Ethanol Purification Using Active Natural Pahae Zeolite by Adsorption Distillation Method

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EthanolPurificationUsingActiveNaturalPahaeZeoliteBy Adsorption
Distillation
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Ethanol Purification Using Active Natural Pahae Zeolite By
Adsorption Distillation Method
Susilawatir/*, Nrsruddin M Nr., Chandra Kumiawanrr lrwtnl Nainggolan3'aand
Yuan Alfinsyah Sihombingt'a
IPhysics Departrnent, Faculty of Mathematic and Natural Science, Universitas
Sumatera Utara, Indonesia
2PhysicsDepallrnent, Faculty of Mathematic and Natural Science, University of
Quality, Berastagi, lndonesia.
3Chemistry Deparbnent, Faculty of Mathematic and Natural Science, Universitas
Sumatera Utara, Indonesia
aPusatUnggulan Inovasi Green Chitosan dan Material M{u Universitas
Surnatera
Utara
.E-mail

: susilawati.T1274@y ahaa.com.

Abstract. A researchof ethanolpurificationusingNaruralPahaeZeoliteas activematerialhas

beei, carried. This researchaims to analizethe processof ethanolpurification by using
adsorptiondistillation method followed analyzeby the influencesof the variantsof it's
variables.Natural PahaeZeolite which has beenchemically activatedby HzSO+6% and
physicallyby the variantsof calciningtemperatures
at 500t, 600oC,700oC,800oCand 900
oC.Theh, continuedby applying an adsorbentin the ethanolpurification with the varioustime
in 30 minutes,45 minutes,60 minutes,75 minutes,and 90 minutes.The final ethanolwhich
hasbeenpurified then analizedby using GasChromatography(GC) to classi$ the level of it's
purlty. From the result of the researctqthe most effective processin ethanolpurification was
the processof adsorptiondistillation by usrngnaturalpahaezeolite as the adsorbentwhich has
beenactivatedat 700"Cin 60 minutesandheatedat 78oCwhichresultedethanolas93.28Yo1. Introduction
Nowadays, the growth of industries and transportation come out with the growth of ftel oil
consuming. It causesthe decreaseof fuel oil stock. The prediction of the decreaseof fuel oil stock in
the future and a bigger dependency of the fuel oil energy resourse, make many scientists go on
researchesto find out and develop the alternate energy resource from renewable natural resources.
Not only thaf the issue of global warming comes out from the increment of fuel oil consuming.
The gas of the fuel which freed to atnospheres has caused a significant environment issue such global
warrning [1]. The using of ethanol as a fuel will decreasethe pollution which causedby the emission
of fuel oil in the environment [2]. Ethanol is one of alternate energy resource which is prospective to
be developed in Indonesia as a subtition or additives fossil fuel which has been using now, such as

gasolene. It is because ethanol's material comes from Indonesia which is renewable and
environmentally freindly. But the using of ethanol as a fuel isn't a sollution becauseit costs a lot. The
minimum production of ethanol and a high production fee make ethanol limited and costs more. PT.
Content from this work may be used under ttre terms of theCreative Commons Attribution 3.0 licence. Any further distribution
of this work must maintain attribnrtion to the author(s) and the title of the wort, joumal ciration and DOI.
Rrblished under licence by IOP Rrblishing Ltd

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Pertamina Perssro even has to stopped the ethanol production because those kinds of factors. So, now
there are some researcheswhich aim to press the ethanol cost by using the cheap provides material
and certainly will produce a high level of ethanol.
Many researches has used zeotiie as the adsortent on the bioethanol pwification. Novitasari
reported [2] the purification of bioethanol using adsorption process and adsorption distillation in 50
minutes and at 78"C. In the other hand, by using zeolite as adsorbent which has been activated in 300

oC could increasethe purity of bioethanol from 80% to 98.42%.
Khaidir report6d [3] the dehidration of ethanol by using natural zeolite which has been modifred
could level up 1.38% for 90% bioethanol and level up l,27Yo for 95Yobioethanol. The resemchusing
the aluminate method such as oxids aluminium, nitrate aluminium, alun: and kaolin as the zealite
preparation. Dehidration was done by distillation method in 30 minutes and heated in 75 oC.
The using of natural zeolite as the water adsorbent in the purification process basically from the
nature of zeolite itself which is as adsorbent, and the other supporting factor is the limitless of zeolite
in Indonesiq low costs, and many relate supported researcheswhich have been done before. In the
research, the natural zeolite which use are taken from sub-distict Pahae, district of North Tapanuli.
2. Materials And Method Of Research
2.1 Materials
Materials which were used natural Pahae zeolite which was taken from North Tapanuli, HzSO+ 6olo,
Ethanol PA 99.8%, Ethanol90%, frlterpaper, and destilled water.
2.2 Tools
Tools which were used in the research adalah Energl Dispersive X-ray Spectrometer (EDX), Gas
Chromatography (GC), strainer 200 mesh, firrnace, oven, analytic scale,beaker glass in various size,
measuringcup, spatula,bunche cone, mortar, magnetic stirer, and another set of adsorptiondestillation
tools as the figure follows.

Fignre 1,.AdsoqptionDestillationToolsSeries

2.3 Procedure
Therewere two stepsin the processof ethanolpurification. First of all was the preparationof zeolite
as the adsortent.First crushingthe chunckof naturalzeolite into powderwhich size is 200 mesh,then
soakedinto HzSO+6Yofor 3 hours then stir using stirer, then zeolite was washedby destilled water
until reachthe neutralpH. Next zeolitewas dried by heatingin'an oven at 110"Cfor an hour. After
that the dried zeolite was calcinatedat 500 "C to 900 .C for 3 hours.After that zeolite is readyto be
used. In this step, we need to do a characterizationtest on the abilrty of water adsorption,and
identification on the unsure to define whether the natural pahae zeolite u'hich has been activated
suitable to be usEd as water adsorbentin the ethanol purification by using adsorptiondistillation

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method. The second step was the application of zeolite as the adsorbent. Zeolite and ethanol were put
into the filling materials column then stired based on certain variable of time. Then, adsorption
distillation was done at temperafure 78 "C constantly.


3. Result And Discussion
The results will be discussed in 3 subsections, they are water adsorption ability, unsure identification,
and purification tdst result
3. 1. WaterAdsorptian Ability
The result of nonactivated natural zeolite water adsorption ability, natural zeolite activated physically
and natural zeolite activated physically-chemical in calcining at 500oC, 600oC, 700oC, 800oC, and
900"C were shown in Figure 2.

50
*

6+o
o

.E30

+Zeolit

920


r{r2gslils

o,

T'

non activated
activated

10

500

500

700

800

900


CalcinationTemperature{ "C}

Figure 2. Graphof RelationBstweenAdsorptionability with Temperature
In Figure 2, the highestpercentageof water adsorptionwas shown by natural zeolitewhich has
been activatedphysical-chemicallyactivated 53,82yo in calcining at 700 oC, meanwhilethe lowest
percentageof water adsorptionwas shownby naturalzeolitewhich hasbeenactivatedonly physically
at 900 oC.Nonactivatedzeolitehas the lowest water adsorptionability becausethe poresof zeolite
havenot fully formed and therewas still dirt or anotheruselessparticleson the poressurface.Zeolite
Activated has more ability comparedto zeolite which has beennot activatedbecausethe poreshas
fully forrned,eventhoughtherewas still dirt or anotler particleson the poressurface.Zeolite that has
been physical-chemicallyactivated has the highest absorptionif comparedby the zeolite was not
activatedand activatedzeolite only physically due to the zeolite pores alreadyfully formed and no
longer there concentrategrade on the surface of the zeolite. It can be concludedthat the water
absorptionin relation to the straight path with porosity. The higher the porosity, the adsorptionalso
will be higher and vice versa.The influence of the temperaturecan be identified that the activation
reactionhasa high activationenergy(700qC),this is dueto the riicro componentsof zeolite still much
water. At a temperatureof 700 oCmore steamthat was relea$edby the zeolite to changethe sffucture
of thezeolitebecomemoreactiveso that theability of zeolitein adsorbingbecomebetter[4].


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3.2. Unsureldmtification
Energy Dispersiveanalysisof X-ray Speckometer(EDE nonactivatednatural zeolite particles and
activatednaturalzeolite physical and chemically is intendedto know the elementsthat are contained
in the particlesof natural zeolite through the graphof the relationshipbetweenour two elements
{V)
againstthe intensity count per second(cps) which meansthe greaterthe intensity of that upp"*r, ihi
more the content elementsin a substance.Figure 3 and 4 presenttfte results of testsEDX data on
physicsactivationzeolite-chemicalandnonactivated.

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Figure 3. TheResultsof rests EDX on Physical-chemically
Activatedzealite

spectrm:
Elment

Car bon
oxygen
sodium
Itagnesium
Al,rrminium
silicon
Potassie
calciw
r itanim
Ir on
copper

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:

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Figure 4. The Results cf Tests EDX onNon-Activated Zeolite

4

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Zeolite contains the main elements, aluminum, silicon and oxygen and bind a certain water
molecules in its pore. Other elernents are also found in the zeolite are the element of the alkali metal
and ground alkali. This is supported from the results of the EDX analysis of natural zeolite particles
activation results which are shown in Figure 3 which is known the dominant elements found on natural
zeolite particles activation results were O (Oxygen) of 48.31 %. C (carbon) of 25.68 %, Si (Silica) of
15.77 Vo,Al (Aluminum) of 5.l7yo, while the other elementswere impurity (dirt concentrategrade
element).
Figure 4 shows thE dominant elements that are located in the zeolite nonactivated were elements of
O (Oxygen) of 50.64 %, C (carbon) of 16.57 %, Si (Silica) of 19.65 %, N (Aluminum) of 6.350/o,
while the other elements wsre impurity (dirt concentrate grade element). From the picture is also seen
that the natural zeolite before and after the activation is still contain substances - organic substances
(the existence of atoms C) that would affect the abikty of the zeolite adsorption against water vapor.
From the analysis result of EDX on Figure 3 and 4, the ratio of Si/Al nonactivatedzeolite is 3.09
and the ratio of Si/Al activated zeolite is 3.03. It can be concluded that the activation on the zeolite
affects the ratio Si/Al even though the value is not significant. But the results of composition ana$sis
with EDX is generally still give the percentage of error so to provide more accurate analysis of
composition it is recommended to use the atomic absorption spectrophotometer (ASA) [5].
Some types of zeolite based on the ratio of SilAl, zeolite filter silica with ratio of Si/Al I - 1.5, it
has a high concentration of the most abrmdant cation and have the nature of optimum adsorption, the
examples of low silica zeolite is zeolite A and X; silica zeolite medium, which has a comparison of
Si/Al is 2 -5, examplesof tiis type of zeolite is Mordenite zeolite; high silica, with the comparison of
the level of SilAl between 10 - 100"even moFq such as is ZSM -5 t6].
The ratio which obtained from the EDX analysis results show that the natural pahae zeolite is
classified in silica medium zeolite such as Mordenite type. Type of Mordenite zeolite is the ability of
adsorptingmuch HZO so natural pahaezeolite suitableto be applied as adsorbentof H2O in a mixture
of ethanol-water.
.3.3. Purification TestResult
The testing of zeolite as an adsorbenthas done by using adsorpfion distillation method, it is a method
of sepamtionof nvo mixhrres of liquid substancebased on the difference of boiling point that includes
the adsorptionofdissolved substances[7].
The pwities of ethanol adsorption distillation results follow AOAC method 2003 [8] (Association
of Official Analytical Chemist) is tmted by using Gas Chromatography stated in percent (7o). The
measurement of the indicator using Ethanol Absolute with purities 99.8 %. Purities were obtained by
determining the comparison peak ethanol area that has been analyzed with the peak area of the ethanol
times with the percentage of the indicators.
It has been obtained zeolite which has the highest water adsorption ability the zeolite which has
been activated physical-chemically at a temperature calcining 700 oC, zeolite was then used for the
process of adsorption distillation with contact time variations 30 minutes, 45 minutes, 60 minutes, 75
minutes and 90 minutes. The increasein the level of ethanol can be seenin the Table 1.

of EthanolLevel asRezultof AdsorptionDistillation
Table 1. Increasement
r\o
I
2
J

4
5

Contact
Time (minute)
30
45
60
75
90

EthanolLevel
Before(%)
90
90
90
90
90

EthanolLevel
After (%)
91,04
91,86 t
93,28
92,1t
90,19

Percentage
of Ethanol
Level (%)
Increasement
l, l6
2,07
3,64
2,34

a,2r

Then, the relation between ethanol purity level with contact time is shown in Figure 5

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93

8gz
o
391

EE

{-zeolite

non activated


e0
|rI

rfrlsslilg

activated

89
88

Fqgure 5. Graph of Relation Between ethanol Purity level With Contact Time
Figure 5 shows the optimal contact time of 60 minutes which is able to increase the level of ethanol
as 3,64Yofrom purities 90% to 9328%. The results of the study showed that the length of the mixing
time effects the amount of ethanol that can be adsorbed by adsorbent. The longer the time stirring, the
more ethanol and water is sequestered.This is becausethe contact time between the solution and
adsorbentincreasingly, so that the masstrnsfer processof ethanol into adsorbentalso increased[9].
Comparisonof the amount of ethanol and zeolite in the processof adsorptiondistillation may affect
purities ethanol which was obtained. If the amount of zeolite is more than the amount of ethanol and
not only the water in the ethanol participating in but ethanol alsojoined. This would causea reduction
in the level of purity, instead if the amount of ethanol is more than the amount of zeolite and water
content in the ethanol could not be entirely adsorbedby the number of the zeolite. Comparison of the
composition of the ethanol and zeolite used in this researchis only specified 2:1. This may cause a
significant rise in the level of purity of ethanol. Therefore to get purities more optimum the suitable
comparison of ethanol and zeolite need to be deterrnined.
The process of soaking the zeolite in the ethanol before the process of adsorption distillation also
allows affect purities ethanot obtained. Ever soaking of course has influence in increasing the level of
purity. The shorter time zeolite was soaked in ethanol then the adsorption of water in the ethanol also
the less that cause water content does not fully traps by zeolite, rather more long time zeolite was
soaked in ethanol then the amount of water that increased accompanied with the amount of ethanol
that participate in [2]. In this resemch there wasn't any soaking step. This is also may cause an
increase in the level of purity ethanol not significant which is 3,640/o.The process of soaking the
zeolite in ethanol is important and the soaking time variation has been applied in order to get the
optimum purity levels. The results of the test using Gas Chromatography shown in Figure 6.

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