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ORI GI NAL PAPER

Production of biodiesel as a renewable energy source


from castor oil
Farah Halek

Armin Delavari

Ali Kavousi-rahim
Received: 23 July 2012 / Accepted: 20 November 2012 / Published online: 27 December 2012
Springer-Verlag Berlin Heidelberg 2012
Abstract The constantly increasing demand for energy
can result in a huge crisis at the end of fossil fuels era.
To prevent such an awkward situation, studies on nding
alternatives have been seriously undertaken since the rst oil
crisis in the 1970s. Biodiesel, with a history of more than a
century, has always been a potential candidate. In this
research, the process of producing biodiesel from castor oil,
which is a highly adaptable plant to Irans climates was
studied. Methanol and castor oil as reactants with 10:1 molar
ratio and sulfuric acid as catalyst with mass percent of 3 were
allowed to react through trans-esterication reaction under
mild conditions. The results fromgas chromatographymass
spectrometry (GCMS) showed the purity of more than
94 % esters for any conducted experiments which count as a
success for an oil with more complicated structure than other
rawvegetable oils. GPCanalysis illustrated that the castor oil
has a molecular weight of 1,068, which is almost three times
that of colza oil. Some signicant chemical and physical
properties of the product, such as kinematic viscosity, ash
point, pour point, etc. were calculated to approve conformity
to ASTM D6751 standards. Eventually, the polluted emis-
sions were measured by an Orsat gas analyzer. The outcomes
completely corroborate the assumption which claims that
adding biodiesel to conventional diesel fuels has a strong
inuence on lowering CO
2
, CO, HC, and smoke.
Keywords Biodiesel Castor oil Renewable energy
Trans-esterication Motor emissions
Introduction
Depletion of fossil-based fuel resources and harmful effects
of their use on environment are the two most compelling
motives that instigate researchers to focus on ways of nding
alternative energy sources instead of oil and the fractions.
Among the renewable fuels, the ones that are produced
from oilseeds and food waste as the sources are favored by
the majority of researchers because of their ability to
minimize air pollution and emission of greenhouse gases
and also to achieve reduction of dependency on fuel
import, which result in reducing the overall energy cost.
Vegetable-based fuels are the main alternative sources for
fossil-based fuels. Since these bio resources are used mostly in
ordinary diesel engines, it is known as biodiesel. There is a vari-
ety of vegetable species from different climate regions, which
have been used for this purpose including soybean, canola, sun-
ower, coconut, castor, palm, corn, cottonseed, etc. eachof which
can carry special amount of oil with its own specic characters.
Another possible source is the waste edible oil. In this case, the
production seems to be more economic and efcient (Demirbas
2007; Singh and Sharma 2009; Wang and Yang 2007).
Recent ofcial statistics show the thriving market for
this product in almost 21 countries with a bright future in
terms of demand.
One commonmethodemployedrecentlyfor decreasingraw
oils viscosity in accordance with the standards is to convert
oils having one type of ester to modied fuels with more than
one ester in their chemical structure, which is known as trans-
esterication reaction. Technically, vegetable oils are formed
by triglyceride molecules which, in the three series of equi-
librium reaction with an alcohol, such as methanol or ethanol,
convert to fatty acid esters or biodiesel. In the rst stage, one
molecule of ester from triglyceride is replaced by a hydroxide
derived from alcohol to form diglyceride. In the second and
F. Halek (&) A. Delavari A. Kavousi-rahim
Department of Energy and Environment, Materials and Energy
Research Center (MERC), P.O. Box 14155-4777, Tehran, Iran
e-mail: f-halek@merc.ac.ir
1 3
Clean Techn Environ Policy (2013) 15:10631068
DOI 10.1007/s10098-012-0570-6
third stages, the processes are the same as the rst-stage
replacement step, then proceeding further to form monoglyc-
eride and nally glycerin. The important point to note is that
every stage yields one molecule of methyl ester or biodiesel so
as to enable us obtain the desired product of our objective
(Gerpen 2005; Gerpen et al. 2004; Ghobadian et al. 2009).
Biodiesel, an appropriate alternative for conventional
fuels
The combustion of biofuels reduces CO
2
emission by almost
60 % compared with fossil fuels and also prevents emission
of the most dangerous pollutants which are normally pro-
duced by conventional fossil fuels (Ghobadian and Rahimi
2006). Many of the developed countries have decided to
develop an orientation toward agriculture as a main resource
for biofuels. The most signicant reasons for choosing bio-
diesel as a potential alternative fuels can be as follows;
(Environmental Protection Agency 2002; He and Bao 2002;
Kahraman 2008; Nwafor et al. 2000):
Renewability: the gestation period of planting oil seeds
and the possibility of extracting oil in the longest
scenario is less than a year, while the production of
fossil fuels takes millions of years.
Reduction of emissions from combustion.
Longer engine life caused by combustion of benign and
green fuel.
Natural decomposition: 99.6 % in less than 21 days and
100 % in 30 days.
No need for modifying diesel engines.
Higher ash point which results in facile transportation
and storage.
The absence of aromatics and sulfur compounds.
Higher cetane number.
Ability to blend with petrodiesel in different levels.
Castor
It is a owering plant with large claw-shaped leaves
including 511 deep serrated lobes. This plant with almost
1-m height has a special ability to grow even under arid
conditions and in uncultivated regions. The fruit has a cap-
sule containing three large seeds extraction of which can
yield large amounts of oils. Castor seeds include a variety of
constituents such as malic acid, glucose, and mostly ricino-
lein-containing oil (Ashok 2009; Murugesan et al. 2009).
Theoretical basis
Reactants including vegetable oil and alcohol through the
trans-estericationreactionyieldbiodiesel. Trans-esterication
has greater number of notable advantages compared with
other methods such as dilution, microemulsion, and pyro-
lysis (Banerjee and Chakraborty 2009; Demirbas 2009;
Georgogianni et al. 2009; Nezahat et al. 2009).
In this reaction, oxygen atoms are kept attached to the
esters chain, so that the efciency of combustion rises,
and the emissions are also decreased. Hence, the
biofuels produced by this method are known as
oxygenated fuels, whereas in the pyrolysis, oxygen
atoms are removed due to high temperature.
Among the mentioned methods, trans-esterication has
the highest yield.
The process is not complicated, and there is no need to
have special facilities.
After synthesizing the biodiesel, the product should be
evaluated by comparing the chemical and physical char-
acteristics with standards such as ASTM D6751. Conse-
quently, those parameters that have the most signicant
effects on operation need to be determined: kinematic
viscosity, ash point, pour point, water and sediment
contents, and cetane number (Mustafa and Havva 2008;
Sharma et al. 2009, Srivastava and Prasad 2000).
Experimental section
In this section, the highlighted results out of series of
experiments are mentioned briey. The main objective is to
determine the optimal factors for realizing the most ef-
cient and economic condition, such as oil-to-alcohol
(methanol) ratio, amount of catalyst (sulfuric acid), tem-
perature, and time. The materials and instrument used in
this research are listed in Table 1.
The structure of oil was studied using gas chromatog-
raphymass spectrometry (GCMS) analyzer. As the free
fatty acid (FFA) content is close to 10 %, we decided to
use a catalyst that is not sensitive to FFA, and sulfuric acid
was chosen consequently (Gerpen et al. 2004).
The reactor includes mainly a 2-l ask container with
two necksone for thermometer and the other for coupling
Table 1 List of materials and
instruments
Biodiesel
production
Material Oil
Methanol
Sulfuric acid
Instrument Heating mantle
Distillation tube
Volumetric ask
Beakers
Thermometer
1064 F. Halek et al.
1 3
distillation tubefor the recovery of methanol. A heating
mantle was also employed to maintain the temperature,
with the container being kept stirred. For all the couplings,
vacuum oil was used for the calibration.
To determine the best molar ratio, samples with three
different retios are considered: 6:1, 10:1, 15:1. GCMS
analyzer shows that after 90 min, the purity values of the
products were, respectively, 70.4, 94.2, and 94.5 %, from
which we nd that the last two are extraordinarily good in
terms of purity; however, considering the economic viability
aspect, we concluded that 10:1 was the most optimal alcohol-
to-oil ratio. Details of the percent composition are as follows:
ricinoleic acid methyl ester80.7 %; linoleic acid
methyl ester5.3 %; oleic acid methyl ester4.9 %;
stearic acid methyl ester1.6 %; and palmitic acid
methyl ester1.7 %.
In another experiment, the result after 3-h was about
97 %. Details of percent composition are as follows:
ricinoleic acid methyl ester83.3 %; linoleic acid
methyl ester5.5 %; oleic acid methyl ester5.1 %;
stearic acid methyl ester1.6 %; and palmitic acid
methyl ester1.7 %.
However, when the reactants were kept under constant
reaction condition for more than 3 h, the result illustrated
that some of the methyl esters, formed previously, under-
went decomposition over time, and so the yield of reaction
decreased. Accordingly, the optimum time of reaction was
concluded to be between 90 and 120 min. In addition, the
temperature was maintained at a constant temperature of
63 C, just because it is the boiling point of methanol.
The stages of the whole process are depictedinFigs. 1and2
After production and separation, the characteristics, as
mentioned before, should be evaluated for some designated
experiments and nally, they are compared with the stan-
dards. The results are displayed in Table 2.
Evaluation of emissions
In this experiment, a Belgium orsat gas analyzermodel
AVL4000was employed to calculate the parameters of
pollution (Fig. 3). The analysis included measurement of
vol.% of CO
2
and O
2
and, in addition, the concentrations of
HC, CO, and NO
x
in ppm (Murugesan et al. 2008; Shiwu
et al. 2009).
As the whole analyzing process needs a volume of
product more than a small laboratory sample, the men-
tioned reaction with 2-l ask container was conducted ten
times under same conditions; the products obtained from
all of them were then evaluated by GCMS analyzer to
verify the structural resemblance.
Carbon dioxide
The responses of four different blends to 1,400 and
2,000 rpm are explicitly displayed in Fig. 1. The results
Fig. 1 Process of biodiesel
produced through trans-
esterication reaction from
castor oil
Production of biodiesel as a renewable energy source 1065
1 3
conrm the assumption of biodiesels contribution to cause
the decrease in CO
2
emission. Statistically, CO
2
emissions
in 1,400 rpm for biodiesel blends of 20, 10, and 5 are,
respectively, decreased by 3.6, 12.16, and 7.9 %, whereas
for the same blends in 2,000 rpm, they are decreased by
21.2, 15.2, and 9.5 %.
Clearly, by increasing biodiesel in fuel blend, the CO
2
emission decreases which is a sign of better combustion. The
differences between 1,400 and 2,000 rpm can be explained
by air-to-fuel weight (A:F) ratio. In 2,000 rpm, this ratio is
approximately 24.6 which results in better combustion in
comparison with A;F ratio = 18.3 in 1,400 rpm.
Carbon monoxide emission
Fig. 2 shows the same procedures as above, which were
conducted in the analysis for CO in 1,400 and 2,000 rpm.
The outcomes conrmed the decline in CO emission.
The decreasing slope of 2,000 rpm curve is clearly steeper,
which again is because of air-to-fuel weight (A:F) ratio.
Unburned hydrocarbons
As in the case of carbon monoxide, the generation of
unburned hydrocarbons or incompletely burned hydrocar-
bon is due to the lack of adequate amount of available air for
combustion. The origin of these types of pollutants can be
spotted somewhere inside the engines with no combustion
ame. The amounts of HC in 1,400 rpm decreased by 50,
37.5, and 12.5 % for biodiesel blends of 20, 10, and 5 %,
respectively. The corresponding results under the condition
of 2,000 rpm are 60, 40, and 20 %, respectively (Figs 4, 5).
According to Fig. 6, adding biodiesel to the nal prod-
uct brings down the amount of produced HC.
Outlet smoke from exhaust
The study of the amount of smoke released by combustion
was carried out by the same analyzing method as applied
for the pollutants discussed above The outcomes represent
decreasing levels of smoke with the addition of biodiesel.
Details of the outcomes indicate a better picture in favor of
conrming the assumption. Under condition of 1,400 rpm
for blends, and 20, 10, and 5 %, smoke decreased by 29.5,
25, and 12.05 %, respectively. The corresponding results
for 2,000 rpm are 34.5, 23.7 and 16.3 % (Fig. 7)
Concentration of outlet smoke is decreased with increas-
ing oxygen content and decreasing C/H ratio. Existence of
oxygen in biodiesel structure causes to obtain better fuel
oxidation. Another reason for decrease in smoke is the lower
C/H ratio for biodiesel than for conventional diesel fuels.
Results and discussion
Results
Since there exist a variety of oilseeds resources in Iran,
biodiesel produced from castor seeds can be treated as a
Fig. 2 a Biodiesel production setup; and b samples of biodiesel
Table 2 Some of the physical and chemical properties of biodiesel
from castor oil compared with ASTM
Property Units Biodiesel
from
castor oil
Limits ASTM
method
Flash point C 220 Min 130 D93
Water and sediment vol.% 0.05 Max 0.05 D2709
Kinematic viscosity mm
2
/s 6.2 1.96 D445
Copper strip corrosion 2 Max 2 D130
Cetane number 48 Min 47 D613
Pour point C -17 D97
Fig. 3 Orsat gas analyzer AVL4000
1066 F. Halek et al.
1 3
potential opportunity for investment especially because
of the favorable weather conditions for cultivation and
also the existence of non-edible species of castor seeds.
Analysis for determining structural properties of castor
oil was conducted using gas chromatographymass
spectrometry (GCMS). Results show that about 10 %
of oil contains FFA.
Trans-esterication reaction was chosen to synthesize
biodiesel from reactants including raw castor oil and
methanol, in the presence of sulfuric acid as catalyst.
The yield is more than 94 %.
Signicant properties of produced biodiesel are within
the ASTM D6751 stipulated limits. Therefore, it is
considered as safe for consumption.
The largest decreases in the amounts of CO
2
, CO, HC,
and smoke existing in emission gas were observed for
B20, which means that increasing the amount of
biodiesel in the fuel blend can lower the amount of
the released pollutant after combustion. Thus, it can be
concluded that B20 is the best candidate as green fuel
among all the blends studied in the above experiment.
Suggestion
It is advisable to utilize more efcient catalysts such as
nano-catalysts.
The passageway of uids mix or any parts of setup in
contact, such as lters, diaphragm pump, injector pump
etc. should constantly be under observation to prevent
erosion mostly caused by acidic catalyst
Vibration levels of not only diesel fuels but also
biodiesel fuels should be evaluated.
Economic optimization for industrial production scales
is absolutely necessary.
The effects of additives on stability and cold weather
performance should be considered.
To better understand the process of combustion, both
practical and theoretical simulations have to be carried
out.
Elimination of subsidies for fossil-based fuels and
instead, imposition of lower levies of taxes and tariffs
for direct or indirect sectors attached to biofuel
industries should be considered.
Fig. 4 Effect of biodiesel blends on CO
2
emission
Fig. 5 Effect of biodiesel blends on CO emission
Fig. 6 Effect of biodiesel blends on HC emission
Fig. 7 Effect of biodiesel blends on outlet smoke
Production of biodiesel as a renewable energy source 1067
1 3
Acknowledgments This work was supported by the Iran National
Science Foundation (INSF).
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