Energy Conversion and Management 50 (2009) 498502

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Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman

Biodiesel production from waste animal fat and improvement

of its characteristics by synthesized nickel and magnesium additive
Metin Gr a,*, Bursev Dogan Artukoglu a, Ali Keskin b, Atilla Koca c
a

Gazi University, Engineering and Architecture Faculty, Chemical Engineering Department, 06570 Ankara, Turkey
Mersin University, Technical Education Faculty, 33500 Mersin, Turkey
c
Gazi University, Technical Education Faculty, 06500 Ankara, Turkey
b

a r t i c l e

i n f o

Article history:
Received 15 April 2008
Accepted 20 November 2008
Available online 10 January 2009
Keywords:
Biodiesel
Animal fat methyl ester
Alternative fuel
Nickel additive
Magnesium additive

a b s t r a c t
The purpose of this study is to produce trimethyl ester from waste animal fat at optimum conditions and
improve its characteristics by synthesized nickel and magnesium additives. In this study, a two step catalytic process for synthesis of biodiesel was studied by reacting waste animal fats with methanol. The
temperature, amount of methanol and type and amount of catalyst are investigated as parameters,
and the changes in viscosity and ash point of animal fat biodiesel were determined. Furthermore, the
effects of organic based Ni and Mg additives on the methyl ester pour point were specied. Optimum producing conditions were determined experimentally. At the end of these experiments, the maximum yield
of 89% was obtained in two steps with total 0.35 (w/w) methanol/fat, at 62 1 C reaction temperature
for 2 h reaction period and by catalysing with 0.08 (w/w) H2SO4/fat and 0.01 (w/w) NaOH/fat ratios.
Organic based metal compounds were synthesized by reacting abietic acid in the tall oil resinic acid with
NiO and MgO compounds in order to improve the animal fat methyl ester characteristics. Reduction of
the pour point was achieved by adding organic based nickel and magnesium compounds to biodiesel
at a ratio of 12 lmol/l oil methyl ester. Also, the blend of animal fat methyl esterDiesel fuel was tested
in a direct injection Diesel engine. The maximum effect of the new fuel blend on the engine performance
was reached at 2200 min 1 of engine torque. The lowest specic fuel consumptions were obtained at
2200 min 1 for both fuels.
2008 Elsevier Ltd. All rights reserved.

1. Introduction
Investigations of alternative energy resources have been continuing widely because of increasing dependence on petroleum products, energy crisis and environmental issues. Also, sulphur in Diesel
fuel has limited its usage extensively due to corrosion and environmental pollution. So, research and development activities are
forced to study clean and renewable energy investigations. The
European Community recommends using biodieselDiesel blends
by increasing ratios in the countries. The 2003/30/EC directive
forces fuel producers to use 2% of biodiesel in Diesel fuel mixtures.
This ratio is planned to increase to 5.75% by the end of 2010 in Turkey. Unfortunately, the blends can not be used widely in Turkey
because they are non-economic and non-feasible. Projections indicate that environmental hazards, economics and energy needs will
increase the focus on the production of methyl ester fuels derived
from non-edible waste oils or fats, among others. Also, the literature has shown that vegetable oils are not suitable replacements
directly for Diesel fuel, due to their longer molecule chain, higher
* Corresponding author. Tel.: +90 312 2317400x2555; fax: +90 312 2308434.
E-mail address: mguru@gazi.edu.tr (M. Gr).
0196-8904/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.enconman.2008.11.001

viscosity and higher ash point [1]. Furthermore, it is impossible

to combust animal fats in Diesel engines directly because of its
negative physical properties. These features cause poor atomisation, poor vapourair mixing, low pressure, incomplete combustion and engine deposits. It is possible to reduce the viscosity
and develop better physical features of vegetable oil and animal
fat by means of dilution, pyrolysis, micro-emulsion and esterication [2]. Nowadays, the last method is the current method that is
used efciently. Esterication is a kind of catalytic reaction in
which the oil or fat is reacted with alcohol to form esters (biodiesel) and glycerol. Biodiesel can be used in neat form, or mixed with
Diesel fuel in any unmodied Diesel engine and boilers.
Generally, two types of raw materials have been used in the biodiesel processes as vegetable oils and animal fatty acids. Some vegetable oils such as sunower oil [3,4], olive oil [1,5], soybean oil [6],
cotton oil [7], hazelnut oil [8], rubber seed oil [9], mahua oil [10],
jojoba oil [11], tobacco seed oil [12], rapeseed oil [13], etc. have
usually been used for producing biodiesel fuel. Also, tall oil distilled
was esteried with alcohol and tested in a direct injection Diesel
engine at full load condition [14]. For the purpose of biodiesel
improvement, organic based magnesium, molybdenum, manganese and nickel additives were synthesized, dosed into the tall

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M. Gr et al. / Energy Conversion and Management 50 (2009) 498502

oil methyl ester and performance and emission data were recorded
with the additives [15,16]. Also, four metallic type additives have
been studied in order to improve Diesel fuel [17].
Even though Vegetable oil esters have advantages such as low
viscosity, low ash point, high vapour pressure and easy processing compared to animal fatty acid esters, they are non-economic
and non-feasible because they are very expensive, whereas, animal
fatty acid esters are usually very cheap but have negative physical
properties such as high pour point, high viscosity, high ash point
and hard processing. Also, when some animal fats were used in
foods, they created health hazards. Therefore, researchers produced biodiesel from animal fatty acids such as salmon oil [18],
animal fat [19,20], etc. It is important to synthesize from waste
non-edible fatty acids and to eliminate the disadvantages by
means of additives for economical and feasible production.
In this study, waste animal fat was used for production of animal fat methyl ester in two steps in a novel process. Animal fat
methyl ester was produced at optimum conditions by reacting animal fatty acids with methyl alcohol, and the properties of test fuels
with and without Ni and Mg additive were determined rstly. A
blend of animal fat methyl ester with Diesel fuel (20%) was tested
in a direct injection Diesel engine at full load condition.

2. Materials and methods

Waste animal fat, supplied from a slaughter house, was produced by cooking. Moisture in the fat was removed at about
110 C, and this dried fat was used directly in the esterication
reaction. The chemicals were bought from Merck.
Transesterication and magnesium and nickel abietate reactions were carried out separately in a 1000 ml spherical pyrex vessel equipped with a three necked, reux condenser, stirrer and
thermometer. All the experiments were performed with 300 g animal fat. Since the homogenous catalysts (H2SO4 and NaOH) gave
higher rates of biodiesel reaction [21], the reaction of animal fat
was performed in two steps: with acid catalyst and with alkaline
catalyst. In order to determine the optimum sulphuric acid
amount, pre-study was performed with 0.06, 0.08 and 0.10 (w/w)
acid/fat. According to the experimental results, animal fat was
esteried for 1 h with the methoxy compound that was produced
by reacting 0.20 (w/w) methyl alcohol/fat ratio and 0.08 (w/w) sulphuric acid/fat ratio at 40 C for 30 min. At the end of the free acid
transesterication, the mixture was transferred to a separating
funnel in order to remove the bottom phase which is known as
glycerine. The top phase was washed and neutralized in the funnel
with hot sodium bicarbonate solution. Sodium bicarbonate solution has an alkaline feature, and therefore, it reduces the acidity
of the crude methyl ester when sulphuric acid was used as a catalyst. Then, the top phase was reacted with the methoxy compound,
which was catalysed at 40 C for 30 min by various amounts of sodium hydroxide. At the end of the reaction period, the reactor content was re-transferred to the separating funnel. The mixture was
washed with the 500 ml distilled hot water at 85 C temperature,
and the pH of the ester product was adjusted by means of a stearic
acid solution. The stearic acid solution, which has an acidic feature,
reduces the alkalinity of the crude methyl ester when sodium
hydroxide was used as a catalyst. Then, the bottom phase was removed by means of the separating funnel. After washing and neutralization, the separated top phase was distilled. The reaction
temperature was controlled within 1 C by means of a thermostat
and thermometer. The reactor content was mixed by the magnetic
stirrer throughout the reaction period. The parameters of catalyst,
alcohol/oil ratio, reaction temperature and period were investigated in order to determine the optimum conditions for highest
efciency biodiesel production.

Table 1
Technical properties of test engine.
Engine model
Engine type
Number of cylinder
Bore  stroke (mm)
Displacement (cm3)
Compression ratio
Maximum power
Maximum torque

Lombardini 6LD400
Direct injection, diesel, air cooled, naturally aspirated
1
86  68
395
18:1
5.4 kW at 3000 min 1
19.6 Nm at 2200 min 1

Table 2
Properties of test fuels.

Cetane number
Sulphur (w/w)%
Density (kg/m3)
Caloric value (kJ/kg)

Diesel fuel (SD)

Biodiesel blend (B20)

45.245
0.5227
0.8308
45411.52

47.925
0.3395
0.8343
44667.48

Magnesium and nickel based additives were synthesized as reported in previous studies [15,16]. Each one of these additives was
separately added into the animal fat methyl ester for preparing test
fuels up to 12 lmol/l. The effects of these additives on the methyl
ester physical properties such as viscosity, pour point and ash
point were investigated. The viscosities of biodiesel with and without the additive were measured by Brookeld DV-III rheometer. In
order to determine the freezing point of biodiesel fuels, a thermometer was placed in a special glass sample tube containing
40 ml of fuel. The sample was immersed in a container with liquid
nitrogen, and the fuel was converted into the solid phase. The transition temperature was recorded as the freezing point. Moreover,
the ash points of biodiesel with and without additives were determined by the Cleveland cup according to EN ISO 3679.
In order to test the biodiesel soapstock in a Diesel engine, the
animal fat methyl ester was blended at the ratio of 20% with Diesel
fuel and called B20. A magnesium based additive was added into
the blend at a rate of 12 lmol/l because it is cheaper than nickel.
In this experimental study, a single cylinder Lombardini 6LD 400
Diesel engine was used. An electrical DC dynamometer was coupled with engine. The DC engine dynamometers maximum power
absorption is 10 kW at 4000 min 1. Fuel consumption was measured with the Ohasus GT 8000 digital scale with accuracy of
0.1 g. Temperatures were measured by K type thermocouples with
accuracies of 1 C. Engine and test fuels specications are given in
Tables 1 and 2. In this study, mixtures of animal fat based biodiesel
fuel (B20) and standard Diesel fuel (SD) were evaluated as test
fuels. The test fuels were tested at full load condition. Engine speed
was changed from 1800 to 3000 min 1 with an interval of
200 min 1. Before each test, the engine was warmed up with Diesel
fuel. Engine temperatures were kept stable at about 70 C 5 for
each test. Technical characteristics of the test engine are shown
in Table 1.
3. Results and discussion
3.1. Effects of temperature on biodiesel properties
The temperature of the animal fat methyl ester reaction becomes highly important due to the high melting point of animal
fat. While the reaction temperatures were changed between 50
70 C, the other parameters were xed throughout the experiments, as can be explained in Fig. 1. When the reaction temperatures were adjusted at 50 1 and 55 1 C, the reaction could
not been started, and the glycerine phase could not been formed

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M. Gr et al. / Energy Conversion and Management 50 (2009) 498502

100

90

80

Yield. %w

Yield. %w

88

86

60

40

84
20

82
62

64

66

68

0
0.5

70

1.0

1.5

Temperature. C
Fig. 1. Effects of the reaction temperatures on the animal fat methyl ester yield: 1.
step: 0.20 (w/w) alcohol/fat, 0.08 (w/w) H2SO4/fat, 1 h; 2. step: 0.15 (w/w) alcohol/
fat, 0.01 (w/w) NaOH/fat, 1 h.

2.0

2.5

3.0

3.5

4.0

NaOH/fat. (w/w)
Fig. 2. Effects of NaOH amount on the animal fat methyl ester yield: 62 C, 1. step:
0.20 (w/w) alcohol/fat, 0.08 (w/w) H2SO4/fat 1 h; 2. step: 0.15 (w/w) alcohol/fat, 1 h.

100

3.2. Effects of catalyst ratio on biodiesel properties

It is known that sulphuric acid generally affects the animal fat
methyl ester reaction very much as a catalyst. So, 0.08 (w/w) of sulphuric acid/animal fat ratio was used in the conversion of the free
acid as a catalyst in the rst step of the animal fat methyl ester
reaction according to the pre-study results. After washing and neutralization of the rst step ester, the NaOH/fat ratio was the second
parameter to be investigated in the second step for producing animal fat methyl ester at 15% (w/w) alcohol/fat, 62 C temperature
for 1 h. The other experimental conditions, which were explained
in Fig. 2, were xed throughout the experiments. As shown in
Fig. 2, the increase in the rate of NaOH/fat as (w/w) from 0.005
to 0.015 led to a considerable rise, whereas higher ratios of
NaOH/fat led to slight decreases. Although saponication was observed very little at 0.015 (w/w) NaOH ratio, it was seen very much
at 0.04 (w/w) NaOH/fat ratio. Also, the viscosity and ash point of
biodiesel with 0.01 (w/w) NaOH/fat, were recorded lower than
that of the products with higher catalyst ratio. So, 0.01 (w/w)
NaOH/fat ratio was chosen as a constant parameter for the following experiments.

90
80

Yield. %w

due to the low temperature. As the temperature was increased to

60 1 C, the reaction started slowly, and a very little amount of
the glycerine phase was observed at the bottom. Temperature
and time are interaction parameters in the reaction. It is thought
that this low yield results from a very slow reaction at about these
temperatures. So, the reaction cannot been completed for two
hours and these three data could not been illustrated in Fig. 1.
The yields versus between 62 C and 70 C temperatures were plotted on the graph. Increases in temperature in the range from 62 C
to 70 C caused slight decreases in the yield. It is thought that the
decreasing yield was caused by releasing methanol from the liquid
phase at the higher temperatures due to its vaporization. In addition, the decomposition of animal fat methyl ester at higher temperatures probably contributes to the low yield.
A slight increase in the viscosity of biodiesel at 20 C from
6.800 mm2/s to 6.886 mm2/s by increasing the reaction temperature from 62 C to 70 C was recorded. Similarly, by increasing
the temperature, an increase in the ash point from 138 C to
147 C was detected. Lopez et al. recommended the reaction temperature of larger triglycerides in vegetable oils and fats with
methanol as 60 C [21]. So, the reaction temperature (62 C), which
corresponds to the maximum yield (89% (w/w) according to the
fat) and the lowest viscosity and ash point, was chosen as a constant parameter for the following experiments.

70
60
50
40
30
0.3

0.32

0.34

0.36

0.38

0.4

Alcohol/fat. w/w
Fig. 3. Effect of alcohol/oil ratio on the animal fat methyl ester yield; 62 C, 1. step:
0.20 (w/w) alcohol/fat, 0.08 (w/w) H2SO4/fat, 1 h; 2. step: 0.01 (w/w) NaOH/fat, 1 h.

3.3. Effects of methyl alcohol ratio on biodiesel properties

Since methyl alcohol has some advantages compared to ethyl
alcohol such as being cheaper and a developer of physical properties [19], it was used in esterication reaction. The 20% (w/w) ratio
of alcohol had been used in the rst step with acid catalyst. The total alcohol ratio for the rst and second step was changed from
0.25 (w/w) to 0.40 (w/w) according to animal fat. The other experimental parameters, which were explained in Fig. 3, were xed
throughout the experiments.
As can be seen from Fig. 3, the increase in the rate of alcohol/oil
as (w/w) from 0.25 to 0.35 led to a considerable rise, whereas higher ratios of alcohol/fat led to a slight rise. On the other side, the viscosity and ash point decreased by increasing the alcohol ratio;
0.35 (w/w) alcohol/oil ratio was chosen as an appropriate ratio
for the following studies.
It is detected from the optimization experiments that the producing conditions for maximum biodiesel yield (89% (w/w) with
respect to fat) from animal fat and methanol can be recommended
as (20 + 15) (w/w) alcohol/fat, 0.08 (w/w) H2SO4/fat, 0.01 (w/w)
NaOH/fat, 62 C reaction temperature for (1 + 1) h.
3.4. Effects of nickel and magnesium additives on the biodiesel physical
properties
Animal fat methyl ester has some advantages such as high cetane number (see Table 2), non-corrosive, clean and renewable
properties and some disadvantages such as high freezing point,
high viscosity and high ash point. Unfortunately, these negative

M. Gr et al. / Energy Conversion and Management 50 (2009) 498502

19
18

Torque (Nm)

17
16
15
14
13
SD

12
11

BD

10
1800

2000

2200

2400

2600

Engine Speed

2800

3000

3200

3400

(min-1)

501

both test fuels. As seen in Fig. 4, higher engine torques were obtained for standard Diesel fuel in general compared with B20 biodiesel. The torque reduction of biodiesel fuel is 2.07% at maximum
torque speed, and the highest difference is 4.27% at the engine
speed of 3000 min 1. The reason for this torque reduction is probably due to the lower caloric value of biodiesel (see Table 2). Similar results are reported by Keskin et al. [16].
The lowest specic fuel consumptions (sfc) were obtained at
2200 min 1 for both fuels (see Fig. 5). The increase in sfc is 3,12%
for biodiesel fuel at 2200 min 1, and the maximum increase
in sfc is 4,79% at 3000 min 1. This may be probably due to the
relatively higher density and lower caloric value of biodiesel compared with Diesel fuel.

Fig. 4. Variations of engine torques at full load condition.

4. Conclusion
600

SFC (g/kW-h)

550
500
450
400
350
SD

300

BD

250
200
1800

2000

2200

2400

2600

2800

3000

3200

3400

Engine Speed (min-1)

Fig. 5. Variations of specic fuel consumptions.

features limit the usage of biodiesel fuels in Diesel engines. So, they
should be improved. For this purpose, magnesium and nickel based
additives were synthesized stoichiometrically at 225 C for 1 h in a
1 l glass reactor with details as given in previous studies [15,16].
The effects of the additives on pour point, viscosity and ash point
of pure animal fat methyl ester were investigated by dosing additives up to 12 lmol/l. Increases in the additive concentrations from
0 to 12 lmol led to a reduction in the freezing point, viscosity and
ash point. A dosage of 12 lmol Mg and Ni into the animal fat
methyl ester causes to 5 and 3.5 C pour point decreases, respectively. This is attributed to the additive effects on the fuel colligative properties. Since the fall of the freezing point of biodiesel
obtained with the Mg based additive was much more than that
of the biodiesel with the Ni based additive and the MgO reactant
was cheaper than the NiO reactant for preparing the additive, the
Mg based additive was preferred for use in the following experiments. Viscosity and ash point tests were conducted with and
without the Mg based additive. The increase in the magnesium
concentration from 0 to 12 lmol/l led to a decrease from 5.40 cSt
to 4.95 cSt in the viscosity at 40 C and from 138 C to 132 C in
the ash point. The additives caused reductions in the ash point,
viscosity and freezing point compared with the biodiesel fuel without additive. This means that the additive increases the vapour
pressure. These improvements support the idea that the catalytic
cracking effect of the additive results in smaller particles of hydrocarbons. Thus, the other properties of biodiesel, except the freezing
point, have been brought close to the EN 14213, EN 14214 and EN
690 standards by means of the Mg based additive.
3.5. Diesel engine performance of animal fat methyl ester
Diesel fuel and biodiesel blend fuel were tested seperately in
the Diesel engine. The variation of engine torque is indicated in
Fig. 4. Maximum engine torque was obtained at 2200 min 1 for

It is thought that animal fat is a kind of waste oil because of the

creation of health risks when it is consumed in the food industry.
Waste animal fat as a cheap raw material and its low operating
cost in biodiesel production make this study a promising one for
technological application. Animal fat methyl ester blended with
Diesel fuel can be used as an alternative fuel in conventional Diesel
engines, generators and boilers without any major modication.
Low sulphur and aromatic contents are advantages of animal fat
methyl esterDiesel fuel blends. Magnesium and nickel based
additives reduced the pour point, ash point and viscosity of biodiesel fuel, depending on the amount of additive. As can be seen
in the engine test graphs, there are no considerable differences in
engine performance between standard Diesel fuel and the animal
based biodiesel blend with magnesium additive. On the other side,
the biodiesel blend (B20) cetane number is higher than that of
standard Diesel fuel, and therefore, the engine runs very smoothly
with biodiesel fuel. The optimum conditions recorded in this study
may be applied to biodiesel processes economically, and this
methyl ester blend with Diesel may be consumed as an alternative
fuel that is environmentally friendly.
Acknowledgement
This study was supported by the State Planning Organization of
Turkey under Project No. 2001 K 120590.
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