Fuel 90 (2011) 220232

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Fuel
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Application of biomass gasication y ash for brick manufacturing

C. Fernndez-Pereira a,, J.A. de la Casa b, A. Gmez-Barea a, F. Arroyo a, C. Leiva a, Y. Luna a
a
b

Chemical and Environmental Engineering Department, Escuela Superior de Ingenieros, University of Seville, Camino de los Descubrimientos s/n, E-41092 Seville, Spain
Cermica MALPESA, S.A. Ctra. N-IV Km. 303, 23710 Bailn, Jan, Spain

a r t i c l e

i n f o

Article history:
Received 18 January 2010
Received in revised form 29 July 2010
Accepted 30 July 2010
Available online 13 August 2010
Keywords:
Bricks
Fly ash
Gasication
Biomass
Olive oil mill residues

a b s t r a c t
Biomass gasication technology offers an attractive way to use low-grade fuels in energy production with
high efciency and low environmental impact. However, an issue calling for further development is the
volume and quality of y ash, since biomass gasication y ash contains more un-reacted carbon compounds than y ash from direct combustion of similar fuels. This restricts direct gasication ash utilisation for many applications and makes some pre-treatment necessary, representing a signicant share of
the overall operating cost of gasication-based systems for energy production. Therefore, economical
methods for the management of this type of ash without any pre-treatment are attractive.
In this paper, we present an initial study on the manufacture of bricks made of gasication ash. Our
goal was to come up with a product which satises two basic requirements: (a) it has elevated percentages of y ash; and (b) it enables utilisation of ash without any pre-treatment. We have manufactured
bricks by means of conventional moulding and curing methods, using ash percentages of up to
20 wt.%. No special additives were added to provide the bricks with acceptable mechanical and/or insulating properties. The y ash used was generated in a uidised bed pilot plant for processing olive mill
cake, a by-product of the olive oil industry produced in large quantities in several EU countries.
Some mechanical and environmental properties of ash gasication bricks were studied and compared
with typical values for commercial bricks. The results lead us to conclude that the bricks could be used
commercially as low density clay masonry units with a good thermal insulating capacity and, therefore,
the potential for commercial development is promising. In addition, the environmental benet of waste
gasication added to the ash utilisation makes the overall process more attractive.
2010 Elsevier Ltd. All rights reserved.

1. Introduction
Atmospheric air gasication of biomass in a bubbling uidisedbed reactor is an attractive and simple process to convert a solid
material to a gaseous fuel [1]. This process leads to a fuel gas suitable for co-ring in existing boilers and, if a proper gas cleaning
section is installed, for feeding efcient gas engines and gas turbines for generating electricity. Apart from the energy value and
the quality of the produced gas, one of the key factors limiting gasication is related to y ash quality, especially the carbon content
of the ash.
In practice, the uses developed for combustion ashes cannot be
directly transferred to gasication ashes. For instance, the utilisation in the cement and concrete industry without pre-treatment
is not possible for most gasication ashes and the need for pretreatment has a direct impact on the nal cost of the overall process. Consequently, lessening the cost of the biomass and waste
gasication by developing sustainable and economical methods
for ash utilisation and management is an urgent need.
Corresponding author. Tel.: +34 954487271; fax: +34 9554461775.
E-mail address: pereira@esi.us.es (C. Fernndez-Pereira).
0016-2361/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2010.07.057

In many developing countries, due to the increasing cost of raw

materials and the reduction of natural resources, the use of secondary materials is a potential alternative in the construction industry.
Waste materials, such as slag and ash, when properly processed,
have shown themselves to be effective as construction materials
and readily meet design specications [26]. Studies on utilisation
routes for y ash from biomass gasication process are, however,
very limited [7,8].
Clay bricks are usually manufactured from clay, sand and small
amount of suitable organic material like sawdust that burns off at
the sintering process and gives to the bricks the desired porosity.
Often some inert material, such as crushed and milled recycled
bricks or coal ash, is also added to the mix to control the properties
of the nished product.
In the brick making industry, there has also been research into
how to reuse different waste products in order to manufacture better quality bricks. However, y ash has rarely been applied to
bricks [9]. In our research we use ash as a potentially suitable organic material and also as inert material. Carbon containing ash,
such as olive mill cake (also called in Spanish orujillo) gasication ashes, would bring inert material to the brick mass and
produce porosity at the sintering phase. The high carbon ash

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C. Fernndez-Pereira et al. / Fuel 90 (2011) 220232

produced in the orujillo gasication is expected to behave like organic material in the sintering leaving small cavities in the brick
matrix. Also there are some advantages using y ash as raw material of bricks such as ring energy can be saved because of the
amounts of carbon contained in y ash [10].
This article aims to increase knowledge about the direct utilisation of y ash from biomass gasication in uidised beds. In particular, it deals with a preliminary study on the use of biomass ash as
a component of bricks with potential thermal and sound insulating
properties. The ashes were generated in a 150 kWth bubbling uidised bed pilot plant that processed orujillo [11]. Approximately
2 Mt/year of this agroindustrial waste is generated in Spain.
Though references can be found in the literature indicating that
coal gasication ashes may be used in the manufacture of bricks
[12,13], to the best of our knowledge this work describes in detail
the application of biomass gasication ash for brick manufacturing
for the rst time.
2. Materials and methods
2.1. Pilot plant description
The biomass gasication ashes used for the present study were
generated at a pilot plant located at the Engineering School of the
University of Seville. Pilot plant gasication tests were carried out
at atmospheric pressure and temperatures of 700820 C in order
to assess the technical viability of gasifying orujillo. Experiments
were carried out in an experimental rig described in detail in a previously published article [12]. Therefore, only a brief description is
given here. Fig. 1 presents a schematic diagram of the pilot plant.
The gasication reactor is a bubbling uidised bed gasier designed to process up to 30 kg/h of solid biomass. It consists of a
4.2 m height refractory stainless steel reactor tted with a perfo-

rated distributor plate. The ash is purged from the bottom of the
gasier. Different air ow rates and air/biomass ratios were used
giving an equivalent ratio (ER) within the range of 0.170.31. A series of parameters, such as gasication efciency, thermal efciency, gas yield, overall carbon conversion, gas quality and
composition were measured vs. ER. General results and conclusions with regard to these technical parameters were fully discussed [13,14] and correlations between operating conditions
and ash quality are given in a previous work [15].
Apart from the hydrodynamic role of the bed material in uidised bed processes, there is also a major impact caused by the
physico-chemical bed material properties of the resulting y ash
[16]. The bed material used in the pilot plant tests was ote, a
subvolcanic rock with a mineralogical formula (Ca
Mg
Fe
Ti
Al)2

(Si
Al)2O6. The ote used had an average particle size of 380 lm
and an apparent particle density of 2620 kg/m3. Approximately
12 kg of bed material was used during each test.
The gas leaving the freeboard section passes through two cyclones in series to collect entrained particles and, through a wet
scrubbing system, to remove the condensable tars. Solid material
is collected in bins placed under the cyclones.
2.2. Materials
The main characteristics of the solid materials used in the gasication tests are shown in Tables 1 and 2. In particular, Table 1
shows the main chemical characterization of the bed material ote
and ash whereas Table 2 reports the ash size-distribution. Potassium content of the ash is very high, and the high amount of unburned matter content is also noteworthy (Table 1). The HHV of
the gasication y ash can be used to determine whether or not
the y ash ring can contribute to the heat requirements during
the fabrication process [18].

Outlet
gas

Gasifier

Chimeney

Filters

Cyclones
Isolation Blanket
Water
Scrubber

Hoppers
Overflow

To Water
Tratement

Flexible

After Burner

Screw feeder
High-speed screw
Preheater

Propane

Ashtray
Fig. 1. Bubbling uidised bed 150 kWth pilot plant facility.

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C. Fernndez-Pereira et al. / Fuel 90 (2011) 220232

Table 1
Chemical compositions of fuel, bed material and ash.

Parameter

Fuel (orujillo) (wt.%)

Parameter

Ote (wt.%)

Fly ash (wt.%)

Clay F_A (wt.%)

Clay F_B (wt.%)

Clay F_C (wt.%)

LHV (MJ/kg)
HHV (MJ/kg)
C
H
N
O
Moisture
Ash
Volatile matter
Fixed carbon

14.09
15.02
36.57
3.71
1.00
27.32
10.82
20.41
53.34
15.44

Moisture (105 C)
LOI (750 C)
CaOa
MgOa
Fe2O3a
Al2O3a
SiO2a
K2Oa
Na2Oa
HHV (MJ/kg)

0.47
0.64
11.15
7.90
9.15
13.61
53.93
0.48
3.49

1.31
18.24
23.23
8.10
5.53
8.53
43.48
6.83
1.51
5.08

2.96
3.97
23.91
1.95
4.06
15.93
50.34
2.80
0.43

3.53
3.37
1.47
1.18
3.26
11.25
77.56
3.55
0.19

2.21
4.68
3.02
2.37
7.91
18.48
60.35
4.60
0.35

Referred to the calcined sample at 750 C.

gasication y ash and ote diffractograms are shown in Figs. 2

and 3. The major mineral phases detected are: mainly quartz, sylvite, calcite, talc and magnesioarfvedsonite in y ash and quartz,
magnesiohornblende and paragonite in ote.
The selected clays: F_A, F_B and F_C, used in the bricks were
provided by Cermica Malpesa, S.A. (Bailn, Spain) and they are
representative of the products in the facing brick manufacturing
company. Their main crystalline phases are quartz, illite and calcite
(type F_A and F_B) and quartz, illite, calcite and hematite (type
F_C) (Figs. 46).
The contents of SiO2 and Al2O3 are lower in gasication y ash
(FA) than those in clays, but the content of MgO and CaO are higher
(except in the case of clay type F_A that has almost the same content than FA). On the other hand, the K2O content is higher in the
gasication y ash than that in clays (Table 1).
More information about the chemical and mineralogical characterization of the clays has been published elsewhere [17].
The comparison among of the mineralogical species of the used
components and the overall composition of common raw materials

Table 2
Ash size-distribution.
Particle size-distribution
(lm)

Ash
(wt.%)

>300
300150
15090
9075
7545
<45

0.6
6.8
9.0
9.3
16.2
58.2

The characterization results are given for average values of the

y ashes, that is, cyclones 1 and 2 for all the tests. A detailed characterization of ashes obtained in the different gasication trials
carried out with orujillo can be found elsewhere [15].
The crystalline phases of the samples were determined by XRD
using a SIEMENS D501 powder diffractometer with a graphite
monochromator, NaI(Tl) detector and Cu Ka radiation. The biomass

600

500

Counts

400

300

200

100

0
4

10

20

30

40

2 Theta
Ref. Ceniza - File: IDAEA15-0241.RAW - Type: 2Th/Th locked - Start: 4.066 - End: 60.0
00-046-1045 (*) - Quartz, syn - SiO2
00-041-1476 (*) - Sylvite, syn - KCl
00-023-0495 (N) - Magnesioarfvedsonite - (Na,K)3(Fe,Mg,Al)5Si8O22(F,OH)2
00-041-1487 (I) - Graphite-2H - C
00-019-0770 (I) - Talc-2M - Mg3Si4O10(OH)2

00-005-0586 (*) - Calcite, syn - CaCO3

Fig. 2. XRD diagram of y ash.

50

60

C. Fernndez-Pereira et al. / Fuel 90 (2011) 220232

223

Fig. 3. XRD diagram of ote.

Fig. 4. XRD diagram of clay F_A.

used for ceramic products [17] reveals that these materials contains the appropriate species to be considered as potentially suit-

able for structural ceramic products. The raw materials contain

high amounts of silica and alumina, mainly due to the illite, kaolin-

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C. Fernndez-Pereira et al. / Fuel 90 (2011) 220232

Fig. 5. XRD diagram of clay F_B.

Fig. 6. XRD diagram of clay F_C.

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C. Fernndez-Pereira et al. / Fuel 90 (2011) 220232

7 and 8). Samples of 100150 mg for the TG-SDTA measurements

were taken from the surface of the test bricks. A heating rate of
10 C/min was chosen from room temperature up to 1150 C, using
air and nitrogen as purging gases.

ite and pyrophyllite of the clays (Figs. 46). CaO and Fe2O3 are
mainly due to the presence of calcite and hematite in the mixtures.
A thermo-gravimetric study (TG-SDTA Mettler Toledo 851) of
y ash, clays and unred (green) bricks was also carried out (Figs.

100

0,00020

95

Mass loss ofite

Mass loss FA
Mass loss unfired brick
Mass loss clay

90

0,00010

-0,00010
75
-0,00020
70

65

-0,00030

First derivative ofite

First derivative FA
First derivative unfired brick
First derivative clay

60

-0,00040

55

50

200

400

600

800

1000

-0,00050
1200

Temperature (C)
Fig. 7. Mass loss and rst derivative in thermal analyses of ote, gasication y ash (GFA), unred brick and clay.

100

15

90
10
Mass loss FA
Mass loss unfired brick
Mass loss clay

80

70

60

0
50
SDTA FA
SDTA unfired brick
SDTA clay

40

30

-5

-10

20
-15
10

200

400

600

800

Temperature (C)
Fig. 8. SDTA and mass loss of GFA, unred brick and clay.

1000

-20
1200

SDTA (C)

Mass Loss (%)

Mass Loss (%)

80

First derivative (1/s)

0,00000

85

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C. Fernndez-Pereira et al. / Fuel 90 (2011) 220232

1075 C, according to the refractoriness of the composition and

thermal analyses (Fig. 7).
For each composition two ring cycles were employed: one
slow ring cycle and another normal one (Fig. 9). In the normal ring cycle a ring similar to the used in tunnel kilns for facing bricks
was used (from 110 to 400 C at 4 C/min, from 400 to 700 C at
3 C/min, from 700 C to Tmax at 2 C/min, at Tmax for 240 min, from
Tmax to 110 C at 4 C/min). In the slow ring cycle (the cooling
stage is identical and the heating stage is produced in the same
temperature range at a slower heating rate of 1 C less/min: from
110 to 400 C at 3 C/min, from 400 to 700 C at 2 C/min, from
700 C to Tmax at 1 C/min, at Tmax for 240 min, from Tmax to
110 C at 4 C/min) the heating phase is carried out at a slower
pace to permit the total combustion of the carbon contained in
the ash and the possible organic material which the clays could
contain.

The results were analyzed to decide the sintering temperature,

in the range 10001075 C, which is slightly higher than that commonly used for clay bricks (9501000 C) [10]. Orujillo is gasied
at a temperature of 800 C and the y ash is then cooled down in
the air. Therefore, large amounts of Si glassy materials are formed
in y ash that is conrmed by the border diffraction pattern in
Fig. 2. Fly ash loses the hydration and structural water up to
200 C and between 350 C and 500 C suffers the removal of organic matter (the most important mass loss); around 600700 C,
the release of carbon dioxide from carbonates occurs and nally,
over 900 C, the coalescence of particles is produced transforming
powder into solid by sintering (Fig. 7). Since ote is an inert material, the mass loss is very low. During heating of the clay F_B, the
interlayer or absorbed water is lost until 200 C, and an important
mass loss is shown around 800 C. Above 900 C, the clay does not
suffer any signicant transformation (Fig. 7).
Regarding the thermal analysis of the unred brick F_B, the
interlayer or absorbed water is lost at 100250 C (mainly due to
the clay water content), the combustion of the unburned matter
from y ash occurs at 350500 C and the de-hydroxylation (due
to the clay properties) begins at 600900 C. Above 900 C, the
material does not suffer any signicant transformation (Fig. 7).
In Fig. 8 an exothermic peak is shown in the heating of unred
brick between 350 and 575 C due to the combustion of unburned
matter of gasication FA. The information supplied by the thermal
techniques is useful to t the cycle of ring and indicates the range
of temperatures in which the gasication FA HHV is generated and
the amount released, contributing important savings to the heat
requirements of the manufacturing process.
The difference in physico-chemical composition and mineral
phases between y ash and clay would cause the ring parameters
and mechanism and performance of y ashclay bricks to be different from that of clay bricks.

2.4. Bricks characterization

The mechanical quality of the different sintered products was
evaluated by means of the tests for clay compositions extruded
at normal consistency, and destined for clay masonry units type
H (high density) (UNE-EN 771-1 [19]). In Table 3 the measured
parameters and the typical laboratory values usually obtained
are indicated.
The moisture content was determined by drying at 110 C until
constant weight, linear drying and ring shrinkages were measured with an indent marker KROEPLIN S 1636, the mass loss on
ring was determined by weighing; drying and ring exural
strength were evaluated by three-point modulus of rupture using
an universal MECMESIN 2500 N Versatest machine according to

Table 3
Ceramic characterization tests.

2.3. Brick preparation

The clay bricks were produced by extrusion procedures incorporating gasication ash to the ceramic bodies currently being
used in Cermica Malpesa, S.A. Process details have been previously published by the authors [18].
Test probe extrusion casts of approximately 130  30  20 mm
with different ceramic compositions of the previous clays were
prepared. The test probes were dried in a drying chamber until
constant weight and subsequently red in an electric kiln. The
maximum ring temperatures tested were 1000, 1025, 1050 and

Ceramic test

Nomenclature

Typical values
for facing bricks

Units

Water (mixing water)

Moisture content
Drying linear shrinkage
Firing linear shrinkage
Dry bending strength
Fired bending strength
Water absorption
Net density

MW
H
DLS
FLS
DBS
FBS
WA
D

2022

04
05
58
2040
324
16502350

%
%
%
%
N/mm2
N/mm2
%
kg/m3

1100

Temperature (C)

1000
900

N-1075

800

S-1075
N-1025

700

S-1025

600

N-1050

500

S-1050

400

N-1000
S-1000

300
200
100
0

120

240

360

480

600

720

840

960

Time (min)
Fig. 9. Normal (N) and slow (S) ring cycles.

1080

1200

C. Fernndez-Pereira et al. / Fuel 90 (2011) 220232

227

Fig. 10. Biomass gasication of ash bricks.

the machine instructions, water absorption was calculated according to UNE 67027-1987 standard [20] and red bulk density was
determined following UNE-EN 772-13:2001 standard [21]. The
amorphous and crystalline phases were determined by XRD for
the sintered products after being crushed.

2.5. Environmental study

Given that the gasication ash is a waste material, an environmental assessment study has been carried out to evaluate the
leaching of heavy metals for a better characterization of the product. The study involved subjecting the ash to the EN12457-4 [22]
and TCLP (USEPA 1311) [23] leaching tests, as well as CEN/TS
14405 upow percolation column tests [24]. Finally, the bricks
were also subjected to one of the most commonly used leaching
tests for monolith samples in the waste management eld, the
NEN 7345 diffusion test or tank leaching test [25]. Metal analysis
in leachates was carried out using Atomic Absorption Spectrophotometry and Inductively Coupled Plasma techniques (ICP-OES and
ICP-MS). Hg has been measured using an Atomic Fluorescence
Spectrometer (Analytik Jena Mercur).

3. Results and discussion

3.1. Brick preparation
Some mixtures of y ashclays were undertaken. Their nomenclature indicates rst the name of the clay with a number indicating the clay percentage content followed by the name of the ash (in
this work CG) and its percentage (the percentage of ash is the difference to 100) then another number showing the ring temperature used in the brick manufacture.
The optimum substitution level of individual combustion or
gasication residues in clay products will always be limited by
the level at which the addition begins to cause an unacceptable
deterioration in the properties of the host products inasmuch as
it can no longer maintain existing specications or if within specications, the appearance of the product makes it unacceptable to
the commercial market [8].
Different weight percentages of ash were evaluated and nally
the ash content in the clay bodies was 1520% by mass in order to
consume a considerable amount of ash in the clay body, but without exceeding certain limits which could give rise to problems in
the masonry units during the extrusion, drying and ring stages

in the manufacturing process, or defects in the red unit (such as

Black core).
The three compositions (F_A85CG15, F_B80CG20 and
F_C85CG15) were successfully red following the slow and normal
cycles previously described without any defects in the red test
probes. However, in the results section, only the corresponding
tests of ring with the normal cycle are represented, as they allow
for greater industrial production.
Fig. 10 shows various bricks manufactured for testing during
the present research. As can be seen, the red test probes do not
present defects.

3.2. Brick characteristics

As concerns the mineralogical composition of the red bodies
determined by XRD (Figs. 1113), the red mineralogical assemblage consists mostly of quartz, diopside, anorthite, leucite and a
vitreous phase (bricks type A and B) and quartz, hematite, albite
and iron (brick type C).
Table 4 shows the main results of the ceramic tests carried out
with three compositions and two temperatures. The more signicant effects of the ash addition were:
(a) A notable increase in mixing water necessary for the extrusion compared to similar compositions without ashes.
(b) Moderate drying linear shrinkage.
(c) High reduction of the ceramic body strength (dry bending
strength). The DBS of the F_A mixture is high enough for
the bricks to be manipulated for the usual furnace carrying
systems, for which a minimum strength of 4.0 N/mm2 is
required [18].
(d) A considerable increase in the water absorption (WA) coupled with a higher porosity with respect to similar compositions without ashes. WA values in the cases of the bricks
made with clays type F_A and F_B are higher than the usual
values, but in case of the brick with clay type F_C WA is
inside the typical range, and it coincides with the values
published elsewhere for bricks made from different residues
[18].
(e) A substantial decrease in the net density of the ceramic
bodies compared to similar compositions without ashes.
(f) An appreciable decrease in the dry and red bending
strengths of the probes.
(g) FLS increases with the temperature in all the cases, as often
occurs [18].

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C. Fernndez-Pereira et al. / Fuel 90 (2011) 220232

Fig. 11. XRD diagram of brick type F_A.

Fig. 12. XRD diagram of brick type F_B.

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C. Fernndez-Pereira et al. / Fuel 90 (2011) 220232

Fig. 13. XRD diagram of brick type F_C.

Table 4
Extrusion, drying and ring results.
Ceramic composition

F_A85CG15
F_A85CG15
F_B80CG20
F_B80CG20
F_C85CG15
F_C85CG15

Firing temperature (C)

1050
1075
1050
1075
1000
1025

Ceramic test
WM (%)

H (%)

DLSH?0 (%)

FLS (%)

DBS (N/mm2)

FBS (N/mm2)

WA (%)

D (kg/m3)

35.7
35.7
36.4
36.4
27.3
27.3

21.7
n.d.
31.2
32.1
18.9
19.2

0.2
0.3
1.3
1.7
0.4
0.3

2.0
2.6
1.2
1.9
2.3
2.5

4.4
4.4
2.9
2.9
2.6
2.6

11.5
11.4
4.6
4.3
10.5
10.3

32.1
29.8
37.1
35.6
13.4
12.6

1340
1370
1280
1290
1680
1710

(h) FBS are lower in those mixtures in which a great amount of

ash is used, giving values approximately constant at different temperatures. The measured values are lower than typical values for facing bricks, probably due to a higher
porosity of the bodies.
(i) No black core defect was observed for any samples. Additives, such as plastic clays, are sometimes used in brick manufacturing to enhance plasticity or to increase strength. The
presence of organic matter in clays can cause a ring defect
known as black core if the organic carbon is not completely
burned during ring. Factors favouring black core occurrence are a high organic matter and the vitrication of the
brick, which can hinder combustion of the organic matter
[18].
Of all the aforementioned effects, the most important are the
decreases in dry bending strength and red bending strength.
Bending strength is an important factor for any construction material. The tested compositions are not suitable for the manufacture
of a product that complies with the market specications for facing
bricks. However, the decrease in strength observed varies according to the composition of the clay tested. Therefore, bearing in

mind the possibility of employing other clays in the compositions

whose effect on the strength increases when dry and red is
known, it can be deduced that it is possible to correct the negative
effect of the ashes on the mechanical resistance. This study also
shows that the red bending strength was slightly affected by
the sintering temperature in the range studied, decreasing when
the temperature increases.
Other important effect derived from the use of the ashes is the
increase in water absorption and the parallel density decrease, due
to a higher porosity. Water absorption is an effective index in evaluating the quality and densication of building bricks and it is
based on the amount of open pores in sintered specimens, so the
high water absorption indicated that the sintered specimens had
a large number of open pores, mainly due to the pore-forming
property of the ashes tested. The water absorption also has repercussions for the compressive strength and density of the sintered
specimen. The water absorption of sintered specimens decreases
slightly with rising sintering temperatures (Table 3) due to the
open porosity of sintered specimens which decreased with increasing sintering temperatures. This effect can be useful if what is intended is to produce a light material, but contraindicated if a
dense material is desired. The lower the density of the material,

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C. Fernndez-Pereira et al. / Fuel 90 (2011) 220232

types of product, such as tiles, facing bricks, paving blocks, etc.,

the technical characteristics of the probes are not suitable unless
different compositions of clays are used, which are usually too
expensive for these products. Fig. 14 shows a photo of one of the
F_A85 CG15 samples before and after ring.
3.3. Environmental study

Fig. 14. F_A85CG15 brick samples before and after ring.

the lower the thermal conductivity will be, which is why in principle, a light material offers better insulation properties in
construction.
Other effects of the ash addition are the increase in mixing
water for extrusion and the probable high suction derived from
the elevated porosity of the red probes, although this was not
measured. The mixing water requires high water consumption in
the moulding stage and heat during the drying process. The high
suction can create problems in the positioning of the unit being
used if a suitable mortar is not used.
The colour of the red probes, yellowish in F_A and F_B formulas and reddish in the F_C formula, is similar to that visible in formulas without ashes, although somewhat clearer. The ashes
calcined at 1000 C exhibit a light yellow colour. The appearance
of whitish yellow drier scum in composition F_C85CG15
(Fig. 10) is noteworthy. This scum can be seen clearly against the
red colour of the probes. The other two compositions (the yellow
ones) do not reveal the scum or it is not visible to the naked eye.
The composition which presents the best technical characteristics is F_A85CG15 (F_A is the most calcareous clay composition of
the three compositions tested). According to these characteristics,
the type of product that can be produced is a red clay unit L
(low density) UNE-EN 771-1 [18], as long as it improves the
mechanical resistance in green, dried and red units. For other
Table 5
Concentrations of metals in the ash column test leachates (CEN/TS 14405 test), with
and without insulation categories limit values for column test leachate concentrations according to the DSQ, and concentration limit of metals in EULFD for NHW and
IW (all measurements are expressed in mg/kg).
Element

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

CEN/TS 14405
test
Orujillo
gasication ash

DSQ

EULFD

Without
insulation

With
insulation

NHW
limits

IW
limits

0.49
6.05
<0.05
0.28
<0.05
1.61
<0.01
0.81
1.34
<0.49
<0.10
<0.49
<0.49
0.10
3.52

0.90
22.0
0.04
0.54
0.63
0.90
0.02
1.00
0.44
2.30
0.16
0.15
0.40
1.80
4.50

2.00
100
0.06
2.40
7.00
10.0
0.08
15.0
2.10
8.30
0.70
3.00
2.30
20.0
14.0

2.00
100
1.00

0.50
20.0
0.04

10.0
50.0
0.20
10.0
10.0
10.0
0.70
0.50

0.50
2.00
0.01
0.50
0.40
0.50
0.06
0.10

50.0

4.00

Given the scarcity of standards existing in Spain regarding the

reuse of secondary materials in the construction sector, the Dutch
regulations stated in the Dutch Building Materials Decree (DBMD)
[26] have been considered. The DBMD and its successor the Decree
on Soil Quality (DSQ) [27] contains rules related to the use of stony
building materials in construction and other works. The aim of the
DBMD and DSQ is to prevent pollution of the soil and surface
water. Both decrees prescribe a standardized column leaching test
for granular building materials (NEN 7343) [28], and a tank leaching test (NEN 7345) [25], for bound or shaped materials.
Table 5 shows the gures for the concentrations of different
metals analyzed in the ash column test leachates obtained using
the CEN/TS 14405 test [24], a leaching test similar to the NEN
7343 [29]. In general, the concentrations of the metals are in all
cases at the part per billion levels (ultratraces). A comparison is
made with the limits stated in the DSQ for with and without insulation categories. With insulation limits are not exceeded for any
metal. Without insulation limits are exceeded for Cu and Ni, with
some detection problems for Cd, Hg, Se and Sn.
The EU waste landll directive (EULFD, 2003/33/EC) [29], in
which the three following waste categories are dened: inert
(IW), non-hazardous (NHW) and hazardous wastes (HW), also
examines the possibility of deciding between the three types of
waste on the basis of compliance with the concentration limits of
certain contaminants in the column test CEN/TS 14405 leachates.
In Table 5, the metal concentration limits in EULFD for NHW and
IW are collected. The ash leaching meets the limits of NHW for
all elements.
As previously mentioned, since the bricks studied are used as
monoliths, it seems reasonable to attend to the leaching of the conformed product. Thus, Table 6 shows the results of the leachability
study carried out according to the NEN 7345 diffusion test [25],
that is, the concentrations of some metals in the NEN 7345 leachates of the bricks accumulated at 64 days. As shown in Table 6,
practically all the heavy metals analyzed are under detection limits, except for Ba, Mo and V in some samples. Therefore, no serious
environmental problems are expected for the unrestricted use of
the bricks developed in this study according to DSQ, at least from
the point of view of heavy metals. Besides the DSQ limits, the
NEN 7345 leachate concentrations measured have also been compared with the stricter limits stated in the Landll UK regulations
for HW. As can be seen, all the elements analyzed meet the limits
except Mo (and only in some cases) (Table 6). Molybdenum, as is
well known, is an element frequently present in anionic forms
which are very soluble in water. This high water solubility supposes many problems to meet a low leachate limit according to different environmental regulations.
In addition to the environmental study carried out on the conformed products (bricks) a more unfavorable case has been studied
to evaluate the degree of metal immobilization achieved by the
brick manufacturing process. Therefore, EN12457-4 [24] and TCLP
[23] leaching tests have also been applied to pulverized brick samples. The EN12457-4 results are presented in Table 7. The leachate
concentrations measured (Table 7) have been compared with the
limits stated in EULFD [29] for granular waste acceptable at landlls for inert and non-hazardous waste. As can be seen, the bricks,
although in some cases the IW limits are met (which indicates a
certain degree of immobilization in the metals studied), in others

231

C. Fernndez-Pereira et al. / Fuel 90 (2011) 220232

Table 6
NEN 7345 accumulated leaching test results after 64 days (mg/m2). Limit values for column test leachate concentrations according to the DSQ and UK regulations.
Component

Accumulated results after 64 days

F_A85CG15

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

F_B80CG20

DSQ limits

HW UK limits

260
1500
3.80
60
120
98
1.40
144
81
400
8.70
4.80
50
320
800

20
150
1

F_C85CG15

1050

1075

1050

1075

1000

1025

<11.7
5.78
<0.25
<1.17
<1.17
<7.04
<0.03
14.61
<2.35
<11.7
<2.35
<0.47
<11.7
30.3
<4.64

<11.7
6.40
<0.23
<1.17
<1.17
<7.04
<0.03
33.4
<2.35
<11.7
<2.35
<0.47
<11.7
<36.6
<3.70

<11.8
6.06
<0.24
<1.18
<3.41
<7.06
<0.01
<10.6
<2.35
<11.8
<2.35
<0.47
<11.8
102
<11.8

<11.8
7.56
<0.24
<1.18
<8.06
<7.06
<0.01
14.4
<2.35
<11.8
<2.35
<0.47
<11.8
127
<0.68

<11.0
3.48
<0.22
<1.10
<2.93
<6.58
<0.01
23.8
<2.19
<10.3
<2.19
<0.44
<11.0
239.1
<0.58

<11.0
2.14
<0.22
<1.10
<1.10
<6.58
<0.01
<21.6
<2.19
<10.3
<2.19
<0.44
<11.0
203
<0.85

25
60
0.40
20
15
20
2.50
5

100

Table 7
EN12457-4 leaching test results (mg/kg). Limit values for the leachate concentrations apply for granular waste acceptable at landlls for inert and non-hazardous waste according
to the EU waste landll directive.
Sample

As

Sb

Ni

Zn

Hg

Mo

Se

Cu

Co

Sn

Ba

Cd

Cr

Pb

F_C85CG15-1025
F_C85CG15-1000
F_B80CG20-1075
IW limits
NHW limits

0.31
<0.05
<0.05
0.5
2.0

<0.015
<0.015
<0.015
0.06
0.7

<0.05
0.37
0.14
0.4
10

0.33
5.23
0.84
4.0
50

<0.001
<0.001
<0.001
0.01
0.2

6.58
10.74
4.9

2.06
1.43
0.25
0.5
10

<0.025
<0.025
<0.025
0.1
0.5

<0.015
0.83
0.42
2
50

0.07
0.22
0.11

<0.01
<0.01
<0.01

0.59
12.38
5.74
20
100

<0.01
<0.01
<0.01
0.04
1

0.52
0.38
0.2
0.5
10

<0.015
<0.015
<0.015
0.5
10

Table 8
USEPA TCLP leaching test results (mg/L) and the maximum concentration of contaminants for toxicity characteristic.
Sample

As

Zn

Hg

Se

Cu

Ba

Cd

Cr

Pb

F_C85CG15-1025
F_C85CG15-1000
F_B80CG20-1075
USEPA

0.1
0.036
0.77
5

0.053
0.016
0.011
300

60.0001
60.0001
60.0001
0.2

60.0025
60.0025
60.0025
1

60.0015
60.0015
60.0015
5

0.283
0.051
0.077
100

60.001
60.001
60.001
0.5

0.017
0.023
0.016
5

60.0015
60.0015
60.0015
5

there is a problem with Mo, a particularly soluble and difcult to

stabilise element as was already mentioned. Anyway, in all the
cases the bricks meet the NHW limits.
Table 8 contains information concerning TCLP leaching of some
brick samples. As can be seen, there are no problems in meeting
the USEPA limits.
4. Conclusions
This work demonstrates that y ash from uidised bed gasication of biomass can be used in the manufacture of clay bricks since
bricks without defects have been manufactured by adding up to
20 wt.% y ash to clay mixtures.
The mineralogical species and the chemical composition of the
used mixtures revealed that this material contains the appropriated species to be considered as potentially suitable for structural
ceramic products.
Although further research is needed, preliminary conclusions allow us to be quite optimistic. The results obtained to date have
shown that the three clay bodies tested are very close to (but slightly
under) the requirements for facing bricks, i.e. high density clay masonry units. A possible solution to this problem is the optimisation of
the type of clay (although this measure could possibly lead to higher
costs in the process) and/or the addition of a lower proportion of ash.

These two measures are under current investigation. In addition, low

density clay masonry units, according to UNE-EN 771-1 [19], with a
high thermal insulating capacity, can probably be manufactured
with orujillo ashes, provided that the ceramic body strength is
slightly improved or the proportion of ash is lowered.
The ring cycle of these kinds of FA-clay brick should arise temperatures higher than 900 C to assure the complete transformation of materials. Two industrial ring cycles were employed and
the red test probes did not present defects.
The addition of such amount of y ash changed some properties
of nal bricks, being the most important: a decrease in dry bending
strength, in red bending strength and in density; and an increase
in water absorption due to a large number of open pores. The drying linear shrinkage and the ring linear shrinkage were also
acceptable, despite having such high water content. Other properties, such as appearance are normal.
Regarding the environmental study, no serious environmental
problems are expected for the unrestricted use of the bricks developed in this study according to DSQ [28].
In summary, the results here obtained are quite satisfactory for
this utilisation option, although further study is needed. Furthermore, the use of olive mill cake (orujillo) gasication ash in this
application provides attractive ways to valorise a difcult y ash
yielding relatively high-quality products.

232

C. Fernndez-Pereira et al. / Fuel 90 (2011) 220232

Acknowledgements
The authors acknowledge the nancial support for this research
by the European Commission under the EU 5th framework programme, project number NNE5-2001-00598. The cooperation of
Cermica Malpesa (Bailn, Spain) in the characterization work with
bricks is greatly appreciated.

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