Preparation of Zeolites by Different Bases With 1.5 of Initial Ratio Si/Al: The Effect of Crystallization Temperature

IOSR Journal of Applied Chemistry (IOSR-JAC)
e-ISSN: 2278-5736.Volume 8, Issue 12 Ver. I (Dec. 2015), PP 63-66

www.iosrjournals.org
Preparation of zeolites by different bases with 1.5 of initial ratio

Si/Al: the effect of crystallization temperature
Khalid Yamni, Najib Tijani, Adnane Aouidate
Dpartement de chimie, Equipe Matriaux, Membranes et Procds de Sparation
Universit Moulay Ismail, Facult des Sciences, Mekns, Maroc
Abstract: In this study, the behavior of prepared zeolites with a 1.5 Si/Al ratio in different crystallization
temperatures was investigated. In this work, the samples were synthesized from hydrogel solution which being
prepared using silica solution and sodium aluminate powder as precursors in the presence of different bases.
The sodium hydroxide, potassium hydroxide and ammonium hydroxide are the most bases used in the present
paper. The amount of precursors materials which used in resulting hydrogel with appropriate mole ratio was
calculated. All samples for this research were prepared by agitation at room temperature for one hour then the
mixture was aged for one day at the same temperature. All others parameters of the synthesis were stayed the
same. The crystallization temperature was done at 60,80, and 100 C for 24 hours. The obtained product is
dried in an oven at 100C for 8-12H.
Keywords: Crystallization temperature, Sodalite, Zeolite, Bases.
I.
Introduction
Zeolites are the mostly hydrated aluminolicates of alkalines elements. Alkaline soils elements , or on
rare occasions other cations, such as these material find wide application in diverse area, thats return to their
proprieties(sorption[1], catalytic,molecular-sieve ,ion exchange[1] ,and other proprieties)are the results of the
specific structure of its alumniosilicate skeleton, this zeolitic structure comprises a system of channels and
cavities , which are the results of sequential combining of alumino-silico-oxygen tetrahedra rings. These
tetrahedral rings form so-called secondary building units (SBU) which are the most often used criteria for
zeolite separation into different structural types.
One of the most distinguished types of synthesized structural zeolites is sodalite[2]. The first describe
doft he mineral sodalite with chemical composition Na8 (Al-SiO4)6Cl2 was in 1811 by Thompson, and its
structure was solved in 1930 by Pauling[3]. The framework of sodalite is completely made up of regular
truncate doctahedral cages called sodalite cages. These cages consist of six four-member rings and eight sixmember rings. Therefore, the largest pore size is about 2.4. The smallest among all zeolites. In addition to
many studies on the theoretical and experimental principles of zeolite chemistry, there have been wide
investigation on industrial applications of sodalite in different filed of pigments , synthesis of nano-composites
and special ,synthesis of nanocomposites and special host matrices for quantum dot materials,and waste
management[4-9].
Aluminosilicate sodalites can be synthesized by low-temperature condensation reactions in basic
solution [1012], high-temperature, solid states interring [13], or structure transformation[14,15] .
In the other hand we find an other important structural zeolite is the LTA (Linde Type A) structure. It
has a 3-dimensional pore structure with pores running perpendicular to each other in the x, y, and z planes, and
is made of secondary building units 4, 6, 8, and 4-4. The pore diameter is defined by an eight member oxygen
ring and is small at 4.2. This leads into a larger cavity of minimum free diameter 11.4. The cavity is
surrounded by eight sodalite cages (truncated octahedra) connected by their square faces in a cubic structure.
The unit cell is cubic (a = 24.61) with Fm-3c symmetry. Zeolite A has a void volume fraction of 0.47, with a
Si/Al ratio of 1.0. It thermally decomposes at 700C. [16, 17, 18].
Such as Zeolite A is of much interest because its supercage structure is useful in spacio-specific catalysis. The
inner cavity is large enough for structure changing reactions to take place, but the small pore means only a
specific structure can get into the cavity for reaction, typically n-paraffins and olefins. One use is in paraffin
cracking. The small entry pore is selective towards linear paraffins, and cracking can occur on sites within the
supercage (alpha-cage) to produce smaller chain alkanes. Zeolite A is also widely used in ion exchange
separation. [19]
Zeolite A, like other zeolites, is synthesized in a gelling process. Sources of alumina (usually sodium
aluminate) and silica (usually sodium silicate) are mixed in basic aqueous solution to give a gel. The alkali agent
can be NaOH or solutions of quaternary ammonium salts, amines, or other polar organics. The gel is then heated
DOI: 10.9790/5736-081216366
63 |Page
Preparation of zeolites by different bases with 1.5 of initial ratio Si/Al: the effect of crystallization
to 70-300C to crystallize the zeolite. The zeolite is normally synthesized in the Na +,K+ Na+ and NH4+ Na+ form.
[18]
The present study comprehends a systematic study of the synthesis A zeolite and zeolite-sodalite by a
hydrothermal process in a basic solution (sodium hydroxide , potassium hydroxide, or ammonium hydroxide),
and the behavior of structures transformation in different temperature, such as the aim of this work is to
investigate the effect of temperature on a prepared zeolite with a 1.5 Si/Al ratio by different bases.
II. Experimental
A)
Material
In the present work, silica solution (Na2Si3O7, 27 % SiO2, 17% NaOH) was used as a silica source.
Sodium Aluminate (65% Al2O3), distilled water and sodium hydroxide, potassium hydroxide or ammonium
hydroxide were also used to prepare alumina source solution. These two prepared solutions were needed to get
synthesis (hydrogel) for the synthesis of different products in different temperatures.
B) Preparation of zeolites samples by using hydrothermal process:
In order to prepare synthetic zeolite by hydrothermal process, hydrogel solution (synthesis gel) was
prepared by agitation of 0,786 g of silica source and 0,522 g of Alumina source in a polyethylene flask
containing water and Sodium hydroxide, potassium hydroxide, or ammonium hydroxide, with mechanic stirring
at 250 rpm for one hour at room temperature, then the resulting hydrogel was aged for 24 hours at room
temperature.
After aging the mixture was transferred to a sealed container and put into oven to hydrothermal
crystallize, at different temperatures for 24 hours .After completing crystallization, the resultant precipitate was
separated from the mother liquor by vacuum filtration and washed with distilled water until reaching pH range
of 9-10 and dried at 100 C for 8-12 hours.
C) Characterization of prepared zeolite by X-Ray diffraction
X-ray powder diffraction data were collected with diffractometer Shimadzu 6100 using CuK radiation
and a monochromator. The measured 2 theta range (560) was scanned in steps of 0.02 with a counting time
of 3s/step. The aperture and the soller slits were set at 1.0.
III.
Results and discussion
A. Effect of crystallization temperature on zeolite formation by sodium hydroxide

In this study of the effect of crystallization temperature, it can be observed that when the hydrogel
solution was crystallized at 60C for 24 hr, the zeolite formed is the zeolite NaA. Then the temperature was
increased to 80C, we obtain a mixture of phases: zeolite NaA and Sodalite. Finally the sodalite is the
favorable sample in 80C.
In the XRD patterns in Fig.1, all the peaks confirmed the presence of zeolite NaA. In Fig.2, the peaks at
14, 24, 31, 35, 37 and 42 are typically the 2 values of the sodalite. The Fig3 shows the XRD pattern of
sodalite.
The table I summarizes the results.
Table I: Effect of crystallization Temperature on Zeolite obtained by sodium hydroxide.
Crystallization temperature
60 C
80C
100 C
Zeolites phases and other synthesis

products
Zeolite NaA
Zeolite NaA +Sodalite
Sodalite
B. The effect of crystallization temperature on zeolite formation by potassium hydroxide

According to the XRD spectra, when the crystallization temperature is 60C the product zeolite is the
amorphous phase with some unknown peaks (fig 4). And when the crystallization temperature increases to 80C
and 100 the product zeolite is Unnamed Zeolite (fig 5,6).
The results are listed in Table II.
Table II: Effect of crystallization Temperature on Zeolite obtained by potassium hydroxide
60 C
80C
100 C
DOI: 10.9790/5736-081216366

products
amorphous
Unnamed Zeolite
Unnamed Zeolite
64 |Page
C. The effect of crystallization temperature on zeolite formation by ammonium hydroxide
The effect of crystallization temperature on zeolite preparation with ammonium hydroxide was studied
by varying temperature from 60C, 80C and 100C (.Fig 7, Fig. 8 and fig 9). We note the apparition of some
peaks with amorphous phase at 60 C. When the temperature increase to 80C for 24hrs, the product obtained is
only NH4NaA. At 100C, we can note the formation of sodalite. The table III gives the zeolite formed in
different crystallization temperature.
Table III :Effect of crystallization Temperature on Zeolite obtained by ammonium hydroxide
60 C
80C
100 C

products
Zeolite NH4NaA + amorphous
Zeolite NH4NaA
Sodalite
IV. Conclusion
In the present work, it is concluded that the optimum conditions to prepare zeolite A depended on the
bases and the crystallization temperatures. It is possible to synthesize the zeolite A with sodium hydroxide and
the ammonium hydroxide as bases and 80C as crystallization temperature. If we increase the temperature to
100C, we obtain the sodalite. With our experimental conditions, we note the absence of the formation of zeolite
A in the case of the of the potassium hydroxide.
DOI: 10.9790/5736-081216366
65 |Page
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Preparation of Zeolites by Different Bases With 1.5 of Initial Ratio Si/Al: The Effect of Crystallization Temperature

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IOSR Journal of Applied Chemistry (IOSR-JAC)

e-ISSN: 2278-5736.Volume 8, Issue 12 Ver. I (Dec. 2015), PP 63-66

Preparation of zeolites by different bases with 1.5 of initial ratio

Results and discussion

A. Effect of crystallization temperature on zeolite formation by sodium hydroxide

Zeolites phases and other synthesis

B. The effect of crystallization temperature on zeolite formation by potassium hydroxide

Zeolites phases and other synthesis

Zeolites phases and other synthesis

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