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Bioresource Technology 99 (2008) 6434–6438

Influence of tall oil biodiesel with Mg and Mo based fuel additives

on diesel engine performance and emission
Ali Keskin a, Metin Gürü b,*, Duran Altıparmak c
a
Technical Education Faculty, Mersin University, 33500 Mersin, Turkey
b
Engineering and Architectural Faculty, Gazi University, 06570 Maltepe, Ankara, Turkey
c
Technical Education Faculty, Gazi University, 06500 Ankara, Turkey

Received 10 March 2007; received in revised form 16 November 2007; accepted 20 November 2007
Available online 4 March 2008

Abstract

The purpose of this study is to investigate influences of tall oil biodiesel with Mg and Mo based fuel additives on diesel engine
performance and emission. Tall oil resinic acids were reacted with MgO and MoO2 stoichiometrically for the production of metal-based
fuel additives (combustion catalysts). The metal-based additives were added into tall oil biodiesel (B60) at the rate of 4 lmol/l, 8 lmol/l
and 12 lmol/l for preparing test fuels. In general, both of the metal-based additives improved flash point, pour point and viscosity of the
biodiesel fuel, depending on the rate of additives. A single cylinder DI diesel engine was used in the tests. Engine performance values did
not change significantly with biodiesel fuels, but exhaust emission profile was improved. CO emissions and smoke opacity decreased by
56.42% and by 30.43%, respectively. In general, low NOx and CO2 emissions were measured with the biodiesel fuels.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Biodiesel; Tall oil; Additive; Diesel engine; Emission

1. Introduction is commonly known as transesterification or alcoholyses

Nowadays, research on alternative fuels for internal
combustion engines has been increasing due to an increase
in the price of petroleum and increase in the environmental
concerns (Marchetti et al., 2007; Canakci, 2007). A great
deal of research has been conducted on biobased-fuels.
One of these fuels is biodiesel which has industrial and
commercial interest.
Biodiesel, an alternative diesel fuel, is derived from
renewable domestic sources such as vegetable oil and ani-
mal fat. Oil or fat is reacted with alcohol to form esters
(biodiesel) and glycerol. Glycerol which is a by-product
of the process is used in pharmaceutical, cosmetic and in
a lot of other industries. Alkali or acid catalyst is usually
used to improve the reaction rate and yield. This reaction
*
Corresponding author. Tel.: +90 312 2317400/2555; fax: +90 312
2308434.
E-mail address: mguru@gazi.edu.tr (M. Gürü).
(Ma and Hana, 1999). The fuel properties of biodiesel are
very close to diesel fuel and therefore it can be used in neat
form, or mixed with petroleum diesel fuel in diesel engines
(Canakci and Van Gerpen, 1999).
In biodiesel production process, the amount of free fatty
acids in oil are a key parameter for determining the cata-
lyst. Because, during the reaction, free fatty acids may react
with an alkali catalyst to form soap and water, which
diminishes the ester yield (Haas, 2005; Zhang and Dube,
2003). Therefore, if vegetable oil or animal fat has higher
free fatty acid content, acid catalysts such as sulphuric acid,
phosphoric acid, hydrochloric acid and organic sulfonic
acid are suitable for transesterification or esterification.
However, acid-catalyzed esterification reaction of free fatty
acids is relatively faster than acid-catalyzed transesterifica-
tion reaction of triglycerides (Altıparmak et al., 2007; Van
Gerpen et al., 2004).
The advantages of biodiesel, such as high Cetane num-
ber, oxygen content and sulphur-free, promote combustion

0960-8524/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2007.11.051
 A. Keskin et al. / Bioresource Technology 99 (2008) 6434–6438
process and improve emission profile of exhaust gas. Previ-
ous researches had shown that biodiesel-fuelled engines
produce less carbon monoxide, unburned hydrocarbons,
sulphur oxides and less particulate emissions comparing
with diesel fuel (Monyem and Van Gerpen, 2001; Joshi
and Pegg, 2007). However, nitrogen oxides emissions are
slightly increased depending on the ratio of biodiesel in
the fuel.
A large variety of fuel additives are added to the diesel
fuel to improve the engine efficiency and to reduce emis-
sions. Many researches on influences of fuel additives have
been continuing (Burtscher et al., 1999). A group of addi-
tives are metal-based fuel additives that have been used
as combustion catalysts for hydrocarbon fuels. These met-
als are manganese, iron, copper, barium, cerium, calcium
and platinum which have catalytic activity in combustion
process. The metal-based additives reduce diesel engine
pollution emissions and fuel consumption values. Reason
of emission reduction is that the metals function either by
reacting with water to produce hydroxyl radicals, which
enhance soot oxidation, or by direct reaction with the car-
bon atoms in the soot, thereby lowering the oxidation tem-
perature (Yang et al., 1998). The effect of platinum-based
additive on diesel engine was studied by Kelso et al.
(1990). Three engines for various periods were operated
with treated fuels with the additive. Test result showed that
the use of the platinum additive reduced CO and HC emis-
sion and improved brake specific fuel consumption values.
May and Hirs (2005) studied the influence of iron–magne-
sium catalyst on steam boilers and compression-ignited
reciprocating engines. They have found that the additive
when added to diesel and heavy fuel oil supplies, promotes
complete and more efficient combustion in the engine,
resulting in increased power, improved fuel economy and
radically reduced smoke emission. Caton et al. (1990) stud-
ied the effects of platinum-based additive (organometallic
compound) on the performance and fuel consumption of
the diesel engine. The additive reduced the brake specific
fuel consumption after 236 h of engine operation, by an
average of 9% at 1300 rpm, 5% at 1600 rpm and negligibly
at 1900 rpm, with an uncertainty of ±1.7%. Keskin et al.
(2007) studied the effects of tall oil biodiesel with Mn and
Ni based additives on fuel consumption and emissions.
CO emissions and smoke opacity decreased up to 64.28%
and 30.91%, respectively. Low NOx emission was also
observed in general for the biodiesel fuels.
In this study, crude tall oil was used for the production
of biodiesel and metal-based fuel additive. Crude tall oil is
a major by-product of cellulose production (Bokis et al.,
1999). Characteristically, crude tall oil contains 40–50%
resinic acids related to rosin or abietic acid, 30–40% fatty
acids related to oleic and linoleic acids, and 10% neutral
or unsaponifiable matter of less importance in which the
most important component is b-sitosterol (Nogueira,
1996). The chemical composition varies with the age, pine
species, geographical location of the coniferous trees and
pulping process (Üstün and Civelekoğlu, 1991).
6435
Fatty acids and resinic acids were obtained from crude
tall oil by distillation method. Tall oil fatty acids were used
for the production of biodiesel. Resinic acids were reacted
with metallic compounds (MgO and MoO3) for the synthe-
sis of metal-based fuel additive. Each of the metallic addi-
tives was dosed into B60 fuel. Influence of the test fuels on
engine performance and emissions was investigated in single
cylinder direct injection diesel engine at full load condition.
2. Methods
2.1. Material
In the study, crude tall oil sample of SEKA Çaycuma
paper plant in Turkey was used. The results of crude tall
oil analysis are acid value (154.5), saponification value
(162.3), viscosity (51 mm2/s at 70 °C), pour point (63 °C),
calorific value (39 676 kJ/kg), dien value (11.88), unsapo-
nifiables (4.5%), flash point (212 °C), water content
(5.6%), resin acids (53.6%) and fatty acids (36.3%).
By the distillation of crude tall oil, free fatty acids
obtained were used in esterification reaction and resinic
acids were used for the production of metal-based additives.
In the esterification reaction, methyl alcohol was used as
reactant, and sulphuric acid (Merck) was used as a catalyst.
Sodium bicarbonate solution was prepared in distilled hot
water, to wash and neutralize the ester product. In the study
of additive preparation, abietic acid in the resinic acids was
reacted with MgO (Merck) and MoO3 (Merck) for the pro-
duction of magnesium abietate and molybdenum abietate.
Ethyl alcohol was used to solve metal abietates.
2.2. Methods
Batch distillation apparatus was used for separating
fatty acids and resinic acids from crude tall oil. Tempera-
tures were recorded for the interval of 5 min starting from
20 °C. After removing the water, free fatty acids and resinic
acids were collected separately.
Esterification reaction was carried out in a spherical
glass reactor equipped with reflux condenser, stirrer and
thermometer. In this reaction, 1000 g of tall oil fatty acids,
200 g of methyl alcohol and 50 g of sulphuric acid were
mixed. According to theoretical esterification, the ratio of
methyl alcohol excess is about 150%. Minimum usage of
methyl alcohol in the reaction was aimed for the reduction
of cost. The mixture was heated up to 75 °C and kept at
this temperature for 3 h by stirring. Test conditions were
used as optimized in the previous study (Altıparmak
et al., 2007; Keskin et al., 2007). Later, deep phase contain-
ing water and catalyst was removed by a separating funnel.
Top phase containing ester product was washed with the
solution of sodium bicarbonate to eliminate suspended
impurities, unreacted methanol and residual catalyst. Since
sodium bicarbonate solution has an alkaline feature, it
reduces acid value of raw methyl esters. To purify raw
methyl ester, it was distilled.
6436 A. Keskin et al. / Bioresource Technology 99 (2008) 6434–6438

After drying the metallic compounds at 110 °C, metal- Table 1

based additives were synthesized stoichiometrically at Chemical and physical properties of B60 diesel fuel
225 °C for 1 h in a 1000 ml glass reactor equipped with B60 EN 14214 D EN 590
reflux condenser, stirrer and thermometer. The synthesized 3
Density at 15 °C (kg/m ) 0.867 860–900 835 820–845
additive was dissolved by ethanol at 60 °C, and then they Viscosity at 40 °C (cSt) 5.3 3.5–5.0 2.6 2.0–4.5
dissolved in test fuel (B60). The metal-based additives were Calorific value (kJ/kg) 41 511 – 43760 –
Cetane number 50 Min 51 47 Min 51
added into B60 (60% biodiesel + 40% diesel fuel) for pre- Sulphur content (mg/kg) 10.29 Max 10.0 25.79 Max 50
paring test fuels at the rate of 4 lmol/l, 8 lmol/l and CFPP (°C) 6 – 8 –
12 lmol/l. The test fuels with additives were abbreviated Flash Point (°C) 88 Min 120 73 Min 55
as dose ratio and symbol of metal, i.e. ‘‘B60–8Mg”. Diesel Cloud point (°C) 2 – 6
fuel was referred to as ‘‘D”. Water content (mg/kg) 94 Max 500 126 Max 200
Copper strip corrosion (3 h, 50 °C) 1 1 1 1
In this experimental study, the test fuels tests were per-
formed with 395 cm3, a single cylinder, four stroke, air-
cooled, 18:1 compression ratio, direct injection diesel and cloud point. In addition, viscosity of test fuels with
engine Lombardini 6LD 400. This test engine’s maximum the additives was appropriate on large scale for EN 14214.
power is 6.3 kW and maximum speed is 3600 rpm. The engine torque and the power output values did not
Test fuels were tested from 1800 to 3200 rpm with an inter- change significantly when the fuels are changed. Further-
val of 200 rpm at full load condition. An electrical dynamom- more, 4 lmol/l of additives has no considerable influence
eter was used for the determination of torque and power on fuel consumption and emissions of the test fuels. There-
output. Fuel consumption was measured on volumetric basis. fore, effects of 8 and 12 lmol/l additives on fuel consump-
To measure the emissions, two different equipments were tions and emission values were focused in the study.
used: CO, NOx and CO2 emissions were measured by using The measured specific fuel consumption values in bio-
Gaco-SN, and smoke value emissions were measured by diesel fuels were higher in comparison with diesel fuel in
using VLT 2600 S test devices. Measurement accuracy of general. This is probably because of the lower calorific
Gaco-SN is ±1 ppm for CO, 0.1% for CO2 and ±1 ppm for value of biodiesel fuels. Maximum increase of fuel con-
NOx. Measurement capacity of the device is 0–10000 ppm sumption was 5.51% with B60 at 2800 rpm, and minimum
for CO, 0–3000 ppm for NOx and 0–50% for CO2 emission. increase was 3.08% with B60–8Mo at 1800 rpm. Specific
The accuracy of VLT 2600 S device is ±0.01 m 1 for K factor fuel consumption of B60 with metal-based additives
and the measurement capacity is 0–10 m 1. slightly decreased. The specific fuel consumption values
obtained with B60–8Mo were lower than the other test
3. Results and discussion fuels. This is probably because of the catalyst effect of
metal-based additives and better fuel properties of biodiesel
At the beginning of the process, 5.6% water was sepa- that increase the thermal efficiency of the engine.
rated from crude tall oil between 100 °C and 105 °C. Distil- As seen in Fig. 1, lower CO emission values were mea-
lation was paused, while the temperature was increasing. It sured with all biodiesel fuel in comparison with diesel fuel.
was observed that condensing starts again after 180 °C. A Reduction of CO emission values with biodiesel fuels ran-
small amount of distillate can be obtained by increasing ged from 19.52% to 56.42%. It is clearly seen that CO emis-
up to 220 °C gradually. More distillate was obtained after sion of biodiesel fuel decreased with Mg and Mo based
the temperature of 220 °C and continued up to 328 °C. additives. In comparison with B60, maximum reduction
Total mass (36.3%) was collected as fatty acids at the tem- with Mg and Mo based additives was 36.21% with B60–
peratures between 180 °C and 328 °C. Resin acids were dis- 12Mg at 2600 rpm and 24.12% with B60–12Mo at
tilled between 328 °C and 340 °C. The distillates collected 2400 rpm, respectively. In general, when comparing to
were similar to the crude tall oil analysis results. Mo-based additive, relatively lower CO emission was mea-
According to diesel fuel, some fuel properties of B60 sured with Mg-based additive. Due to fuel properties of
such as cetane number, sulphur content, water content biodiesel such as higher oxygen content, low sulphur con-
and flash point are better than thosse of diesel fuel (Table tent and higher cetane number and catalyst effect of the
1). In addition, because of a little saturated fatty acids con- metal-based additives, the CO emission decreased.
tent in tall oil-free fatty acids, cold filter plugging point NOx emissions of test fuels are shown in Fig. 2. At low
(CFPP) and cloud point of B60 are lower than many of engine speed, although lower NOx emissions were mea-
the other vegetable oils. sured with B60–8Mg and B60–12Mg, the higher NOx emis-
Influence of Mg and Mo based additives on the fuel sions were recorded with other biodiesel fuels. An increase
properties are seen in Table 2. Both of the metal-based of NOx is probably because of the higher oxygen content
additives reduced flash point, pour point and viscosity of and better combustion of biodiesel fuels, and as a conse-
the biodiesel fuel, depending on the rate of additives. The quence, the combustion temperature increases. As it can
same effects were seen for the diesel fuels in the study of be seen from Fig. 2, in general, NOx emissions reduced
Gürü et al. (2002). Transportation of the test fuel in cold with all biodiesel fuels at high engine speed. According to
weather condition improved with reducing pour point diesel fuel, the ratio of maximum increase is 12.78% with
 A. Keskin et al. / Bioresource Technology 99 (2008) 6434–6438 6437

Table 2
Effects of metallic additives on fuel properties of B60
B60 B60–4Mg B60–8Mg B60–12Mg B60–4Mo B60–4Mo B60–4Mo
Pour point (°C) 14 16 21 22 18 19 24
Viscosity at 40 °C (cSt) 5.3 4.9 4.5 4.4 5 4.8 4.3
Flash point (°C) 88 87 83 80 83 81 77.5

350 6000
Specific Fuel Consumption (g/kWh)

Specific Fuel Consumption

5000
300

4000

CO (ppm)
250
3000
200
CO 2000

150
1000

100 0
1600 1800 2000 2200 2400 2600 2800 3000 3200 3400
Engine Speed (rpm)

D B60 B60-8Mg B60-12Mg B60-8Mo B60-12Mo

Fig. 1. Specific fuel consumption values and CO emissions at full load condition.

500 18
NOx

400 16
NOx (ppm)

300 14

CO2 (%)
200 12
CO2

100 10

0 8
1600 1800 2000 2200 2400 2600 2800 3000 3200 3400
Engine Speed (rpm)
D B60 B60-8Mg B60-12Mg B60-8Mo B60-12Mo

Fig. 2. NOx and CO2 emissions at full load condition.

B60–12Mo at 2200 rpm and the maximum reduction is Smoke opacity values of the test fuels are shown in
23.19% with B60–8Mo at 2800 rpm, respectively. Fig. 3. The measured smoke opacity of exhaust gas is in
The results indicated that lower CO2 concentration in fact an indication of particulate matter (PM). Due to oxy-
exhaust gases was obtained with biodiesel fuel (Fig. 2). This gen content of biodiesel fuels and catalyst effect of the
is probably because of the lower carbon content of biodie- metal-based additives, smoke opacity of biodiesel fuels
sel fuels. The reduction of CO2 concentration was higher at reduced at all engine speeds when compared with diesel
low engine speeds. Maximum reduction was 8.82% with fuel. Reduction of smoke opacity with biodiesel fuels ran-
B60–12Mg at 1800 rpm. In addition, in comparison with ged from 5.35% to 30.43%. As it can be seen from Fig. 3,
Mo-based additives, lower CO2 concentration was mea- the reduction ratio was higher at low and high engine
sured with Mg-based additive. speeds.
6438 A. Keskin et al. / Bioresource Technology 99 (2008) 6434–6438
Smoke Level (K factorm-1) 2
0
1600 1800 2000
D B60
Fig. 3. Smoke level of exhaust gas at full load condition.
4. Conclusion
The crude tall oil is cheaper than the other kinds of veg-
etable oils or animal fat, which is an important advantage
for biodiesel production.
Some fuel properties of B60 such as cetane number, sul-
phur content, water content and flash point are better than
those of diesel fuel. In addition, Mg and Mo based addi-
tives improved the pour point and the viscosity of B60
depending on the rate of additives.
In comparison with diesel fuel, higher specific fuel con-
sumption values were measured with biodiesel fuels. This
is more likely because of lower calorific value of biodiesel
fuels. However, as a result of the catalyst effect of metal-
based additives, specific fuel consumption slightly
decreased.
Exhaust gas emission profile improved. CO emissions
and smoke opacity decreased by 56.42% and by 30.43%,
respectively. In general, low NOx and CO2 emissions were
measured with the biodiesel fuels.
Acknowledgements
This study was supported by the State Planning Organi-
zation of Turkey under Project No. 2001 K 120590 and by
Gazi University, Research Project No. 07/2003-13.
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