depending on the building product

[48]. In the case of SFE or SBE the addition of 1 wt% by
weight to the clay body represents 61 kJ/kg or 178 kJ/kg,
respectively, equivalent to 2.06.1% or 6.018% of the heating
requirements, which can be saved when these wastes are used
for brick manufacturing.
Thermal behavior of clay and waste was studied by TGA
DTA with maximum temperature of 1000 1C (Fig. 2). The
most signicant weight loss processes associated to brick
manufacturing from typical clays were physically-adsorbed
or free water, water elimination by dehydroxilation of clay
minerals and carbonate decomposition. Weight loss of free
water mainly occurred at temperatures below 100 1C, although
the process is extended up to 200 1C in the clay sample
(Fig. 2a). An endothermic DTA effect is observed in the range

Q: quartz
Mi: microcline
A: anorthite
C: calcite
H: hematit e
G: gehlenite

Intensity (a.u.)

Mi

10

(a)
Mi A

20

C Q
Mi

30

Q
H

A Mi

40

50

60

70

2 theta ()

C: cristobalite low
Q: quartz
E: enstatite
A: anorthite
D: dolomite
M: muscovite
C
A C DC

C C DC

(c)

Q
A

Q
AE

E
+
A

Q
Q

(b)

Fig. 1. XRD patterns of (a) clay; (b) spent ltration earth (SFE) ash and (c)
spent bleaching earth (SBE) ash used as raw materials in the preparation of
bricks.

Fig. 2. TGADTA analysis of (a) raw clay; (b) spent ltration earth (SFE) and
(c) spent bleaching earth (SBE).

Table 2
Organic matter content, CNHS analysis and higher heating value (HHV) of raw materials.
Sample

Organic matter contenta(%)

%C

%H

%N

%S

HHV (kJ/kg)

Clay
SFE
SBE

3.5070.37
21.270.11
51.470.18

2.3070.004
13.9570.02
35.0870.50

0.5070.004
3.0470.02
6.0670.08

0.0570.0
0.0770.001
0.0370.00

0.0370.008
0.001870.007
0

6,117
17,824

Determined according ASTM D-2974.

D. Eliche-Quesada, F.A. Corpas-Iglesias / Ceramics International 40 (2014) 1667716687

from room temperature up to 200 1C, and the weight loss

associated to this process is 1.4 wt%. There are other thermal
events within the range 200600 1C, with weight loss of
2.3 wt%, associated to the combustion of organic matter and
dehydroxilation of the silicate layer identied in this sample
(Fig. 1a). However, a broad exothermic effect is observed by
DTA with a shoulder. A small endothermic DTA peak is
detected at ca. 565 1C, being associated to the transformation
to quartz. Calcium carbonate (calcite) decomposition took
place in the range 600800 1CC with the release of CO2,
associated with an endothermic DTA effect, centered at 750 1C
in the clay sample, with weight loss of 7.8 wt%. Since bricks
were red at 950 1C, decomposition of carbonates is expected
and a development in porosity of the red samples.
TGADTA curve of spent ltration earth (SFE) (Fig. 2b)
showed that after the moisture is volatilized, which is
accompanied by an endothermic DTA effect centered at
100 1C, the organic matter content started to leave the material,
as indicated the two exothermic peaks centered at 375 and
450 1C. The volatile compounds or oil burned rst (rst strong
peak), followed by non-volatile components (second light
peak). The endothermic DTA effect at ca. 820 1C could be
due to the decomposition of calcite. The SFE at ca. 840 1C
there was not weight loss. The TGADTA curve of SBE
(Fig. 2c) showed that thermal decomposition of this waste
revealed a multistage process; that was; weight loss rates
displayed three stages. Weight loss of sample between 25
260 1C, exothermic peak centered at 335 1C, may be mostly
due to the evaporation processes, which are associated with the
evolution of volatile products or oil from SBE sample. On the
other hand, weight loss between 260 and 580 1C, the occurrence of the second and third peaks at temperatures of 380 and
500 1C could be attributed to the decomposition and burning
of organic content. Waste completely combusted at 540 1C.
3.2. Technologycal properties of waste-clay mixtures
Experimental tests have been carried out with mixtures of
SFE or SBE in different proportions (030 wt%) and clay in
order to study their technological properties. First of all, no
defects as cracks and bloating were observed after ring the
waste-clay mixtures at 950 1C. No signicant colour differences were either observed between the red clay as reference
and the compositions containing SFE or SBE waste. Despite
their high content of organic matter, adding SFE or SBE does
not give rise to the appearance of black core and other
structural alterations (Fig. 3). The black core, also called core
reduction, is a dark discoloration that appears on the inside of
the part due to combustion insufcient, causing swelling,
discoloration of parts and even loss of mechanical strength.
The appearance of black core is due to the presence of organic
matter in the raw material, together with a locally reduction
ring The heating of raw materials, in the absence of oxygen,
will do that in the combustion of organic matter, instead of
producing carbon dioxide (CO2), origin of carbon monoxide
(CO), which in the presence of ferric oxide (Fe2O3), will
produce ferrous oxide (FeO) of dark gray.

16681

C - 5SBE

C - 10SBE

C - 15SBE

C - 20SBE

C - 5SFE

C - 10SFE

C - 15SFE

C - 20SFE

C - 25SBE

C - 25SFE

C - 30SBE

C - 30SFE

Fig. 3. Spent ltration earth (SFE) and spent bleaching earth (SBE) bricks.

Table 3 showed linear shrinkage of samples after ring at

950 1C. Clay bricks showed a linear shrinkage of 0.10% to the
ring temperature. Sintering mechanisms encourage greater proximity among particles, causing shrinkage. The addition of lower
quantities of SFE (20 wt%) or SBE (15 wt%) produced slight
expansion in the samples resulting in a typical behavior of porous
bodies. This can be due to the high content of quartz in clay and
waste, as well, as, to the increase in the porosity due to the high
content of organic matter in the organic wastes. Quartz is inert at
950 1C and reduces the contraction of the ceramic body. However,
incorporating more than 20 wt% of SFE or 15 wt% of SBE residue
produced contraction. The amount of liquid phase generated during
the ring process determines the degree of contraction of bricks,
while the degree of expansion is caused by the amount of gases
caused by decomposition of gaseous components that expand the
pores [49].
Loss of ignition (LoI) of the brick mixtures, after ring is related
to the dehydroxilation reactions, loss of humidity and carbonates
decomposition in clay minerals and the combustion of organic
matter present in clay and, mainly, in wastes (Table 3). Standard
bricks (clay-bricks) had a LoI of 10.99%. The addition of SFE or

D. Eliche-Quesada, F.A. Corpas-Iglesias / Ceramics International 40 (2014) 1667716687

35

1800

Table 3
Technological properties of construction bricks made from clay, spent ltration
earth and spent bleaching earth from oil rening industry.

C
C5SFE
C10SFE
C15SFE
C20SFE
C25SFE
C30SFE
C5SBE
C10SBE
C15SBE
C20SBE
C25SBE
C30SBE

Loss on
ignition (%)

Suction water
(kg/m2/min)

0
5

0.1070.08
 0.1770.02

10.9970.15
11.5770.03

2.3870.21
2.4770.20

10

 0.2570.03

12.3670.10

2.7670.70

15

 0.3070.06

12.8670.15

2.8670.05

20

 0.3370.07

13.4170.12

3.3170.16

1700

Bulk density (kg/m3)

Sample Waste content

Linear
(wt%)
shrinkage (%)

SFE
SBE

1600

25

1500

20
WA
15

1400

10

1300
0

25

0.1470.07

14.4070.12

3.6770.13

30

0.1670.10

15.1270.11

3.5270.08

 0.6370.09

12.3570.23

2.6970.27

10

 0.4170.12

14.0170.12

2.9170.14

15

 0.2070.13

15.4870.34

3.4770.06

20

0.2870.10

18.4770.06

3.7570.15

25

0.4770.14

19.9270.48

4.0970.18

30

0.8970.14

22.9170.94

4.1970.08

SBE showed higher values of LoI. The higher the percentage of

SFE or SBE was, the more LoI values increased. The increasing
organic content of SBE waste (Table 2) produced an increase in
mass loss.
Water absorption and bulk density as a function of residue
content are shown in Fig. 4. Bulk density of red clay was
1760 kg/m3. The addition of SFE (530 wt%) produced a decrease
of ca. 15.3% in bulk density (1488 kg/m3), whereas the addition of
SBE (530 wt%) produced a greater decrease of 23.7% in this
property (1341 kg/cm3), as expected, due to the higher organic
matter content in SBE waste. Therefore, the incorporation of SBE
produced a higher increase in total porosity. Total porosity of the
red samples is the addition of open and closed pores.
Water absorption is a key factor affecting the brick durability
and a measure to open porosity. Incorporating waste produced an
increase in water absorption of clay (16.29%). In fact, the increases
in waste content, SFE or SBE engender an increasing release of
CO2 and, consequently, an intensication of open porosity. By
incorporating SBE, the highest values of water absorption were
reached, with this parameter increasing up to 29.8% when 30 wt%
of SBE waste was added. The results obtained using SFE waste
showed that this residue provoked lower values in water absorption. The incorporation of up to 30 wt% of SFE produced an
increase in water absorption obtaining values of about 22.5%.
Therefore, the waste addition and content waste increases open
porosity of ceramic bodies, being this increase more pronounced
when SBE waste is incorporated. The organic matter in SFE and
SBE wastes was transformed during the thermal process, leading to

30

BD

Water absorption (%)

16682

10

15

20

25

30

Waste content (wt%)

Fig. 4. Bulk density and water absorption of the red bricks as a function of
SFE o SBE addition (030 wt%) to the clay.

an increase in open porosity of ceramic bodies [50]. Such behavior

reects the effect of the porosity formed in the clay-material is
greater than the effect provided by the melting effect of glass,
which increased in lower proportion the nal vitrication in the
clay-material.
Results of water suction tests (Table 3) showed the same trend
compared to water absorption data. Water suction of clay was
2.38 kg/m2/min and increased with the addition of SFE or SBE
waste. Water suction increased from 2.47 kg/m2/min when 5 wt%
of SFE was incorporated, reaching a peak value of 3.52 kg/m2/min
in samples with 30 wt% of SFE. The addition of SBE wastes
produced a higher increase in this parameter, ranging from 2.69
kg/m2/min when 5 wt% of SBE is incorporated to 4.19 kg/m2/min
when 30 wt% of SBE was added. Therefore, the incorporation of
SFE or SBE to the clay produced an increase in the interconnected
surface porosity, which is related to the property of water suction in
red bricks. However, all samples meet the UNE, which states that
water suction values should stay lower than 4.5 kg/m2/min.
3.3. Microstructure of the red samples
The microstructure of samples containing clay and SFE or
SBE red at 950 1C for 4 h have been studied by SEM on
fracture surfaces. Fig. 5 illustrated the general features of the
microstructures.
It can be observed by SEM (Fig. 5a) that clay porosity is due
mainly to open porosity, which is formed by ne, interconnected,
irregularly-shaped pores and a lower proportion of small-sized
and closed pores. At 950 1C, the amount of liquid phase and its
viscosity are not sufcient to efciently close open porosity.
Adding low amounts of SFE or SBE (5 or 10 wt%) hardly
modied clay porosity. It can see a higher proportion of porosity
in the samples, with a higher proportion of pores closed spherical
and elongated. Therefore, the addition of lower proportion of
wastes produced a higher amount of glassy phase, and capillary
pressure tends to approach the particles due to the surface tension
in the liquid phase, resulting in more closed porosity with isolated
spherical pores. A balance between forming pores effect and
melting capacity of wastes can be observed. However, the

D. Eliche-Quesada, F.A. Corpas-Iglesias / Ceramics International 40 (2014) 1667716687

Fig. 5. SEM micrographs of bricks without residues added; with 5, 10, 20 and 30 wt% of SFE and 5, 10, 20 wt% of SBE.

16683

D. Eliche-Quesada, F.A. Corpas-Iglesias / Ceramics International 40 (2014) 1667716687

3.4. Thermal conductivity

The reduction in thermal conductivity of bricks is encouraging
for higher energy saving potential in building applications. One of
the most effective ways for lowering thermal conductivity of
traditional ceramics is achieved by raising their porosity, for which
different combustible organic pore former are typically used
[51,52]. Bulk density is a major factor that governs thermal
conductivity of solids in general. Samples with low bulk density
tend to present a higher percentage of air volume lling the voids
that act as a useful insulator and decreasing the thermal conductivity of the entire solid matrix. The decrease in bulk density in
turn leads to an increase in the total porosity of samples, decreasing
their thermal conductivity. The variation of thermal conductivity as
a function of bulk density is plotted in Fig. 6a. It can be observed
that, in the range of tested densities, there is a linear relationship
between both factors (R2 0.92 and 0.97 for SFE and SBE,
respectively). Therefore, when bulk density of pieces increases, the
thermal conductivity increases also. This relationship has been
described in numerous studies and is attributed to the insulating
effect of pores in the pieces [17,51,5355]. Therefore, all thermal
conductivity values obtained with samples containing SFE or SBE
waste are lower than those in the control sample of 100 wt% clay
(0.990 W/mK) (Fig. 6b). The reduction in thermal conductivity
with the addition of 5 wt% of SFE was 4.9% while the
incorporation of 20 wt% of SFE reduced this property up to
22.2%. However, the addition of SBE waste lowered thermal
conductivity by 7.3% with the addition of 5 wt% SBE waste and
increased it up to 24.5% when 20 wt% of this waste was added.
Samples containing SEB waste had lower bulk density and higher
water absorption values than SFE samples. Also, SEB samples
have a higher content of amorphous phase (Fig. 5) that reduced
thermal conductivity. Certain studies [56] indicate that, in materials
with the same chemical composition, those with crystalline phases
exhibit higher thermal conductivity than those containing amorphous or glassy phases. Therefore, although bulk density is the
determining factor in thermal conductivity, other factors impact
thermal conductivity in a less extent, as the mineralogical
composition or the microstructure of the bricks [55,57,58].
3.5. Compressive strength results
A key aim of the ceramic industry is to improve thermal
insulation of ceramic products without impairing their mechanical properties. One of the disadvantages resulting from the use
of lightening additives, which increase porosity when organic

SBE
SFE
Thermal conductivity (W/mK)

incorporation of higher amount of SFE or SBE (20 wt% or 30 wt

%) produced a considerable increase in open porosity as indicated
by water absorption data, due to the predominance of the pore
formation and lower effect of the melting effect of the wastes,
which do not increase the nal vitrication in clays. The
morphology is less compact, with a lower denser and worsedeveloped structure. The incorporation of higher amounts of SFE
or SBE waste increased open porosity as a result of macropore
connection (Fig. 5) and produced larger pores due to the burning
of oil, organic matter and calcite.

0.9
y = 0.0008x - 0.4601
R = 0.971

y = 0.0009x - 0.6286
R = 0.913

0.8

0.7
1400

1500

1600

1700

1800

Bulk density (kg/m3)

1.2

SFE
1
Thermal conductivity (W/mK)

16684

SBE

0.8
0.6
0.4
0.2
0

10

20

Waste content (wt%)

Fig. 6. (a) Relationship between thermal conductivity and bulk density of the
red bricks; (b) effect of waste concentration on thermal conductivity of the
red bricks.

additives burn out during the ring stage, is the impairment

of the mechanical properties of bricks that have structural roles
in buildings. The impact of SFE or SBE additions in the
compressive strength of the red samples depends on the waste
amount (Fig. 7a). Compressive strength values decreased with
the addition of SFE or SBE waste. It can be observed that the
addition of 5 wt% of SFE or SBE wastes is not just a decrease
in compressive strength. This strengthening may be related to
the presence of optimum amounts of vitreous phase and closed
porosity, which is higher in samples with low waste content as
indicated SEM micrographs. The addition of 20 wt% of SFE or
SBE decreased the compressive strength a 37.9% and 46.9%,
respectively, obtaining values of 29.8 MPa and 25.5 MPa
respectively. The minimum value was obtained for the highest
content in SFE or SBE, 30 wt%. In samples with high waste
content, an increase in open porosity, since angular pores and
ssuring at pore edges can concentrate pressures, caused a

Compressive strength (MPa)

D. Eliche-Quesada, F.A. Corpas-Iglesias / Ceramics International 40 (2014) 1667716687

60

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

50

Component (ppm)

Sample

USEPA regulated
TCLP limits (ppm)

SFE
40

SBE

30
20
10
0

10
15
20
Waste content (wt%)

25

30

60

Compressive strength (MPa)

16685

50

SFE
SBE

y = 0,0877x - 102,21
R = 0,965

40
30
y = 0.0997x - 125.16
R = 0.967

20
10

0
1300

1400

1500

1600

1700

1800

Bulk density (kg/m3)

Fig. 7. (a) Compressive strength of the red bricks as function of waste
addition; (b) relationship between compressive strength and bulk density of the
red bricks.

decrease in the mechanical resistance of red bricks. The

addition of SBE waste produced a higher decrease in compressive strength, since these samples have lower bulk density
(more total porosity) and higher water absorption (more open
porosity) than those in which SFE waste was incorporated.
Fig. 7b shows the variation of mechanical strength with bulk
density, where linear dependences were obtained for SFE and
SBE ring probes. When bulk density of the red pieces
decreased (by adding SFE or SBE waste), their mechanical
strength is also observed to have dropped, owing to higher
porosity and bigger average pore size (Fig. 5).
3.6. Leaching test
To identify the environmental impact of red bricks,
leaching tests on crushed samples were performed, with
concentrations of heavy metals (As, Cd, Cr, Cu, Hg, Ni, Pb
and Zn) in the leachates presented in Table 4. In general, as
can be seen by the present results, red clay bricks with SFE
(20 wt%) or SBE (20 wt%) indicated that concentrations of

As
Ba
Cd
Co
Cr
Cu
Ni
Pb
Sb
Se
Sn
V
Hg
Zn

C-20SFE

C-20SBE

0.025
0.014
0.011
0.230
0.100
0.114
0.001
0.002
0.005
0.050
0.0234
0.029
0.259
0.001
0.037
0.022
0.002
0.008
0.139
0.480
0.288
2.665
0.008
0.005
0.0014
0.0006
0.014
0.0046
0.0020
0.0032
0.0003
0.0014
0.0018
0.013
0.073
0.088
0.00009
0.00005 0.00005
0.561
181.14
48.59

5
100
1

5
5

0.2
300

heavy metals are far below the thresholds prescribed by the

USEPA regulating TCLP limits and Spanish legislation on
hazardous waste disposal [59]. They would be classied as
acceptable at landlls for inert and non-hazardous waste.
Therefore, lixiviation tests indicated a degree of immobilization of heavy metals, suggesting that the incorporation of SFE
or SBE into ceramic products is an efcient inertization
method. Hence, no environmental problems due to heavy
metals disposal can be expected from the use of SFE-clay or
SBE-clay red bricks.
4. Conclusions
The results of this research show that spent ltration earth
and spent bleaching earth can be used as pore forming since,
due to their organic substances content, during combustion;
they bring an energetic support in the ring brick step,
conrmed by higher heating values.
This work proposes sustainable solutions using wastes and
natural clay as raw materials for producing an environmentalfriendly ceramic with lower thermal conductivity.
Technological properties indicated that using SFE or SBE
waste in a percentage of 10 wt% into a brick formulation
showed good results: bulk density, mechanical strength and
thermal conductivity decrease and total porosity and water
absorption increase, with respect to the pure clay brick. SFE
waste showed better results than SBE waste. These results
conrm the balance between the role of wastes as pore forming
agents and the effect provided by the melting capacity of waste
as silica source. Lower amount of waste produced bricks with
higher closed porosity and mayor content of glassy phase, well
visible on representative SEM micrographs.
High mechanical strength (3025 MPa) are obtained with
the addition of 20 wt% of SFE or SBE waste, respectively,
with values that fall within the range required by the specic
standards for bricks, however high water absorption values are

16686

D. Eliche-Quesada, F.A. Corpas-Iglesias / Ceramics International 40 (2014) 1667716687

obtained (21.125.5%) as a result of macropores connection

and prevalence of the effect of forming pores.
The recycling of these industrial wastes can be economical
and technological attractive due to reduction of costs related to
low prices of the raw materials industrial wastes; reducing
waste disposal costs; the reduction open quarry extraction of
natural construction materials and energy savings during the
ring process.
Acknowledgements
The authors thank South OilsCoosur, S.A. of Vilches
(Jan, Spain) for the supply of SFE and SBE and the Technical
Research Services of the University of Jan (UJA) for help in
some determination of properties of samples. The nancial
support of Junta de Andaluca to Research Group TEP-222 is
acknowledged.
References
[1] B. Peng-Lim, G. Shangeetha, M. Gaanty Pragas., M.H.A. Dafaalla,
Ultasound aided in situ transestercation of crude palm oil adsorbed on
spent bleaching clay, Energy Convers. Manage. 52 (2011) 20812084.
[2] C. Svensson, Use or disposal of by products and spent material from the
vegetable oil processing industry in Europe, J. Am. Oil Chem. Soc. 53
(1976) 443445.
[3] J.T.L. Ong, Oil recovery from spent bleaching earth and disposal of the
extracted material, J. Am. Oil Chem. Soc. 60 (1983) 314315.
[4] W.T. Tsai, Y.M. Chen, C.W. Lai, C.C. Lo, Adsorption of ethyl violet dye
in aqueous solution by regenerated spent bleaching earth, J. Colloid
Interface Sci. 289 (2005) 333338.
[5] V. Mymrine, M.J.J.S. Ponte, H.A. Ponte, N.M.S. Kaminari,
U. Pawlowsky, G.J.P. Solyon, Oily diatomite and galvanic wastes as
raw materials for red ceramics fabrication, Constr. Build. Mater. 41
(2013) 360364.
[6] M.J. Ribeiro, D.U. Tulyaganov, J.M. Ferreira, J.A. Labrinca, Recycling
of Al-rich industrial sludge in refractory ceramic pressed bodies, Ceram.
Int 28 (2002) 319329.
[7] R.J. Galn-Arboledas, A. Merino, S. Bueno, Use of new raw materials
and industrial wastes to improve the possibilities of using materials form
Bailn (Jan, sourthern Spain), Mater. Constr 63 (2013) 553568.
[8] D. Eliche-Quesada, S. Martnez-Martnez, L. Prez-Villarejo, F.
J. Iglesias-Godino, C. Martnez-Garca, F.A. Corpas-Iglesias, Valorization of biodiesel production residues in making porous clay brick, Fuel
Process. Technol. 103 (2012) 166173.
[9] D. Eliche-Quesada, F.J. Iglesias-Godino, L. Prez-Villarejo, F.A. CorpasIglesias, Recycling of differents spent earth from ltration in the
production of ceramic materials, in: C. Jeremy Cullery (Ed.), Recycling
Technological Systems, Management Practices and Environmental
Impact, Nova Science Publishers Inc, New York, 2013, pp. 177192.
[10] J. Sorvary, By-products in earth constructionenvironmental assessments,
J. Envion. Eng 29 (2003) 3746.
[11] M.C. Shinzato, R. Hypoloto, Solid waste from aluminium recycling
products: characterization and reuse of its economically valuable constituents, Waste Manage. 25 (2005) 3746.
[12] A.M. Segades, Use of phase diagrams to guide ceramic production from
wastes, Adv. Appl. Ceram. 105 (2006) 4654.
[13] W. Lee, A.R. Boccaccini, J.A. Labrincha, C. Leoneli, C.H. Drumond III,
C.R. Cheeseman, Green engineering: ceramic technology and sustainable
development, Am. Ceram. Soc. Bull 86 (2007) 1825.
[14] M. Dondi, M. Masigli, B. Fabbri, Recycling of industrial and urban
wastes in brick production: a review (Part 1), Tile Brick. Int. 13 (1997)
218225.

[15] M. Dondi, M. Masigli, B. Fabbri, Recycling of industrial and urban

wastes in brick production: a review (Part 2), Tile Brick. Int. 13 (1997)
302309.
[16] R. Caligaris, N. Quaranta, M. Caligaris, E. Benavidez, Non traditional
raw material in ceramic industry, Bol. Soc. Esp. Ceram. Vidr. 39 (2000)
623626 (in Spanish).
[17] I. Demir, Effect of organic residues addition on the technological
properties of clay bricks, Waste Manage. 28 (2008) 622627.
[18] D. Eliche-Quesada, F.A. Corpas-Iglesias, L. Prez-Villarejo, F.I. IglesiasGodino, Recycling of sawdust, spent earth from oil ltration, compost
and marble residues for brick manufacturing, Constr. Build. Mater. 34
(2012) 275284.
[19] S.N. Monteiro, C.M.F. Vieira, M.M. Ribeiro, F.A.N. Silva, Red ceramic
industrial product incorporated with oily wastes, Constr. Build. Mater. 21
(2007) 20072011.
[20] B.C.A. Pinheiro, J.N.F. Holanda, Processing of red ceramics incorporated
with encapsulated petroleum waste, J. Mater. Process. Technol. 209
(2009) 56065610.
[21] M. Hajjaji, A. Khalfaoui, Oil shale amended raw clay: ring transformations and ceramic properties, Constr. Build. Mater. 23 (2009) 959966.
[22] S. Maschio, E. Furlani, G. Tonello, N. Faraone, E. Aneggi, D. Minichelli,
Fast ring of tiles containing paper mill sludge, glass cullet and clay,
Waste Manage. 29 (2009) 28802885.
[23] Y. Qi, Q. Yue, S. Han, M. Yue, B. Gao, H. Yu, Preparation and
mechanism of ultra-lightweight ceramics produced from sewage sludge,
J. Hazard. Mater. 176 (2010) 7684.
[24] D. Eliche-Quesada, C. Martnez-Garca, M.L. Martnez-Cartas, M.
T. Cotes-Palomilo, L. Prez-Villarejo, N. Cruz-Prez, The use of different
forms of waste in the manufacture of ceramic bricks, Appl. Clay Sci. 52
(2011) 270276.
[25] S.R. Teixeira, G.T.A. Santos, A.E. Souza, P. Alesio, A.S. Souza, N.
R. Souza, The effects of incorporation of a Brazilian water treatment plant
sludge on the properties of ceramic materials, Appl. Clay Sci. 53 (2011)
561565.
[26] M. Devant, J.A. Cusid, C. Soriano, Custom formulation of red ceramics
with clay, sewage sludge and forest waste, Appl. Clay Sci. 53 (2011)
669675.
[27] E. Furlani, G. Tonello, S. Maschio, E. Aneggi, D. Minichelli,
S. Brucknera, E. Lucchini, Sintering and characterization of ceramics
containing paper sludge, glass cullet and different types of clayey
materials, Ceram. Int. 37 (2011) 12931299.
[28] J.A. Cusid, L.V. Cremades, Environmental effect of using clay bricks
produced with sewage sludge: leachability and toxicity studies, Waste
Manage. 32 (2012) 12021208.
[29] J.A. De la Casa, I. Romero, J. Jimnez, E. Castro, Fired clay masonry
units production incorporating two-phase olive mill waste (alperujo),
Ceram. Int. 38 (2012) 50275037.
[30] M.D. La Rubia-Garca, A. Yebra-Rodriguez, D. Eliche-Quesada, F.
A. Corpas-Iglesias, A. Lpez-Galindo, Assessment of olive mill solid
residue (pomace) as an additive in lightweight brick production, Const.
Build. Mater 36 (2012) 495500.
[31] L. Barbieri, F. Andreola, I. Lancellotti, R. Taurino, Management of
agricultural biomass wastes: preliminary study on characterization and
valorization in clay matrix bricks, Waste Manage. 33 (2013)
2307 (-2015).
[32] W. Acchar, E.G. Ramalho, Y.A. Fonseca, D. Hotza, A.M. Segades,
Using granite rejects to aid densication and improve mechanical
properties of alumnina bodies, J. Mater. Sci 40 (2005) 39053909.
[33] A.M. Segades, M.A. Carvalho, W. Acchar, Using marble and granite
reject to enhance the processing of clay products, Appl. Clay Sci. 30
(2005) 4252.
[34] H.F. El-Maghraby, M.M. El-Omla, F. Bondioli, S.M. Naga, Granite as
ux in stoneware tile manufacturing, J. Eur. Ceram. Soc 31 (2011)
20572063.
[35] S.N. Monteiro, L.A.P. Fonseca Jr., C.M.F. Vieira, Reformulation of
roong tile body with granite waste from sawing operation, J. Eu. Ceram.
Soc. 24 (2004) 23492356.

D. Eliche-Quesada, F.A. Corpas-Iglesias / Ceramics International 40 (2014) 1667716687

[36] Y. Pontikes, L. Espsito, A. Tucci, G.N. Angelopoulos, Thermal
behavior of clays for traditional ceramics with soda-lime-silica waste
glass admixture, J. Eu. Ceram. Soc. 27 (2007) 16571663.
[37] D.G. Pinatti, R.A. Conte, M.C. Borlini, B.C. Santos, I. Oliveira, C.M.
F. Vieira, S.N. Monteiro, Incorporation of the ash from cellulignin into
vitried ceramic tile, J. Eu. Ceram. Soc. 26 (2006) 305310.
[38] M. Aineto, A. Acosta, I. Iglesias, The role of coal gasication y ash as a
clay additive in building ceramic, J. Eu. Ceram. Soc. 26 (2006)
37833787.
[39] M. Dondi, G. Ercolani, G. Guarani, M. Raimondo, Orimulsion y ash in
clay bricks. Part 1: Composition and thermal behavior of ash, J. Eu.
Ceram. Soc. 22 (2002) 17291735.
[40] M. Dondi, G. Guarani, Raimondo, I. Venturi, Orimulsion y ash in clay
bricks. Part 2: Technological behavior of clay/ash mixtures, J. Eu. Ceram.
Soc. 22 (2002) 17371747.
[41] M. Dondi, G. Guarani, M. Raimondo, A. Rufni, Orimulsion y ash in
clay bricks. Part 3: Chemical stability of ash-bearing products, J. Eu.
Ceram. Soc. 22 (2002) 17491758.
[42] ASTM D-2974, Standard Test Method for Moisture, Ash, and Organic
Matter of Peat and Other Organic Soils, 1987.
[43] ASTM, 1997. ASTM C326test method for drying and ring shrinkage
of Ceramic Whiteware Clays. American Society for Testing and
Materials.
[44] ASTM, 1994a. ASTM C373Test Method for Water Absorption, Bulk
Density, Apparent Porosity, and Apparent Specic Gravity of Fired
Whiteware Products. American Society for Testing and Materials.
[45] UNE 67031: 1986, Burned Clay Bricks. Suction Test.
[46] UNE EN 772-1: 2002, Methods of Test for Masonry UnitsPart 1:
Determination of Compressive Strength.
[47] J.A. de la Casa, M. Loriteb, J. Jimnez, E. Castro, Valorisation of
wastewater from two-phase olive oil extraction in red clay brick
production, J. Hazard. Mater. 169 (2009) 271278.
[48] O. Rentz, A. Schmittinger, R. Jochum, F. Schultmann. Exemplary
Investigation into the State of Practical Realisation of Integrated
Environmental Protection Within the Ceramics Industry Under

[49]

[50]
[51]

[52]

[53]
[54]
[55]

[56]
[57]

[58]

[59]

16687

Observance of the IPPC-directive and the Development of BAT

Reference Documents, Research Project 298 94 313/07, Environmental
Research Plan of the Federal Minister for the Environment, Nature
Conservation and Safety, French-German Institute for Environmental
Research University of Karlsruhe 2001; 4452.
H. He, Q. Yue, Y. Su, B. Gao, Y. Gao, J. Wang, H. Yu, Preparation and
mechanism of the sintered bricks produced from Yellow River silt and
red mud, J. Hazard. Mater. 203-204 (2012) 5361.
C.H. Weng, D.F. Lin, P.C. Chiang, Utilization of sludge as brick
materials, Adv. Environ. Res. 7 (2003) 679685.
M. Sutcu, S. Akkurt, The use of recycled paper processing residues in
making porous bricks with reduced thermal conductivity, Ceram. Int 35
(2009) 26252631.
M. Sutcu, J.J. del Coz Daz, F.A. lvarez Rabanal, O. Gencel, S. Akkurt,
Thermal performance optimization of hollow clay bricks made up of
paper waste, Energy Build. 75 (2014) 96108.
M. Dondi, F. Mazzanti, P. Principi, M. Raimondo, G. Zanarini, Thermal
conductivity of clay bricks, J. Mater. Civ. Eng 16 (2004) 814.
R.W. Wallace, G.H. Criss, Thermal conductivity of castable refractories
in relation to bulk density, Am. Ceram. Soc. Bull 47 (1986) 176179.
J. Garca-Ten, M.J. Orts, A. Saburit, G. Silva, Thermal conductivity of
traditional ceramics. Part I: Inuence of bulk density and ring
temperature, Ceram. Int. 36 (2010) 19511959.
T.Z. Harmathy, Thermal properties of concrete at elevated temperatures,
J. Mater 5 (1970) 4774.
J. Garca-Ten, M.J. Orts, A. Saburit, G. Silva, Thermal conductivity of
traditional ceramics. Part II. Inuence of mineralogical composition,
Ceram. Int. 36 (2010) 20172024.
M.L. Gualtieri, A.F. Gualtieri, S. Gagliardi, P. Rufni, R. Ferrari,
M. Hanuskova, Thermal conductivity of red clays: effects of mineralogical and physical properties of the raw materials, Appl. Clay Sci. 49
(2010) 269275.
Ministerio de Agricultura, Alimentacin y Medio Ambiente, Orden AAA/6
61/2013 sobre eliminacin de residuos en vertederos. MAM, BOE no. 97 2
3/4/2013. Spain. http://www.boe.es/diario_boe/txt.php?id=BOE-A-2013-429.