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Synthesis and characterization of zeolite 4A using swat kaolin

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 Journal
Amin of Chemical
Ur Rahman, Technology
Farid andWaheed
Ullah Khan, Metallurgy, 53, 5, 2018,
Ur Rehman, 825-829
Sanum Saleem

SYNTHESIS AND CHARACTERIZATION

OF ZEOLITE 4A USING SWAT KAOLIN

Amin Ur Rahman, Farid Ullah Khan, Waheed Ur Rehman, Sanum Saleem

Materials Science Center, PCSIR Labs. Received 19 May 2017

Complex Peshawar, Pakistan Accepted 15 Decembet 2017
E-mail: aminpcsir@gmail.com

ABSTRACT

Zeolites are microporous crystalline materials of a wide range of application. They are commonly used for wa-
ter purification and for toxic heavy metals removal. Zeolite 4A was synthesized from local kaolin containing 45.39
% SiO2 and 32.57 % Al2O3. Kaolin was initially converted to metakolin at 800○C. Sodium was then incorporated
in its structure by a hydrothermal process. The X-ray diffraction study carried out verified the successful formation
of zeolite 4A. The zeolite metal exchange rate for calcium, cadmium, chromium, lead and nickel was determined.
Keywords: zeolite 4A, clay, kaolin, metakaolin, XRD, ion exchange.

INTRODUCTION the zeolites pores.

Zeolites are crystalline microporous hydrated alu-
minosilicates of alkali and alkaline earth metals. They
consist of tetrahedral units producing three dimensional
frameworks of uniform pores and regular cavities of
molecular dimensions [1]. The tetrahedral AlO4-5 and
SiO4-4 units are linked with each other through shared
oxygen. Zeolites are high internal surface area crystal-
line materials and exhibit a very high surface activity
inside its pores of molecular dimensions. They consist
mainly of silicon and aluminum and are described by
chemical formula Mx/n[(AlO2)x(SiO2)y]wH2O, where
M is alkali or alkaline charge balancing non framework
cation of a valence n, y/x ratio has a value ranging from
1 to 5, while w stands for the amount of molecular water
in empty spaces. Silica (SiO2) is an uncharged solid,
whose framework becomes negatively charged [2] when
combined with Al. The framework requires an extra
cation within its structure to stay neutral. These cations
can be exchanged and as a result the zeolite is an ion-
exchangeable material. The cations Na+, NH+, K+, H+,
Zn2+, Mg2+ and Ca2+ are small enough to move through
There are three classes of zeolites - low silica or Al
rich zeolites, intermediate silica zeolites and high silica
zeolites. Low silica zeolites have Si/Al ratio of 1 to 2.
Zeolites A and X whose ion-exchange capability is ex-
cellent belong to this group. Intermediate silica zeolites
have Si/Al ratio varying from 1.5 to 3.8, while that of
high silica zeolites ranges from 10 to 100.
The chemical formula of zeolite 4A is Na12[(AlO2)
(SiO2)12].27H2O. Its structure contains two types of
polyhedra. The octahedron (α-cages) connects 24-hedron
(β- cages) creating thus a three dimensional structure of
pores of 4.2 Å [3].
Zeolites have three main applications - as catalysts
and adsorbents, as sensors and separation membranes, as
participants in ion exchange and solar energy conversion
processes. They have also health related application.
Zeolite 4A is used for water softening and hazardous
gases cleaning.
The aim of the investigation reported was to prepare
zeolite 4A from indigenous available clays. Swat kaolin
was selected as a raw material. The process variables
were optimized to obtain the desired product.

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 Journal of Chemical Technology and Metallurgy, 53, 5, 2018

EXPERIMENTAL kaolin of Si/Al ratio of 1 is best suited for the synthesis

Synthesis
Kaolin was analyzed by XRF (S4 Pioneer, Bruker,
Germany). For the laboratory scale synthesis of zeolite
4A, pre-washed kaolin was calcined at 800○C in a muf-
fle furnace for 1 h. The metakaolin obtained was mixed
with sodium hydroxide in a ratio of 1: 1.4. Water was
subsequently added (10 g clay/80 ml water). The resultant
mixture was stirred for 3 h. The suspension thus obtained
was stirred for 5 h at 90○C. The product formed was filtered
and washed till pH dropped to 10 and then dried at 60○C
[8, 9]. The flow diagram is shown in Fig. 3. Commercial
sodium hydroxide was used as a sodium source for the
zeolite synthesis.
Characterization
X-Rays diffractometer (JDY 3532, JEOL, Japan) was
used to characterize metakaolin and the zeolite prepared.
of zeolite 4A [4]. Pakistan has rich deposits of kaolin in
Nagarparker (Sindh) and Swat (Khyber Pakhtunkhwa).
These clays are mainly used in ceramic industry and as
fillers in plastics, rubbers and paper. Swat kaolin deposits
are among the largest known deposits of Pakistan with
an estimated reserve of 2.5 million tons [5]. Extensive
studies have been carried out for its evaluation. The
chemical composition of Swat kaolin is given in Table
1. It is evident that the clay is mainly composed of silica
and alumina. It contains also iron oxide (1.91 %), which
affects greatly the brightness of the product.
Synthesis of zeolite from kaolin is a two step pro-
cess, i.e. metakaoliniziation and zeolitilization. The
volatile matter of the clay evolves and dehydroxylation
takes place in the course of calcination at 800○C:
2Al2Si2O5(OH)4 → 2Al2Si2O7 + 4H2O

Application tests The kalonite structure collapses during the heating

The zeolite powder was mixed with kaolin in a ratio and the clay becomes amorphous [6].
of 2:1 ratio aiming to prepare zeolite granules. A granu- This amorphous form of the clay is known as me-
lator was used. This step was followed by calcination takaolin. The XRD patterns of metakaolin are given in
for 1 h in a muffle furnace at 700○C. The metal uptake Fig. 1. They show that the characteristic peaks of kaolin-
efficiency of the powder zeolite in respect to calcium, Table 1. XRF analysis of Swat Kaolin.
lead, chromium, cadmium and nickel were studied. 25 Constituents mass %
ml of the metal solution were taken from each stock
solution (100 ppm) prepared in advance on the ground SiO2 45.39
of 1000 ppm standard solutions (Merck, Germany). 1 g Al2O3 32.57
of the zeolite was added and the mixture was stirred for
MgO 0.93
10 min. The solution obtained was analyzed for metal
concentration using an atomic absorption spectropho- CaO 3.08
tometer (Z-8000, Hitachi, Japan) and a flame photom- Na2O 1.18
eter (Jenway, PFP7, UK). The zeolite regeneration was
K2O 0.30
carried out by adding 25 ml of 0.1 M NaOH solution to
1 g of the zeolite. The mixture was stirred for 10 min. Fe2O3 1.91
The regenerated zeolite was isolated from the solution. TiO2 0.13
Then it was washed and dried. The metal exchange rate
Cr2O3 0.01
of the regenerated zeolite was tested as described above.
MnO 0.03
RESULTS AND DISCUSSION SrO 0.09
The clay containing kalonite as a major constituent
P2O5 0.09
is known as china clay. It contains silica and alumina
and is a convenient starting material for the synthesis SO3 0.03
of zeolites. Extensive work has been carried out to pre- LOI 14.57
pare zeolite 4A from kaolin. These studies reveal that

826
 Amin Ur Rahman, Farid Ullah Khan, Waheed Ur Rehman, Sanum Saleem

Fig. 1. XRD patterns of metakaolin.

Fig. 2. XRD patterns of zeolite 4A.

ite disappear during the calcination step. The small peaks
observed in metakaolin spectrum refer to iron oxide. They
match those of ICCD Pattern No. 39-1346 (Maghemite).
Metakaolin is more reactive than kaolin due to its
disordered structure [7]. It accepts readily sodium ions
during the zeolitization step. They reside in its structure:
H2O
Al2Si2O7 + 2NaOH → Na2O-Al2O3-2Si O2-4.5H2O
The appearance of peaks in the zeolite powder XRD
diffractogram (Fig. 2) and their matching to those of zeo-
lite 4A (ICCD Pattern No. 39-0222) verifies the success-
ful zeolitilization of metakolin at 90C○. The additional
peaks in the pattern indicate the presence of crystalline
impurities. Table 2 illustrates the metal uptake rate of the
zeolite powder. The metal ions concentration is drasti-
cally decreased in this case. The zeolite metal uptake

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 Journal of Chemical Technology and Metallurgy, 53, 5, 2018

Table 2. Metal exchange rate of zeolite Table 3. Metal exchange rate of regenerated
4A powder. zeolite 4A granules for calcium.
Metal exchange rate Metal
Metal Ion (ppm/g) in 10 minutes
exchange
Material
rate for Ca
Ca2+ 96.00
(ppm/g) in
Pb2+ 98.22
10 minutes
Cr 3+
99.53 Virgin zeolite 96
st
Regenerated zeolite (1 time) 92
Cd2+ 99.98 nd
Regenerated zeolite (2 time ) 92
2+
Ni 97.43 rd
Regenerated zeolite (3 time ) 92

Fig. 3. Flow diagram for the preparation of zeolite 4A from kaolin.

rate in respect to Ca2+ , Pb2+, Cr3+, Cd2+ and Ni2+ is more
or less same. Table 3 shows the calcium exchange rate
of virgin and regenerated zeolite. Ca2+ exchange rate of
the regenerated zeolite is less than that of the virgin one.
Besides, it does not change with successive regeneration.
CONCLUSIONS
Swat kaolin is suitable for the preparation of zeolite
4A. The iron content in the clay is high and so the product
formed is yellowish in color. The calcium uptake rate
of the prepared zeolite is sufficient to be used for water
softening. It is also evident from its heavy metal uptake
rate that it could be used for removal of heavy metals
from waste water.
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 Amin Ur Rahman, Farid Ullah Khan, Waheed Ur Rehman, Sanum Saleem
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