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STUDY OF ACIDIC ACTIVATION OF IRAQI KAOLIN CLAYS AND ITS EFFECT ON

THE SURFACE AREA PROPERTIES AND CATION EXCHANGE CAPACITY

Research · July 2020

DOI: 10.35124/bca.2020.20.1.949

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 DOI : 10.35124/bca.2020.20.1.949
Biochem. Cell. Arch. Vol. 20, No. 1, pp. 949-955, 2020 www.connectjournals.com/bca ISSN 0972-5075

STUDY OF ACIDIC ACTIVATION OF IRAQI KAOLIN CLAYS AND ITS

EFFECT ON THE SURFACE AREA PROPERTIES AND CATION EXCHANGE
CAPACITY
Othman Hamad Farhan, Sattar Salim Ibraheem* and Sabri Mohammed Hussein
Department of Chemistry, College of Science, Anbar University, Iraq.
*e-mail: sattar_salim1976@yahoo.com
(Received 26 July 2019, Revised 29 October 2019, Accepted 11 November 2019)

ABSTRACT : The current study used the Iraqi kaolin clays by activated with hydrochloric acid (M 6) and heating the mixture
at a temperature ranging between (71 - 680C) for the periods (5, 4, 3, 2, 1 hrs.). The activated samples were diagnosed by Fourier
Transform Infrared Spectroscopy (FTIR) and X-ray diffraction (XRD) and comparing it with the raw samples. The results
showed that changes in the structural composition of the kaolin clays due to activation. The value of the surface area and cation
exchange capacity was calculated; the highest value is the activated sample by acid when heated for (5) hours.
Key words : Kaolin, acid activation, surface area, cation exchange capacity.

INTRODUCTION Kaolin has a clay mineral whose chemical formula

Clays are nature substance, having several
properties; used in many industries. Clay is usually
defined is natural materials of fine particles that show a
lamellar structure due to the crystalline arrangement
consisting of silicon and aluminium oxides, which are the
main components of clay. The tetrahedral structure of
silicon oxide combines with the octagonal structure of
the aluminium oxide to form a structure in which the
tetrahedral sheets and octahedron sheets intertwine with
each other, which leads to structural changes such as (1:
2), one plate octahedron sheets between two tetrahedral
sheets and (1: 1) one tetrahedral plate into one octahedron
sheets that distinguishes various clay minerals (Ibrahim
et al, 2014). Activated Iraqi clays are well effective for
removing toxic environmental pollutants, and clay
materials can be activated by using chemical or physical
treatment (Al-Saade and AL-Ani, 2016). Acid treatment
of clay leads to changes in the pore and acidity properties
of the surface. The results obtained by acid activation
vary according to the type and nature of clay used, acid
concentration, temperature, and treatment time. Acid
activated clay is widely used in the industry as a bleaching
and decontamination agent, adsorbent material, and as
auxiliary agents (Hechi et al, 2009). Kaolin is one of the
clay materials widely used in many applications such as
ceramics, paperboard, rubber filling, oil refining processes,
paints, cement and water treatment (Eze et al, 2012).
[Al2Si2O 4(OH) 4], consists of a mixture of different
minerals whose main component is kaolinite. In addition
to that, it often contains (quartz, mica, feldspar, elite, and
montmorillonite), Kaolin is considered a good adsorbent
material due to the large surface area and highly reactive
surfaces. Kaolin was used to absorb toxic substances in
the gut and diarrhoea treatment associated with food
poisoning (Ali, 2009). This clay consists two
layers structure (1: 1) from four-layer silicates sheet (SiO4)
and octahedral sheets of alumina [Al2(OH)4], The two
plates are bound together by a hydrogen bond between
the surface hydroxyl groups on the side of the octahedral
layer, and the basic oxygen atoms on the side of the
tetrahedral layer (Sabar, 2017). Fig. 1 shows the general
composition of kaolin (Torres-Luna and Carriazo, 2019).
Kaolin is described as ground rocks and is characterized
by white colour and these rocks are characterized as
chemically inert and have a wide range of pH (Al-
Sumaidaie, 2017). Kaolin contains (30-35%) of alumina
in the composition, so it can be a suitable material for the
production of γ-alumina (Kshash and Baha’a, 2018).
Kaolin has a low capacity to swell and has a weak ability
to exchange cations, where the value of the cation
exchange capacity (CEC) (1 - 15 meq/100 g) (AL-Ani
and Hussein, 2012). The activation of natural kaolinite
can be performed by using the acid by dissolving and
partially extracting the aluminium types using inorganic
950 Othman Hamad Farhan et al
acids. By activating the kaolinite with the acid, the acid
breaks down the (Si - O - Al) bonds, destroys the crystal
structure, removes the trivalent aluminium ions (Al3 +)
from the octahedron sheets and produces a porous
structure. However, the layer sequence (stacking or
structural arrangement) of kaolinite is determined by many
hydrogen bonds between the unit layers, which makes
the acid attack difficult. Loss of protons when hydroxyl
is removed may remove these bonds and destroy the layer
sequence arrangement and thus heating may be an
effective method to facilitate the activation of kaolinite
by an inorganic acid attack (Torres-Luna and Carriazo,
Fig. 1: General composition of the kaolinite metal.
2019).
MATERIALS AND METHODS temperature of (900C) for one day, after which the clay
models are milled into particles to size of (75 µm ≥), then
Devices used
activate with hydrochloric acid by adding (50) grams of
1. Laboratory oven memmort / W. Germany raw kaolin to 300 cm3 of 6 molar concentration of
2. Electronic balance sartorius, W. Germany hydrochloric acid and heating the mixture at a temperature
3. Hot plate with magnetic stirrer. of (71 - 680C) for one hour with stirring using the refining
device (Reflex). The same process was repeated at (2,
4. Infrared spectroscopy (FT-IR)
3, 4, 5) hours, later washed the resulting models for several
(FT-IR) - 8400 Shimadzu - Japan. College of Science times with distilled water and filtration to remove the salts.
- University of Baghdad - Iraq. The models are dried using an electric oven at a
5. X-ray diffraction (XRD) temperature of 700C) for two days, then the samples are
XRD Schimadzu XRD 6000 - Japan (40kv, 30Ma) in ground to a size of (75 µm ≥) and examined them, as in
the ministry of technology in Iraq.
Materials used
1. Clay kaolin : The kaolin used in this study
represents the clay extracted from the Duykhela quarry,
which is located in the koara in the Western Desert within
Anbar Governorate. Table 1 shows the chemical analysis
of kaolin.
Table 1 : Chemical analysis of kaolin.
Constituents Wt %
SiO2 48.57
AL2 O3 35.05
CaO 0.6 Fig. 2 : A- activated kaolin model with acid, B- raw kaolin sample.
MgO 0.77
K2O 0.08
Fe2O 3 1.34
TiO2 1.19
Moisture 0.08
L.O.I. 12

2. Hydrochloric acid (HCl) has a purity (99.9%)

(BDH).
The method
The raw kaolin clay is purified from water-soluble
impurities by washed these clays with distilled water for
several times and then filtered and dried the clay at a Fig. 3 : A- heating for five hours, B- heating for one hour.
 Acidic activation of Iraqi kaolin clays and its effect on the surface area properties and cation exchange capacity 951
Fig. 2 that showed the raw model and the activated model RESULTS AND DISCUSSION
with the acid. FT-IR test
A slight gradual change in colour was observed at Fig. 4 shows several bundles of raw kaolin spectrum
each heating period, but it can be distinguished when (FT-IR), one of which is at (3464 cm-1). This bundle is
comparing the model when heating with one hour five due to the presence of adsorbed water on the outer
hours as shown in Fig. 3. surface of the clay (Valášková et al, 2007). The bundles
at (3695 cm-1, 3620 cm-1) are attributed to the Stretching

Fig. 4 : (FT-IR) test of raw kaolin clay.

Fig. 5 : (FT-IR) test of the kaolin activated with acid during heating for one hour.
952 Othman Hamad Farhan et al

Fig. 6 : FT-IR test of the kaolin activated with acid during heating for two hours.

Fig. 7 : FT-IR test of the kaolin activated with acid during heating for three hours.

(Al - OH) group. The internal hydroxyl groups that lie
between tetrahedral plates and octahedral layer give
absorption at (3620 cm-1), Whereas the bundle at (3695
cm-1) is related to the Symmetric Stretching. In the
bending region, kaolin shows absorption bundles at (795
cm-1, 914 cm-1,1634cm-1) the bundles at (1634 cm-1) is
due to the bending vibration of the Physisorbed water on
the surface of the free silica that is resulting due to
leaching, the bundles at (914 cm-1) is attributed to the
vibrations of the group (Al - Al - OH) and the bundles at
(795 cm-1) is attributed to the vibrations of the group (Al
– Mg – OH ) in the clay layers (Kumar et al., 2013).
The bundles at (1030 cm-1, 1014 cm-1) are due to the
Stretching group (Si - O) in kaolin, the bundles at (1030
 Acidic activation of Iraqi kaolin clays and its effect on the surface area properties and cation exchange capacity 953

Fig. 8 : (FT-IR) test of the activated kaolin with acid during heating for four hours.

Fig. 9 : (FT-IR) test of the kaolin activated with acid during heating for five hours.

cm-1) can correspond to the quartz impurities (Timofeeva
et al, 2016). Also, the clay spectrum showed an absorption
bundles at (698 cm-1) belonging to the Stretching group
(Si-O) and the bundles (532cm -1) belonging to the
Stretching group (Si-O-Al) ( octahedral ) and two bundles
at (463 cm-1, 430 cm-1) due to Bending Vibrations of the
(Si-O) group (Aung et al, 2015), when kaolin Clays were
treatment with hydrochloric acid a concentration (6 M)
it was found that there changes happening in spectrum
(FT-IR) for all samples, which were treatment such as in
Figs. 5, 6, 7, 8, 9; it was observed that the bundles at
(1030 cm-1, 1014 cm-1) which correspond with stretching
vibrations for (Si-O) group in kaolin decreased its intensity
during treatment with hydrochloric acid due to structural
changes in tetrahedral ions (Aung et al, 2015). This
indicates a change in the chemical composition of kaolin
after acid treatment (Timofeeva et al, 2016). The results
of kaolin treated with the acid showed, that the intensity
of some peaks gradually decreased with the increase of
the heating period until it disappeared, which indicates
the penetration of protons in the clay mineral layers and
the attack on the structural hydroxyl groups, which led to
the removal of the hydroxyl and the leaching of ions from
the octahedron layers. Also, our results noticed that
954 Othman Hamad Farhan et al

Fig. 10 : [XRD] A-kaolin activated with acid during heating for one hour, B - Raw kaolin.

treating kaolin clays with the acid, the bundle at 914 cm- Table 2 : Values (2è), d (Å) values and density of raw kaolin
1
which is caused by vibration of the internal (OH) groups No 2è d(Å) Intensity (counts) Assigned to
decreased in intensity in all the treated samples. The 1 12.0331 7.34909 80 Kaolinite
present results showed a change in the shape and location 2 19.1779 4.62424 8 Illite
of the bundles in the region (1120-1000 cm-1) which is 3 20.5238 4.32393 3 Kaolinite
caused by a stretching (Si-O) group due to changes in 4 25.4561 3.49622 11 Kaolinite
the tetrahedral cations (Kumar et al, 2013). Our results 5 29.1810 3.05785 18 Calcite
explained a significant increase in the intensity of the 6 31.4077 2.84595 59 Illite
bundles (1634 cm -1) for all acid-activated samples 7 33.1522 2.70007 12 Dolomite
compared to the raw kaolin samples. 8 35.6123 2.51899 10 SiO2
9 39.3259 2.28925 11 Kaolinite
XRD test
10 40.2837 2.23700 3 Gibbsite
XRD test results showed in Fig. 10, the kaolin clays 11 43.5232 2.07771 4 SiO2 Quartiz
contain mostly kaolinite and quartz minerals with small
amounts of illite and gibbsite (Adebowale et al, 2014). The treatment of kaolin with hydrochloric acid with a
Table 2 showed the values of (2θ) and the values of d concentration of (6 M) resulting in a slight increase in
(Å) and the density of some kaolin clay minerals. the kaolin surface area, and the surface area increases
with increasing the heating period as shown in Table (3),
The acid treatment caused dissolving and disturbance
these results agreed with results of Timofeeva et al (2016).
the kaolin synthesis, and there are found that some
minerals in kaolin that are significantly affected, some This increase in surface area may be explained by
are less and others are not affected when kaolin is the acid treatment working to free the bonds between
activated by the acid. the clay sheets and replace ions (H+) that coming from
the acid to replace other Cations that are replaceable
Surface area analysis
accompanied by the loss of some triple aluminium ions
The surface area analysis of the kaolin clays used in (Al3+) and other Cations from all tetrahedral layers, the
the current study found that the value to be (17.9 m2/g). octahedron layers, the remaining SiO4 groups are not
 Acidic activation of Iraqi kaolin clays and its effect on the surface area properties and cation exchange capacity
Table 3 : Surface area values for raw and activated kaolin.
No Samples Surface area (m /g)
2
1 Kaolin raw 17.90
2 Kaolin + HCl (1 h) 18.60
3 Kaolin + HCl (2 h) 18.95
4 Kaolin + HCl (3 h) 19.20
5 Kaolin + HCl (4 h) 19.80
6 Kaolin + HCl (5 h) 20.60
Table 4 : CEC values for raw and activated kaolin.
No Samples CEC (meq/100 g)
1 Kaolin raw 10.728
2 Kaolin + HCl (1 h) 17.496
3 Kaolin + HCl (2 h) 17.501
4 Kaolin + HCl (3 h) 17.533
5 Kaolin + HCl (4 h) 17.540
6 Kaolin + HCl (5 h) 17.568
affected by the acid, and this process leads to an increase
in the surface area (Bhattacharyya and Sen Gupta, 2007).
Cation exchange capacity
The cation exchange capacity of the clay minerals is
due to structural defects, broken bonds and structural
hydroxyl transfer processes. The activation of the kaolin
with acid has increased the Cation exchange capacity
(CEC) as shown in Table 4.
This increase in the (CEC) value may be explained
by the acid treatment of the kaolin clays resulting
replacement of a number of different Cations with (H+)
ions, during heating dehydroxyl process will occur, leaving
behind a number of Lewis sites, may be the cause of the
increase in the (CEC) value is an increase in Lewis acidity
(Bhattacharyya and Gupta, 2006).
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