World Journal of Engineering
INCREASING THE OCTANE NUMBER OF GASOLINE USING PRASEODYMIUM(III)ETHYLENE DIAMINE TETRA ACETATE/ACTIVATED CLINOPTILOLITE ZEOLITE
Dewi Tristantini*, Eny Kusrini, and Vino Hasyim
Chemical Engineering Department, Faculty of Engineering, University of Indonesia, Depok 16424,
Indonesia
Introduction
Lanthanides (rare earth) in a form of oxides and
a complex used as a catalyst since a few years
ago. For example, it was used in oxidation
and/or combustion reaction, isomerization,
dehydrogenation, dehydration, control of sulfur
oxidation, carbon oxides metanation, DielsAlder reaction etc. [Kilbourn, 1986].
Gasoline octane number can be increased by
adding the TEL (Tetra Ethyl Lead) but after
some time used, the researchers found that TEL
weakness can lead to fuel emissions that
endanger human health. Many studies were
conducted to find materials that able to raise
octane number of gasoline as a substitute for
TEL. One of active agent to subtitute TEL is
Praseodymium.
Praseodymium (Pr-III) is a member of
lanthanide. Properties of lanthanide complexes
can be studied better when Ln(III) complexes
change into a form of lanthanide complex
nanoparticles than in a form of large crystal
(bulk crystal) [Kusrini et al. , 2009]. The catalyst
based complex Praseodymium (Pr) is made by
impregnation of large crystal (bulk) Pr(III)EDTA complexes and nanoparticles Pr(III)EDTA respectively into zeolite and then the
catalysts were characterized to determine its
properties. Fabrication of lanthanide complexes
in the form of Gd(III) with EDTA ligands by
hydrothermal method has been reported
previously [Kusrini et al., 2010].
Clinoptilolite zeolite is one of the catalyst
supports that has almost all good support
properties required. One of the properties that
must be possessed of gasoline is the high octane
number of the fuel. In this study we explore a
subtance that can increase the octane number of
gasoline by creating a large crystal and
nanoparticles catalysts Praseodymium (III)EDTA which impregnated into Clinoptilolite
zeolite. Then this ingredients will be a gasoline
additive to increase the octane number.
Experimental
Large crystal impregnation of Praseodymium
(III)-EDTA complex on Clinoptilolite Zeolite
Zeolite is weighed for 4 grams. Zeolite
immersed in solution of 2% weight/weigt large
crystal Pr-EDTA complex and stired evenly for
1 hour while heated on a hot plate at 60oC. Then
the imprenated-zeolite was put into a sentrifuge
at 2000 rpm for 10 minute continue with heat it
up in an oven at 105oC to remove the excess
water. Thr catalyst then calcinated at 400oC for 4
hours. The catalyst of Pr(III)-EDTA/zeolite
large crystal then characterized by surface area
analyzer, XRD, XRF and FTIR.
Impregnation
of
Pr-EDTA
complex
nanoparticles on Clinoptilolite Zeolite
The same procedure with the previous catalysts
was done to make nanoparticles of Pr-EDTA
complexes, except the solution is made of PrEDTA complexes solution 2% w/w.
Impregnation of Praseodymium (Pr6O11) Oxide
on Clinoptilolite Zeolite
A similar prfocedure with the two previous
catalysts was done to make Praseodymium
(Pr6O11) Oxide on Zeolite but the solution is
made
from
1
gram
Praseodymium
oxidedissolved into 10 mL HCl 10% solution.
Test of Pr/zeolite oxide catalyst activity was
done to determine the increasing gasoline octane
number.
Activity Test of increasing gasoline octane
number
Balanced 3 grams of each catalyst and put it into
60 ml gasoline respectively then stired for 2
minutes. The precipitates were filtered using
whatman filter paper No.41. Filtrat octane
numbers were measured by Octane meter
SHATOX SX-200. Gasoline obtained from the
filtration was analyzed using GC-MS.
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World Journal of Engineering
Table 1. Gasoline octane number measurement
with and without addition of Pr(III)EDTA catalysts
Octane
Name of Mixture
Number
Gasoline (pure)
88.2
Gasoline + Zeolit Catalyst
88.8
Gasoline + Large Crystal
Catalyst
Pr(III)-EDTA/
Zeolit
89.2
Gasoline + Nanoparticle
Catalyst
Pr(III)EDTA/Zeolit
89.6
Gasoline + Pr Oxide
88.4
Gasoline + Pr/Zeolit Oxide
88.4
Results And Discussions
Based on XRF characterization, the Pr content
in the Pr(III)-EDTA/Zeolite large crystal catalyst
and Pr(III)-EDTA/Zeolite nanoparticles is
0.42% and 0.52% respectively. This result
shows that the Pr succesfully impregnated into
zeolite, although impregnation efficiency is still
low (20-26%).
The BET test result shows that most of zeolite
pores is less filled by large crystal than Pr(III)EDTA nanoparticles (BET : initially 30.86 m2/g,
24.09 m2/g and 9.91 m2/g respectively catalyst).
Based on the results of FTIR analysis of the
visible spectrums (Fig. 1.) are almost the same
between the zeolite and the impregnated catalyst
with Pr (III)-EDTA large crystals or Pr (III)EDTA nanoparticles. This is likely caused by
the Pr (III)-EDTA only interact physically with
the zeolites without changing the crystal
structure of zeolite.
Conclusion
The impregnation of Praseodymium (III)-EDTA
large crystal and Praseodymium (III)-EDTA
complex nanoparticles into the Clinoptilolite
zeolite are succes. It is proved from the results
of the catalyst characterization result by XRF.
The result of GC-MS shows an increase of iso
oktane component (C8H18) % peak area after
addition of zeolite, Pr(III)-EDTA/Zeolite large
crystal catalyst and Pr(III)-EDTA/Zeolite
nanoparticles catalyst respectively. In addition,
it shows a decrease of n-oktana component
(C8H18) % peak area when the catalyst of Pr(III)EDTA/Zeolite nanoparticles is added to
gasoline.
(c)
(a)
(b)
(a) Zeolite
(b) Pr(III)-EDTA/Zeolite Nanoparticle
(c) Pr(III)-EDTA/Zeolite Large Crystal
Fig. 1. FTIR Spectrum of Zeolite Catalyst,
Pr(III)-EDTA Large Crystal Catalyst,
Pr(III)-EDTA Nanoparticle Catalyst
References
1. Chen L., Wang X.*, Guo H., Guo X., Wang
Y., Liu H, Li G. 2007. Hydroconversion of
n-octane over nanoscale HZSM-5 zeolites
promoted by 12-molybdophosphoric acid and
Ni. Catalysis Communications 8 ,pp. 416–
423.
2. Kilbourn, B.T. (1986). The Role Of
Lantanida. J. Less-Common Metals, 126, pp.
101-106.
3. Kusrini, E., Saleh, M.I. (2009). Luminescence
and structural studies of yttrium and heavier
lanthanide- picrate complexes with pentaethylene glycol, Inorg.
Chem.
Acta,
362, 4025.
Activity Test of increasing gasoline octane
number
Table 1 shows the result of catalyst activitiy test
in increasing gasoline’s octane number.
The activity of catalyst on gasoline is probably
caused by a trace conversion of straight chain
alkanes to branched chain alkanes. The
increasing amount of catalytically converted of
straight chain alkanes to branched chain alkanes
correspond to the quality of gasoline [Chen et
al., 2007].
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