SIVRIKAYA & AROL (2014)

ALTERNATIVE BINDERS TO BENTONITE FOR IRON ORE PELLETIZING - PART II:

EFFECTS ON METALLURGICAL AND CHEMICAL PROPERTIES

O. SIVRIKAYA1 and A.I. AROL2

1
Adana Science and Technology University, Faculty of Engineering and Natural Sciences, Dept. of Mining and
Mineral Processing Eng., 01180, Adana, Turkey, [email protected]
2
Middle East Technical University, Mining Engineering Department, Ankara, Turkey, [email protected]

Artigo submetido em novembro/2013 e aceito em março/2014

DOI: http://dx.doi.org/10.15628/holos.2014.1759

ABSTRACT
This study was started to find alternative binders to boron compounds such as colemanite, tincal, borax
bentonite and to recover the low preheated and fired pentahydrate, boric acid together with organic binders
pellet mechanical strengths of organic binders-bonded such as CMC, starch, dextrin and some organic based
pellets. Bentonite is considered as a chemical impurity for binders, into magnetite and hematite pellet mixture was
pellet chemistry due to acid constituents (SiO2 and tested. After determining the addition of boron
Al2O3). Especially addition of silica-alumina bearing compounds is beneficial to recover the low pellet physical
binders is detrimental for iron ore concentrate with high and mechanical qualities in the first part of this study, in
acidic content. Organic binders are the most studied this second part, metallurgical and chemical properties
binders since they are free in silica. Although they yield (reducibility - swelling index – microstructure –
pellets with good wet strength; they have found limited mineralogy - chemical content) of pellets produced with
application in industry since they fail to give sufficient combined binders (an organic binder plus a boron
physical and mechanical strength to preheated and fired compound) were presented. The metallurgical and
pellets. It is investigated that how insufficient preheated chemical tests results showed that good quality product
and fired pellet strengths can be improved when organic pellets can be produced with combined binders when
binders are used as binder. The addition of a slag compared with the bentonite-bonded pellets. Hence, the
bonding/strength increasing constituent (free in acidic suggested combined binders can be used as binder in
contents) into pellet feed to provide pellet strength with place of bentonite in iron ore pelletizing without
the use of organic binders was proposed. Addition of compromising the pellet chemistry.

KEYWORDS: iron ore pelletizing, bentonite & organic binder, boron compounds, colemanite, chemical and
metallurgical properties.

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1 INTRODUCTION
Bentonite is the most widely used binder in iron ore pelletizing. The use of bentonite is
favorable in terms of physical, mechanical and metallurgical pellet qualities, however, because of
its acid constituents (SiO2 and Al2O3) it is considered as an chemical impurity especially for
concentrate with high SiO2 content. These acid oxides are known for their adverse effects on the
iron-steel making economy. For example, the addition of 1% bentonite, containing 85% SiO2+Al2O3,
decreases the iron content of pellets by 0.6-0,7% by wt (de Souza et al.,1984, Kater and Steeghs,
1984).Any increase in silica content can lead to appreciable cost increases of the steel production
(Chizhikova et al., 2003, Schmitt, 2005). In the case of direct reduced pellets, every percent of acid
gangue addition is associated with an increased energy consumption of 30 kWh/ton (Heerema et
al., 1989).
The main disadvantage of bentonite and other binders based on silicate minerals is that
they add silica to the finished product pellet. Since the purpose of iron ore processing is to remove
silicate minerals from the ore, adding silicates back in the form of binder is counterproductive. This
has prompted long-term interest in developing or discovering binders that contain no silica.
Therefore alternative binders to bentonite have been tested for many years. Because of good
binding properties without contaminating the product pellets, organic binders have attracted
attention among researchers. (Eisele and Kawatra, 2003, Sivrikaya, 2011).
Organic binders provided good wet pellet strength; however, they have found limited
application in industry. Ripke and Kawatra (2000) gave a statistic about the pellet plants in USA.
Eight of the nine plants utilized bentonite clay as a binder, while the ninth plant used an organic
binder. The reason behind the failure of organic binders in industry is their low burning
temperatures. Organic binders which burnt out at relatively low temperatures (<250oC) with
virtually no or little residue can not provide bonding to iron oxide grains at higher induration
temperatures. Therefore, in literature the results showed that organic binders produce good
quality wet and dry pellets. However, they fail to impart enough strength to the pre-heated and
fired pellets as a result of reduced slag bonding (Kater and Steeghs1984, Goetzman et al., 1988,
Sivrikaya, 2011) which is especially more important in pelletizing of hematite ores due to lack of
oxide bonding. As such, organic binders have hitherto failed to be an alternative to bentonite,
except a few cases of straight-grate pelletizing, where there is no dynamic pellet bed. In recent
years efforts have been focused on improving the pre-heated and fired strength of pellets
produced with organic binders. In this context, boron compounds have been considered as an
additive in conjunction with organic binders (Sivrikaya, 2011). A few researchers have investigated
the use of boron compounds in iron ore agglomeration and found promising results on physical
and chemical properties of product pellets (Köroğlu, 1980, Timuçin et al., 1986, Malysheva et al.,
1996, Schmitt, 2005, Akberdin and Kim 2008)
This study was conducted to investigate how insufficient preheated and fired pellet
strengths can be improved when organic binders are used as binder. Boron compounds free in
acidic contents are suggested to overcome the lack of slag forming constituents encountered with
organic binders as they are known for their low melting temperatures and also to decrease the
melting temperatures of silicates. Addition of a slag bonding/strength increasing boron compounds

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into pellet recovered the low preheated and fired pellet strength with the use of organic binders
(Sivrikaya and Arol, 2013).
In this part of the study, the effects of addition of boron compounds such as colemanite,
tincal, borax pentahydrate, boric acid together with organic binders such as CMC, starch, dextrin
and some organic based binders (OBB), into magnetite and hematite pellet mixture was tested on
metallurgical and chemical qualities of product pellets. Metallurgical and chemical properties of
thermally treated pellets (reducibility - swelling index - microstructure - mineralogy - chemical
content) of pellets produced with combined binders (an organic binder plus a boron compound)
were determined and presented.

2 MATERIALS AND METHODS

Detailed information about raw materials used in the pelletizing experiments, their
characterization and the pelletizing experiment procedure are given in the first part of this study
(Sivrikaya and Arol, 2013).

2.1 Determination of chemical and metallurgical pellet properties

2.1.1 Reducibility of pellets:

Reducibility is the degree of ease with which oxygen can be removed from pellet
composition. In standard, the product pellets is heated upto 900 oC under nitrogen and then the
reducing test gas is passed through the pellets at this temperature with the required flow rate.
Gakushin reducibility test method standatds were utilized for reducibility experiments. The
reducibility experiments of product pellets was carried out with an reducibility apparatus
consisting of a vertical split furnace, a sensitive balance and a control unit.

2.1.2 Swelling index of pellets:

Pellets tend to swell during chemical reduction process in the reduction furnaces. Swelling
of the product pellets should not exceed 20% by volume for a trouble-free operation in the
reduction facilities. Swelling index of reduced pellets according to Gakushin method was calculated
according to volume change of pellets before and after reducibility test.

2.1.3 Microstructures of pellets:

In order to understand the reason for compressive strength increase of pellets containing
boron compound, the microstructures of thermally treated pellets were examined under a
scanning electron microscope. The bonding mechanism of combined binders added to magnetite
pellets was explained by the physical changes (crystal change and crystal growth) in mineral grains
of pellets after thermal process. JEOL JSM-6400 scanning electron microscopy was used to obtain
micro images of pellets heated at 800-1300oC to see the effect of heating temperature and
different binders on crystal changes.

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2.1.4 Mineralogy of pellets:

In order to understand the reason underlying the strength increase after addition of boron
compound, changes in the mineralogy of the fired pellets were investigated by XRD method. A
Rigaku MiniFlex II XRD analyzer (X-ray diffractometer) was used to obtain the mineralogy of
thermally treated pellets.

2.1.5 Chemical content of pellets:

Iron and chemical impurity contents are important for product pellets in terms of an
economic iron production in reduction facilities. In order to see the efect of addition of different
binders on pellet chemistry, chemical analyses of product pellets were determined with XRF
method using a Spectro IQ X-Ray fluorescence spectrometer.

3 RESULTS AND DISCUSSION

The results of the physical and mechanical tests are presented in the first part of the study
(Sivrikaya and Arol, 2013) and according to those results; pellets with sufficient physical and
mechanical qualities were selected to determine their chemical and metallurgical properties. The
results of chemical and metallurgical tests of selected pellets are presented below and all results
were presented in the Ph.D. dissertation by Sivrikaya, 2011. The mean values of 20 randomly pellet
samples were given with the 95% confidence level (P95) in the graphs.

3.1 Reducibility of pellets

The reducibility tests of fired pellets at 1300oC revealed that the pellets produced with
bentonite binder were more reducible than those of produced with calcined colemanite addition
(Figure 1). The reason of the low reducibilities of calcined colemanite added pellets may be related
with the heavy melting of calcined colemanite at 1300oC. While the addition of calcined colemanite
increases the compressive strength of fired pellets through physical melting between ore grains, it
most probably blocks the porosity and cause closed pores then make difficult to remove oxygen
from the interior part of pellets during reducibility test. Therefore, by means of calcined colemanite
addition the mechanical strengths of fired pellets were increased at the same time the reducibility
of these pellets were affected adversely. Lower reducibilities of pellets made with calcined
colemanite addition are as a result of high temperature selected for sintering, namely 1300oC.
Hence the lower firing temperatures such as 1100oC which provided the sufficient industrial
compressive strength may recover the low reducibilities of pellets containing calcined colemanite.

3.2 Swelling index of pellets

The swelling indices of both fired magnetite and hematite pellets were determined
between 10.32% and 17.88% (Table 1). These swelling indices are in the desired range since the
industrially acceptable swelling index should be lower than 20% for trouble-free reduction furnace
operation. Therefore, the additions of tested alternative binders do not have negative effect on
swelling indices of product pellets.

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Figure 1. Reducibility of magnetite pellets sintered at 1300 oC and reduced at 900oC for 3 hour

Table 1. Swelling indices of pellets sintered at 1300oC and reduced at 900oC for 3 hours

3.3 Microstructures of pellets

SEM micro-images of pellets thermally treated at 800-1300oC were taken and only images
for pellets sintered pellets at 1100oC are given in Figure 2. In the images, separate grains of pellets
can be seen and the grains of pellets seem to be granular, sharp, cubic or angled (not rounded) for
pellets heated at 800 and 1000oC. The grains start to be rounded for pellets contain calcined
colemanite and heated at 1100oC as a result of relatively high temperature. However, this rounded
grain surface cannot be observed entirely for pellets bonded with bentonite and heated at same
temperature.
At 1200 and 1300oC the shape of grains are more rounded due to complete melting of
bentonite or calcined colemanite. Throughout the induration process bentonite or calcined
colemanite used as binder provided solid state bonding by inter-diffusion of contacting grains. This
bonding type can be shown as example for sinter bridges, partial melting or crystallization of
soluble substances as explained by (Pietsch, 2005).

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Figure 2. Microstructures of pellets; bentonite bonded at left, calcined colemanite bonded at right.

3.4 Mineralogy of pellets

The X-ray diffraction patterns of magnetite pellets contain either bentonite or calcined
colemanite showed no new peaks arising from binder addition (Figure 3). As the addition levels of
bentonite or calcined colemanite were very low (0.50% of dry magnetite concentrate), the possible
new compounds formation and their differential peaks cannot be detected by XRD analyses.
Oxidation pattern of magnetite pellets and the peaks detected by XRD analyses well confirm with
earlier reports.

Figure 3. X-ray diffraction patterns of dry magnetite concentrate (purple) and pellets made from this concentrate
and produced with 0.50% bentonite (red) or 0.50% calcined colemanite (blue) and heated at 600-800-1000-1300oC
for 30 minutes.

3.5 Chemical content of pellets

The Fe content of magnetite concentrate and product pellets made with this concentrate
were determined to be approximately 65.00%. (Table 2) The main impurities of concentrate were
SiO2 and Al2O3 and they were found 4.87% and 0.09%, respectively. No big differences in SiO2 and
Al2O3 contents were detected in pellets with addition of alternative tested binders. Since, the
addition levels of binders are not so much. Therefore, the detected contents of product pellets are

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more or less similar to each other. However, the SiO2 contents of pellets contain bentonite binders
are a little greater than those produced with organic binders or calcined colemanite combination.

Table 2. Chemical analyses of product pellets produced with different binder addition

4 CONCLUSION
In the first part of the study, the addition of boron compounds into pellet mixture was found
to improve the lower preheated and fired pellet physical strength encountered with use of organic
binders. According to those results found in first part, pellets with sufficient physical qualities were
selected to determine their chemical and metallurgical properties. The results showed that good
metallurgical and chemical quality product pellets can be produced with combined binders when
compared with bentonite-bonded reference pellets. Swelling indices of reduced pellets were found
in the range of industrial desired values. The other reducibility, microstructure and mineralogy of
pellets produced with combined binders were found to be comparable to those of bentonite-
bonded reference pellets. It was found that, organic binders and boron compounds did not
contaminate the pellet chemistry and thus not interfere with iron making, since the organic binders
are being eliminated during thermal processes and boron compounds do not contain acidic
impurities. As a result, the suggested combined binders can be used as binder in place of bentonite
in iron ore pelletizing without contaminating the pellet chemistry.

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