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4112 Energy & Fuels 2009, 23, 4112–4115

Alkali-Catalyzed Biodiesel Production from Mixtures of Sunflower


Oil and Beef Tallow
Sevilay Taravus, Hakan Temur,* and Ahmet Yartasi
Engineering Faculty, Department of Chemical Engineering, Ataturk UniVersity, 25240 Erzurum, Turkey

ReceiVed March 10, 2009. ReVised Manuscript ReceiVed June 3, 2009

In this study, some physical properties of biodiesel obtained from different mixtures of sunflower oil and
beef tallow are investigated. The biodiesel cold-flow specifications, such as viscosity, pour point, cloud point,
and cold-filter plugging point, were tested for the different sunflower oil/beef tallow (SO/BT) ratios. Also, the
sulfur content and heat value of the biodiesel samples have been determined. It was observed that the examined
physical properties of the methyl esters changed negatively as the beef tallow ratio in the mixture increased.
However, until the ratio of 40% beef tallow and 60% sunflower oil, there was no important deterioration in
the properties of methyl esters. When beef tallow contents were higher than 40%, some specifications of
methyl esters were beyond the biodiesel standards of ASTM D 6751 and EN 1424.

1. Introduction the biodiesel industry.3 Used frying oils, soapstock, and animal
fats are potential feedstocks to lower the cost of biodiesel.4
Biodiesel is an alternative and renewable fuel for diesel Rough projections of the cost of biodiesel show that the cost
engines and produced from vegetable oils and animal fats mostly of biodiesel based on animal fats is less by 30-50% than that
through a transesterification process. This is carried out chemi- based on vegetable oils in the U.S.4,5 Furthermore, exhaust
cally by reacting vegetable oils or animal fats with an alcohol, emissions from beef-tallow-based biodiesel and its blends are
preferably methyl alcohol, with the presence of usually a strong lower than that of petroleum-based biodiesel, similar to those
base catalyst, such as sodium hydroxide or potassium hydrox- that are obtained from vegetable oils.6 However, there are some
ide.1 The instability of oil prices, limited fossil fuel resources, problems with using animal fats as a feedstock in the biodiesel
and environmental problems resulting from fossil fuels have production, such as poor solubility of tallow in methanol and
pushed countries to focus on more national, sustainable, and high free fatty acid content, which causes soap to form with
environmentally friendly fuel resources, such as biodiesel.2 The alkali catalysts. In addition, oils and fats can contain water as
alkali-catalyzed biodiesel production process is commercially a result of the extraction method (water from vegetable or animal
preferable, in the case of high free fatty acid contents of the tissues released during crushing or melting), a solvent used for
feedstock; acid catalysis can be used as an alternative process extraction or the transformation method. Liquid oils and fats
route. However, in this case, the conversion rate of the often contain water that is soluble in lipids at about 0.05-0.1%.7
transesterification process is slow. The use of enzymes as The water content has a significant effect on the transesterifi-
catalysts is tolerable for the free acid content but expensive and cation of glycerides with the alkaline or acidic catalysts.2
unable to provide the degree of reaction completion.3 Although Furthermore, cold-flow properties, such as high pour point, cloud
a few of them are used in industrial scale, there are plenty of point, cold-filter plugging point (CFPP), and viscosity, of the
biodiesel have been reported to show poor performance values
raw material types from which biodiesel is attempted to be
in the case of animal fats as a feedstock.8 Although there is an
produced, such as palm oil, soybean oil, sunflower oil, corn
ongoing effort to improve the specifications of animal-fat-based
oil, coconut oil, rapeseed oil, tung oil, waste cooking oils, tallow,
biodiesel,9–11 to use animal fats as a lower cost feedstock
and cottonseed oil. Furthermore, algae, bacteria, fungi, microal-
extensively, more research and technological development will
gae, terpenes, and latexes were also studied as alternative diesel be needed.
fuels.2
In this study, it is aimed to determine the properties of
The major barrier to commercialization of biodiesel is its biodiesel obtained from animal fat and sunflower oil blends in
relatively high cost in comparison to petroleum-based diesel.
Because 70-95% of this cost comes from the vegetable oils used, (4) Canakci, M.; Sanli, H. Biodiesel production from various feedstocks
focusing on low-cost materials is an important step in developing and their effects on the fuel properties. J. Ind. Microbiol. Biotechnol. 2008,
35, 431–441.
(5) Bender, M. Economic feasibility review for community-scale farmer
* To whom correspondence should be addressed: Engineering Faculty, cooperatives for biodiesel. Bioresour. Technol. 1999, 70, 81–87.
Department of Chemical Engineering, Ataturk University, 25240 Erzurum, (6) Oner, C.; Altun, S. Biodiesel production from inedible animal tallow
Turkey. Telephone: 90-442-231-4587. E-mail: htemur@atauni.edu.tr. and an experimental investigation of its use as alternative fuel in a direct
(1) Gerpen, J. V. Biodiesel processing and production. Fuel Process. injection diesel engine. Appl. Energy 2009, doi: 10.1016/j.apenergy.
Prod. 2005, 86, 1097–1107. 2009.01.005.
(2) Fangrui, Ma; Hanna, M. H. Biodiesel production: A review. (7) Oils and Fats Manual; Karleskind, A., Ed.; Intercept Ltd.: Bedford-
Bioresour. Technol. 1999, 70, 1–15. shire, U.K., 1996; Vol. 2.
(3) Zhang, Y.; Dube, M. A.; McLean, D. D.; Kates, M. Biodiesel (8) Canakci, M.; Sanli, H. Biodiesel production from various feedstocks
production from waste cooking oil: 2. Economic assessment and sensitivity and their effects on the fuel properties. J. Ind. Microbiol. Biotechnol. 2008,
analysis. Bioresour. Technol. 2003, 90, 229–240. 35, 431–441.

10.1021/ef900211n CCC: $40.75  2009 American Chemical Society


Published on Web 07/07/2009
Alkali-Catalyzed Biodiesel Production Energy & Fuels, Vol. 23, 2009 4113

Table 1. Typical Compositions and Some Physical Properties of Table 2. Fatty Acid Contents of the Beef Tallow and Sunflower
Crude Beef Tallow and Sunflower Oila Oil
characteristics beef tallow (range) sunflower oil (range) fatty acids beef tallow (wt %) sunflower oil (wt %)
iodine number 40.0–49.0 133 C14:0 2.27
saponification number 190–202 188–194 C14:1 0.20
titer (°C) 40.0–49.0 16–20 C16:0 19.14 6.28
melting point (°C) 45.0–48.0 from –18 to –20 C16:1 2.54
C18:0 13.34 3.27
Fatty Acid Composition (wt %)
C18:1n9c 40.46 20.55
myristic (C-14:0) 2.0–8.0 <1.0
C18:2n6t 1.51 0.70
palmitic (C-16:0) 24.0–37.0 4.0–6.0
C18:2n6c 2.57 67.56
stearic (C-18:0) 14.0–29.0 3.0–5.0
C18:3n3 1.69 0.10
oleic (C-18:1) 40.0–50.0 50.0–65.0
C20:0 0.17 0.22
linoleic (C-18:2) 1.0–5.0 25.0–35.0
C20:1 0.14
Triglyceride Composition (%) C22:0 0.59
trisaturated (GS3) 15.0–28.0 0.5 C24:0 0.19
disaturated (GS2U) 46.0–52.0 2.8
monosaturated (GSU2) 20.0–37.0 22.4 the city of Erzurum) and at the temperature of 60 °C to prevent
triunsaturated (GU3) 0–2.0 74.1
beef tallow from freezing. The experimental procedure followed
a G, glycerides; S, saturated; U, unsaturated. in the study is shown in Figure 1. The constant parameters in the
experiments were chosen as reaction time, 60 min; oil/alcohol ratio,
the presence of an alkali catalyst. The motivation behind the 1:6 (in weight); catalyst ratio, 1% NaOH (in weight); reaction
study was to what extent beef tallow can be used as a feedstock temperature, 60 °C.
along with the sunflower oil without going beyond the standards After each experiment, viscosity (at 40 °C), pour point, cloud
set for the biodiesel. An optimum mixture ratio has been found, point, CFPP, density (at 15 °C), sulfur content, and heating value
beyond which properties of biodiesel started to deteriorate of the each sample were measured using proper analysis instruments
according to present American Society for Testing and Materials according to related EN standards. No matter what the blend ratio
is, 100% biodiesel samples (B100) were used in all of the
(ASTM) and EN standards.
measurements. The effects of blend ratios of sunflower oil/beef
tallow on the biodiesel specifications were investigated in terms of
2. Experimental Section properties given above. The ratios of sunflower oil/beef tallow (SO/
BT) blends examined are shown in Table 3.
The edible beef tallow used in this study was supplied from a
local slaughterhouse in Erzurum, Turkey. The acid value and density
at 20 °C for the beef tallow was 2.55 mg of KOH/g and 0.896 3. Results and Discussion
g/mL, respectively. The average molecular weight was measured
as 897 g/mol. The sunflower oil used in the experiments was The effects of the ratio of sunflower oil/beef tallow mixtures
supplied from a local market, which was refined, winterized, and on the physical properties, such as cloud point, pour point,
deodorized. Its acid value, density at 20 °C, and average molecular kinematic viscosity, CFPP, sulfur content, and heating value,
weight were 0.045 mg of KOH/g, 0.921 g/mL, and 988 g/mol, were examined in the study. The results are plotted as related
respectively. A typical composition and some characteristic physical property versus decreasing sunflower ratio in the blend. The
properties of beef tallow and sunflower oil are shown in Table 1.2,12 effects can be shown as follows.
Fatty acid methyl esters included in beef tallow and sunflower
oil were analyzed by a gas chromatograph (Agilent 6890N gas Effect of the Ratio of SO/BT on the Pour Point, Cloud
chromatograph, Waldbronn, Germany) with a capillary column Point, and CFPP of the Biodiesel. Poor low-temperature flow
(DB23, 60 m × 250 µm × 0.15 µm), temperature (increasing from properties are one of the most important hurdles for biodiesel.
100 to 200 °C with a rate of 5 °C/min and from 200 to 250 °C The cloud point of petroleum products is the temperature at
with a rate of 4 °C/min), flame ionization detector (FID) (H2 and which a cloud of wax crystals first appears in the liquid when
dry air) at 280 °C, helium gas (1.2 mL/min), and injection block
temperature of 250 °C. The fatty acid contents of both materials
are shown in Table 2. It can be seen from both Tables 1 and 2 that
saturated fatty acid content in the beef tallow is very high, whereas
the level of unsaturated fatty acids is lower as compared to
sunflower oil.
The methyl alcohol (99.9% purity) and NaOH catalyst (99.99%
purity) used in the experiments were products of Merck and Co.,
Inc. The experimental system basically consisted of a constant
temperature circulator, a jacketed glass reactor, a mixer, and a
condenser to condense the methanol vapors. The experiments were
carried out under the normal atmospheric pressure (610 mmHg for

(9) da Cunha, M. E.; Krause, L. C.; Moraes, M. S. A.; Faccini, C. S.;


Jacques, R. A.; Almeida, S. R.; Rodrigues, M. R. A.; Caramao, E. B. Beef Figure 1. Experimental procedure.
tallow biodiesel produced in a pilot scale. Fuel Process. Technol. 2009,
doi: 10.1016/j.fuproc.2009.01.001.
(10) Chung, K. H.; Kim, J.; Lee, K. Y. Biodiesel production by Table 3. Examined Ratios of SO/BT Blends
esterification of duck tallow with methanol on alkali catalysts. Biomass SO/BT ratios
Bioenergy 2009, 33, 155–158.
(11) Guru, M.; Artukoglu, B. D.; Keskin, A.; Koca, A. Biodiesel 1 100% SO + 0% BT
production from waste animal fat improvement of its characteristics by 2 80% SO + 20% BT
synthesized nickel and magnesium additive. Energy ConVers. Manage. 2009, 3 60% SO + 40% BT
50, 498–502. 4 40% SO + 60% BT
(12) O’Brien, R. D. Fats and Oils, 2nd ed.; CRC Press: Boca Raton, 5 20% SO + 80% BT
FL, 1980. 6 0% SO + 100% BT
4114 Energy & Fuels, Vol. 23, 2009 TaraVus et al.

Figure 4. Effect of the ratio of SO/BT on the sulfur content of the


Figure 2. Effect of the ratio of SO/BT on the pour point, cloud point, biodiesel.
and CFPP of the biodiesel.

Figure 5. Effect of the ratio of SO/BT on the heating value of the


biodiesel.
influencing viscosity subordinately. Moreover, kinematic viscos-
ity values measured at 40 °C for the common methyl esters are
Figure 3. Effect of the ratio of SO/BT on the viscosity of the biodiesel. well-known.17 For instance, kinematic viscosity values for the
oleic acid, lineloic acid, palmitic acid, and stearic acid methyl
esters were respectively measured to be 4.51, 3.65, 4.38, and
it is cold.13 The pour point is the lowest temperature for 5.85 mm2/s.
movement of the sample under the prescribed conditions.14 The The main fatty acid components in the beef tallow sample
CFPP is described as the highest temperature, expressed in used in the present study are oleic acid (40.46%), palmitic acid
multiples of 1 °C, that a given volume of fuel fails to pass (19.14%), and stearic acid (13.34%), whereas those of the
through a standardized filtration devise in a specified time when sunflower oil are the linoleic acid (67.56%) and oleic acid
cooled under the conditions prescribed in the test method.14 The (20.55%). The increase in the kinematic viscosity of biodiesel
cloud points, pour points, and CFPPs of biodiesel samples as the sunflower oil ratio drops off to 60% in the mixture, as
increased as the percentage of beef tallow in the mixtures seen in the Figure 3, is referred to the simultaneous effect of
increased, as shown Figure 2. The increase in the saturated fatty decreasing linoleic acid and increasing oleic acid methyl ester
acid ratio and the decrease in the unsaturated ones were seen ratios in the biodiesel.
responsible for these increases, as affirmed in the literature.8 Effect of the Ratio of SO/BT on the Sulfur Content. Sulfur
Effect of the Ratio of SO/BT on the Viscosity. Viscosity content in the biodiesel is important in terms of minimizing
of the biodiesel is important because of a proper operation corrosion, wear, and tear in the combustion system and
engine, flowing of fuel through pipelines, injector nozzles, preventing environmental pollution because of combustion
orifices, etc., and finally, effective atomization of the fuel in products.15 As seen in Figure 4, as the amount of beef tallow
cylinders.15 All viscosity measurements in the study were carried increases in the blend, the sulfur content of the biodiesel
out at 40 °C and under an open atmosphere. Viscosity of the increases as well. Sulfur in the vegetable oils is a result of the
biodiesel almost remained unchanged as the beef tallow ratio compounds, such as thioglycosides, which are included in
increases until the ratio of the biodiesel sample obtained from the oils, such as rapeseed, crambe, and mustard seed oils.16 The
60% sunflower oil and 40% beef tallow, as shown in Figure 3. results obtained from the present study showed that the sulfur
After this point, it began to increase. content is increasing in the biodiesel produced from sunflower
It is previously reported that kinematic viscosity increases oil and beef tallow mixtures as the beef tallow ratio in the blend
for the fatty compound with an increase in the number of carbon increases. However, the point is that sulfur content of 100%
atoms (chain length) and decreases with an increase in the beef tallow is lower than 0.03, which is an acceptable level for
number of double bonds primarily.8,17 Other than these factors, biodiesel sulfur content with regard to common biodiesel
position and nature of the double bond are other parameters standards, as seen in Table 4.
Effect of the Ratio of SO/BT on the Heating Value. In
(13) Ali, Y.; Hanna, M. A.; Cuppett, S. L. Fuel properties of tallow opposition to the other parameters, an increased amount of beef
and soybean oil esters. J. Am. Oil Chem. Soc. 1995, 72 (12), 1557–1564.
(14) Tayal, S. Detection of cold properties of diesel and biodiesel fuel (16) Patterson, H. B. W. Hydrogenation of Fats and Oils; Applied
using optical sensor. M.S. Thesis, University of MissourisColombia, Science Publishers: New York, 1983.
Columbia, MO, May 2006. (17) Knothe, G.; Steidley, K. R. Kinematic viscosity of biodiesel fuel
(15) Srivastava, A.; Prasad, R. Triglycerides-based diesel fuels. Renew- components and related compounds: Influence of compound structure and
able Sustainable Energy ReV. 2000, 4, 111–133. comparison to petrodiesel fuel components. Fuel 2005, 84, 1059–1065.
Alkali-Catalyzed Biodiesel Production Energy & Fuels, Vol. 23, 2009 4115

Table 4. Experimental Values and Standards of the Biodiesel


petroleum diesel EN experimental value
parameters unit Europe EN 14214:2003 U.S. ASTM D 6751-07b 590-1999 SO/BT ) 60:40
density at 15 °C g/cm3 0.86–0.90 0.820–0.860 0.88
kinetic viscosity at 40 °C mm2/s 3.5–5.0 1.9–6.0 2.0–4.5 4.5
flashpoint °C 120 min 130 min 55 min 150
CFPP °C country specific country specific –2
cloud point °C report –18 12
pour point °C –25 –2.2
sulfur mass (%) 10 max 0.05 max 350 max 0.015
water mg/kg 500 max 500 max 200 max 110
heating value kJ/kg 42525 41320

tallow in the blend is beneficial for the biodiesel quality in terms of sunflower oil and beef tallow were tested in this study. The
of the heating value. As seen from Figure 5, the beef tallow, parameters examined were kinematic viscosity, pour point, cloud
which is composed of a higher percentage of saturated methyl point, CFPP, sulfur content, and heating value of the biodiesel
esters, has a slightly higher heating value than pure sunflower- samples. It was observed that the physical properties of biodiesel
oil-based biodiesel when burnt. obtained from the 60% sunflower oil and 40% beef tallow blend
When the results obtained were assessed throughout the study, were sufficient in view of present ASTM and EN standards. At
the B100 biodiesel sample obtained from the 60% sunflower this mixture ratio, the levels of parameters were found to be
oil and 40% beef tallow blend was found to be in unison with
pour point, -2.2 °C; cloud point, 12 °C; kinematic viscosity at
American (ASTM D 6751-03) and European (EN 14214)
40 °C, 4.5 mm2 s-1; CFPP, -2 °C; sulfur content, 0.015 (in
standard specifications. The consistency between the common
standards and experimental data obtained from the present study wt); and heating value, 41 320 kJ kg-1. In addition to this, the
is shown in Table 4.8 flash point was 150 °C, the water content was 110 mg kg-1,
and the density at 15 °C was 883 kg m-3 for this ratio of the
4. Conclusions blend. As a result, it can be put forward that the beef tallow
can be used as a biodiesel raw material in high percentage along
Although beef tallow has poor properties, such as high with the sunflower oil without lowering biodiesel quality
viscosity and pour and cloud points as a feedstock in biodiesel significantly. The use of beef tallow slightly increases the heating
production, it is a necessity to take adventage of it to reduce
value of the biodiesel as well.
the raw material cost, which consists of up to 70% of the total
cost of biodiesel. The biodiesel samples of different blend ratios EF900211N

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