Characterizations of activated zeolite using

hydrolysis method
Cite as: AIP Conference Proceedings 2175, 020019 (2019); https://doi.org/10.1063/1.5134583
Published Online: 20 November 2019

Halimatuddahliana Nasution, Hamidah Harahap, Setiaty Pandia, Danil Maha Putra, and M. Thoriq Al Fath

AIP Conference Proceedings 2175, 020019 (2019); https://doi.org/10.1063/1.5134583 2175, 020019

© 2019 Author(s).
 Characterizations of Activated Zeolite Using Hydrolysis
Method
Halimatuddahliana Nasutiona, Hamidah Harahapb, Setiaty Pandiac, Danil Maha
Putrad, and M. Thoriq Al Fathe

Department of Chemical Engineering, Faculty of Engineering, Universitas Sumatera Utara, Padang Bulan, Medan
20155, Indonesia.
a)
Corresponding author: h_dahliana@yahoo.com
b)
hamidah_usu@yahoo.com
c)
setiaty_pandia@yahoo.com
d)
danniilmaha@gmail.com
e)
thoriqal10@gmail.com

Abstract. The characteristics of activated zeolite were evaluated using Fourier Transform InfraRed (FTIR), Scanning
Electron Microscopy-Energy Detector Dispersive (SEM-EDS) and X-Ray Diffraction (XRD). Zeolite was activated by
hydrolysis method using 2 M HCl solution. Zeolite is a mineral contain an alumina silicate with porous structure. The
existing pores will be maximized by applying the activation process. The purpose of this study is to obtain a comparison
of the characteristics of zeolite with and without activation. Functional group characteristics obtained from FTIR have
shown the intensity of some groups decreases due to the impurities of the missing metals. The morphological
characteristics using SEM-EDS showed the surface morphological differences between silica without and with activation,
where the surface of the silica activated showed a clearer pores. Furthermore, characterization using XRD has shown an
increase in the degree of crystallinity of zeolite.

INTRODUCTION
One of the natural resources that is very beneficial for the chemical industry in Indonesia is zeolite. Zeolites are
formed from volcanic ash that has settled millions of years ago. Zeolites are alumino crystalline silicate mineral with
microporous structure, the crystals are porous with a size of 10-15 microns, have a large surface area, high thermal
stability and are not toxic. To get porous material with a large absorption capacity, the material must have a large
specific area, so that it shows a porous structure with the existence of micropores. The crystal and porous structure
of zeolite can be filled by water and cations that can be exchangeable and have a certain pore size. Therefore zeolite
can be used as a molecular filter [1], ion exchange compounds [2], filters [3], and fillers in composites [4] and
catalysts [5].
Zeolite still commonly contains impurities that can close zeolite’s pores, therefore modifications need to be made
by the activation method. The activation process can change the type of cation, the ratio of Si/Al and the
characteristics of zeolite to improve the quality where the empty cavity is formed so that the absorption ability of the
matrix becomes optimal. In general, there are three activation processes that can be performed on natural zeolites,
which are physical activation by heating, chemical activation with acids and chemical activation with alkali. The
activation process by heating can be carried out at temperatures between 200-400 oC for several hours. While
activation by alkali can be done using NaOH solution, where a decrease in the Si/Al ratio will occur in activation
with high pH [6].
Activation of natural zeolite by using HCl solution at various concentrations and temperatures gives the result
that activation with HCl causes the process of dealumination of zeolite. From the process of zeolite activation, both

Proceedings of the 5th International Symposium on Applied Chemistry 2019

AIP Conf. Proc. 2175, 020019-1–020019-7; https://doi.org/10.1063/1.5134583
Published by AIP Publishing. 978-0-7354-1922-3/$30.00

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acidic and basic, the results showed that zeolites activated by alkali will be more polar when compared to acid-
activated zeolites [7]. Treatment with acid against zeolite is also proven to cause zeolites to become more
hydrophobic so that their adsorption capacity of water will decrease. The higher the concentration of acid used, the
less the zeolite’s adsorption power on water vapor. As the research conducted by Ola, et al. (2013) where natural
zeolite is activated using HCl [8].
The ability of zeolite as filler in composite has been applied widely, for example as in the reearch of Katjar, et.al
(2017) where the interaction of composite interfae and filler in zeolite thermoplastic which combined zeolite as filler
that can absorb water thus preventing contact with moisture [9]. Also the research of Barbosa, et.al (2015) about the
design and characterization of chitosan/zeolite as commposite film, where zeolite which possess good ion exchange
capacity makes the composite film better [4].

METHOD

Material
The natural zeolite used as modified sample is obtained from Sukabumi. Chloride acid (HCl) as An activator
and aquadest (H2O) is used as washing liquid.

Natural Zeolite Preparation

The sample was prepared and sieved with a 100 mesh sieve, then washed with distilled water and continued with
sun drying.

Zeolite Modification
2M HCl solution was prepared and mixed into natural zeolite with a ratio of natural zeolite: HCl (1:10) w/v,
stirred with a stirrer for 2 hours at 50 rpm. The HCl solution was separated from the zeolite by using filter paper.
Zeolite was then washed with distilled water and stopped until neutral pH was obtained. The activated zeolite was
sun dried for 2 hours and heated with furnace at 600 oC for 1 hour.

Characterizations
Fourier Transform Infrared

Non-activated and activated FTIR zeolite spectrums were analyzed using the Fourier Transform Infrared
Spectrometer Shimadzu IR-21. Bands were recorded in the region from 4000 to 500 cm-1.

Scanning Electron Microscopy - Energy Dispersive Spectrometer (SEM-EDS)

The morphology of both non-activated and activated zeolite were analyzed using SEM EVO MA 10 ZEISS.

X-Ray Diffraction (XRD)

The crystallinity of both non-activated and activated zeolite were analyzed using Shimadzu 6100. The
crystallinity index (CrI) was determined with Segal’s empirical method by using equation:

I 002  I AM
Crl   100 (1)
I 002
Where:
CrI = crystallinity index (%)
I002 = maximum intensity diffraction of crystalline region
IAM = minimum intensity diffraction of amorphous region

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 DISCUSSION

Fourier Transform Infrared (FTIR)

The non-activated and activated zeolite FTIR spectrum are shown in Fig. 1.

FIGURE 1. FTIR Spectrum of Non-activated and Activated Zeolite

From Fig. 1, it can be observed that there are several key peaks that can indicate a group as a special
characteristic of a compound. The absorption peak at wave number 3603 cm-1 have been found in non-activated and
activated zeolite indicates the presence of OH groups. It can be seen that the sharpness of non-activated OH zeolite
groups is reduced, due to the activation treatment using HCl which causes the impurities of the zeolite to disappear,
thereby changing the internal structure of zeolite. This is supported by the research of Heraldy et al. (2003), with
zeolite activation changing the internal structure of zeolites [10].
The absorption peak at 1631 cm-1 have been found in non-activated and activated zeolites indicated the preence
of OH groups. It can be seen that the sharpness of the OH group intensity is reduced after activation by using HCl,
due to the release of water molecules bound in zeolite. Water molecules are bound to zeolite cavities before HCl
treatment. This is supported by the research of Madejova, et.al (2013) where acid treatment can damage the structure
of OH groups in zeolite minerals [11].
The absorption peaks at 1049 and 1037 cm-1, which were found in non-activated and activated zeolites, indicated
the presence of T-O4 groups. Based on Fig. 1, it can be seen that the reduction in sharpness after activation caused
by the reduction of Al-O vibrations in zeolite’s structures, because Si-O bonds are stronger than Al-O bonds. Based
on the results of non-activated and activated zeolite FTIR changes in wave intensity due to the treatment with
activation of HCl, the presence of open pores is more due to the loss of impurities in the zeolite pore.

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 Scanning Electron Microscopy Energy Dispersive Spectrometer (SEM-EDS) Analysis
The morphology of non-activated and activated zeolites are shown in Fig. 2.

The pores are The pores of

covered by zeolite have
impurities been exposed

(a) (b)
FIGURE 2. The Morphology of (a) Non-activated Zeolite and (b) Activated Zeolite

From Fig. 2(a) it can be seen that the surface of non-activated zeolite is still covered with metal impurities that
cover the pores of zeolite. Zeolite is a porous tetrahedral silica alumina mineral which has a three-dimensional
structure. Zeolite is often used as an adsorbent because it has silica alumina crystal structure with cavities containing
metal ions. Non-activated zeolite tends to be low because it contains a lot of metal impurities, thus needs a
modification through activation [12]. The activation process can be done by chemical and physical method. Physical
activation can be done by reducing the size and heating at high temperatures, while chemical activation is done by
acid addition [13].
In Fig. 2(b) which is the morphology of activated zeolite shows a clearer surface with cavities previously
covered with metal impurities. Zeolite can be multifunctional if it has been modified both physically and chemically.
Activation is the step in modifying, which aims to clean the pore surface and remove impurities [14]. It can also be
seen in Fig. 2(b) that empty cavities of zeolites which were previously occupied by impurities have formed.
The results of Scanning Electron Microscope-Energy Dispersive analysis (EDS) for non-activated zeolite are
shown in Fig. 3 and Table 1 below.
cps/eV

C Fe Mg
K O Al Si K Fe
3

0
1 2 3 4 5 6 7 8 9 10
FIGURE 3. Scanning Electron Microscope- Energy
keV
Dispersive (EDS) of Non-Activated Zeolite

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 In Fig. 3 and Table 1, it can be seen that the composition of zeolite consists of the element of O, Si, Al, Fe, Mg,
K, C with the composition of 38.26; 30.95; 6.89; 10.05; 1.44; 1.36 (wt.%), respectively. Here, the Si and O content
being the most dominant content as result of the main elements of zeolite. Electron beam energy in the form of X-
rays will be detected and calculated by the energy dispersive spectrometer (EDS) and the output will be produced in
the form of a graph of peaks representing the elements contained. It has been shown the highest peaks are Si, Fe and
followed by Al and K metals. It is also seen that impurity metal elements (Fe, Mg and K) are still bound to the
zeolite’s structure so that the properties of zeolite are not maximal, therefore modifications are needed.
TABLE 1. Scanning Electron Microscope- Energy Dispersive (EDS) Composition of Non-Activated Zeolite
Unn. C Norm. C Atom. C
El AN Series
(wt. %) (wt. %) Error (at. %)
O 8 K-series 38.26 40.37 56.26
Si 14 K-series 30.95 32.65 25.93
Fe 26 K-series 10.05 10.60 4.23
Al 13 K-series 6.89 7.27 6.01
K 19 K-series 5.83 6.15 3.51
Mg 12 K-series 1.44 1.52 1.39
C 6 K-series 1.36 1.44 2.66
Total 94.78 100.00 100.00

The loss of metals and other impurities was evidenced by the results of the Scanning Electron Microscope-
Energy Dispersive analysis (EDS) of activated zeolite in Fig. 4 and Table 2 below.
cps/eV

C O Al Si

0
1 2 3 4 5 6 7 8 9 10
keV
FIGURE 4. Scanning Electron Microscope- Energy Dispersive (EDS) of Activated Zeolite

It can be seen that the composition of impurity metals is reduced and vanished. This is caused by the activation
treatment of zeolites which cause decationization, i.e. cations will be released in zeolite pores. From Fig. 4 and
Table 2, the remaining elements O, Si Al and C with their respective compositions are 31.27; 21.86; 15,18; 2.26
(wt.%). It can be seen that the composition of zeolite has decreased the amount of composition after activation with
HCl. This is due to the process of dealumination with 2 M HCl. This activation process causes the metal content of
zeolite to decrease, as evidenced by Fig. 4 where metal elements have been lost, while the main element of zeolite
i.e. Si, O, Al and even increased. The activated zeolite will increase the ability of zeolite.

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 TABLE 2. Scanning Electron Microscope- Energy Dispersive (EDS) Composition of Activated Zeolite
Unn. C Norm. C Atom. C
El AN Series
(wt. %) (wt. %) Error (at. %)
O 8 K-series 31.27 44.31 56.10
Si 14 K-series 21.86 30.97 22.34
Al 13 K-series 15.18 21.51 16.15
C 6 K-series 2.26 3.20 5.40
Total 70.58 100.00 100.00

One of the factors that can determine the ability of zeolite is the ratio of Si/Al in zeolite structure. From Fig. 4
and Table 2 above, it can be seen that the impurity metal content of activated zeolite using HCl has been vanished
and the O and S elements have decreased in composition. This is inversely proportional to Al and C which have
increased composition after activation. According to Wirawan, et.al (2015), HCl with dilute or strong concentrations
can dissolve metals such as Fe, Zn, Mn, Mg, therefore the total percentage of impurity metals in zeolites after the
activation process changes including Si/Al ratio [15].
From Table 1 and 2, the Si/Al ratio of non-activated and activated zeolite can be calculated. The ratio can be
calculated by comparing the composition of silicates with aluminum. The non-activated Si/Al zeolite ratio is 4.4,
while the Si/Al ratio of activated zeolite decreases to 1.44. The smaller the ratio of Si/Al, the more water can be
absorbed by zeolite. According to Horňáčková, et al. (2013), the inability of the Si element can substitute the lost Al
content. And changes in the Si/Al ratio in a material will affect the nature of the material. The higher the Si / Al ratio
of a material, the more hydrophobic the material is [16].

X-Ray Diffraction (XRD)

Figure 5 shows the XRD spectrum of non-activated zeolite and activated zeolite.

FIGURE 5. XRD spectrum of Non-Activated and Activated Zeolite

Non-activated zeolites tend to have high peak in the range of diffraction angles (2θ) between 25.60 - 280, whereas
those in activated zeolites in the angular range 25.70 - 27.70. This can be seen from sharp peaks on activated and
non-activated zeolites. Based on the peak at 2θ angle of 190 - 270 between non-activated zeolite and activated zeolite
with 2 M hydrochloric acid (HCl), it shows that there is a 2θ angle shift that is not too far between non-activated
zeolite and activated one. According to Treacy & Higgins (2001), the shift that occurred was due to a phase change
after being activated with HCl. This shows that the metal that has been lost from the zeolite pore causes a change in
angle of 2θ [17].

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 By modifying zeolite by activation using HCl, there was no change in structure and little change in the
crystallinity of zeolite. This is indicated by the appearance of a typical peak zeolite activated at 2θ = 20o - 30o which
is relatively similar to non-activated zeolites. The crystallinity value for non-activated zeolite is 50.6%, while for
modified zeolite it has 66% crystallinity. This increase in crystallinity is caused by an acid treatment which results in
the loss of impurities in the zeolite [13]. It is proven by Fig. 4 that the reduction in impurity metal content has been
lost after activation. Therefore, the process of modifying zeolites by activation is one way to improve crystallinity.

CONCLUSION
The presence of pores in zeolite can be maximized by the activation method through the hydrolysis process using
HCl 2 M. Comparison of characteristics obtained from zeolite with and without the activation process shows that the
intensity of the several groups decreases due to the reduction impurities in zeolite. Whereas from the morphology it
has been found a clearer surface on activated zeolite. Furthermore, the crystallinity of activated zeolite is higher than
without modification.

ACKNOWLEDGEMENT
The authors gratefully acknowledge that the present research is supported by Directorate of Research and
Community Service Director General Strengthening Research and Development Ministry of Research and
Technology and The Higher Education Republic of Indonesia on year of grant 2019.

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