Proceedings of The 1th Almuslim International Conference on Science, Technology and Society (AICSTS) 2015

November 7-8, 2015, Bireuen, Indonesia

Preparation and Characterization of Zeolite MFI Membrane

For Biofuels Purification Application

1*Jufriadi, 2 Hens Saputra, 3 A.G.E Sutjipto, 4 Hamdani, and 5 Zulkifli.

1 Department of Manufacturing and Materials Engineering, International Islamic University Malaysia.

Department of Mechanical Engineering, State Polytechnic of Lhokseumawe, Jl. Banda Aceh-Medan
Km. 280,3 Buketrata, Lhokseumawe, Aceh Indonesia.
2 Center for Process Industry Agency for the Assessment and Application of Technology (BPPT) Jl. M.H.
Thamrin 8 Jakarta, Indonesia.
3 Department of Material Technology, Faculti of Industrial Science & Technology, Universiti Malaysia
Pahang, Malaysia.
4 Department of Mechanical Engineering, State Polytechnic of Lhokseumawe, Jl. Banda Aceh-Medan
Km. 280,3 Buketrata, Lhokseumawe, Aceh Indonesia.
5 Department of computer Science, Almuslim University, Bireuen, 24261, Indonesia;

*Corresponding Author: bjufriadi@gmail.com

Abstract
The most common renewable biofuel today is bioethanol, which can be blended with
petrol or used as neat alcohol in dedicated engines taking advantage of the higher
octane number and higher heat of vaporization. In the process of ethanol fermentation
production, ethanol dehydration has been proved to be a difficult task due to formation
of ethanol/water azeotrope. Pervaporation process with a distinct advantages including
low energy cost, environment friendly and unrestraint of vapor liquid equilibrium, is
considered as a promising alternative for bioethanol purification. The Zeolite MFI
membrane have been sinthesized on asymetri pore structure alpha alumina support
with pore diameter of top layer being about 0,1 m. In this experiment, the method
performed was a hydrothermal process being done at temperature 313 K by using Silica
colloidal with the composition of 30 % SiO2, 0.04 % Al2O3, 0.4 % Na2O and NaOH 4 N.
The Membranes produced were characterized by scanning electron microscope (SEM),
X-ray diffraction (XRD) and gas permeation. Based on the SEM observation, the top
layer of MFI zeolite membrane produced was about 20 m. From the gas permeation
test, the permeance of nitrogen increased while the temperature encreased. This
membrane has a good stability at high temperature, in organic solvent and was able to
increase the concentration of bioethanol from technical grade (90%) to fuel grade
(99.4%).
Key words: Biofuels, Fuel grade, Membrane, Pervaporation, Zeolite MFI.

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Proceedings of The 1th Almuslim International Conference on Science, Technology and Society (AICSTS) 2015
November 7-8, 2015, Bireuen, Indonesia

Introduction

Biofuel is defined as liquid, solid, or gaseous fuel derived from renewable biological sources for transport
purpose. Biomass can be burned directly for thermal energy or converted to other high-value energy
sources including ethanol, biodiesel, methanol, hydrogen, or methane. Currently, bioethanol from
sugarcane, tapioca, corn grain, shorgum, algae and biodiesel from rapeseed, CPO, castor oil, cooking oil
waste are produced in some countries on an industrial scale (Chew, and Bhatia, 2009).

The increasing interest for biofuels production is due to the depletion of fossil fuel. Plant oils have
attracted attention of researchers to develop an environmentally friendly and high quality fuel, which is
free of nitrogen and sulfur (Dodic, et al., 2009).

Ethanol has a higher octane rating than gasoline i.e. about 113-116 compared to 95 for gasolina (Ahmed,
et al., 1989). The higher octane rating will give the better fuel is at preventing engine "knocking" caused
by inefficient fuel combustion. In other words, the higher-octane fuel provides better performance
because it is used more efficiently to generate power rather than heat. If engines were optimized to take
advantage of the higher octane rating of ethanol, they could achieve fuel economy more similar to that of
gasoline engines.

In the process of ethanol fermentation production, ethanol dehydration has been proved to be a difficult
task due to formation of ethanol/water azeotrope. The conventional distillation can purify the ethanol
maximum until 95%. The prevailing industrial technologies such as azeotropic distillation and extractive
distillation suffer from high-energy consumption and need for an auxiliary agent. Membrane pervaporation
technology is considered as a promising alternative, due to its distinct advantages including the ability to
purify ethanol more than 99% with low-energy cost, environment-friendly and unrestraint of vaporliquid
equilibrium (Mulder, et al., 1983 and Wee, et al., 2008).

Synthetic membranes can be produced from organic materials such as polymers and liquids, as well as
inorganic materials such as zeolite, ceramic, metal, glass, etc. Most pervaporation membranes that are
used in industrial applications are of polymeric type. Polymeric membranes are attractive because they
are relatively economical to fabricate. However, a major drawback of these polymeric membranes is their
limited solvent and temperature stability. Swelling that occur in polymeric membranes also tends to alter
the membrane properties and generally leads to higher permeability and lower selectivity. Inorganic
membranes, also called as ceramic membranes made from silica, alumina or zeolite are of high solvent-
resistant properties, high temperature stability and free of swelling (Nishiyama, et al., 1996 and Saputra
and Rosyidi, 2004). Therefore, these membranes can be used for broad range of applications and at the
same time have both high selectivity and permeability. The industrial use of ceramic membranes could
lead to a higher product quality and broaden the application range of pervaporation. In particular, porous
inorganic membranes exhibit high permeabilities relative to dense membranes and high thermal stability
relative to organic membranes (Dyer, 1988).

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Proceedings of The 1th Almuslim International Conference on Science, Technology and Society (AICSTS) 2015
November 7-8, 2015, Bireuen, Indonesia

In this research, a zeolite MFI membrane was developed for increasing the purification of bioethanol from
technical grade about 90% to fuel grade (more than 99%). The morphology and mass transfer in the
membrane were also studied.

Materials and Methods

Procedure

Membrane Preparation

Zeolite MFI membrane was prepared on asymmetry alpha alumina support with the smallest top pore size
100 nm by hydrothermal method. Membrane was formed on the surface of the support by direct
crystallization. The membrane was synthesized by using colloidal silica with the composition in weight
percentage 30% SiO2, 0,04% Al2O3, 0,4% Na2O and NaOH. Cation tetrapropylammonium (TPA) was
used as organic template. The synthesis process block diagram of zeolite MFI membrane is shown in
Figure 1.

The parent solution was obtained from the mixture of colloidal silica, tetrapropylammonium hydroxide
(TPAOH) and 4N NaOH. All the materials was stirred 200 rpm at 313 K for 2 hr. Then alpha alumina
support immersed in the parent solution for 1 hour at 313 K. Then carefully the solution and alpha
alumina support inserted into Teflon chamber in stainless steel autoclave then sealed. The crystallization
process was conducted at 453 K for 24 hours in autoclave without stirring. After crystallization process
completed, then as-synthesized membrane was washed using distilled water, followed by drying to
remove water content from membrane. Finally, the organic template was removed from the membrane by
calcination process at 773 K for 5 hours with the increasing temperature 1 C/min.

Characterization

Membrane structure was identified by using X-ray diffraction (XRD) using Cu K radiation (Philips X's
Pert-MRD). The morphology was observed by Scanning Electron Microscope (SEM). Mass transfer in the
membrane was studied by gas permeability. Gas permeation test was conducted using some pure gas
such as helium, nitrogen, methane and i-butane.

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Proceedings of The 1th Almuslim International Conference on Science, Technology and Society (AICSTS) 2015
November 7-8, 2015, Bireuen, Indonesia

Colloida l Silica , TPAOH, Na OH

Mixing
313 K, 2hr

-Alum ina
Im m ersion
Support
313 K, 1hr

Crysta lliza tion

453 K, 24hr

Wa shing

Drying

Ca lcina tion
773 K, 5 hr

Zeolite MFI m em bra ne

Figure 1. Block diagram process of zeolite MFI membrane preparation.

Pervaporation

The pervaporation test of as-synthesized zeolite MFI membrane for purification of bioethanol was carried
out at room temperature. The schematic pervaporation test setup is shown in Figure 2. Technical grade
bioethanol (90%) was used as the feed.

Figure 2. Schematic diagram of membrane pervaporation system

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Proceedings of The 1th Almuslim International Conference on Science, Technology and Society (AICSTS) 2015
November 7-8, 2015, Bireuen, Indonesia

Results and Discussion

Figure 3 shows the X-ray diffraction (XRD) pattern of as-synthesized membrane. The XRD patterns of the
sample showed peaks corresponding to MFI-type zeolite. In the structure of the MFI-type zeolite,
continuous chains of five-member rings are connected by the four- and six-member rings. The pores and
channel system of zeolite MFI materials is as shown in Figure 4 (Burggraaf and Cot, 1996, and Xu, et al.,
2007).

Figure 3. XRD Pattern of as-synthesized zeolite MFI membrane

(a) (b)
Figure 4. MFI pores and channel system : a) porous sheet parallel to the (100) plane, b) channel structure

The SEM micrograph of top surface and cross section as-synthesized zeolite MFI membrane is shown in
Figure 5. Zeolite MFI structure observed clearly on the top surface of alpha alumina support. According to
SEM observation the thickness of membrane was about 20 m.

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Proceedings of The 1th Almuslim International Conference on Science, Technology and Society (AICSTS) 2015
November 7-8, 2015, Bireuen, Indonesia

(a) (b)
Figure 5. SEM image of as-synthesized zeolite MFI membrane ; (a) top surface, (b) cross section

The fluid flow properties of porous media are extremely sensitive functions of the pore size distribution
and additional pore structural characteristics (shape, connectivity). By dynamic technique, the useful data
concerning the structure of membrane can be provided and evaluate their overall quality simultaneously.
We may note that open pores can be either conductive of blind (dead-end). Both open pore types
contribute to adsorption, while permeation occurs through conducting pores only. The study of the
transport of gaseous species through the pore space of porous membranes, analysis and understanding
of the mechanisms that are involved in this process are very important.

The results of gas permeation test using as-synthesize Zr-MCM-41 membranes at room temperature,
transmembrane pressure of 300 kPa, shows that before calcined membranes were impermeable to N 2
gas. It is considered that Zeolite MFI particles were densely packed in the pores of support. The
permeance of some pure gases through zeolite MFI membrane is shown in Figure 6. According to the
permeability results indicated that permeability of the gases decreased with the increasing of kinetic
diameter. Gas permeation in zeolite MFI membrane followed the molecular diffusion mechanism.

Figure 6. Permeability of some pure gases through zeolite MFI membrane

The pervaporation test of bioethanol was carried out using technical grade at 90% ethanol at room
temperature. The separation factor was ca.18 delivered the concentration of bioethanol at permeate was
99.4%. According to ASTM D4806 Standard of ethanol fuel grade, zeolite MFI membrane is able to
enhance the concentration of bioethanol from technical grade (90%) to fuel grade (99.4%).

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November 7-8, 2015, Bireuen, Indonesia

Conclusions

Zeolite MFI membrane has been synthesized on alpha alumina support by hydrothermal method. The
thickness of membrane was ca. 20 m. Structure of Zeolite MFI has a good thermal stability and organic
solvent resistant. Permeability of some pure gases were following the molecular diffusion mechanism.
Zeolite MFI membrane is able to enhance the purification of bioethanol from technical grade (30%) to fuel
grade (99.4%) with separation factor about 18.

Acknowledgements

The authors would like to thank International Islamic University Malaysia, Center for Process Industry
Agency for the Assessment and Application of Technology (BPPT), and Politeknik Negeri Lhoseumawe
for providing equipment of research and supported.

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