Beruflich Dokumente
Kultur Dokumente
H O S T E D BY
Egyptian Petroleum Research Institute
Department of Chemical Engineering & Materials Sciences, Centre of Excellence in Advanced Materials & Green Technologies,
School of Engineering, Amrita Vishwa Vidyapeetham, Amrita University, Ettimadai, Coimbatore 641 112, India
KEYWORDS Abstract The trans-esterification of cottonseed oil using strong alkali catalyst and using multi
Biodiesel; walled carbon nano tubes as catalyst to produce biodiesel was studied. The interaction effects of
Cottonseed oil; various factors such as temperature, amount of alkali used, alcohol to oil ratio and reaction time
Trans-esterification; on yield of biodiesel were studied. The maximum yield of 95% biodiesel was obtained. The biodiesel
Factorial design produced was characterized using FT-IR spectral analysis and GC–MS analysis to ascertain the
various functional groups and compounds available in it. The properties of biodiesel using homo-
geneous alkali catalyst and heterogeneous multi walled carbon nanotubes such as calorific value
(36.18 MJ/kg, 33.78 MJ/kg), flash point (160 °C, 156 °C) and other properties such as viscosity,
cloud point, pour point and density were found to determine the quality of biodiesel produced.
The studies were done by blending the biodiesel produced with diesel and properties of blended
samples were estimated to ascertain the use of blended samples in internal combustion engines.
Ó 2016 Egyptian Petroleum Research Institute. Production and hosting by Elsevier B.V. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
2.1. Biodiesel preparation and purification The normal procedure for finding the optimum parameters of
a process studied is to get the response for each parameter
The refined cottonseed oil was tested for quality by measuring while keeping the other parameters as a constant. But the
the standard parameters of oil testing such as acid value, interaction effect of one parameter upon another in the resul-
density and saponification value as per standard methods tant response is not captured here. Hence we use the statistical
[28]. The values of various properties obtained for the design of experimental tools to study the interaction effects of
cottonseed oil are shown in Table 1 and were found to be in various factors on the response. The design of experiments
accordance with the standard oil quality [29]. The constituent chosen for the study was 24 half factorial design for four inde-
fatty acids present in the cottonseed oil are given in Table 2 pendent variables namely temperature of trans-esterification
[30]. The density was measured using specific gravity bottle (X1), amount of NaOH used (X2), alcohol to oil molar ratio
(X3) and reaction time (X4). The behavior of the system is
explained using a quadratic equation given below for yield (Y):
Table 1 Physical properties of cottonseed oil. Y ¼ b0 þ b1 X1 þ b2 X2 þ b3 X3 þ b4 X4 þ b5 ðX1 X2 Þ þ b6 ðX1 X3 Þ
Property Value þ b7 ðX1 X4 Þ þ b8 X2 X3 þ b9 X2 X4 þ b10 X3 X4 þ b11 X1 X2 X3
Acid value 1.11 mg KOH/l of oil
þ b12 X1 X2 X4 þ b13 X1 X3 X4 þ b14 X2 X3 X4 þ b15 X1 X2 X3 X4
Saponification value 186.175 mg KOH/g of oil
Density 0.905 g/cc
Iodine value 107 g of iodine/100 g oil where b0 represents the global mean and bi represents the
regression coefficient corresponding to the main effects and
Biodiesel synthesis from cottonseed oil 127
The contour plot for the yield of biodiesel for variation of reac-
tion time against alcohol to oil ratio, amount of alkali and
temperature is given in Figs. 1–3 respectively. The contour of
variation of alcohol to oil ratio with amount of alkali and tem-
perature for study on biodiesel yield is given in Figs. 4 and 5
respectively. The interaction matrix for the biodiesel yield
variation with four variables studied namely temperature of
trans-esterification, amount of NaOH used, alcohol to oil
molar ratio and reaction time is given in Fig. 6.
It can be observed from Fig. 1 that the alcohol to oil ratio
of 6:1 yields above 92% biodiesel for the reaction time within
60–120 min. The increase in alcohol to oil ratio to 8:1 provides
reduced yield in the range of 88–90% biodiesel over the range
of reaction time studied within 60–120 min. The maximum
Figure 5 Contour plot for % yield of biodiesel for variation of yield of biodiesel was obtained for 6 parts of alcohol and the
alcohol to oil ratio with temperature for homogeneous catalyst. presence of excess alcohol beyond this reduces the yield of bio-
diesel significantly.
The contour plot shown in Fig. 2 for reaction time versus
affecting the reaction like temperature of trans-esterification, amount of alkali for yield of biodiesel provides that the maxi-
amount of NaOH used, alcohol to oil molar ratio and reaction mum yield of 91% was obtained for 0.5 g of NaOH/l of oil
time. The study range of variables affecting the biodiesel yield and increasing the catalyst amount beyond this level reduces
is given in Table 3. The values of factors studied in the half fac- the yield of biodiesel by trans-esterification. It can be observed
torial design along with the experimental biodiesel yield are that the yield of biodiesel obtained reaches maximum by 60 min
given in Table 4. The regression correlation for % yield of bio- of reaction time and an increase in reaction time beyond this
diesel regardless of the significances based on the regression even up to 120 min has less impact on biodiesel produced.
coefficients obtained is given below: It can be observed from the overlaid contour plot of reaction
Y1 ¼ 89:938 þ 1:813X1 2:312X2 3:062X3 þ 1:062X4 time versus temperature shown in Fig. 3 that the yield of biodie-
sel was significant at around 90–92% for the trans-esterification
þ 2:563X1 X2 þ 3:812X1 X3 3:813X1 X4
temperature range of 60–65 °C for the entire reaction time
80 96 Alcohol
to oil
Alcohol to oil ratio
88 ratio
6
80 10
96
Reaction
88
Reaction time (min) time
(min)
80 60
50 70 6 10
120
Figure 7 FT-IR spectra of glycerol obtained during trans-esterification of cottonseed oil for homogeneous catalyst.
range of 60–120 min studied. From Figs. 4 and 5 the best yield 3.3. Biodiesel properties estimation from cotton seed oil
of biodiesel was observed using 6 parts of alcohol to 1 part of
oil for concentration of 0.5 g/l homogeneous alkali catalyst The biodiesel synthesized using trans-esterification process
used in the temperature range of 60–65 °C during trans- using cottonseed oil was analyzed by estimating the various
esterification of cottonseed oil.
physical properties. The various properties of biodiesel synthe-
The interactions of all factors studied except the compar-
sized like acid value, viscosity, flash point, density, calorific
ison between using homogeneous and heterogeneous catalysts
during biodiesel production are given in Fig. 6. It can be value, pour point and cloud point estimated are shown in
observed that the alcohol to oil ratio from 6 to 10 and the Table 5. The results obtained were compared with ASTM
amount of alkali catalyst added during the reaction from D975 and EN14214 standards and were observed to be in
0.5 g/l to 1.5 g/l has negative effect on yield of biodiesel. The the range meant for quality biodiesel as shown in Table 5.
temperature of trans-esterification from 50 °C to 70 °C has The estimation of various properties of biodiesel produced
strong positive interaction on yield of biodiesel as observed is done to ascertain its quality [34]. The calorific value was
from Fig. 6 interaction matrix. The increase in reaction time measured using bomb calorimeter-Isoperibol, with a Stainless
from 60 min to 120 min has no much significant impact on steel 25 mm diameter crucible with 2 g capacity and at operat-
yield of biodiesel. ing oxygen pressure of 30 bars. In the bomb calorimeter the
130 A.A. Shankar et al.
sample of biodiesel was completely combusted in excess air volumes of aniline and oil are continuously stirred in a test
and the amount of energy released when this sample of fuel tube and heated until they merge into a homogeneous solution.
was completely combusted in air was estimated. The calorific The temperature at which the phases separate gives the aniline
value of biodiesel produced was estimated at 36.18 MJ/kg. point. The aniline point of the biodiesel produced is 41 °C.
The estimated value is comparable to 35 MJ/kg obtained for The properties of biodiesel produced by trans-esterification
biodiesel as per EN 14213 standards. of cottonseed oil using multi walled carbon nanotubes are
The flash point is the lowest temperature at which the given in Table 5. The flash point of biodiesel is 156 °C which
vapors of a fuel or any flammable liquid catch fire when is greater than ASTM D975 standards of minimum 130 °C.
exposed to a flame. It was measured using Pensky Marten’s The calorific value of biodiesel is 33.78 MJ/kg which match
closed cup method [35]. The flash point of biodiesel produced the EN14214 standards of 35 MJ/kg. The viscosity of biodiesel
is 160 °C. is 2.496 mm2/S which is in the range of ASTM D975 standards
The estimation of pour point was done based on ASTM of 1.9–6 mm2/s.
D5853 standards. The biodiesel sample was cooled inside a
cooling bath to form paraffin wax crystals. When the biodiesel
does not flow when tilted for 5 s the pour point is recorded. 3.4. Fourier transform infrared spectroscopy studies on biodiesel
The pour point estimated for the biodiesel produced is 2 °C. and glycerol from cottonseed oil
The estimation of cloud point was done based on
ASTM D2500 standards. The cloud point estimated for the The Fourier transform infrared spectroscopy (FT-IR) is used
biodiesel produced is 9 °C. The acid value is a measure of to characterize the biodiesel and glycerol obtained by trans-
the free fatty acid content in any fatty substance. In the case esterification of cotton seed oil. The glycerol obtained as top
of biodiesel, it also expresses the level to which a sample has layer was distilled above 100 °C to remove excess ethanol
been oxidized and denatured. It is the amount of KOH in and water. The FT-IR spectra of glycerol obtained as shown
milligrams that the sample of biodiesel consumes per liter. in Fig. 7 provides that the OH- peak around 3000 cm1 and
The acid value of biodiesel was estimated as 0.39 mg KOH/l. the CAH peak near 2800–3000 cm1 reveal that the compound
The aniline point is the minimum temperature at which obtained is glycerol. The Fig. 8 shows the FT-IR spectrum of
biodiesel and aniline of equal volumes are miscible. The equal biodiesel produced as bottom layer. The absence of the
Figure 8 FT-IR spectrum of biodiesel synthesized by trans-esterification of cottonseed oil for homogeneous catalyst.
Biodiesel synthesis from cottonseed oil 131
Figure 9 FT-IR spectrum of biodiesel synthesized by trans-esterification of cottonseed oil for heterogeneous catalyst.
OH- peak and the presence of ester peak at 1750 cm1 and
CAH peak near 2800–3000 cm1 shows the presence of chain
fatty ester.
Most of the carbons are all single bonded carbons CAC,
and sp3 hybridized and hence CAH bond stretching is
observed at 2800–3000 cm1. The CAH bending will show
good absorbance around 1350–1480 cm1 as observed in
Fig. 8. The CAO bond in the range of 1000–1300 cm1 is pre-
sent in the ester group, and can be seen as more than one peak.
Since there are C‚C bonds also present due to linolenic acid
and other unsaturated acid ethyl ester as observed from peak
at 1653 cm1 characteristic of C‚C stretching. The ‚CAH
stretching is observed at wave number 675–1000 cm1.
The FT-IR spectrum of biodiesel produced by trans-
esterification of cottonseed oil using multi walled carbon nan-
otubes as catalyst shows the ester peak at 1745 cm1 as pro-
vided in Fig. 9.
3.5. Gas chromatograph mass spectrometer (GC–MS) studies Figure 10 Gas chromatography spectrum of biodiesel – Total
on biodiesel synthesized from cotton seed oil Ionic Concentration for homogeneous catalyst.
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