Journal of Saudi Chemical Society (2013) xxx, xxxxxx

King Saud University

Journal of Saudi Chemical Society

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Transesterication of soap nut oil using novel catalyst

R. Mathiarasi, C. Mugesh kanna, N. Partha

Department of Chemical Engineering, Anna University, Chennai 600025, India

Received 15 October 2012; accepted 29 July 2013

KEYWORDS
Fatty acid methyl ester;
Transesterication;
Spent catalyst;
EDAX;
SEM;
TGA;
1
H NMR;
Fuel properties

Abstract There is a growing interest in biodiesel (fatty acid methyl ester or FAME) because of the
similarity in its properties when compared to those of diesel fuels. Diesel engines operated on biodiesel have lower emissions of carbon monoxide, unburnt hydrocarbons, particulate matter, and air
toxics than when operated on petroleum-based diesel fuel. In the present study soap nut oil is used
for the production of fatty acid methyl ester (FAME) by using a new catalyst. In this work the catalyst employed for transesterication reaction was the residue collected from coal burnt boilers
from industries. Similar to wealth from waste the residue is completely utilised as a catalyst in this
study. The physical and chemical properties of the residue catalyst were examined by scanning electron microscope (SEM) measurements, energy dispersive X-ray (EDAX) analysis and Thermo
gravimetric analysis (TGA). The maximum yield of methyl ester was obtained as 89 wt% with
3 h reaction time at 60 C, 3.5 wt% catalyst and 1:15 oilmethanol ratio. The obtained biodiesel
was characterised by 1H NMR (Nuclear magnetic resonance spectroscopy). The fuel properties
of methyl ester were analysed and found to be within the limit of ASTM.
2013 Production and hosting by Elsevier B.V. on behalf of King Saud University.

1. Introduction
In recent years energy demand increased due to the limited
source of fossil fuels. Hence research is concentrated towards
alternative renewable fuels. Essentially, no engine modications are required to substitute biodiesel for diesel fuel that
can maintain engine performance, since its molecular similarities with biodiesel. It is biodegradable, nontoxic and has low
emission problems and so it is environmentally benecial.
And also this renewable fuel has the potential to reduce the
* Corresponding author. Tel.: +91 44 22359123.
E-mail address: npartha62@yahoo.co.in (N. Partha).
Peer review under responsibility of King Saud University.

Production and hosting by Elsevier

level of pollutants and the level of potential or probable carcinogens (Krawczyk, 1996). Biomass has been found to produce
low-molecular-weight organic liquids, which can be used or
is proposed for a vehicle which is called biodiesel. Biodiesel
is a potential substitute for petroleum fuel which consists of
methyl esters of fatty acids produced by the transesterication
reaction of triglycerides of vegetable oils with methanol with
the help of a catalyst (Sarin et al., 2007).
Fats and oils are primarily water-insoluble, hydrophobic
substances in the plant and animal kingdom that are made
up of one mole of glycerol and three moles of fatty acids
and are commonly referred to as triglycerides (Sonntag,
1979). Any fatty acid source may be used to prepare biodiesel.
The use of edible vegetable oils and animal fats for biodiesel
production has recently been of great concern because they
compete with food materials food versus fuel (Srinivasan,
2009). In addition, biodiesel is better than diesel fuel in terms

1319-6103 2013 Production and hosting by Elsevier B.V. on behalf of King Saud University.
http://dx.doi.org/10.1016/j.jscs.2013.07.006

Please cite this article in press as: Mathiarasi, R. et al., Transesterication of soap nut oil using novel catalyst. Journal of Saudi
Chemical Society (2013), http://dx.doi.org/10.1016/j.jscs.2013.07.006

R. Mathiarasi et al.

of sulphur content, ash point, aromatic content and biodegradability (Martini and Schell, 1997). When biodiesel is produced from rened edible oils, the cost of biodiesel is very high
since the cost of feed stocks is very high (Ali et al., 1995) and
the consumption of oil for biodiesel production will deplete the
quantity for food requirements (Lam et al., 2009). Because of
these reasons it is necessary to choose an inexpensive feedstock
for biodiesel fuels. The use of inexpensive, non-edible feedstock and the utilisation of by-products in the biodiesel production may signicantly reduce the cost of biodiesel (Ali
and Hanna, 1994). Transesterication of vegetable oil to biodiesel (fatty acid methyl ester, FAME) can be catalysed by
bases, acids and enzymes (Du et al., 2004). Currently, most
commercial processes used for biodiesel synthesis employ a
homogeneous base catalyst, such as NaOH or KOH. The consumption of sulphuric acid, separation of sulphates (from neutralisation processing) and purication of the product also
involve substantial energy and material use (Ramos et al.,
2008). This produces tremendous waste as it consumes more
water and increases corrosion due to sulphuric acid. The catalyst of solid types are easily produced that are non-corrosive in
nature, leading to safer, cheaper and more environmentfriendly operations, and therefore in the recent past has
become a centre of attraction. However, majority of the heterogeneous catalysts are quiet expensive or complicated to prepare, which limits their industrial application (Kafuku et al.,
2010). Thus, it is desirable to nd more efcient and cheap catalysts for the transesterication of vegetable oils for their
application in commercial production. In the present investigation a new catalyst was used for biodiesel production. The processing cost of catalyst is very less since it is a waste catalyst
collected from thermal industry. In this work soap nut oil
which is a non-edible oil was used for the synthesis of biodiesel
using a new heterogeneous catalyst.
The soap nut tree can be used for multiple applications such
as rural building construction and oil and sugar presses, and
agricultural implements would help community forestry to
produce more seeds as potential sources for the biodiesel feedstock. Among others, the plant grows very well in deep loamy
soils and leached soils so cultivation of soap nut in such soil
avoids potential soil erosion. Soap nut is a fruit of the soap
nut tree generally found in tropical and sub-tropical climate
areas in various parts of the world including Asia, America
and Europe. Two different species (Sapindus mukorossi and
Sapindus trifoliatus) are widely available in India, Nepal,
Bangladesh, Pakistan and many other countries (Arjun et al.,
2008). The oil from soap nut has been considered as a non-edible oil having a signicant potential for biodiesel production
from the material which otherwise is a waste material. The
main aim of this study is utilisation of industrially used coal
burned boiler waste as a catalyst for the production of biodie-

products

side

since

Figure 1

the

sel, hence lowering the production cost of biodiesel as well as

reducing environmental issues.
2. Experimental
2.1. Materials and catalyst preparation
All chemicals were purchased from known chemical companies. Methanol and potassium hydroxide (98%) were purchased from Merck. Soap nut seeds (S. mukorossi) were
collected from various parts of Tamilnadu, India. The kernels
were separated from the shells for oil extraction. The seeds
were selected according to their condition, where damaged
seeds were discarded and seeds in good condition were cleaned,
de-shelled and dried at high temperature of 100105 C for
60 min. Seeds were grounded using a grinder prior to extraction. The bottom ash was collected from various thermal
industries in and around the Tuticorin district, Tamilnadu.
The oversized particles were removed by simple ltration and
the catalyst was crushed well and sieved. The nest particles
were collected and used for the production of biodiesel. The
prepared catalyst was dried and stored under ambient conditions before being placed in the reactor.
2.2. Catalyst characterisation
The scanning electron microscope (SEM) was used to examine
the surface morphology at a higher magnication. SEM micrographs were obtained using JEOL-6360 (Japan) microscope.
The catalyst was analysed by thermo gravimetric analyser
using Mettler Toledo Switzer instrument. A typical TGA
instrument consists of a precision mass balance, which records
the initial and instantaneous mass of a sample, and a furnace,
which increases the temperature in a linear relationship with
time (the range of temperatures between 50 C and 900 C).
Mass measurements are performed in nitrogen medium. A
mass of 1.5 mg was heated at a constant rate of 10 C/min with
a nitrogen purge rate of 20 ml/min in a pan. The component
present in the catalyst was analysed by Edax.
2.3. Extraction of oil
Extraction is carried out in a batch process by the solvent
extraction method. The seeds were collected and dried in an
oven to remove the moisture. The process was repeated several
times to attain a constant weight. The seed coat was removed
from the seed and the seed was crushed to pass through a 40
mesh sieve. The oversized particles were crushed again and
made to pass through the 40 mesh sieve. The undersized particles were taken to extract oil. Seed and the solvent are taken by

reaction

is

reversible

Triglyceride alcoholysis.

Please cite this article in press as: Mathiarasi, R. et al., Transesterication of soap nut oil using novel catalyst. Journal of Saudi
Chemical Society (2013), http://dx.doi.org/10.1016/j.jscs.2013.07.006

Transesterication of soap nut oil using novel catalyst

Figure 2

Thermo gravimetric analysis.

weight ratio of 1:3 in a 250 ml screw cap conical ask. The setup was kept inside the shaker for 8 h. It was then taken out
and ltered using a 0.5 lm polyester lter to obtain oilsolvent
mixture. The solvent was separated from this mixture by simple distillation process.
2.4. Transesterication reaction
Transesterifcation (also called alcoholysis) is the reaction of a
fat or oil with an alcohol to form esters and glycerol. The
reaction is shown in Fig. 1. A catalyst is usually used to improve the reaction rate and yield. Excess alcohol is used to
shift the equilibrium to the products side since the reaction
is reversible.
Transesterication as an industrial process is usually carried out by heating an excess of the alcohol with vegetable oils
under different reaction conditions in the presence of an inorganic catalyst. The reaction is reversible and therefore excess
alcohol is used to shift the equilibrium to the products side.
The alcohols that can be used in the transesterication process
are methanol, ethanol, propanol, butanol and amyl alcohol.

3. Results and discussion

3.1. Characterisation of catalyst
Volatility of catalyst was analysed by Thermo gravimetric
analysis (TGA). From Fig. 2, the temperature range employed
was 50900 C. According to TGA the catalyst weight loss was
observed when the temperature exceeded 420 C which continued until 500 C. Based on the result the catalyst is stable under the operation temperature of transesterication. Scanning
electron microscope (SEM) is a type of electron microscope
that images a sample by scanning it with a beam of electrons.
The electrons interact with the atoms that make up the sample
producing signals that contain information about the samples
surface topography and other properties such as electrical conductivity. The morphology of the spent catalyst particles was
studied using the SEM micrographs presented in Fig. 3. The
gure shows the SEM photograph of a solid particle size in

2.5. Biodiesel characterisation

Nuclear magnetic resonance spectra were used to analyse the
biodiesel using CDCl3 as a solvent. The obtained results were
recorded on a Bruker AV-III 500 MHz NMR, Switzerland.
The peak differences in the 1H NMR were used to nd the conversion of bio-diesel.
The conversion was calculated using the equation
Conversion in%

2AME
 100
3AaME

where AME is the integration value of the methoxy protons of

the methyl esters and Aa-ME is the integration value of methylene protons. The fuel properties of biodiesel were analysed by
ASTM standards.

Figure 3

Scanning electron microscope.

Please cite this article in press as: Mathiarasi, R. et al., Transesterication of soap nut oil using novel catalyst. Journal of Saudi
Chemical Society (2013), http://dx.doi.org/10.1016/j.jscs.2013.07.006

R. Mathiarasi et al.

Figure 4

Energy diffraction X-ray.

the average range of 600 nm. The various elemental components present in the catalyst were determined by energy diffraction X-ray. As the energy of the X-rays is characteristic of the
difference in energy between the two shells, and of the atomic
structure of the element from which they were emitted, this
allows the elemental composition of the specimen to be measured. The components present in Fig. 4 were found to be
Oxygen (O) 29 wt%, Magnesium (Mg) 1.7 wt%, Aluminium (Al) 1.06 wt%, Calcium (Ca) 3.1 wt%, Silicon (Si)
4.33 wt%, and Ferrous (Fe) 2.9 wt%.
3.2. Production of biodiesel
20 g of soap nut seed oil was weighed and poured into a 250 ml
round bottom ask. The oil was made to react with the

Figure 5

Effect of catalyst.

Figure 6

Figure 7

Effect of temperature.

Effect of oil methanol ratio.

Please cite this article in press as: Mathiarasi, R. et al., Transesterication of soap nut oil using novel catalyst. Journal of Saudi
Chemical Society (2013), http://dx.doi.org/10.1016/j.jscs.2013.07.006

Transesterication of soap nut oil using novel catalyst

5
3.4. The effect of catalyst
The amount of catalyst used affects the conversion efciency of
the production process. The effect of spent catalyst concentration over the non-edible oil was investigated with its varying concentrations from 1.5 g to 4.5 g. For the whole process, the
operation conditions were xed at the optimum level: reaction
temperature 60 C, reaction time 2 h and 1:15 oil:methanol ratio.
The effect of catalytic activity in the transesterication process
was shown in Fig. 5. The gure reveals that 3.5 wt% catalyst
loading is optimal for achieving higher yield of biodiesel.

Figure 8

Effect of reaction time.

3.5. Effect of temperature

mixture of spent catalyst and methanol. The ask was kept in a

magnetic stirrer for 45 h at a temperature of 60 C. The mixture was allowed to settle in two layers, the lower layer is a
methanolglycerol mixture and the top layer is a biodiesel
layer. The two layers were separated with the help of a separating funnel. The bottom layer was separated and distilled to
recover the methanol. The top layer was washed with water
to remove the traces of methanol and glycerol and the biodiesel is dried in the hot air oven and stored for analysing.
3.3. Optimisation
The optimum value of each parameter involved in the process
was determined while the rest of them remained constant.
After each optimum value was obtained, the value was considered to be constant during the optimisation of the next
parameter.

Figure 9

The fatty acid triglyceride primarily needs to activate its own

carbonyl functions to start the reaction. The transesterication
process can occur at different temperatures depending on the
oil used. Generally the process reaction is carried out close
to the boiling point of methanol (6070 C) at atmospheric
pressure at molar ratio (alcohol to oil) of 6:1 (Srivastava and
Prasad, 2000). From Fig. 6, it is observed that temperature
clearly inuences the reaction rate and yield of esters. The
experiments were conducted at temperature ranging from
40 C to 70 C at 10 C interval. The product yield was utmost
at a temperature of 60 C.
3.6. Effect of reaction period
The production yield is nearly independent of reaction time
but the methyl ester concentration increases with increased
reaction time. In the present investigation, the reaction was

H MNR analysis of biodiesel.

Please cite this article in press as: Mathiarasi, R. et al., Transesterication of soap nut oil using novel catalyst. Journal of Saudi
Chemical Society (2013), http://dx.doi.org/10.1016/j.jscs.2013.07.006

R. Mathiarasi et al.
Table 1

Fuel properties of soap nut bio-diesel with diesel.

Fuel properties

Soap nut bio-diesel

Diesel method with limits

Kinematic viscosity
at 40 C (ny)

5.3

ASTM D445
1.96.0

Density
at 40 C (rho)
Flash point
C
Cetane number

.8381

51

Specic gravity

0.856

ASTM D975
0.8295
D93
> 100
D613
>47
ASTM D975
0.847

Distillation range
Initial boiling point (C)
At 10%
At 50%
At 90%
Final boiling point

277
315
329
350
350

95

conducted for 1, 2, 3, and 4 h to evaluate the effect of reaction

time on transesterication reaction. From Fig. 7, it was accomplished that the maximum yield was achieved at 3 h of reaction
time, and excess reaction time does not increase the conversion
but favours the backward reaction (hydrolysis of esters) which
results in a reduction of product yield. Similar kind of result
was reported by Leung and Guo (2006).
3.7. Molar ratio of alcohol to triglyceride
One of the most important variables affecting the yield of ester
is the molar ratio of alcohol to triglyceride. The stoichiometric
ratio for transesterication requires three moles of alcohol and
one mole of triglyceride to yield three moles of fatty acid alkyl
esters and one mole of glycerol. However, transesterication is
an equilibrium reaction in which an excess of alcohol is required to drive the reaction to the right (Maa and Hannab,
1999). On the other hand an excessive amount of alcohol
makes the recovery of glycerol difcult, so that the ideal alcohol/oil ratio has to be established empirically (Krawczyk,
1996). For a maximum conversion to ester, a molar ratio of
6:1 is the most acceptable. Fig. 8 shows clearly that 1:15 ratio
of oilmethanol gives a maximum yield of about 89 wt% of
methyl ester. The obtained data revealed that the product yield
gradually increases with molar ratio up to 1:15, then decreases
due to the production of water.
3.8. Biodiesel characterisations
The conversion of triglyceride into soap nut oil at this stage
was analysed using 1H NMR. The protons of the methylene
group adjacent to the ester moiety in triglyceride and the protons in the alcohol moiety of the product methyl esters were
used (Knothe, 2001). From Fig. 9, disappearance of the resonance signal was observed between 4.22 ppm and 4.42 ppm
and the emergence of new signal at 3.72 ppm is an indication
of biodiesel formation. The biodiesel samples produced by
using spent catalyst were tested for their fuel properties. The
fuel properties of biodiesel are shown in Table 1. The diesel
fuel which posses high viscosity does not burn completely

and forms a deposit in the diesel engine. Hence the biodiesel

should have low viscosity. The viscosity of S. mukorossi biodiesel at 40 C is 5.3 mm2/s which is easier to pump, atomise and
attain ner droplets in the fuel injection system. Cetane number is the important factor in the diesel engine. Cetane number
is the ability of fuel to ignite quickly after being injected. From
Table 1, the Cetane number of S. mukorossi biodiesel was
found to be 51 which is above the minimum value of 47 specied by ASTM standards. From the results, the biodiesel had
comparable fuel properties with those of diesel and the values
and parameters were within the limits prescribed in the latest
ASTM standards for biodiesel.
4. Conclusion
Conventional homogeneous catalyst for transesterication of
vegetable oil is associated with many problems which incur
in high production cost. Heterogeneous catalysts can solve
these problems and convert current bio-diesel production system to low cost commercial products. The important fact to be
stressed is that the cost of catalyst is very low and hence can be
used for the production of biodiesel. In this study soap nut
seed was selected as a non-edible oil crop from natural resources for bio-diesel production. A high yield of 89 wt% of
bio-diesel was achieved by optimising parameters such as
amount of catalyst, reaction time, temperature and oilmethanol molar ratio. The new catalyst derived from industrial boiler waste was examined by TGA, SEM, and EDAX. Based on
the result the spent catalyst was identied as promising, low
cost and effective for bio-diesel production.
References
Ali, Y., Eskridge, K.M., Hanna, M.A., 1995. Bioresour. Technol. 53,
243254.
Ali, Y., Hanna, M.A., 1994. Bioresour. Technol. 47, 131134.
Arjun, B. et al, 2008. Int. J. Mol. Sci. 9, 169180.
Du, W., Xu, Y., Liu, D., Zeng, J., 2004. J. Mol. Catal. B Enzym. 30,
125129.
Kafuku, G., Lam, M.K., Kansedo, J., Lee, K.T., Mbarawa, M., 2010.
Fuel Process. Technol. 91, 15251529.

Please cite this article in press as: Mathiarasi, R. et al., Transesterication of soap nut oil using novel catalyst. Journal of Saudi
Chemical Society (2013), http://dx.doi.org/10.1016/j.jscs.2013.07.006

Transesterication of soap nut oil using novel catalyst

Krawczyk, T., 1996. INFORM 7, 801.
Knothe, G., 2001. Trans. ASAE 44, 193.
Lam, M.K., Tan, K.T., Lee, K.T., Mohamed, A.R., 2009. Renew.
Sust. Energ. Rev. 13 (67), 14561464.
Leung, D.Y.C., Guo, Y., 2006. Fuel Process. Technol. 87, 883
890.
Martini, N., Schell, S. (Eds.), 1997. Plant oil as fuels: present state of
future developments. Proceedings of the Symposium, 1997.
Springer, p. 6.
Maa, F., Hannab, M.A., 1999. Bioresour. Technol. 70, 115.

7
Ramos, M.J., Casas, A., Rodriguez, L., Romero, R., Perez, A., 2008.
Appl. Catal. 346, 7985.
Sarin, R., Sharma, M., Sinharay, S., Malhotra, R.K., 2007. Fuel 86,
13651371.
Sonntag, N.O.V., 1979. Structure and composition of fats and oils,
fourth ed.. In: Baileys Industrial Oil and Fat Products, vol. 1 John
Wiley and Sons, New York, p. 1.
Srinivasan, S., 2009. Renew. Energ. 34 (4), 950954.
Srivastava, A., Prasad, R., 2000. Renew. Energ. 4, 111133.

Please cite this article in press as: Mathiarasi, R. et al., Transesterication of soap nut oil using novel catalyst. Journal of Saudi
Chemical Society (2013), http://dx.doi.org/10.1016/j.jscs.2013.07.006