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Journal of Chemical Technology and Metallurgy, 48, 2, 2013

168

Journal of Chemical Technology and Metallurgy, 48, 2, 2013, 168-173
A STUDY ON THE SYNTHESIS AND STRUCTURE OF ZEOLITE NAX
D. Georgiev
1
, B. Bogdanov
2
, I. Markovska
2
, Y. Hristov
1
1
Department of Material Science and Technology,
2
Department of Inorganic Substances and Silicates
Assen Zlatarov University, Bourgas, Bulgaria
E-mail: dgeorgiev@btu.bg
ABSTRACT
The synthesis of zeolite with valuable properties is a serious task, requiring numerous laboratory studies. Zeolite
NaX (also called zeolite X, NaX, Linde X and molecular sieve 13X) is an analogue of the natural zeolite faujasite.
The aim of the present paper is to investigate the most important stage of synthetic zeolite production - the process
of its granulation. The granulation is obtained on the basis of three mechanisms involving different types of granulators or
installations. The subject matter of the work is zeolite granulate of type Zeolite NaX with or without a binding substance.
For this purpose, a laboratory installation of fuidized bed was designed and manufactured. The method of fuidized
bed is a very effective method by which the synthesis takes place in the micro-volumes of the material. The granules
obtained have an average particle size within the range of about 1 to 4 mm and also good mechanical strength.
Keywords: zeolite NaX, natural zeolite, faujasite, zeolite granulate, fuidized bed.
Received 09 November 2011
Accepted 20 December 2012
INTRODUCTION
The studies on synthetic zeolites nowadays are
focused mainly on the use of cheap initial or waste
materials, as well as on the implementation of modern
highly effective methods for their preparation. There
are reports for studies on the preparation of granulated
synthetic zeolite type NaX using a fuidized bed in-
stallation [1 - 3].
The zeolites of class FAU (NaX, NaY, Linde X, Ul-
trastabl Y) are used mainly as ion exchangers, adsorbents
or catalysts in chemical, oil refning and gas industries.
Besides, they can be applied in purifcation of natural
gas from sulfur compounds, for drying oils and gases
(air), as cooling agents, in separation of hydrocarbon
mixtures, sorption of radio nuclides, etc. [4-5].
Traditionally, the basic raw material used to obtain
zeolites with low content of silicon dioxide containing
(like NaX and NaY) kaolin. Kaolin belongs to the large
group of minerals known as clays. Its structure is built
of silicon layers (Si
2
O
5
) bonded to similar aluminium
hydroxide layers (Al(OH)
4
), called Gibbsite layers.
Gibbsite is an aluminium hydroxide mineral which
is bonded to the silicate layer (Silicate/Gibbsite) in a
common layer called S/G layer. The relatively weak
bonding between these S/G layers explains the plastic
properties of the mineral. A similar structure have also
the minerals of the kaolin group like Halloyzite, Dickite
and Nacrite [6-9].
EXPERIMENTAL
Raw Material
The following initial materials were used for the
preparation of zeolite NaX: kaolin from the Kaolin
Company (Bulgaria). NaOH, LiOH, SiO
2
and Al
2
O
3
.
NaOH, LiOH, SiO
2
and Al
2
O
3
used were of Laboratory
Reagent (LR) grade. The kaolin (grade BoExtra) has
the following chemical composition, according its pro-
ducer, shown in Table 1.
D. Georgiev, B. Bogdanov, I. Markovska, Y. Hristov
169
Metakaolinisation
The kaolin was calcined in a muffe furnace at
temperature 600-700C with a uniform gradation of
50C giving a soaking period of 3 h each to get the
metakaolins MK600 to MK700 (Fig. 1).
The metakaolinisation of the initial material was car-
ried out at a temperature of 650C for 3 h. As can be seen
from the results of the DTA/TGA analysis in Fig. 1, the
crystallization water (of the initial material at 543.3C)
was eliminated after this thermal treatment but the newly
formed spinel phase formed again at 1007.7C. The mass
loss was 0.59 % (the same as at 700C) [10].
Synthesis of zeolite NaX
The activated (metakaolinated) natural product
was dry mixed with amorphous SiO
2
to prepare a homo-
geneous mixture. Then sodium-alumosilicate solution
(SAS) was added to obtain a gel-like product. The
sodium alumosilicate solution was prepared from fresh
solutions of sodium silicate (SS) and sodium aluminate
(SA).
Sodium silicate (SS) was prepared to have the SiO
2
concentration in the solution in the range 160-170 g/L,
and that of Na
2
O 60-65 g/L. In the (SA) solution, the
Al
2
O
3
concentration was 210-220 g/L, while that of
Na
2
O 300-320 g/L.
The blend obtained was mixed for 1 h in a special
mixer at a temperature of 50-70C. The next stage was
granulation of the amorphous blend and thermal treat-
ment of the granules.
The granulation was carried out in a specially de-
signed and manufactured fuidized-bed installation for
Table 1. Chemical analysis of kaolinite mineral.
Component Mass.%
SiO
2
49.00 2.00
Al
2
O
3
36.50 0.50
TiO
2
0.30 0.05
Fe
2
O
3
0.75 0.05
CaO 0.15 0.05
MgO 0.25 0.05
Na
2
O 0.15 0.05
K
2
O 0.60 0.20
LI
*
12.00 0.60

* Loss of ignition.
Particle size distribution in % (Sedi-
Graph 5100)
10 m 2.00
5 m 87.00
2 m 67.30
Fig. 1. DTA/TGA curve: (a) non-calcined kaolinite;
(b) - kaolinite calcined at 650
o
C (650).
Fig. 2. Photograph of granules prepared in fuidized bed.
Journal of Chemical Technology and Metallurgy, 48, 2, 2013
170
granulation of clayish products. It allows simultane-
ous mixing and drying (up to 60-80C) of the ceramic
blends, preparation and separation of granules sized
from 0.5 to 4 mm [11]. For the purpose of the present
work, the sizes of the granules obtained were 1-3 mm.
The binding agent in this case was water. Fig. 2 shows
a photograph of granules prepared from ceramic blends
in the fuidized-bed installation.
Obviously, the granules obtained were of the Black-
berry type, as illustrated in Fig. 2.
These are granules of a geometrically irregular
shape; they do not release powder;are easily dissolving
and have compact structure; their size can be precisely
controlled and they have low wear resistance. Besides
their excellent technical characteristics, the main advan-
tage of this type of granules is that they can be obtained
comparatively easy from dispersed powders and formed
with a low content of binder. This is of crucial impor-
tance, since the binder might deteriorate the sorption
properties of the material.
The granules obtained were dried at a temperature
of 90C under fuidized bed conditions. They were then
subjected to thermal activation in a muffe furnace at
temperature of 720C for 1 h on order to achieve an ini-
tial strength of the granules (called also green strength)
since they are to be further processed.
Table 2 shows the exemplary compositions of the
initial amorphous blends from which the granules were
obtained.
The next very important stage is the crystallization
(zeolitization) of the formed and granulated amorphous
blend. It was carried out using crystallization solutions
containing: aqueous solutions of NaOH, LiOH and SS.
The NaOH and LiOH solutions were 260 g/l with respect
to Na
2
O and 200 g/l with respect to Li
2
O. Exemplary
compositions of the crystallization solutions are pre-
sented in Table 3.
The ratio between the amorphous blend and the
crystallization solution was 1 to 5. The reactive mixture
prepared crystallized (zeolitized) for 30-40 h at tempera-
ture of 80-100C. The granules were then washed, dried
and thermally treated (720C, 2 to full dehydration).
RESULTS AND DISCUSSION
The present paper discusses problems concerning
the use of a natural material as a basic raw material for
synthesis of granulated zeolite, type NaX. One of the
technical possibilities to produce such a zeolite involves
the use of lithium hydroxide as an additive in the alkali
solution for crystallization (zeolitization) of the amor-
phous granules.
The crystallization was carried out under isothermal
conditions (temperature 9010! for more than 30 h)
depending on the sodium hydroxide concentration in the
crystallization solution, the amount of lithium hydroxide
additive and granules sizes (the bigger the granules, the
longer the treatment time). The essence of this solution is
that the lithium hydroxide addition to the alkali solution
allows creating optimal conditions for the crystallization
of the faujasite zeolite NaX within the granule, under
the crystallization in a hydrothermal medium.
Lithium ions, having signifcantly smaller ion radius
than sodium ions, penetrate easier into granule pores
and, simultaneously, they transport with themselves
Table 2. Compositions of the initial amorphous blends.
Zeolite,
index
MK(650),
g
Amorphous
SiO
2
, g
SS,
ml
SA,
ml
Z
1
100 18 90 42
Z
2
100 17 85 45
Z
3
110 19 95 43
Z
4
110 18 80 45
Z
5
110 20 95 40

Solution
index
Aqueous
solution of
NaOH, ml
Aqueous
solution of
LiOH, ml
SS, ml
R
1
100 4 25
R
2
100 6 30
R
3
110 4 30
R
4
120 6 30
R
5
130 6 35


Table 3. Compositions of the crystallization solutions.
D. Georgiev, B. Bogdanov, I. Markovska, Y. Hristov
171
water contained in the hydrate coating. It, in turn, serves
as a transport agent for sodium ions. Thus, the additive
in the alkali crystallization solution allows for obtain-
ing zeolite NaX of high phase purity. Furthermore, it
facilitates the realization of a chemical equilibrium with
respect to the fnal product and helps ensuring decreased
crystallization (zeolitization) times and decreased alkali
concentration in the crystallization solutions.
Fig. 3 shows the X-ray diffractogram of a zeolite
NaX sample synthesized. JCPDS fles for automatic
recognition were used. It can be seen that the main crys-
talline phases were zeolite Na and a small quantity of
quartz (SiO
2
) and Andalusite (AI
2
(SiO
4
)O) [12].
Fig. 4 shows the results from the DTA/TGA studies
of Zeolite Z3 (R2, 95C, 36 h). It can be seen from the
thermal curves that the material lost more than 20 % of
its mass under heating to 500C which is considered
enough to deduce that it can absorb signifcant amounts
of water. Above this temperature, mass losses were only
0.40 % which means that the zeolite obtained was struc-
turally stable. This is an important property for a zeolite
which is to be used as a sorbent and for catalysis. The
zeolite synthesized was found to be structurally stable
up to 900C and a new spinel-like phase was formed
above this temperature.
Fig. 3. XRD pattern of Zeolite Z3 (zeolitization R2 ,
95

, 36 h).
CONCLUSIONS
The possibility to prepare synthetic zeolite NaX
from Bulgarian kaolin as the basic raw material was
studied. The synthesis of zeolite NaX involves prelimi-
nary formation of granules by the method of fuidized
bed, followed by crystallization (zeolitization). Thus,
the following experimental results were obtained:
Fig. 4. DTA/TGA of Zeolite Z3 (zeolitization R2 , 95

, 36 h).
Journal of Chemical Technology and Metallurgy, 48, 2, 2013
172
The conditions for thermal treatment of the initial
material of Bulgarian origin (kaolin BoExtra) were
studied and the treatment was found to be suitable for
the synthesis of zeolite NaX.
Using the method of fuidized bed, the conditions
for preparation of suitable granules (Blackberry type)
with a preset size (1-3 mm) were studied with fve amor-
phous ceramic blends containing kaolin, amorphous
SiO
2
, sodium silicate and sodium aluminate at appropri-
ate quantitative ratios.
Five crystallizing reactive solutions containing
sodium hydroxide and lithium hydroxide as additive
were developed. The role of the additive in the crystal-
lization process in the optimization and in the achieve-
ment of a high phase purity of the zeolite synthesized,
was established.
The conditions for hydrothermal crystallization
(zeolitization) of granules were found to be: 36 h at
temperature of 95C.
The structure of the synthetic product Zeolite Z3
with zeolitization R2 , 95C, 36 h was studied by the
methods of XRD, DTA/TGA, SEM and IR spectros-
copy. The synthetic product Zeolite Z3 (obtained by
the method of preliminary formation of granules in a
fuidized bed, followed by zeolitization with a suitable
reactive solution from the initial material kaolin of
Bulgarian origin) was proved to have the same structure
as Zeolite NaX.
Acknowledgements
The fnancial support of the Ministry of Educa-
tion and Sciences (National Science Fund), Bulgaria,
contract DO-02-110/2008 is gratefully acknowledged.
REFERENCES
1. R.M. Barre, Hydrothermal Chemistry of Zeolites,
Academic Press, London, 1982, p. 360.
2. D.W. Breck, Zeolite Molecular Sieves: Structure,
Chemistry and Use, 1st Ed., John Wiley, New York,
1974, p.280.
3. R. Lussier, A novel clay-based catalytic material prep-
aration and properties, J. Catal., 129, 1991, 225-237.
4. D. Akolekar, A. Chaffee, R.F. Howe, The transforma-
tion of kaolin to low-silica X zeolite, Zeolites, 19,
1997, 359-365.
5. M. Murat, A. Amokrane, J.P. Bastide, L. Montanaro,
Synthesis of zeolites from thermally activated kao-
linite. Some observations on nucleation and growth,
Clay Miner., 27, 1992, 119130.
6. S. Chandrasekhar, P.N. Pramada, Investigation on the
Synthesis of Zeolite NaX from Kerala Kaolin, Journal
of Porous Materials, 6, 1999, 283-297.
7. A. De Lucas, M.A. Uguina, I.Covian, L.Rodriguez,
Synthesis of 13X zeolite from calcined kaolins and
sodium silicate for use in detergents, Ind. Eng. Chem.
Res., 31, 1992, 2134-2140.
8. A. De Lucas, M.A. Uguina, I. Covian, L. Rodriguez,
Use of Spanish natural clays as additional silica
source to synthesize 13X zeolite from kaolin, Ind.
Eng. Chem. Res., 32, 1993, 1645-1660.
9. V.H. Bekkum, E.M. Flanigen, P.A. Jacobs, J.C.
Jansen, Introduction to Zeolite Science and Practice,
2nd Revised Edn., Elsevier, Amsterdam, 1991, 13-34.
10. D. Georgiev, B. Bogdanov, Y. Hristov, I. Markovska,
I. Petrov, Synthesis of NaA zeolite from natural
kaolinite, 8 th International conference on the
occurrence, properties and utilization of natural
zeolites, 10-18 July 2010, Sofa, p. 95-96.
Fig. 5. An IR spectrum and a SEM micrograph of Zeolite
Z3 with zeolitization parameters R2, 95

, 36 h shows
that the product obtained had the structure of Zeolite NaX.
D. Georgiev, B. Bogdanov, I. Markovska, Y. Hristov
173
11. D. Georgiev, B. Bogdanov, Y. Hristov, I. Markovska,
Iv. Petrov, NaA zeolite synthesized in fuidized bed
reactor, 15th International Metallurgy & Materials
Congress (IMMC 2010), Istambul, November 11-
13, 2010, 210-216.
12. M.M.J. Treacy, J.B. Higgins, Collection of simu-
lated XRD powder patterns for zeolites, Elsevier,
Amsterdam, 2007, p.168.

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