Research Article: Process Optimization For Biodiesel Production From Corn Oil and Its Oxidative Stability

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Hindawi Publishing Corporation

International Journal of Chemical Engineering


Volume 2010, Article ID 518070, 9 pages
doi:10.1155/2010/518070

Research Article
Process Optimization for Biodiesel Production from Corn Oil and
Its Oxidative Stability

N. El Boulifi, A. Bouaid, M. Martinez, and J. Aracil


Department of Chemical Engineering, Faculty of Chemistry, Complutense University, 28040 Madrid, Spain

Correspondence should be addressed to J. Aracil, [email protected]

Received 1 December 2009; Revised 3 March 2010; Accepted 4 March 2010

Academic Editor: Michael K. Danquah

Copyright © 2010 N. El Boulifi et al. This is an open access article distributed under the Creative Commons Attribution License,
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Response surface methodology (RSM) based on central composite design (CCD) was used to optimize biodiesel production
process from corn oil. The process variables, temperature and catalyst concentration were found to have significant influence
on biodiesel yield. The optimum combination derived via RSM for high corn oil methyl ester yield (99.48%) was found to be
1.18% wt catalyst concentration at a reaction temperature of 55.6◦ C. To determine how long biodiesel can safely be stored, it is
desirable to have a measurement for the stability of the biodiesel against such oxidation. Storage time and oxygen availability have
been considered as possible factors influencing oxidative instability. Biodiesel from corn oil was stored for a period of 30 months,
and the physico-chemical parameters of samples were measured at regular interval of time. Results show that the acid value (AV),
peroxide value (PV), and viscosity (ν) increased while the iodine value (IV) decreased. These parameters changed very significantly
when the sample was stored under normal oxygen atmosphere. However, the ν, AV, and IV of the biodiesel sample which was stored
under argon atmosphere were within the limit by the European specifications (EN 14214).

1. Introduction produced on a large scale. More than 95% of biodiesel


production feedstocks come from edible oils since they are
In the last few years, the world’s energy demand is increasing varying considerably with location according to climate and
due to the needs from the global economic development and availability. In the United States, soybean oil is the most
population growth. However, the most important part of common biodiesel feedstock, whereas in Europe and in
this energy currently used is the fossil energy sources. The tropical countries, rapeseed oil and palm oil are the most
problem is fossil fuels are nonrenewable. They are limited in common source for biodiesel, respectively, [8]. However,
supply and will one day be depleted. There is an increased some of these oil sources are commodities whose prices
interest in alternative renewable fuels. As biodiesel is an are strongly influencing biodiesel cost, generally in the
environmentally friendly fuel, it is the best candidate to proportion of 70–80% [9]. In order to reduce the biodiesel
replace fossil-diesel, which has lower emissions than that of cost, many researchers are interested in waste edible oils
fossil-diesel, it is biodegradable, nontoxic, and essentially free [10] and nonedible oils like karanja, mahua and jatropha
of sulphur and aromatics [1]. However, only nitrogen oxides [7, 11, 12].
increase using biodiesel as fuels [2, 3]. Another alternative comes into play when looking to
Renewable feedstocks such as vegetable oils and animal other industries. That is the case of ethanol, whose pri-
fats have been used as raw materials for biodiesel production mary feedstock is corn. Plants ethanol from corn gives
[4]. The general way to produce biodiesel fuels is transesteri- the integrated biorefineries a hydrocarbon-based source of
fication of fat or oil triacylglycerols with short-chain alcohol renewable carbon for the production of fuels and chemicals.
such as methanol or ethanol in presence of alkaline or acid Ethanol is formed when starch is subjected to hydrolysis,
catalysts [5–7]. followed by glucose fermentation. During this process, also
Vegetable oils are promising feedstocks for biodiesel some by-products including corn gluten meal, gluten feed
production since they are renewable origin and can be and corn oil are formed. Therefore, corn oil can be extracted
2 International Journal of Chemical Engineering

as a by-product by using new technology that will make Factorial design of experiments gives more information
ethanol production more efficient. This corn oil can be per experiment than unplanned approaches; it allows to
converted into a biofuel, such as biodiesel [13]. see interactions among experimental variables within the
Biodiesel is being commercialized as a substitute or range studied, leading to better knowledge of the process and
blending stock of fossil-diesel. However, biodiesel is less therefore reducing research time and costs [22].
resistant to oxidation than typical fossil fuel and therefore
doping of biodiesel in fossil-diesel will affect the stability
2. Experimental Section
of fuel significantly [14]. Thus, as the demand and the
production of biodiesel grows fast, the development of 2.1. Equipment. Reactions were carried out in a batch stirred
methods to ensure the quality of the biodiesel industry reactor of 500 cm3 volume, equipped with a reflux condenser
and standardization becomes an urgent topic for market and a mechanical stirrer. The impeller speed was set at
introduction of biodiesel. 600 rpm to avoid external mass transfer limitation [6].
As corn biodiesel chemically is a mixture of long-chain
fatty acid methyl esters (FAMEs), it is more susceptible
2.2. Materials. Corn oil was supplied by Koipe Spain. The
to autoxidation and thus has a higher level of chemical
quality control of the corn oil used in this study is presented
reactivity than fossil-diesel. This oxidation instability is
in Table 1. The characteristics were determined according
dependant on the number and location of methylene-
to AOCS official method. Methanol of 99.8% purity was
interrupted double bounds in the FAMEs. Thus carbons
supplied by Panreac (Spain). The catalyst used was potassium
that are simultaneously allylic to two olefinic groups will
hydroxide purchased from Merck (Barcelona, Spain).
be extremely susceptible to the initiation of peroxidation.
An early study [15] measured the relative rate of oxidation
for the methyl esters of oleic (18 : 1), linoleic (18 : 2) and 2.3. Production of Corn Oil FAMEs. The corn oil FAMEs were
linolenic (18 : 3) acids to be 1 : 12 : 25. produced via a transesterification process in which a strong
A number of reports have appeared on the storage and alkali catalyst was used. This latter is frequently used in the
oxidative stability of biodiesel synthesized from different transesterification reaction, primarily due to its significant
vegetable and frying oils (including sunflower, soybean advantages in terms of the smaller quantity of catalyst used
and rapeseed oil) [16–18]. However, there is no available and the shorter reaction time required [6].
information about storage stability of biodiesel from corn oil. Corn oil was used as the raw oil to be transesterified
These stability studies were carried out under different stor- with methanol in a reacting tank. The temperature values
age condition, such as elevated temperature and exposure are below the boiling point of methanol (63◦ C), to prevent
to light, air, water, and other contaminants. In other studies the methanol in the reactant mixture from evaporating.
biodiesel was subjected to accelerated methods of oxidation, The molar ratio of the methanol and corn oil was set at
including EN 14112 (Rancimat method) and pressurized 6 : 1. The potassium hydroxide was stirred with methanol
differential scanning calorimetry [19, 20]. The oxidation for 10 minutes using an electric-magnetic stirrer to form
stability does not only depend on the raw material on the potassium methoxide, which was then poured into the
production process, but also on how the oil pressed and reacting tank and mixed with the corn oil. The total
refined [21]. reaction time was 60 minutes. Almost total conversion to
In a previous work [16], long-term storage tests on corn oil FAMEs was achieved quickly after a few minutes
biodiesel from different sources have been conducted under from the start of the reaction, depending on the reaction
different storage condition. Some chemicals properties have conditions.
been severely affected by oxidation of the FAMEs, when
the biodiesel was exposed to air and daylight. In order to 2.3.1. Fatty Acid Methyl Esters (FAMEs) Purification. At the
understand whether normal oxygen atmosphere availability end of a run the reaction mixture was allowed to cool down.
can adversely affect these properties, the study of the The upper phase consisted of FAME, and the lower phase was
change in chemical and physical proprieties of biodiesel glycerol.
in absence of oxygen (under argon atmosphere) becomes Once the glycerol and FAME phases have been separated,
necessary. the last one was purified by gentle washing with distilled
In this paper, the storage stability of biodiesel made from water to remove residual catalyst, glycerol, and soaps. The
corn oil was investigated over a storage time of 30 months pH of washing water was initially very high 10.22 due to
under argon atmosphere conditions, whose properties were the dissolved KOH. After 3 successive rinses with water, the
compared to a corn biodiesel sample which stored under washing water became clear and its pH was 7.9. The washing
normal oxygen atmosphere. The focus of the study was on process was continued (twice more) until a pH of about 7
the influence of storage time on the biodiesel properties, was achieved. Finally, the methyl ester phase was distilled to
such as PV, AV, IV and ν. This work also discusses the remove the residual water.
results of experiments carried out to evaluate the different The final water content of the corn oil FAME was less
variables affecting the alkaline methanolysis of corn oil. The than 0.01%. Water in the sample can promote microbial
optimum value for the variables affecting the process will be growth, lead to tank corrosion, participate in the formation
determined by application of factorial design and response of emulsions, as well as cause hydrolysis or hydrolytic
surface methodology. oxidation [23].
International Journal of Chemical Engineering 3

Table 1: Composition analysis results of corn oil.

PV AV ν IV Main fatty acid composition (%)


Palmitic Stearic Oleic Linoleic Linolenic
(meq/Kg) (mg KOH/g) (cst at 40◦ C) (mg I2 /g) other
(C16 : 0) (C18 : 0) (C18 : 1) (C18 : 2) (C18 : 3)
2.26 0.23 39.28 125.4 12 2.4 27.3 55.8 1 1.5
PV: peroxide value; AV: acid value; ν: viscosity; IV: iodine value.

2.4. Analytical Method. Reaction products were monitored Table 2: Experimental matrix and experimental results.
by capillary column gas chromatography, using a Hewlett-
Run XC XT C (%) T (◦ C) Y (%)
Packard 5890 series II equipped with a flame ionization
detector (FID). The injection system was split-splitless. The 1 −1 −1 34.4 0.86 94.40
carrier gas was helium at a flow rate of 1 mL/minutes. The 2 +1 −1 55.6 0.86 98.25
analytical procedures and operating conditions have been 3 −1 +1 34.4 1.18 96.50
described in detail in a previous work [24]. The internal 4 +1 +1 55.6 1.18 99.48
standard technique was used to quantify the amount of the 5 0 0 45 1.02 98.25
chemical species. 6 0 0 45 1.02 97.85
7 0 0 45 1.02 98.30
2.5. Preparation the FAME Samples. Two biodiesel samples, 8 0 0 45 1.02 98.40
three litres each of were stored at ambient temperature 9 −α 0 30 1.02 97.50
for 30 months at two different storage conditions: the 10 +α 0 60 1.02 98.70
samples were stored in closed glass exposed to daylight,
11 0 −α 45 0.80 96.9
one under normal oxygen conditions and the other under
12 0 +α 45 1.24 96.4
atmosphere argon. During storage, samples were taken out
periodically and different quality parameters (PV, AV, IV, and Note: T: temperature; C: catalyst concentration; X: coded value; Y: biodiesel
yield.
ν) were monitored. The analyses were done according to the
following procedures: PV (AOCS Cd 8-53), AV (AOCS-Ca
5a-40), ν (ISO 3104), and IV (AOCS cd 1-25). response, yield of ester, may be thus expressed as a function
of the significant factors.
3. Results and Discussion
3.1.1. Linear Stage. A linear stage was considered in the first
3.1. Statistical Analysis. The synthesis of biodiesel was stud- step. Table 2 shows the experiments corresponding to the
ied using factorial design of experiments. The experimental 22 factorial design (experiments 1–4) and four experiments
design applied to this study was a full two-level factorial in the centre point to evaluate the experimental error
design 22 (two factors each, at two-levels) and extended to (experiments 5–8). A statistical analysis was carried out
response surface methodology (RSM). on these experimental values, and the main effects and
The response selected, Y, was the yield of methyl ester. interaction effects of the variables were calculated. The
The factors chosen were reaction temperature, XT , and initial analysis of the main effects and its interaction for the chosen
catalyst concentration, XC . Initial alcohol/oil molar ratio was response and the test of statistical significance are given in
fixed at 6 : 1. Table 3.
Selection of the levels was carried out based on the Temperature (XT ), catalyst concentration (XC ), and
results obtained in preliminary studies [25]. Temperature catalyst concentration-temperature interaction effects (XTC )
levels were selected according to reactants properties, thus were fitted by multiple regression analysis to a linear model.
the lower value was set at 34.4◦ C and the higher at 55.6◦ C. The response function for the significant main effects and
The levels of catalyst concentration were chosen on the basis interactions is
of preliminary experiments where the amount of catalyst was
progressively increased, and the ester yield monitored versus Y = 97.16 + 1.7XC + 0.83XT − 0.21XTC , r = 0.98.
time. The levels chosen were 0.86 and 1.18 wt.%, based on (1)
the total mass reaction.
The statistical analysis was thereafter applied. The exper- The statistical analysis of experimental results revealed
imental matrix for the factorial design is shown in Table 2. that the most significant factor is the catalyst concentration,
All the runs were performed at random. Four experiments while it also shows a significant value for curvature for the
were carried out at the centre point level, coded as “0”, for chosen responses. These data indicate the nonlinearity of the
experimental error estimation. model and thus justifies planning a more complex design to
The use of analysis and factorial design of experiments fit the data to a second-order model.
allowed us to express the amount of ester produced as a
polynomial model (if the levels of the factors are equally 3.1.2. Nonlinear Stage. To better predict the effect of vari-
spaced, then orthogonal polynomials may be used). The ables, a quadratic model was investigated. Here, the 22
4 International Journal of Chemical Engineering

Table 3: 22 factorial design: statistical analysis.

Response: Y (%)
Number of experiments: 4
Degree of freedom: 3
Results of statistical analysis
Y (average) 97.16
Main effects and interactions
XT = 1.66, XC = 3.41, XTC = −0.43
Statistical Significance of t-test
Confidence level: 95%, Standard deviation, S = 0.24
Student’s t value, t = 3.182, Confidence interval: ±0.38
Significant effects and Interactions: XT (+), XC (+), XTC (−)
Statistical significance of curvature
YC = 98.2, Y = 97.16 Curvature: YC − Y − = 1.04
S = 0.11, t = 3.182 Confidence curvature interval: ±0.54
Curvature: significant
Response equation:
Y = 97.16 + 1.7XC + 0.83XT − 0.21XTC r = 0.98

experiment design was expanded to a circumscribed central


composite design by the addition of 4 new experiments (run
100
9–12 in Table 2), called start points and coded ±α. The value
of α, which is the distance from the center point to the start
point, is 2n/4 , where n is the number of factors (for two 98
factors, α = 1.414). The corresponding model is the complete
Y (%)

quadratic surface between response and the factors, given by


96
the equation


2 
2 
2
94
Y = β0 + βi Xi + βii Xi2 + βi j Xi X j , (2)
i=1 i=1 i=
/ j
92
where Y is the response (methyl ester yield), Xi and X j 30
35
are the uncoded independent variables, and β0 , βi , βii , and 40
T 45 1.2
βi j are intercept, linear, quadratic and interaction constant (◦ 1.1
C) 50
55 1
coefficients, respectively. 0.9 )
The coefficients of (2) were determined by multiple 60
0.8 C (%
regression analysis. This analysis includes all the independent
Figure 1: Experimental yield versus temperature and catalyst
variables and their interactions, regardless of their signifi-
concentration.
cance levels. The best-fitting response surfaces found can be
written as follows:
Y = 98.2 + 1.06XC + 0.32XT − 0.21XT XC + 0.82XT2 significant in the range studied. This effect has a positive
(3)
− 0.1XC2 , r = 0.97. influence on the response. As the temperature increases, the
solubility of methanol in the oil increases and so does the
The statistical model was obtained from coded levels. speed of reaction. As a matter of fact, at low temperatures,
Equation (3) can be represented as dimensional surfaces and methanol is not soluble at all in the oil; when the stirring
contour plots, as shown in Figure 1. These show the ester is started an emulsion appears. The reaction takes place at
yield predicted for the experimental range of temperature the interface of the droplets of alcohol in the oil and then as
and initial catalyst concentration. The influence of these soon as the first FAMEs are formed, the alcohol solubilizes
variables on the ester yield will now be discussed. The progressively because the esters are mutual solvents for the
influence of the main factors and interactions will be derived alcohol and the oil.
from (1) and (3).
3.1.4. Influence of Catalyst Concentration. From the statistical
3.1.3. Influence of Temperature. For both linear and non- analysis it can be concluded that, within the experimental
linear models, the temperature influence is statistically range, initial catalyst concentration is the most important
International Journal of Chemical Engineering 5

Normal probability plot for Y Residual plot for Y


99.9 1.7
99
1.2
95
0.7
Percentage

80

Residual
50 0.2
20 −0.3
5
−0.8
1
0.1 −1.3
−2.2 −1.2 −0.2 0.8 1.8 2.8 3.8 94 95 96 97 98 99 100
Predicted
Figure 2: Normal probability plot for the methyl esters yield.
Figure 3: Residual plot of methyl esters yield for the second-order
model.

factor on the transesterification process. It has a positive


influence on the response; that is, ester yield increases with
increasing catalyst concentration. 99.3

3.1.5. Influence of Interaction. The nonlinear model (Central


98.3
Composite Design) gives the binary influences of all the
factors used in the design. Interaction of significant main
Observed

effects temperature and catalyst concentration (T-C) is 97.3


significant and has a negative influence on the process, this
effect may be due to the formation of by-products (soaps).
96.3
3.1.6. Analysis of Response: Yield of Ester. The ester yield
generally increases with increasing catalyst concentration 95.3
and temperature, but progressively decreases at higher level
of temperature and lower level of catalyst concentration. This
finding may be explained by the formation of by-products, 94.3
possibly due to triglycerides saponification processes, a side 94.3 96.3 98.3
reaction which is favoured at high temperatures. This side Predicted
reaction produces potassium soaps and, thus, decreases the Figure 4: Experimental versus predicted values.
ester yield.
The surface plot and contours of ester yield versus
temperature and catalyst concentration obtained when indi-
vidual experimental data are plotted are shown in Figure 1. 3.2. Long Storage Stability of Biodiesel. The oxidation reac-
A comparison among these plots shows that the maximum tions affect the fuel quality of biodiesel, primarily during
ester yield is achieved at the higher level for both temper- extended storage. The oxidation stability study was con-
ature and catalyst concentration. Figure 2 present a normal ducted for a period of 30 months. At regular intervals,
probability plot of methyl ester yield which confirmed the samples were taken to measure the following physico-
significant influence of catalyst and temperature in the range chemical quality parameters: PV, AV, IV, and ν.
studied. Figure 3 present a plot of the residual distribution, Some of the most important qualities of biodiesel are
defined as the difference between calculated and observed shown before and after storage in Table 4. These parameters
values, over the observed values for the response studied were compared with some of the biodiesel standards (Euro-
FAME. The quality of the fit is good because the residual pean Union Standards, EN 14214).
distribution does not follow a trend with respect to the
predicted variables. All the residuals are smaller than 1.7% 3.2.1. Peroxide Value (PV). Although PV is less suitable
for FAME yield, which indicate that the model adequately for monitoring oxidation [26], and is not specified in the
represent the methyl ester yield over the experimental range biodiesel fuel standards, this parameter influences cetane
studied. number (CN), a parameter that is specified in the fuel
Figure 4 presents the plot of experimental values versus standard. An increase in PV involves an increase in CN,
predicted ones for biodiesel from Corn oil. From this figure, and therefore may reduce ignition delay time [27]. The
it can be observed that there are no tendencies in the linear variation of PV of corn oil FAME in two different storage
regression fit, so the model explains the experimental range conditions is shown in Figure 5. Sample stored under argon
studied adequately. atmosphere showed an increase in PV from 3 to 19.6 meq/kg
6 International Journal of Chemical Engineering

Table 4: Quality control of corn oil biodiesel fuels used in this study before and after storage time of 30 months compared to EN 14214

Corn biodiesel Corn biodiesel after storage Specification EN


Properties Unit
before storage Under argon Under normal 14214
atmosphere oxygen atmosphere
Viscosity at 40◦ C mm2 /s 4.14 4.72 5.82 3.5–5.0
Density at 15◦ C g/cm3 0.865 0.871 0.895 0.86–0.90
Water content wt% 0.15 0.21 0.29 <0.5
Biodiesel yield wt% 99.48 98.7 96.23 >96.5
Monoglyceride content wt% 0.40 0.27 0.3 <0.80
Diglyceride content wt% 0.11 0.1 0.1 <0.20
Triglyceride content wt% 0.0 0.0 0.0 <0.20
Free glycerol wt% 0.01 0.01 0.01 <0.02
Acid value mg KOH/g 0.047 0.21 0.7 <0.5
Iodine value mg I2 /g 126.6 98.4 80 <120
Peroxide value meq/Kg 3.0 14 31.8 —

Cloud point C −5 −4 −3 —

Pour point C −6 −6 −5 —

Cold filter plugging point C −8 −8 −9 <−7

and then a decrease to 14 meq/kg. It can be see that the 35


faster increase rate happens during the first 6 months. The 30
same results were obtained by another author [28]. The
Peroxide value (mg/Kg)

reasons why such behaviours exist are not clearly resolved 25


in prior work. However, the increasing of PV during the
20
first 6 months may be due to the presence of the dissolved
oxygen remaining in the biodiesel sample that allows the 15
formation of compounds like hydroperoxides. Furthermore,
sample stored under normal oxygen atmosphere conditions 10
showed a continuing increase in PV over time. If oxygen 5
is not available in sufficient abundance, the formation of
ROOH can slow or even stop while ROOH decomposition 0
continues. This will tend to cause a peak in the ROOH 0 10 20 30
concentration followed by a decrease. Month
Figure 5: Variation in the peroxide value of corn oil biodiesel
3.2.2. Acid Value (AV). Once the peroxides have formed, stored  under normal oxygen atmosphere and  under argon
atmosphere.
they decompose and interreact to form numerous secondary
oxidation products including aldehydes, which further oxi-
dized into acids. Acids can also be formed when traces
of water cause hydrolysis of the esters into alcohol and 3.2.3. Viscosity (ν). Due to the hydroperoxides decomposi-
acids. Acid value measured in mg KOH/g is one of the tion, the oxidative linking of fatty acid methyl ester chains
significant indicators of oxidative degradation in lipids. The can occur, giving as a result higher molecular weights
change in AV during storage for the two corn oil FAME species. During storage one of the obvious results of polymer
samples is shown in Figure 6. It can be seen that the AV formation is an increase in biodiesel viscosity [29]. The
increase continuously in sample stored under normal oxygen formation of higher molecular weight species, with higher
atmosphere from 0.047 to 0.7 mg KOH/g. In opposition viscosity, is a reason why the viscosity specification in
to it, in the sample stored under argon atmosphere, the biodiesel standards can be used to assess the fuel quality
AV increased fast during the first 4 months, and then status of stored biodiesel. Figure 7 shows the increase in
remained almost constant. This behaviour may be due to the the kinematic viscosity of the two corn oil FAME samples
presence of the dissolved oxygen remaining in the biodiesel versus storage time. Corn oil FAME sample which was stored
sample that allows the formation of shorter chain fatty under argon atmosphere, was found to have lower viscosity
acids [18]. In this case, the specification limit of 0.5 mg compared to the sample which was stored under normal
KOH/g was not exceeded with the corn oil FAME sample oxygen atmosphere. A similar result had been observed
stored under argon atmosphere after a storage time of 30 previously by other researchers [30]; they noted that the
months. oxidation processes led to the formation of free fatty acids,
International Journal of Chemical Engineering 7

0.8 7

Viscosity at 40◦ C (mm2 /s)


0.7
5
0.6
Acid value (mg KOH/g)

4
0.5 3

0.4 2

1
0.3
0
0.2 0 10 20 30
Month
0.1
Figure 8: Variation in the kinematic viscosity of corn oil biodiesel
stored  under normal oxygen atmosphere and  under argon
0
atmosphere.
0 10 20 30
Month
Figure 6: Variation in the acid value of corn oil biodiesel stored  storage time (Figure 8). The sample which was stored under
under normal oxygen atmosphere and  under argon atmosphere.
normal oxygen atmosphere appeared to have the highest rate
of reduction in IV, implying that the largest conversion of
7 polyunsaturated fatty acids to hydroperoxides took place. In
contrast to this result, the sample which was stored under
6 argon atmosphere was observed to have low rate of decrease
Viscosity at 40◦ C (mm2 /s)

5 in IV. Corn oil FAME samples (IV = 126.6) with a relatively


high IV compared to other biodiesel samples [4]; this sample
4 contains low levels of saturated FAME and high levels of
mono- and polyunsaturated FAME which make it much
3
susceptible to oxidation.
2 For biodiesel samples, the peroxide value, acid values,
and viscosity tended to increase, and iodine value to decrease
1 over time. The sample stored under argon atmosphere never
0 exceeded the specification limit of the studied parameters
0 10 20 30 along the 30 months of storage. Biodiesel from corn oil stored
Month under argon atmosphere did not demonstrate rapid increase
in peroxide value, acid value and viscosity, compared to the
Figure 7: Variation in the iodine value of corn oil biodiesel stored 
one stored under normal oxygen atmosphere.
under normal oxygen atmosphere and under argon atmosphere.
When storage is done in argon atmosphere condition,
at ambient temperature without oxygen availability, PV, AV,
and ν increases slowly; while PV peaks and then decreases,
double bond isomerization (usually cis to trans), saturation AV and ν continue to increase, but at a lower rate. Besides IV
and products of higher molecular weight, and viscosity decreases during the storage.
increases with increasing oxidation. Under conditions where Biodiesel kept in an argon atmosphere could increase its
oxygen is available, fatty acid moieties are joined by both stability and also show positive effects retarding oxidative
C–O–C linkages and C–C linkages [31]. When ROOH degradation of the biodiesel produced from corn oil.
decomposition occurs under an inert atmosphere, only C–C
linkages in resulting polymers are observed [31].
4. Conclusions
3.2.4. Iodine Value (IV). One of the oldest and most In this work, a fully central composite design has been
common methods of determining the level of unsaturation applied to optimize the synthesis process of FAME from corn
in a fatty oil or ester is the iodine value [32], it purportedly oil using potassium hydroxide as catalyst. The study of the
addresses the use of oxidative stability and it is included in factors (temperature and catalyst concentration) affecting
the European biodiesel standard. Oxidation, which consists the response shows that, within, the experimental range
of a complex series of chemical reactions, is characterized by considered, the most important factor is the initial catalyst
a decrease in the total unsaturated content of biodiesel due concentration. For the yield of ester, this factor has a
to elimination of hydrogen adjacent to a double bond and positive influence. The temperature has a positive influence
the formation of free radicals [33]. Our experiment shows in both responses. The T-C interaction is small and negative,
that the IV of the two corn oil FAME samples fell along the due to the formation of by-products (soaps). According
8 International Journal of Chemical Engineering

to this study, and from an economical point of view, the [10] F. Ferella, G. Mazziotti, I. De Michelis, V. Stanisci, and F.
maximum yield of ester (98.75%) can be obtained, working Vegliò, “Optimization of the transesterification reaction in
with an initial catalyst concentration (1.1%) and operation biodiesel production,” Fuel, vol. 89, pp. 36–42, 2010.
temperature (55◦ C). These models are useful to determine [11] S. V. Ghadge and H. Raheman, “Process optimization for
the optimum operating conditions for the industrial process biodiesel production from mahua (Madhuca indica) oil using
using a minimal number of experiments with the consequent response surface methodology,” Bioresource Technology, vol.
economical benefit. 97, no. 3, pp. 379–384, 2006.
Biodiesel synthesised, which consists of long-chain [12] A. K. Tiwaria, A. Kumara, and H. Raheman, “Biodiesel
production from jatropha oil (Jatropha curcas) with high free
FAME, generally suffers from lower oxidation stability.
fatty acids: an optimized process,” Biomass and Bioenergy, vol.
Results from this study suggest that for a remarkably stable 31, no. 8, pp. 569–575, 2007.
biodiesel and in order to avoid oxidation, special precautions
[13] GS AgriFuels to Convert Corn Oil into Biodiesel at Ethanol
must be taken during long storage, such as storage under Facilities, GS AgriFuels Corporation, New York, NY, USA,
argon atmosphere. Nevertheless this action delays oxidation 2006.
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