Professional Documents
Culture Documents
5, 2012; P:19-26
Abstract
Biodiesel is usually produced from food-grade vegetable oils using transesterification
process. Base catalyzed transesterification reaction is widely used for biodiesel production from
vegetable oil due to its faster kinetics than that of acid catalyzed process. But if free fatty acid
(FFA) content in the oil is more than 2%, the base catalyzed process is not feasible. In the present
paper biodiesel is prepared from non-edible oils, such as nahor seed oil (NSO) and rubber seed oil
(RSO) by different methods. Oil was extracted by different method from both seeds. The FFA of
NSO reduces from 12.17 wt% to 2.80 wt% and kinematic viscosity reduces from 58.06 mm2/s to
6.64 mm2/s. The corresponding value for RSO were 45 wt% to 1.85 wt% and 33 mm2/s to 4.5
mm2/s respectively. The difficulties and importance of each processes are discussed and the
biodiesel properties of biodiesel produced from both NSO and RSO were measured and compared
with standard value.
1. Introduction
The vast majority of motor vehicles used around the world rely on four-stroke internal combustion engines
run on petroleum-based fuel or biodiesel. Biodiesel, which is a new, renewable and biological origin alternative
diesel fuel, has been receiving more attention all over the world due to the energy needs and environmental
consciousness. In comparison with petro-diesel, vegetable oils have their own advantages: first of all, they are
renewable as the vegetables which produce oil seeds can be planted year after year; secondly, they are available
everywhere in the world; thirdly, they are “greener” to the environment, as they seldom contain sulfur element in
them [1]. Use of biodiesel is catching up all over the world especially in the developed countries. Most developed
countries are moving from voluntarily to obligatory legislations to increase the market share of biofuels within the
transport sector (e.g. set up of a mandatory biofuel target of 10% by the European Commission for the European
transport sector in 2020) [2].
The end cost of the biodiesel mainly depends on the price of feedstock. Although biodiesel is currently
produced from high quality food-grade vegetable oils using methanol and an alkaline catalyst, but it can be made
from any plant oils with over 350 oil-bearing crops being identified for the production of biodiesel [3]. The
predominant feedstock in the Europe is rapeseed, while soybean is the most widely used feedstock in the United
States (US). Feedstocks such as palm, jatropha and coconut are common in Malaysia, India and the Philippines,
respectively [3]. Gui et al [4] made a thorough analysis on the production of biodiesel from edible and non-edible
oils. Generally the cost of raw materials accounts about 70-80% of the total production cost of biodiesel.
Four major techniques (dilution, microemulsion, pyrolysis, and transesterification modification techniques) are used
for biodiesel production, among them transesterification process has been widely used to reduce the high viscosity of
the oil. Transesterification reaction can be catalyzed by both homogeneous (alkalies and acids) and heterogeneous
catalysts. The most commonly used alkali catalysts are NaOH, CH3ONa, and KOH [5]. It has been found that the
alkaline-catalyzed transesterification process is not suitable to produce esters from unrefined oils [6] where the FFA
20 Kaniz Ferdous, M. Rakib Uddin, Maksudur R. Khan and M. A.
Islam
content is higher. In order to prevent saponification during the reaction, FFA and water content of the feed must be
below 0.5 wt.% and 0.05 wt.%, respectively. Because of these limitations, only pure vegetable oil feeds are
appropriate for alkali-catalyzed transesterification without extensive pre-treatment [7]. Homogeneous acid-
catalyzed reaction is about 4000 times slower than the homogeneous base-catalyzed reaction and hence is not
popular for industrial production of biodiesel.
A two-step process is developed recently for the biodiesel production from oil, where in the first step acid-
catalyzed esterification is conducted to convert the FFA to fatty acid methyl ester (FAME) followed by the base
catalyzed transesterification to convert the triglyceride (TG) to FAME. Another approach was reported, where FFA
was produced from oil by saponification-acidification reaction and FAME is produced by acid catalyzed
esterification reaction [8]. In the present paper biodiesel is prepared from non-edible oils, such as NSO and RSO by
different methods. NSO and RSO have high oil content and these two oil seed are available in Bangladesh. For
these reasons both NSO and RSO was selected for biodiesel production. The difficulties of each process are
discussed and the biodiesel properties are measured and compared with standard value.
catalyzed transesterification oil was reacted with methanol in presence of sulfuric acid (2 wt% of oil) as catalyst.
Oil/methanol molar ratio of 1/9 was used. The methanolysis was performed under vigorous stirring at 100 0C. After
6 h the contents were cooled to room temperature, and reaction product was washed with hot water until clear water
found. The organic phase was collected and dried under vacuum at 100 0C for 30 min.
2.3.3.Three-step method
In this method the raw seed oil was saponified, acidified and esterified sequentially. Saponification was
carried out for 30 min with different stoichiometric amount of alcoholic sodium hydroxide solution at 60 0C [8]. In
further study saponification of oil was done by aqueous calcium oxide solution. The reaction time and molar ratio of
oil to calcium oxide were optimized.
After saponification, the soap solution were treated with different stoichiometric amount of concentrated
hydrochloric acid at a temperature of 60 -70 0C with vigorous stirring. After dissolving the soap the fatty acid
contents were separated in separatory funnel. The fatty acid content was determined by titrimetric method.
Esterification of FFA was carried out as similar the first step of the two-step method. The molar ratio of FFA to
methanol, catalyst concentration and reaction temperature were optimised. The biodiesel was washed and dried
under vacuum.
100
90 NSO
RSO
FFA, wt.%
80
70
60
3 4 5 6 7
N a O H /O i l (m o l r a ti o )
Fig.1: Preparation of FFA from NSO and RSO [ Reaction temperature 60 0C and time 30 min.].
In further study, saponification was carried out by aqueous calcium oxide solution and FFA prepared from NSO.
The results are shown in Fig 2.
From Fig. 2, it was seen the optimum molar ratio of oil to calcium oxide was 1:2 for NSO and time was 1 hour.
Comparative Study of Biodiesel Preparation Methods 23
100
95
90
85
O il: C a O = 1 : 3
80
Percent FFA
O il: C a O = 1 : 2
75
O il: C a O = 1 : 1
70
65
60
55
50
45
0 50 100 150 200 250
T im e (m in .)
FFA obtained from oil was subjected to esterification reaction to convert FAME. The reaction was carried out
with different FFA/methanol molar ratio in presence of catalyst (HCl). Effect of methanol/FFA molar ratio was
investigated at 60 0C and HCl used 5 wt% of FFA as catalyst. The results are presented in Fig. 3. The maximum
conversion of FFA to FAME was found for methanol/ FFA molar ratio of 6:1 after 120 minutes for both oil and
conversions were 97.2% and 98.15% for NSO and RSO respectively. Further increase in molar ratio of alcohol to
FFA the conversion of FFA and viscosity remain unchanged.
100
95
90
Conversion, %
85 F F A from N S O
F F A from R S O
80
75
70
65
0 2 4 6 8 10
methanol/F F A , mol ratio
Fig. 3: Effect of FFA/methanol molar ratio on esterification reaction [T= 60°C, Catalyst concentration 5.0% wt of
FFA, Reaction time 120 min].
Effect of Catalyst Concentration was studied at methanol/ FFA molar ratio of 1:6 at 60 0C and the results are
presented in Fig. 4 (a) and (b).
Fig 4 shows that around 98 % conversion of FFA can be achieved by catalyst concentration 5 wt% of FFA. Further
increase in catalyst concentration has no impact on FFA conversion.
24 Kaniz Ferdous, M. Rakib Uddin, Maksudur R. Khan and M. A.
Islam
100 100
(a) NSO (b) RSO
80 80
7 wt% HC l Catalyst Catalyst concentration = 3 wt.% of FFA
5 wt% HC l Catalyst Catalyst concentration = 5 wt.% of FFA
60 60
FFA, wt.%
FFA wt%
40 40
20 20
0 0
0 10 20 30 40 50 60 70 80 90 100110120
0 20 40 60 80 100 120
Time (min) Time (min)
Fig 4: Effect of catalyst concentration on esterification reaction [T = 60°C, FFA / methanol ratio 1:6, Reaction time
120 min].
Effect of Temperature on esterification reaction was studied with NSO derived FFA. The results are presented
in Fig 5. It can be seen that the temperature has a significant effect on the conversion of esterification reaction. As
the temperature increased, the conversion was also increased.
100
0
80 60 C
0
50 C
0
40 C
60 0
FFA wt%
30 C
40
20
0
0 20 40 60 80 100 120
Time (min)
Fig. 5: Effect of temperature on esterification reaction for NSO [methanol/ FFA molar ratio 6:1, Catalyst (HCl)
5.0% wt of FFA, Reaction time 120 min]
4. Conclusion
Biodiesel has been prepared from NSO and RSO by single-step method, two-step method and three-step
methods. Among these methods single-step (transesterification) is best because it requires fewer amounts of
equipment and investment. But base catalyzed tranesterification is not used for the preparation of biodiesel from
NSO and RSO because of their high FFA content. Acid catalysed transesterification reaction was done for the
preparation of biodiesel from both NSO and RSO. The viscosity of oil reduces from 58.06 mm2/s to 14.55 mm2/s
and FFA reduces 12.17 wt% to 2.12 wt% for NSO and 33 mm2/s to 12.00 mm2/s and FFA 45 wt% to 8.5 wt% for
RSO after 18 h of reaction. The product was not used as biodiesel because of its higher viscosity and FFA and the
process was time consuming. Acid catalysed two-step method was performed for the preparation of biodiesel from
both oil. The viscosity of NSO reduces from 58.06 mm2/s to 9.64 mm2/s which was slightly higher than biodiesel
standard. FFA of the oil reduces from 12.17 wt% to 0.64 wt% and for RSO Viscosity changes from 33 mm2/s to
14.5 mm2/s and FFA 45 wt% to 6.2 wt% .
Three-step method, where FFA was produced by saponification and acidification of oil and thereafter
biodiesel was produced by esterification of FFA, showed comparable biodiesel properties and similar optimum
conditions for both oil. Hence three-step method can be used for biodiesel production from non-edible feed stocks.
Biodiesel properties was measured by standard methods and compared with the standard biodiesel properties.
5. Acknowledgement
The authors express their deep gratitude to University Grants Commission (UGC) for financial support and to
Eastern Refinery Ltd. (ERL) for their laboratory facilities for conducting this research.
26 Kaniz Ferdous, M. Rakib Uddin, Maksudur R. Khan and M. A.
Islam
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