INSTITUTE OF TECHNOLOGY, NIRMA UNIVERSITY, AHMEDABAD – 382 481, 08-10 DECEMBER, 2011
Production of Biodiesel using Homogeneous
Alkali Catalyst and its Effect on Vehicular
Emission
Amish P. Vyas, Purvi H. Shukla and N. Subrahmanyam
Abstract-- Biodiesel fuels offer a potentially very interesting
alternative to conventional diesel regarding reduction in harmful
emissions in addition to engine wear, cost and availability. The
present work has focused on the production of biodiesel using Jatropha oil as
a feedstock via homogeneous alkali catalyzed transesterification route, overall
kinetic rate expression development and study of emissions from diesel engine
using produced biodiesel in the Study. The catalyst used is KOH. The
production of the biodiesel w as at the laboratory scale. Quality
checking of the prepared sample is covered. Overall
kinetic study and performance of B20 and B40 on the diesel
engine was also performed. The results show that the yield of the
biodiesel using Jatropha oil is 86 %. The emission of the air
pollutant like SO2 and SPM is decreases with the different
biodiesel blends with different proportion without major
changes in the engine performance.
Index Terms-- diesel, fuel, Jatropha oil, transesterification, engine
emission, catalyst
I. INTRODUCTION
T HE decrease of world petroleum reserves and the
atmospheric pollution caused by petroleum based-fuels
has necessitated the need for an alternative source of energy.
Biodiesel, an alternative fuel, presents a suitable renewable
substitute for petroleum base-fuel [1]. Biodiesel, an
alternative fuel, made from renewable biological sources such
as vegetable oils and animal fats. It is biodegradable and
nontoxic, has low emission profiles and so is environmentally
beneficial [2]. Table 1 shows the average bio-diesel emissions
compared to conventional diesel [3].
TABLE 1
AVERAGE BIODIESEL EMISSIONS COMPARED TO CONVENTIONAL
DIESEL [4]
Even 5% replacement of petroleum fuel by biofuel can save a
country like India Rs. 4000 crores per year in foreign
exchange [5]. Biodiesel has been defined as the mono-alkyl
esters of long-chain fatty acids derived from renewable
feedstock, such as vegetable oils and is synthesized from the
1
triglycerides in vegetable oils by transesterification with
alcohol (Fig. 1).
Fig. 1 Overall transesterification reaction to produce biodiesel from
triglyceride
The usual catalysts used are alkalis (NaOH, KOH), acids
(sulphuric acid, HCl) or enzymes (lipases) [6].
This work explains mainly the effect of biodiesel on gas
emissions instead of production methods of biodiesel. The
objectives of the work are:
Biodiesel production using Jatropha oil
Analysis of the produced biodiesel
Kinetic study for overall rate expression
Testing of the diesel, B20 and B40 on the four
stroke single cylinder diesel engine for study of
performance and emission characteristics of diesel engine
II. BIODIESEL PRODUCTION USING JATROPHA OIL
Conventional alkali catalyzed transesterification method
was used for the production of biodiesel. Jatropha oil, methanol
(99%) and KOH were obtained from local suppliers. Known
quantity of Jatropha oil was taken into a 500 ml beaker. Oil was
preheated to remove unwanted moisture present in the oil.
Transesterification was carried out in basic medium using KOH
as a catalyst. Titration was done to calculate the amount of
KOH required for the process [7]. Known quantity of the
catalyst was dissolved into methanol. Potassium methoxide
(mixture of methanol and KOH) was added to the oil (1.3%
w/w). A full speed propeller coupled to an electric motor was
used for the stirring purpose (700-750 rpm). The reaction
temperature was maintained to 50°C, 60°C and 70 0C. Stirring
and reaction temperature were maintained for 1.5 h. Product
mix was allowed to settle in a separating funnel for 8 hour after
completion of reaction. Two phases (having different density)
are formed as a result of transesterification. Upper layer
consists of bio-diesel and lower layer consists of glycerol.
Purification of upper layer (to obtain bio-diesel) is done in two
 2 INTERNATIONAL CONFERENCE ON CURRENT TRENDS IN TECHNOLOGY, „NUiCONE – 2011‟
steps:
Removal of saponified products – by washing with
water.
Removal of alcohol – by keeping mixture at elevated
temperature ~80 ºC.
Since, water is immiscible with bio-diesel, can be easily
separated. Separation was followed by the recovery of
methanol. Material balance was carried out for the
transesterification reaction and summarized in Table 2. The
analysis of the biodiesel (Table 3) produced was carried out in
the Petroleum Refining and Petrochemicals laboratory, Nirma
University, Ahmedabad. ASTM distillation was carried out for
B20 sample and the results are as shown in Table 4. The
boiling range of even B20 sample is also very high and hence,
good for the use as a fuel. Required quantity of biodiesel was
produced and taken for the diesel engine emission tests.
TABLE 2
BIODIESEL PRODUCTION USING ALKALI CATALYST
Result shows that the conversion of biodiesel is around 86%
and methanol recovery is about 75%.
TABLE 3
COMPARISON OF PROPERTY ANALYSIS OF BIODIESEL PRODUCED
USING ALKALI CATALYST WITH ASTM D6751.
TABLE 4
ASTM DISTILLATION DATA FOR B20 SAMPLE
III. RESULTS AND DISCUSSIONS
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 [8]. The reaction mechanism for
alkali-catalyzed transesterification was formulated as three
steps. The alkali-catalyzed transesterification of vegetable oils
proceeds faster than the acid-catalyzed reaction. The
mechanism of the base-catalyzed transesterification of
vegetable oils was discussed by Demirbas [9]. Gemma et al.
[8] selected four different alkaline catalysts i.e. NaOH, KOH,
CH3ONa, CH3OK for alkali-catalyzed transesterification of
Sunflower oil. The bio-diesel purity was near 100 wt.% for all
catalysts. High bio-diesel yields were obtained by using the
sodium or potassium methoxide (99.33 wt.% and 98.46 wt.%,
respectively), because they only contain the hydroxide group,
necessary for saponification, as a low proportion impurity.
However, when sodium or potassium hydroxides were
utilized as catalysts, biodiesel yields decreased to 86.71 wt.%
and 91.67 wt.%, respectively. This is due to the presence of
the hydroxide group that originated soaps by triglyceride
saponification. Owing to their polarity, the soaps dissolved
into the glycerol phase during the separation stage after the
reaction. In addition, the dissolved soaps increased the methyl
ester solubility in the glycerol, an additional cause of yield
loss [8]. Joana et al. reported higher yields (reaching 97%)
using virgin oils as compared to waste frying oils (reaching
92%) [10]. The base-catalyzed reaction is reported to be very
sensitive to the purity of the reactant. Free fatty acid (FFA)
content should not exceed beyond a certain limit. If FFA
content in the oil were about 3%. It has been found that the
alkaline-catalyzed transesterification process is not suitable to
produce esters from unrefined oils [11]. 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 [12]. Table 5 shows the work carried
out for bio-diesel production from various feedstocks under
different conditions using homogenous base catalyst. Present
work shows 86% conversion with oil to methanol molar ratio
of 1:3 only and also at lower temperature i.e. 60°C.
TABLE 5
HOMOGENEOUS BASE CATALYZED TRANSESTERIFICATION
IV. KINETIC STUDY FOR OVERALL RATE EQUATION
Results of the experimental work are plotted in Fig. 2 and 3.
Fig. 2 shows the graph for the concentration versus time data
and Fig. 3 shows the trend of change in conversion with
INSTITUTE OF TECHNOLOGY, NIRMA UNIVERSITY, AHMEDABAD – 382 481, 08-10 DECEMBER, 2011 3

respect to time. Initially very less conversion was obtained dC A

but with time it increases and reaches to about 86% in case of rA k C An Eq. 1
60°C and 70°C. In case of 50°C it is very less. That is due to dt
late activation of Jatropha oil molecules and hence the Where,
transesterification was started late. The Properties of the CA = concentration of triglycerides.
produced biodiesel are in line with the standards and the k = reaction rate constant
conversion of Jatropha oil to biodiesel is also comparable. n = order of reaction
Value of dCA/dt was obtained from the slope obtained form
the plot of CA vs t.
Now,

dC A dC A
k C An log log k n log C A
dt dt
Eq. 2

dC A
Hence, the plot of log vs log C A will give the
dt
values of slope „n‟ and intercept log k. In turn that will
Fig. 2 Concentration versus Reaction time plot for the biodiesel production provide the values of order of reaction, n and the rate
using alkali catalyst. constant, k. In this calculation dCA/dt was obtained from the
data of concentration, CA and time, t as plotted in Fig. 2. The
trend line was fitted with the data as in Fig. 3 using Microsoft
Excel software.

From the Fig. 4 and Table 6, average intercept ln k = -

2.009 (therefore, k = 0.1352) and average slope of the curve
= n = 0.9209 ≈ 1.0 (i.e. 1st order)
Therefore, the resulting overall rate equation will be,
mol Eq. 3
rA 0.1352C A
ml min

TABLE 6
Fig. 3 Conversion versus Reaction time plot for the biodiesel production ORDER OF REACTION AND RATE CONSTANT FOR DIFFERENT
using alkali catalyst. TEMPERATURES USING ALKALI CATALYSED METHOD

Dependency of rate constant on temperature can be

represented by Arrhenius‟law:
E
RT
Rate constant, k k0 e Eq. 4
Where,
Fig. 4 log (-dCA/dt) vs log (CA) for the biodiesel production using alkali ko = frequency factor
catalyst.
E = activation energy
ln k = ln ko + (-E/RT) Eq. 5
Overall rate equation had been investigated for the reaction
studied based on the experimental data collected.
Experimental data are fitted with an nth order equation of the
form:
4 INTERNATIONAL CONFERENCE ON CURRENT TRENDS IN TECHNOLOGY, „NUiCONE – 2011‟
Fig. 5 Plot of ln k Vs 1/T for homogeneous alkali catalyzed
transesterification.
From Arrhenius‟ law, a plot of ln k vs 1/T will give a
straight line, with large slope for large E and small slope for
small E.
From the Fig. 5 and using Eq. 4 and Eq. 5,
-(E/R) = -1645.1
Therefore, E = 1645.1 x 1.987 (because gas constant, R =
1.987 cal/mol-K)
Hence, E = 3268.81 cal/mol
and, frequency factor, k0 = 18.81
V. TESTING OF BIODIESEL ON DIESEL ENGINE
It is very much essential to test the biodiesel produced on
diesel engine to check the performance of biodiesel as a fuel
and quality of exhaust emissions. Biodiesel produced by using
alkali catalyzed method is tested on diesel engine Diesel
engine (Fig. 6) available at Automobile laboratory of
Mechanical Engineering Department, Institute of Technology,
Nirma University. Detailed specifications of the diesel engine
are as below:
Single Cylinder Four Stroke Diesel Engine (IS – 11170)
• Engine No: CM387283
• Type: FM – II – TRB
• kW /brake horse power (bhp): 5.9 / 8
• RPM: 850
• Specific Fuel Consumption (SFC): 265 g / kWH
• Fuel oil: LDO / HSD
• Lube Oil: SAE – 30
• Governing: Class B
• Mfg By: Field Marshal, P. M. Diesel Limited, Rajkot,
Gujarat, India
The tests were carried out using petro-diesel (PD), B20
(blend of 20% biodiesel and 80% petro-diesel) and B40
(blend of 40% biodiesel and 60% petro-diesel).
Fig. 6 Four stroke single cylinder test engine.
1) Test Procedure
Petro-diesel was used for the preliminary run. The fuel tank
was filled with the petro-diesel fuel. Engine test was carried
out by applying varied dead load on engine. The run was
taken with the no dead load and no spring load condition.
Initial runs were taken to know the performance of the diesel
engine, RPM of the engine, time of fuel consumption and
exhaust air temperature etc.
Exhaust emission gases were collected in gas sampler and
analyzed for the emission parameters like SPM, SO2 and
NOX. Impinger tubes, filled with SO2 and NOX absorbing
solutions, were fitted in the gas sampler. Fig. 8 shows the
arrangement of experimental set up for biodiesel test on diesel
engine. Gas monitoring kit used for exhaust emission
monitoring is as shown in Fig. 9.
The order of impinger during sampling for the collection
was (i) Exhaust of the engine (ii) SPM collector (iii) Impinger
tube filled with SO2 absorbing medium (iv) Impinger tube
filled with NOX absorbing medium (v) Vacuum Pump. This
order of the collection device must follow during the
sampling. (Fig. 7)
Fig. 7 Schematic of the sampling train during engine test experiment using
biodiesel produced by conventional alkali catalyst method.
Exhaust gas flow was regulated. Rotameter was used to
measure the flow in litre per minute. The flow rate of exhaust
gas was maintained at 0.5 lpm during all the experiments. 15
min was taken as gas sampling time. Wattman filter paper was
used to collect the SPM. Samples collected were taken for
analysis in laboratory.
INSTITUTE OF TECHNOLOGY, NIRMA UNIVERSITY, AHMEDABAD – 382 481, 08-10 DECEMBER, 2011
SPM calculation was carried out using weight difference in
the wattman filter paper before and after sampling time.
Similarly the absorbing solutions which are filled into the
impinger tubes were taken to the laboratory for the analysis.
Fig. 8 Experimental set for testing of biodiesel on diesel engine.
Fig. 9 Exhaust gas monitoring kit
Spectrophotometer was used for the analysis of the
samples. The test was repeated for the different dead loads
and parameters were measured accordingly. Prepared B20
and B40 samples were tested on the same engine as used for
petro-diesel tests. Similar parameters were measured and
analyzed under similar conditions as used for petro-diesel.
2) Engine Performance Parameters
1) Fuel consumption
Fuel consumption is "how much fuel the engine burns per
hour." Specific Fuel Consumption (SFC)” is an engineering
term that is used to describe the fuel efficiency of an engine.
It measures the mass of fuel needed to provide a given power
for a given period. The common unit of measure is lb/hp-h i.e.
pounds of fuel consumed for every horsepower generated
during one hour of operation or kg/kWh in metric units.
Therefore a lower number indicates better efficiency. SFC is
dependent on engine design, but differences in the SFC
between different engines using the same underlying
5
technology tend to be quite small. Generally, SFC within a
particular class of engine will decrease when the compression
ratio is increased. Increasing overall pressure ratio on jet
engines also tends to decrease SFC. Diesel engines have
better SFC than gasoline, largely because they have much
higher compression ratios and therefore they can convert
more of the heat produced into power.
Fuel consumption can be calculated using the following
formula:
mf
F .C ;Where, mf = ml of fuel and ρ = density of fuel
time
Brake Specific Fuel Consumption (BSFC) is a measure of
an engine's efficiency. It is the rate of fuel consumption
divided by the rate of power production. BSFC is specific
for the piston engine known as the reciprocating engine. The
general term is specific fuel consumption (SFC).
Value of BSFC can be calculated using the formula,
BSFC = Fuel rate / Power
Where,
Fuel rate is the fuel consumption in grams per hour (g/hr)
Power (produced in kW) = w * Tq / 9549.27
w =engine speed in rpm
Tq = engine torque in N-m
2) Brake Power
Brake power is the output power of an engine measured by
developing the power into a brake dynamometer on the output
shaft. Dynamometers measure the speed and the torque of the
shaft. Brake Power is calculated with the formula
2 NT
B.P
60000
2 N W S g Reffective
B.P KW
60000
where,
D d
Reffective
2
Where,
D = 300 mm; d = 12.7 mm (as per the design of engine
considered for testing) and T is the torque in N-m.
In all cases the torque is T = net brake force x radius.
3) Results and Discussions:
1) Effect of brake power (BP) on brake specific fuel
consumption (BSFC)
Fig. 10 compares the specific fuel consumption of diesel
and various blends of biodiesel and diesel oil at varying brake
power. The dead load associated was in the range of 1 kg
6 INTERNATIONAL CONFERENCE ON CURRENT TRENDS IN TECHNOLOGY, „NUiCONE – 2011‟

Again, the emission of SPM for B40 is less than B20.

Similarly the SO2 emission is also decreases with the use of
both B20 and B40 compare to petro-diesel (Fig. 13). It is
evident from that the sulphur content in the B20 and B40 is
very less compare to petro-diesel. But the NOx emission is
increases compare to the petro-diesel. For B40 the emission
of NOx is high compare to both the petro-diesel and B20
(Fig. 14). That is mainly due to high oxygen content present
in biodiesel. But, so far NOx is not considered as a criteria
pollutant. Biodiesel is more environmental friendly as it can
reduce the emission of the SPM and SO2.

Fig. 10 Effect of Brake Power (kW) on BSFC (gm/kW-hr).

to 15 kg. It was observed that the specific fuel consumption of

the oils as well as the blends was increasing with increase in
dead load. Though the blends maintained a similar trend to
that of diesel, the SFC in the case of the blends was higher
compared to diesel oil in the entire load range. This is mainly
due to the combined effect of the relative fuel density,
viscosity and heating value of the blends.

2) Effect of brake power on exhaust gas temperature

Fig. 11 compares the exhaust temperature of diesel and
various blends of biodiesel and diesel oil at varying brake
Fig. 12 Comparison of effect of biodiesel blends with petro-diesel on SPM
powers. It was carried out at various dead weight of from 1 kg emission.
to 15 kg. It was observed that the Exhaust gas temperature
increased with increase in the brake power in all the case. But
compare to the diesel fuel the exhaust temperature of the B20
and B40 blend is relatively low. That shows that with the use
of biodiesel the exhaust temperature from the vehicles can be
reduced effectively and that can help in reducing the
environmental issues raised due to vehicular pollutant
temperature.

Fig. 13 Comparison of effect of biodiesel blends with petro-diesel on SO2

emission.

Fig. 11 Effect of brake power (kW) on exhaust gas temperature (°C).

4) . Emission Parameters
Results of emission of the main three criteria pollutants
namely, SPM, SO2 and NOX are plotted in Fig. 12, 13 and 14.
Emission parameters were tested using produced biodiesel
with an aim of reducing the emission of pollutants as
mentioned above which are harmful to the environment Fig. 14 Comparison of effect of biodiesel blends with petro-diesel on NOx
emission.
directly or indirectly. The SPM emission is observed (Fig. 12)
less with the use of B20 and B40 compare to petro-diesel.
INSTITUTE OF TECHNOLOGY, NIRMA UNIVERSITY, AHMEDABAD – 382 481, 08-10 DECEMBER, 2011 7

VI. CONCLUSIONS
Transesterification is the preferred method for production
of biodiesel. It is easy and seems economical. Results of
Study carried out are comparable with earlier work. Order of
reaction is one. Engine test using produced biodiesel shows
very good reduction in terms of three criteria pollutants.
Overall, biodiesel can be considered as a fuel for future.
Detailed economic analysis is to be carried out. Jatropha
plantation, seeds collection and other policies required more
attention.

VII. ACKNOWLDGEMENTS
Authors are grateful to authorities of Nirma University for
providing research facilities.

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