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Clay Activation and Color Modification in Reducing Calcination Process:

Development in Lab and Industrial Scale

Article  in  RILEM Bookseries · January 2015

DOI: 10.1007/978-94-017-9939-3_59

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 1st International Conference on Calcined Clays for Sustainable Concrete
June 23rd-25th 2015
Lausanne, Switzerland

CLAY ACTIVATION AND COLOR MODIFICATION IN REDUCING

CALCINATION PROCESS: DEVELOPMENT IN LAB AND
INDUSTRIAL SCALE
Abstract ID Number: 81
Calcined clays have been used in pozzolanic portland cement manufacturing in Brazil for
many years. However, their color imposes commercial limitation when cements show reddish
or pinkish hues.
This work presents two case studies consisting of reducing process calcination of two clays
by reducing process in: electric static furnace to obtain maximum temperature (700-1000ºC)
and burning time (5-20min) conditions, as a function of color and pozzolanic reactivity, and;
rotary kiln for both laboratorial and industrial scales.
Chemical (XRF, TGA/DTA), mineralogical (XRD), physical-mechanical (compressive
strength), pozzolanic reactivity (Chapelle´s method and Strength Activity Index) and color test
(colorimeter spectrometer using CIE color system standard) were applied in clays and
pozzolanic cements characterization. Results show satisfactory performance of grayish
pozzolanic cements, and indicate an alternative process to obtain calcined clays according to
cements specifications.

Keywords: clay pozzolanic color, reducing atmosphere, instrumental analysis, colorimetric

test, laboratory scale test, industrial scale test.

Autor e-mail Tel Postal address

Fabiano F. Chotoli fchotoli@ipt.br (+5511) 37674143
Valdecir Angelo Quarcioni quarciva@ipt.br (+5511) 37674969 (a)
Sérgio S. de Lima sergiolima@ipt.br (+5511) 37674357
Joaquim C. Ferreira joaquim@dynamis-br.com (+5511) 38013761
(b)
Guilherme Martins Ferreira guilherme.ferreira@dynamis-br.com (+5511) 38013761
(a): Instituto de Pesquisas Tecnológicas do Estado de São Paulo - IPT, Av. Prof. Almeida Prado, 532, São Paulo-
SP-Brasil-CEP 05508-010;
(b): Dynamis Mecânica Aplicada, São Paulo, Rua Padre Chico, 85 Cj 11-São Paulo-SP-Brasil – CEP 04747-090.

Contact person for paper: Fabiano F. Chotoli

Presenter of the paper during the Conference: Fabiano F. Chotoli

Number of pages (first pages must be excluded): 6

1st International Conference on Calcined Clays for Sustainable Concrete
June 23rd-25th 2015
Lausanne, Switzerland

CLAY ACTIVATION AND COLOR MODIFICATION IN REDUCING

CALCINATION PROCESS: DEVELOPMENT IN LAB AND
INDUSTRIAL SCALE
Fabiano F. Chotoli (1)*, Valdecir A. Quarcioni (2), Sérgio S. Lima (3), Joaquim C.
Ferreira (4), Guilherme M. Ferreira (5)

(1,2,3) Instituto de Pesquisas Tecnológicas do Estado de São Paulo (IPT) - Laboratório de

Materiais de Construção Civil, São Paulo, Brasil

(4,5) Dynamis Mecânica Aplicada, São Paulo, Brasil

Abstract
Calcined clays have been used in pozzolanic portland cement manufacturing in Brazil for
many years. However, their color imposes commercial limitation when cements show reddish
or pinkish hues.
This work presents two case studies consisting of reducing process calcination of two clays
by reducing process in: electric static furnace to obtain maximum temperature (700-1000ºC)
and burning time (5-20min) conditions, as a function of color and pozzolanic reactivity, and;
rotary kiln for both laboratorial and industrial scales.
Chemical (XRF, TGA/DTA), mineralogical (XRD), physical-mechanical (compressive
strength), pozzolanic reactivity (Chapelle´s method and Strength Activity Index) and color test
(colorimeter spectrometer using CIE color system standard) were applied in clays and
pozzolanic cements characterization. Results show satisfactory performance of grayish
pozzolanic cements, and indicate an alternative process to obtain calcined clays according to
cements specifications.

1. INTRODUCTION
Clay calcination can modify its properties and favor its application as pozzolanic material,
depending on the chemical and mineralogical composition. As example, there are kaolinite
and illite clays that produce metakaolinite and other metastable structures when calcined
between 600°C and 1000°C.
However, the application of reddish and pinkish clays is not well accepted due to non-
conventional Portland cement color. In Brazilian construction materials retail market, reddish

1
Corresponding author: Email fchotoli@ipt.br. Tel +55-11-3767.4143, Fax +55-11-3767.4060.
and pinkish cements are misjudged as low quality cement. Due to this misjudgment, changes
in clay color can be an alternative to allow its application in cement industry.
Color hue variations in clays are a result of inorganic impurities due to changes in
oxidation state of chemical elements as iron, titanium and manganese commonly present in
clay minerals, which can directly affect their color properties [1,2]. Iron impurities researches
in kaolin showed that it can be present as “structural iron” (part of kaolinite structure or
accessory minerals), and “free iron” as oxides, hydroxides, carbonates, sulfides and others.
Researchers [3] described three possible forms of Fe2+ occurrence in clay minerals: structural
iron, complexed iron, as hydroxyl groups, on the surface and associated iron by ionic changes
at siloxane basal surfaces. Iron position within clay mineral structure is very important and
can define reactivity. Other researches [4] associate directly the titanium and iron oxides
content to colorimetric parameters and chromaticity of red, and correlates a* and b* CIE
parameters to free and structural iron content in clay. Thereby, iron in “structural” form
associated to titanium has a more deleterious (reddish) effect in color properties.
To attend the purpose of work, clays were calcined in laboratory, pilot and industrial
scales, under reducing conditions, aiming at both color change from reddish/pinkish to
grayish and increase of pozzolanic reactivity. The clays samples were analyzed in order to
verify color, chemical, mineralogical and physical-mechanical characteristics, according to
technical and normative specifications.

2. EXPERIMENTAL STUDY

2.1. Materials
Two clays, petroleum coke and Ordinary Portland Cements (analogous to Cement I in EN
197-1:2000) were used in this study. Clays were dried in stove at 105°C and after were
grinded in a disks mill to 0.150 mm. The coke was grinded in a disks mill and sieved to obtain
material between 0.850 mm and 0.300 mm.

2.2. Static furnace calcination, laboratorial scale (Clays 1 and 2)

Two mixes of clays containing 10% addition of coke were prepared and homogenized
manually (20g). Portions of these mixture were calcined in electric static furnace, in a covered
platinum crucible for 20 minutes, at different temperatures (700°C to 1000°C), to obtain ideal
temperature through pozzolanic activity by Chapelle’s method. Based on these pozzolanic
activity results, clay and coke mix were calcined for 5, 10, 15 and 20 minutes. All samples
were removed from the static furnace and air cooled quickly to avoid excessive oxidation. The
grayish color hue was the criteria for selecting the best conditions for pilot and industrial
calcinations, regardless Chapelle’s results.

2.3. Pilot scale rotary kiln calcination, laboratorial scale (Clay 1)

Mix of clays containing 30% addition of coke were prepared and homogenized in a rotary
shaker (30 rpm) for 1 h. An electric rotative pilot scale rotary kiln [5] was required in order to
produce enough clay to compressive strength tests. Calcined clay and residual coke were
separated through a 0.180mm sieve. After calcined clay-coke separation, magnetic fraction
was removed from calcined clay employing a magnet. The fractions obtained were weighed in
order to calculate their percentages. Non-magnetic calcined clay was ground in ball mill to
0.075mm and reserved to tests.
2.4. Calcination in countercurrent rotary kiln, industrial scale (Clay 2)
The industrial tests were carried out in a plant designed by Dynamis in 2009 to produce
calcined clay for Cimento Planalto (CIPLAN), located at the Federal District in Brazil. The
pozzolan activation line has a countercurrent rotary kiln of Ø3,0 m x L=52 m with a nominal
production capacity of 600 metric tons per day. The raw material was loaded into a hopper
and fed at the kiln gas outlet through a belt conveyor. The calcined clay was cooled by a
rotary cooler (that also preheats the combustion air) and the de-dusting was done by high
efficiency cyclones and a bag-house filter. The combustion system burns 100% grinded
petroleum coke.
During the tests, the clay feeding rate of the kiln was 25.870 kg/h, the reduction agent
(petroleum coke) feeding rate was 800 kg/h and the combustion system was supplied with
1.610 kg/h of pulverized petcoke. The kiln speed drive was set to 2 rpm and the exhaust gas
had a temperature of 122°C. The raw feed had a moisture of 20,2% and a LOI of 10,35%.

2.5. Methods characterization

X-ray diffraction (XRD) was applied for mineralogical composition analysis. Samples
were manually pressed into a 27 mm diameter sample holder and performed in a Rigaku
Windmax 1000 X-Ray powder Diffractometer, in a rotating sample stage, employing CuK
radiation, 40 kV, 20 mA, step size of 0,02o 2, time per step of 2s, 1º divergence slit. The
minerals identification and phases quantification by Rietveld method was performed in X-Pert
HighScore version 3.0d(3.0.4) and based on standard diffraction data provided by ICDD
(International Center For Diffraction Data). The chemical composition was characterized by
X-Ray Fluorescence (XRF) using a Panalytical Minipal Cement and fused beads were
produced in Claisse M4 fusion machine. A TA Instruments TGA/DSC SDT 2960 was used
for thermogravimetric measurements, with a heating rate of 10ºC/min from room temperature
to 1000ºC. A argon flux was used in the heating chamber. The color parameters "L *", "a *"
and "b *" were measured using a spectrocolorimeter model "Color Guide Sphere d / 8" spin,
manufactured by Byk Gardner, with standard observer D65 and opening angle 10. The
measurements were investigated according international agreements colors CIELAB-CIE [6].
Two mixes of non-magnetic calcined clays and cement type I were used to produce CEM
II/B-P for compressive strength tests according Brazilian Standard NBR 11578:1997
(analogous to European Standards EN 197-1:2000 and EN 196-1: 2005).
According AFNOR Standard NF P 18-513, Chapelle’s method is an accelerated method
for direct determination of the lime consumption by the pozzolan. In this test, a mixture of 2g
of CaO and 1g of pozzolan was placed in a plastic Erlenmeyer with 250 ml of boiled
deionized water, and set in a bath at 90º C during 16 h. The fixed or consumed lime by
pozzolan is calculated by the difference between the added and the free lime in suspension,
valued by basic-acidy titration.

2.6. Results and Discussion

The results obtained from XRF (Table 1) and XRD (Table 2) show presence of typical
compounds on natural clays such as kaolinite and illite. The presence of those minerals were
confirmed by thermal analysis where kaolinite exhibited endothermic peak at 450°C–600°C
due to the dehydration effect, followed by an exothermic peak associated with nucleation of
mullite, while illites exhibit endothermic effects at 100–200°C, 500–650°C, and around
900°C, and an exothermic peak immediately following the third endothermic peak. Hematite
and goethite contributes to reddish (for Clay 1) and pinkish (for Clay 2) clay's color when
calcined in oxidant atmosphere. XRD pattern of calcined clays (with coke; 950ºC; 20min)
showed occurrence of kaolinite decomposition and probable formation of metakaolin as non-
crystalline phase. The presence of kaolinite in the calcined Clay 2 (Table 2) could be
associated to slightly coarse clay grain size when added in industrial rotary kiln. Pozzolanic
activity and visual final color demonstrated that 800ºC were satisfactory burning temperature
to Clays 1 and 2, respectively (Figure 1), in static furnace condition. Gray color was obtained
until 10 min regarding the time of reaction, but color reversion was observed in samples
surface when contacts air inside the furnace. It was observed a tendency of reddish or pinkish
color to vanish and the arising of grayish hues when burning time and maximum temperature
increases.

Table 1: Chemical analysis results of clays, in mass %

Components Clay 1 Clay 2 Components Clay 1 Clay 2
LOI 13,9 14,5 MgO 0,08 0,18
SiO2 40,6 43,0 K2O 0,48 0,33
Al2O3 32,5 35,4 Mn2O3 0,07 ---
Fe2O3 11,8 3,83 TiO2 1,51 1,57
CaO 0,02 0,06 P2O5 0,06 0,05

Table 2: Mineralogical composition data of clays, identified by XRD

Compound Calcined Calcined
Chemical formula Clay 1 Clay 2
name Clay 1 Clay 2
kaolinite Al Si
2 2 5O (OH) 4 75 83 - 1
illite KAl2(Si3Al)O10(OH)2 2 8 - -
quartz SiO2 6 4 6 5
hematite Fe2O3 8 <1 - -
goethite Fe3+O(OH) 7 3 - -
gibbsite Al(OH)3 1 <1 - -
anatase TiO2 3 2 2 <1
rutile TiO2 - - 1 <1
mullite Al 2 (Al Si
2.8 1.2 )O 9.6 - - - <1
muscovite (K,H3O)Al2(Si,Al)4O10(OH)2 4 <1 4 <1
iron Fe - - <1 -
Amorphous or non-crystalline phase Low 87 94

Based on obtained results at electric static furnace mixtures of clays and coke, were
applied the following tests: mix of Clay 1 and coke calcined in a pilot scale rotary kiln at
800ºC, and; mix of Clay 2 and coke calcined in an industrial rotary kiln between 850-950ºC,
although 800ºC is the suitable burning temperature. The temperature interval is a furnace pre-
fixed kiln condition, which could not be modified. In conformity with European Standard EN
197-1:2000, compressive strengths results of cements at 3, 7 and 28 days define cement as
CEM II/B-P 42,5N (Table 3). Both clays showed Strength Activity Index (SAI)≥75%
(analogous to European Standards EN 197-1:2000) and negligible formation of magnetic
fraction.
 Figure 1: Pozzolanic activity and color results for calcined clays on electric static furnace

Table 3: Calcined clays tests results

Parameters Calcined Clay 1 Calcined Clay 2
Pilot Industrial
Coke fraction, % 13 0
Non-magnetic calcined clay fraction, % 87 100
Magnetic calcined clay fraction, % <1 0
Coke consumed, in relation to calcined clay, % 15,0 11,7
Pozzolanic activity, mg Ca(OH)2/g clay 1095 835
Compressive strength, MPa 3d 23,1 37,8
7d 34,1 49,5
28d 44,3 59,6

Table 4: Color coordinates results and respective visual appearance

Color coordinates
Clay 1 in Non-magnetic
Lab Non-magnetic pilot
OPC Cement natura, dried calcined Clay 1 +
calcined fraction Clay 1
and milled OPC Cement
L* 58,8 40,4 40,5 50,5
a* 1,1 21,0 -0,1 0,8
b* 10,5 23,4 -0,6 6,4
Color
Clay 2 in Non-magnetic
Non-magnetic industrial
Lab OPC Cement natura, dried calcined Clay 2 +
calcined fraction Clay 2
and milled OPC Cement
L* 59,4 70,8 65,3 61,7
a* 1,4 9,2 4,3 1,8
b* 8,8 20,4 7,5 8,2
Color
 The XRD analysis showed changes in the mineralogical composition of calcined clays,
absence of hematite and goethite (Table 2). This phenomenon directly reflects the cements
final color. The disappearance of kaolinite as well a decrease in illite content, indicates that
mineralogical transformation has occurred, which influences directly to the pozzolanic
activity (Table 3). The amount of Ca(OH)2 consumed was higher than 700 mg/g of pozzolan,
which could be considered satisfactory to a pozzolanic material according AFNOR Standard
NF P 18-513. The presence of TiO2 contributed to clays darkening. According to instrumental
color analysis, in natura clays strongly tends to red and highly positive a* index (Table 4).
However, the calcined clays in reducing atmosphere and respective cements presented the
tendency to darker hues, with smaller values in the a * and b * coordinates. Calcination in
reducing atmosphere suggests the reduction of iron oxide without formation of metallic Fe,
and allows obtaining cements with the desirable grayish hues. Complementary, in order to
better understand the pozzolanic activity of calcined clays submitted to reducing calcination
process, it is recommend to continue this study by microstructural point of view, applying
SEM-EDS, NMR 27Al and 29Si nuclei and other techniques [7,8] for explain the possible Al
and/or Si replacement by Fe.

3. CONCLUSION
- The laboratorial and industrial reducing calcination process allowed obtaining desired
grayish pozzolanic materials to Portland cement, and presents a solution for the
application of originally reddish or pinkish clays.
- Evaluation of cements color stability, produced with color transformed calcined clays, is
recommended, focusing the durability and performance of pozzolanic cements.
- The fuel consumption of the industrial scale process, when applying the color change
technique, was slightly higher than the recorded at conventional operation. Despite of this,
the kiln industry condition could be optimized by decreasing burning temperature for
increasing performance of the calcined clay.

4. REFERENCES
[1] Gámiz, E. et al. Relationships between chemico-mineralogical composition and color properties
in selected natural and calcined Spanish kaolins. Applied Clay Science, v. 28, p. 269-282, 2005.
[2] Chandrasekhar, S; Ramaswamy, S. Iron minerals and their influence on the optical properties of
two Indian kaolins. Applied Clay Science, v. 33, p. 269-277, 2006.
[3] Hofstetter, T.B. et al. Reactivity of Fe(II) species associated with clay minerals. Environmental
Science and Technology, v. 37, p. 519-528, 2003.
[4] Chandrasekhar, S; Ramaswamy, S. Influence of mineral impurities on the properties of kaolin
and its thermally treated products. Applied Clay Science, v. 21, p. 133-142, 2002.
[5] Castanho, M.P.; Chotoli, F. F.; Costa, R. G. Forno Rotativo Tubular Laboratorial - Estudo de
Perfil Térmico. In: Enqualab, 2008, São Paulo.
[http://www.vertent.net/remesp/enqualab2008/cdrom/pdf/TT036.pdf].
[6] CIE System L*a*b* by L’ECLAIRAGE INTERNATIONAL COMISSION in 1976.
[7] DE Souza, C. M.; Garcia, E.; Jäger, CH. ; Quarcioni, V. A.; Greiser, S. Evaluation of
pozzolanic reactivity of calcined kaolinite. In: 5th Intern Conf Non Traditional Cement & Concrete,
2014, Brno. Non-Traditional Cement & Concrete V. Brno: NOVPRESS, 2014. v. 1. p. 225-228.
[8] Fernandez, R.; Martirena, F.; Scrivener, K.L. The origin of the pozzolanic activity of calcined
clay minerals: A comparison between kaolinite, illite and montmorillonite. Cement and Concrete
Research vol. 41, p. 113–122, 2011.

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