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Energy Procedia 47 (2014) 263 267

Conference and Exhibition Indonesia Renewable Energy & Energy Conservation

[Indonesia EBTKE CONEX 2013]

Characterization and Utilization of Gunungkidul Natural Zeolite

for Bioethanol Dehydration
Satriyo Krido Wahonoa,*, Hernawana, Anis Kristianib, Silvester Tursiloadib,
Haznan Abimanyub
a

Technical Implementation Unit for Development of Chemical Engineering Processes Indonesian Institutes of Sciences,
Jl. Jogja Wonosari km 32, Gading, Playen, Gunungkidul, Yogyakarta, 55861, Indonesia
b
Research Centre of Chemistry Indonesian Institutes of Sciences, Science and Technology Research Center (PUSPIPTEK) Area,
Serpong, Tangerang 15310, Indonesia

Abstract
Bioethanol purification process after the fermentation process was done in two stages, namely distillation and dehydration. The
dehydration can be carried out with molecular sieves, one of them by using natural zeolite. Therefore, the activity tests and
characterization of Gunungkidul natural zeolites and commercial zeolite (import) were conducted. It was observed that the vapor
phase dehydration using modified Gunungkidul natural zeolite has the ability to purify ethanol relatively similar to the
commercial zeolite (purity more than 99%) but has lower yield. Relatively much ethanol was absorbed by natural zeolite, as
evidenced by the addition of adsorbent weight more than 20%.

2014 The
TheAuthors.
Authors.Published
Published
Elsevier
2014
byby
Elsevier
Ltd.Ltd.
Open access under CC BY-NC-ND license.
Selection
andpeer-review
peer-reviewunder
under
responsibility
of Scientific
the Scientific
Committee
of Indonesia
Conex 2013.
Selection and
responsibility
of the
Committee
of Indonesia
EBTKEEBTKE
Conex 2013
Keywords: bioethanol, purification, dehydration, commercial zeolite, Gunungkidul natural zeolite

1. Introduction
Indonesian natural zeolite deposits are large and have high purity with its silica concentration approximately
60%. Several zeolite mines areas are South Lampung, Bayah, Cikembar, Cipatujah, Nangapada-West Java, Ende-

* Corresponding author. Tel.: +62-274-392570; fax: +62-274-391168.

E-mail address: dna_tqim@yahoo.com, satriyo.krido.wahono@gmail.com, satr002@lipi.go.id

1876-6102 2014 The Authors. Published by Elsevier Ltd. Open access under CC BY-NC-ND license.

Selection and peer-review under responsibility of the Scientific Committee of Indonesia EBTKE Conex 2013
doi:10.1016/j.egypro.2014.01.223

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Satriyo Krido Wahono et al. / Energy Procedia 47 (2014) 263 267

NTT, Malang, and Gunung Kidul [1]. Zeolite is a natural resources which is useful for the chemical industry in
Indonesia. The first zeolite was discovered by Baron Axel Frederick C in 1756 at the nature for the hollow structure
of type crystals. Zeolite was formed at various places in the earth, as well as on the sea bottom [2]. Zeolite is an
inorganic polymer, which is composed of the smallest repeating units form of tetrahedral SiO4 and AlO4 [1].
Zeolites are alumino silicates crystalline of group IA and IIA elements such as Na, K, Mg and Ca. It can be stated by
empirical formula M2/n.Al2O3.y (SiO2). wH2O with y equal with 2 or greater, n is the valence of M cation and
w equals the number of water molecules which contained in the pores of the zeolite [3].
Zeolites are the best adsorber for the adsorption process [4]. The utilization of zeolite as adsorber is due to its
porous structure, molecular sieve and absorbing ability for small molecules such as water which can enter the zeolite
[5]. There are about 40 types of natural zeolite, although about 12 types which has commercial value, including
clinoptilolite, mordernit, filipsit, kabasit and erionite [1]. One of the natural zeolite deposits in Indonesia, which has
a fairly large in amount with silica content of approximately 60% is the local zeolite of Gunungkidul Yogyakarta
with the deposit of 55,000,000 m3. These minerals are often found in the hills area of Baturagung, the District
Gedangsari (Hargomulyo Village, Watugajah, Mertelu, and Tegalrejo) and Ngawen District (Tancep Village) [6].
Optimization of the natural zeolite performance needs to be done the activation stage before used as an
adsorbent. Natural zeolite can be activated by heating (calcination) to evaporate the trapped water in the pores of
zeolite crystals, so the surface area was increases [7]. Zeolites can be also activated through dealumination process
by using acid to produce Wonosari (Gunungkidul) natural zeolite which was able to increase the surface area and
pore volume, reducing the mean pore spokes, improving the ratio of Si/Al and acidity of natural zeolite [8]. After
dealumination and calcination, natural zeolite Gunungkidul better than the previous process with higher SiO2/Al2O3
ratio approaching that expected [1].
Natural zeolites have the framework structure, containing blank spaces which occupied by cations and free water
molecules to allow the exchange of ions and absorption of chemical compounds [2]. Zeolite structure can perform
adsorption and absorption of the compound H 2O, CO2, SO2, H2S [9], with the gases absorption ability of zeolite is
up to 25% [7]. Zeolites have the ability to increase the purity of biogas because it can absorb all the main impurity
gases of water vapor (H2O), CO2 and H2S [10]. Natural zeolites have the power to adsorbs more water from the air
than on silica gel [2]. Therefore, the activated natural zeolite can be used as an adsorbent for water in ethanol 9596% which called bioethanol dehydration. The purpose of this research was to characterize and utilize Gunungkidul
natural zeolite for bioethanol dehydration.
2. Material and method
2.1. Zeolite characterization
Natural zeolite, modified natural zeolite and commercial zeolite (import from foreign country) were characterized
on crystallinity by Maxima Shimadzu XRD (X-Ray Diffraction) and specific surface area by Sorptomatic 1800
Carlo Erba Instruments.
2.2. Zeolite pre-treatment
Gunungkidul natural zeolites were crushed to 100 mesh size, dealuminated with HCl for 24 hours, formed pellets
and calcined at 400 C for 4 hours. Commercial zeolite was stored in oven with temperature of 105 C in order to
remain anhydrous.
2.3. Dehydrated trial using zeolite
Dehydration of ethanol was conducted on dehydration column with a length of 30 cm and a diameter of 2 inches.
96% ethanol dehydrated in the vapor phase current through the column which has been filled with zeolite.
Dehydrated ethanol results levels was measured by using alcoholmeter.

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Satriyo Krido Wahono et al. / Energy Procedia 47 (2014) 263 267

3. Result and discussion

Characterization of crystalinity and specific surface area has been done for three type of zeolite which will be
tested for bioethanol dehydration. They are natural zeolite, modified natural zeolite and commercial zeolite which
shown on Figure 1.

(a)

(b)

(c)

Fig. 1. Zeolite sample for characterization : (a) natural zeolite; (b) modified natural zeolite; (c) commercial zeolite.

Figure 2 shows the significant crystallinity changes of the natural zeolite before and after modification. Chemical
and physical treatments have been successful in impurities reduction and crystallinity improvement of the natural
zeolite. XRD pattern of natural zeolite was also compared with commercial zeolite. Commercial zeolite showed
higher crystallinity than the local natural zeolite.

Fig. 2. Zeolite XRD patterns of natural zeolite (blue); modified natural zeolite (red); commercial zeolite (green).

Characterization of specific surface area was done by using BET method as shown in Table 1. Zeolite samples
having high surface area will have greater ability in adsorption. Large surface area allows to better contact between
reactants and adsorbent, so that the reaction can be run more effectively. Specific surface area of the local natural
zeolite zeolite is not much different from commercial zeolite. It indicated that there is similar adsorption ability
between local natural zeolite and commercial zeolite.
Table 1. Specific surface area of zeolite sample.
Sample
BET Area (m2/g)
Natural zeolite

6,0632

Modified natural zeolite

4,1114

Commercial zeolite

6,9196

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Satriyo Krido Wahono et al. / Energy Procedia 47 (2014) 263 267

In comparative characterization of crystallinity and specific surface area, natural zeolite Gunungkidul has
relatively close results with commercial zeolite, but has not been able to surpass or even. It still needs to be pursued
reoptimization of the natural zeolite modification.
Vapor phase dehydration has been done by using modified natural zeolite Gunungkidul and commercial zeolite.
It conducted on vertical dehydration column showed in Figure 3. The comparison results of bioethanol dehydration
can be seen in Table 2.
Table 2 shows that the vapor phase dehydration using local modified natural zeolite was relatively successful
(purity increases or more than 99%), but the dehydration yield is still low. This is possible because there are many
ethanol absorbed by zeolite adsorbents which evidenced by zeolite weight gain more than 20%.

Fig. 3. Vertical column for zeolite adsorbent in vapour phase bioethanol dehydration.
Table 2. The results of bioethanol dehydration using various zeolites.
Volume (ml)
Zeolit Weight (g)
Yield
Zeolite Type
(%)
Before
After
Before
After
Commercial Zeolite
500
420
84
500
512
Modified Natural Zeolite

Increase Weight
(%)
2,4

500

320

64

500

634

26,8

500

294

58,8

500

630

26

500

312

62,4

500

631

26,2

4. Conclusion
Vapor phase dehydration using modified natural zeolite Gunungkidul has been able to purify ethanol relatively
same as with commercial zeolite (purity more than 99%), but lower in the yield.
Acknowledgements
The authors are thankful to UPT BPPTK LIPI Yogyakarta especially for Alternative Energy Team, Chemical and
Environmental Technology Team for support of facilities in this research. Also, thankful to P2K LIPI especially for
PN 8 : Bioethanol Lignocellulose Team.

Satriyo Krido Wahono et al. / Energy Procedia 47 (2014) 263 267

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