Synthesis of an efficient Zeolite 13X in a conventional method and
Characterization
M. Mofarahi (1), M. Rostami (1), R. Karimzadeh(2), D. Abedi Amoli(3)
M. Mahmoudi(3)
(1)
Faculty of Oil, Gas and Petrochemical Engineering, Persian Gulf University, Bushehr, Iran.
+98 77 3344 1495,
[email protected] (2)
Faculty of Chemical Engineering, Tarbiat Modares University, Tehran, Iran
(3)
Behdash Chemical Co., Mahd e- Tage Industrial Group, Qazvin, Iran
1. Introduction Zeolites are aluminosilicate minerals framework with exchangeable metal cations such
as Na, K, Ca, and Mg and water in their structure. These porous materials as a molecular sieve have attracted
growing interest in many scopes of industry for their widespread applications in catalysis, adsorption, and
separation processes, and finding new applications in electronics, magnetism, chemical sensors,
agroindustry, biochemistry and medicine. These materials form in crystalline structure including channels
and cavities with variety of pore sizes and shapes which cause applicability of them in such uses. The ion-
exchange manner of zeolite prepare them as a usable material in filtration of dust, toxin removal, and as
chemical sieves. Besides, considering this fact that zeolites have water as a part of their structure, after the
water has been removed, other molecules are able to be placed in the structure, and therefore, zeolite can
treat as a delivery system for the new molecules. This process has been applied in medicine for drug
delivery, farm animal feed, and other research. In the other word, zeolite is the proper one for environmental
and health care industries [1].
Zeolite structures are divided into two categories of natural and synthetic zeolites. The natural ones exist in
the nature and the synthetics prepared in laboratories, however, the synthetic zeolites are more effective
and applicable compared to natural ones. According to silicon to aluminium elements ratio in zeolite
structure and the kind of ion exists in their frame, there are wide variety types of synthetic zeolites such as
zeolite A, X, and Y. For example in zeolite type X, the Si to Al ratio is about 1-1.5 and the corresponding
ion is Na for zeolite 13X meanwhile this ratio will be about 1 in zeolite 4A containing the same ion [2].
The main procedure for the synthesis of zeolites in crystalline form is hydrothermal method which is using
water as a solvent and reaction media.
Some studies have been done by researchers to synthesis and characterization of porous material such as
zeolites. Each work has subjected to a certain purpose such as catalysts study, adsorption and so on. But
the topic which is in common for all studies is to determination of physical properties to comply with
acceptable values. Therefore, finding these specifications is concern of importance as well.
In this work, zeolite 13X has been synthesized in a hydrothermal process and characterized using
conventional analysis apparatus to confirm zeolite structure and gain some important properties of it. In
some case, the analysis results compared to commercial zeolite 13X to inspect any differences or
similarities in characteristics regard.
2. Experimental A molar ratio has been chosen to synthesis zeolite in a hydrothermal batch as follow:
3.5 Na2O: Al2O3: 2.9 SiO2: 150 H2O. For silica source the sodium silicate solution and for alumina source
the sodium aluminate solution were used as main reactants. The synthesis condition was carried out in a
Teflon autoclave hydrothermally with an overnight digestion time and an 8-hour crystallization time in an
oven at 90C. After the end of the reaction, the product was filtered off, and washed with deionized water
until the filtrate pH reach around 8, and then dried at 100C.
After preparation the powdery zeolite, it is necessary to investigate and analyze the sample to have
informative knowledge. In this regard, some characterization analyzers have been applied such as XRD,
SEM, BET, PSA, and XRF to gain information on synthetic zeolite mentioned and compare with
commercial zeolites.
3. Results and Discussion The specification of mentioned zeolite is the focus of this study. Therefore, in
this part the results of these investigations are presented as follow:
For characterization of zeolite 13X synthesized, in the first step the crystalline structure should be proved.
For this reason, an Inel X-ray diffractometer (XRD) with Cu K radiation apparatus has been applied and
a graph depicted in Image 1 has obtained. Comparing to the references peak related to zeolite 13X [3],
correctness of our obtained zeolite can be found.
The elemental Si/Al ratio in zeolite structure is the other character to demonstrate the zeolite NaX type.
This factor can be determined using X-ray Fluorescence (XRF) analyzer. In this way it is possible to detect
metal compound including SiO2 and Al2O3 in zeolite structure in weight percent and then measure the Si
to Al ratio.
The results obtained from this test showed that the ratio of Si to Al is about 1.2 which falls in the acceptable
range of zeolites type X.
Image 1. XRD pattern of zeolite 13X
Surface propertis are important factors for porous media. As mentioned, the main application of zeolites is
using them in some industrials due to their unique surface properties such as pore volume and large surface
area. These important parameters can be measured using Brunauer - Emmett Teller (BET) analyzer. The
BET specific surface area has been measured by N2 adsorption / desorption isotherms at 77 K as seen in
Image 2 using ASAP 2020 apparatus.
The total pore volume was calculated from the amount of N2 adsorbed at P/P0 = 0.975. The t-plot has been
also shown in Image 3. In this graph the statistical thickness of adsorbed is plotted versus loading and the
area and volume of micropores and external surface were also determined using t-plot method. From this
graph it can be inferred that the deviation of straight line, is the indicator of occurring the capillary
condensation which occurs in mesopores [4]. The textural properties of synthesized zeolite 13X were
presented in Table I.
Table I. Textural properties of synthesized zeolite 13X
t-Plot
BET surface Total pore
Adsorbent Micropore Area External Surface Area Micropore volume
(m2/g) volume (m3/g)
(m2/g) (m2/g) (m3/g)
Zeolite 13X 677.42 0.33 634.75 42.67 0.30
As seen, the BET surface area of our zeolite (after pelletization) is in the acceptable range of this type of
zeolite and also comparable to the commercial ones found in literature [5, 6].
240
Adsorption
Quantity adsorbed (mmol/g)
Desorption
220
200
180
0 0,2 0,4 0,6 0,8 1
Relative pressure(P/P0)
Image 2. N2 isotherm on zeolite 13X at 77K
9,3
Quantity Adsorbed (mmol/g)
9,1
8,9
8,7
2 4 6 8 10
Statistical Thickness ()
Image 3. t-plot of N2 adsorption on zeolite 13X
The particle morphology is another principal parameter that can be understood by scanning electron
microscope apparatus (SEM) in high resolution. Image 4 is a SEM picture of our synthetic zeolite 13X
which might be compared to other results of commercial or synthesized zeolites elsewhere [7, 8]. From
literature, our zeolite has a perfect shape and configuration compared to the same ones.
In addition, a particle size analysis (PSA) carried out to measure the size of particle synthesized. The smaller
size of particle, the higher effective surface area. The results showed a narrow size distribution of particles
within the range of 1-10 micron indicating a homogeneously dispersion and gives them a very high surface
area.
Image 4. SEM image of zeolite 13X
4. Conclusions - According to the analysis results that prove the zeolite structure, it can be concluded that
compared to commercial zeolites, our synthetic zeolite with an appropriate structure making it as a useful
agent to apply in process performed with zeolites due to their important properties such as surface area
which has been measured as about 677 m2/g and a particle size of 98% below 10 micron. Comparing to
some commercial zeolites 13X, our synthetic zeolite has been shown efficient properties such as proper
surface area and excellent configuration of particles (size and shape).
5. References
[1] K. Pavelic, M. Hadzija, in: S. M. Auerbach, K. A. Carrado, P. K.. Dutta (Eds.), Hand book of zeolite
science and technology, Marcel Dekker, New York, 2003
[2] Yang R. T, Benton D. F. Adsorbents: fundamentals and applications John Wiley & Sons (Canada),
John Wiley & Sons (Asia) Pte Ltd, 2007
[4] R.Sh Mikhail,S. Brunauer, E.E Bodor. J. Colloid and Interface Science 26 (1), (1968) p. 45.
[3] M.M.J. Treacy and J.B. Higgins. Collection of Simulated XRD Powder Patterns for Zeolites, Elsevier,
Amsterdam, 2001.
[5] G. Storch, G. Reichenauer, F. Scheffler, A. Hauer, Adsorption, 14, (2008) p. 275.
[6] J. S. Lee, J. H. Kim, J. T. Kim, J. K. Suh, J. M. Lee, C.H. Lee, J. Chem. Eng. Data. 47, (2002) p.
1237.
[7] S. Cavenati, C. A. Grande, A. E. Rodrigues, J. Chem. Eng. Data, 49, (2004) p. 1095.
[8]. X. Zhang , D. Tang, M. Zhang, R. Yang. Powder Technology, 235, (2013) p. 322.
