Bioresource Technology 98 (2007) 241246

Alternative fuel properties of tall oil fatty acid methyl esterdiesel fuel blends
Duran Altparmak a, Ali Keskin a, Atilla Koca a, Metin Gr
b

b,

Technical Education Faculty, Gazi University, 06500 Ankara, Turkey Engineering and Architectural Faculty, Gazi University, 06570 Maltepe, Ankara, Turkey

Received 4 June 2004; received in revised form 4 January 2006; accepted 20 January 2006 Available online 9 March 2006

Abstract In this experimental work, tall oil methyl esterdiesel fuel blends as alternative fuels for diesel engines were studied. Tall oil methyl ester was produced by reacting tall oil fatty acids with methyl alcohol under optimum conditions. The blends of tall oil methyl esterdiesel fuel were tested in a direct injection diesel engine at full load condition. The eVects of the new fuel blends on the engine performance and exhaust emission were tested. It was observed that the engine torque and power output with tall oil methyl esterdiesel fuel blends increased up to 6.1% and 5.9%, respectively. It was also seen that CO emissions decreased to 38.9% and NOx emissions increased up to 30% with the new fuel blends. The smoke opacity did not vary signiWcantly. 2006 Elsevier Ltd. All rights reserved.
Keywords: Biodiesel; Tall oil methyl ester; TransesteriWcation; Alternative fuels

1. Introduction Investigations of alternative renewable energy resources continue, with many studies focused on biodiesel fuels. One of the alternative renewable energy sources for diesel engines is vegetable oil. Use of vegetable oil as an alternative fuel for diesel engines is not a new concept; as early as 1900, a diesel-cycle engine was demonstrated running with groundnut oil at the Paris Exposition (Altn, 1998). In the last decade, several vegetable oils, such as sunXower oil, corn oil, olive oil, soybean oil, cotton seed oil and peanut oil, have usually been used for producing biodiesel fuel. Investigations have shown that pure vegetable oils are not a suitable direct replacement for diesel fuel, due to higher viscosity and higher molecular weight (Dorado et al., 2003; Dunn, 2002). These properties cause poor atomisation, low volatility, incomplete combustion and
* Corresponding author. Tel.: +90 312 2317400/2555; fax: +90 312 2308434. E-mail address: mguru@gazi.edu.tr (M. Gr).

engine deposits (Klass, 1998; Rakopoulos, 1992). Therefore, several methods are used to reduce the viscosity of vegetable oil, including dilution, pyrolysis, micro-emulsion and transesteriWcation (Ma and Hanna, 1999; Solantausta et al., 1993). Nowadays, transesteriWcation is the current method which is used eYciently. The transesteriWcation process involves the reaction of alcohol with the oil to release three ester chains from the glycerine backbone of each triglyceride. The reaction requires heat and a strong base catalyst to achieve complete conversion of the vegetable oil into the separated esters and glycerine (Aydn and Keskin, 2000; Knothe et al., 2002). The esters are called biodiesel and can be used in neat form, or mixed with petroleum diesel fuel in any unmodiWed diesel engines (Canakci and Van Gerpen, 2003). The transformation of sunXower oil by transesteriWcation to produce biodiesel has been studied and the results showed that the biodiesel was an excellent substitute for fossil fuels under optimum conditions (Antolin et al., 2002). Petroleum diesel fuel is made up of hundreds of diVerent hydrocarbon chains (roughly in the range of 1418 carbons

0960-8524/$ - see front matter 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.biortech.2006.01.020

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D. Altparmak et al. / Bioresource Technology 98 (2007) 241246

in length) and contains aromatic hydrocarbons (benzene, toluene, xylenes, etc.), sulphur and crude oil residue contaminants (Klass, 1998). However, the chemical composition of biodiesel is diVerent from that of petroleum based diesel fuel. Biodiesel hydrocarbon chains are generally 16 20 carbons in length and contain oxygen at one end. Biodiesel contains about 10% oxygen by weight. Biodiesel does not contain any sulphur, aromatic hydrocarbons, metals or crude oil residues (Arkoudeas et al., 2003; Kalligeros et al., 2003). These properties improve combustion eYciency and emission proWle. Biodiesel fuel blends reduce particulate material (PM), hydrocarbon (HC), carbon monoxide (CO) and sulfuroxide (SOx) emissions (Tyson, 2004). However, NOx emissions are slightly increased depending on biodiesel concentration in the fuel (Van Gerpen, 2005; etinkaya et al., 2005). Consumption of diesel fuel is 15,000,000 ton/year in Turkey. Biodiesel fuel norms are published to apply in 2005. Therefore, statistical data on production rates are not yet known in Turkey, where many biodiesel production plants are already in operation. World biodiesel production was over 3,000,000 ton/year in 2004 and has increased day after day. Many countries importing crude petrol encourage the production of biodiesel by reducing taxes and by giving low interest credits. The 2003/30/EC directive forces fuel producers to use 2% biodiesel in diesel fuel mixtures and this ratio is planned to increase up to 5.75% by the end of 2010. In this work, free fatty acids were obtained from crude tall oil by fractional distillation for production of tall oil methyl ester as a novel process. Crude tall oil is a by-product in the manufacture of paper pulp by pulping processes. Crude tall oil contains 4050% resinic acids, 3040% fatty acids and 10% neutral or unsaponiWable material (Nogueira, 1996). Elemental analysis shows that tall oil contains 11.0% oxygen, 79.1% carbon and 9.9% hydrogen (Sharma and Bakhshi, 1991). The chemical composition varies with the age, pine species, geographical location of the coniferous trees and pulping process (Drew and Propst, 1981). Crude tall oil in Turkey is obtained at 25,000 ton/year and is cheaper than other vegetable oils. Tall oil is widely

used in industrial applications, e.g. nylon, adhesives, iron steel etc., and also as an additive to improve cetane number in diesel fuel (Feng et al., 1993; Jacoby et al., 2003). In this experimental study, tall oil methyl ester was produced by reacting tall oil fatty acids with methyl alcohol and properties of test fuels were determined. Blends of tall oil methyl ester with diesel fuel were tested in a direct injection diesel engine at full load condition. 2. Methods Crude tall oil was taken from the SEKA Taoucu (in Turkey) paper plant and distilled in a batch distillation apparatus. Temperatures were recorded at intervals of 5 min starting from 15 C. After distilling oV water at temperatures between 98 C and 104 C, free fatty acids used for producing biodiesel were obtained between 235 C and 333 C. The esteriWcation reaction was carried out in a 2000 ml reaction vessel equipped with reXux condenser, stirrer and thermometer. Sulphuric acid was used as catalyst. 1000 g of tall oil fatty acids, 200 g of methyl alcohol and 50 g of sulphuric acid were mixed. The mixture was heated to 65 80 C and held at this temperature with stirring for 2 h. The temperature and ratio of alcohol/oil were investigated as parameters to determine optimal conditions for biodiesel synthesis. After this, the mixture was washed with an aqueous sodium bicarbonate solution to remove suspended impurities, unreacted methanol and catalyst. Sodium bicarbonate solution is alkaline and therefore reduces the acidity of crude methyl ester. Crude methyl ester was distilled to obtain pure methyl ester. A Xow diagram of the tall oil methyl ester production process is shown in Fig. 1. For this experimental study, a single cylinder, direct injection diesel engine was used. The engine characteristics are shown in Table 1. Blends of tall oil methyl ester and diesel fuel were tested at full load condition. Engine speed was changed from 1800 to 3200 rpm with an interval of 200 rpm. Before each test, the engine was warmed up with diesel fuel for about 15 min until the engine temperature stabilised. An

Methyl Alcohol

Catalyst (H2SO4 )

Methoxy Compound Resinic Acids 235 - 333 C Fatty Acids Sodium Bicarbonate Solution

Crude Tall Oil Distilation

Esterification 72 C

Separation

Neutralization + Washing

Distillation Refined Methyl Ester

H2O

Catalyst + H2O

Methyl Alcohol Catalyst Impurities

Fig. 1. Flow diagram of tall oil methyl ester production process.

D. Altparmak et al. / Bioresource Technology 98 (2007) 241246 Table 1 SpeciWcation of the test engine Model of engine Cylinder number Swept volume Bore Stroke Compression ratio Recommended maximum speed Lombardini 6LD 400 1 395 cm3 86 mm 68 mm 18:1 3600 rpm

243

electrical dynamometer was used for the measurement of torque and power output. Two diVerent exhaust emission analysers were used: CO and NOx emissions were measured by using Gaco-SN and smoke opacity was measured by using VLT 2600 S test devices, respectively. Mixtures of tall oil methyl ester (TOME) and diesel fuel (D2) were evaluated as test fuels. These fuels were 100% D2, 50% TOME50% D2, 60% TOME40% D2 and 70% TOME30% D2. Test fuels were mixed on a volume basis. 3. Results and discussion Water comprising 5.2% of the initial mass (see Table 2) was separated when crude tall oil was distilled at a temperature between 98 C and 104 C for 40 min. Distillate producTable 2 Properties of Taoucu crude tall oil Acid value SaponiWcation value Viscosity at 70 C (mm2/s) Pour point (C) CaloriWc value (kJ/kg) Dien value UnsaponiWables (%) Flash point (C) Water content (%) Resin acids (%) Fatty acids (%) Fatty acids composition (%) Oleic acid Linoleic acid Linolenic acid Stearic acid 157.7 165.3 55 67 39,756 11.04 4.1 207 5.2 59.8 30.9 52.7 38.3 6.9 2.1

tion was seen to pause on increasing the temperature, but was observed to start again after 200 C. A small amount of distillate could be obtained by increasing temperature up to 235 C gradually. More distillate was obtained above 235 C and continued up to 333 C. 30.6% of the initial mass was collected as fatty acids at temperatures between 235 C and 333 C. Diesel fuel, blended fuels and base fuel (biodiesel, 100% TOME) properties are shown in Table 3. Blended fuels were generally appropriate to EN 14214, although this norm covers canola and sunXower oil methyl esters. Cold Wlter plugging point (CFPP) and cloud point of tall oil methyl ester were lower than those of other vegetable oil base esters except canola methyl ester. This is because of low saturated fatty acids content in tall oil free acids. The fuel blends for which properties were determined were tested in the diesel engine. The characteristics of the torque curve did not change signiWcantly with the type of fuel (Fig. 2). It was observed that the maximum torque value with all fuels was obtained at an engine speed of 2200 rpm. At low engine speeds, there were no noticeable diVerences in the measured torque of the engine. However, at higher engine speeds, a slight increase in torque was obtained with the blended fuels depending on the amount of TOME. The maximum diVerence in torque was 6.1% with a blend of 30% D270% TOME at 3200 rpm. This is attributed to the higher cetane number of the blended fuels, which ensures improved combustion. The maximum engine power was reached at 3200 rpm for all fuels (Fig. 3). The results showed that there were no noticeable diVerences between diesel fuel and the blends of TOMED2 at low speeds. However, the engine power output increased for all fuel blends compared to with D2 at high engine speeds. The increase in power output for blended fuels varied from 3.2% to 5.9% depending on the amount of TOME and engine speeds. There was a relation between speciWc fuel consumption and the caloriWc value of fuels at low engine speeds. The speciWc fuel consumption increased up to 10.4% with blended fuels, depending on the amount of TOME compared to D2 (Fig. 4). However, speciWc fuel consumption diVerences were decreased at high engine speeds. Combustion eYciency was improved with blended fuels at high

Table 3 Chemical and physical properties of test fuels 50% TOME Density at 15 C (kg/m ) Viscosity at 40 C (mm2/s) CaloriWc value (kJ/kg) Cetane number Sulphur content (mg/kg) CFPP (C) Flash point (C) Cloud point (C) Water content (mg/kg) Copper strip corrosion (3 h, 50 C)
3

60% TOME 892 4.82 41,511 52 102.9 6 80 2 94 1

70% TOME 901 5.12 41,145 53 79.2 6 82 1 87 1

100% TOME 922 7.1 40,023 54 5.0 3 89 1 68 1

EN 14214 860900 3.55.0 Min 51 Max 10.0 Min 120 Max 500 1

D2 835 2.6 43,760 47 257.9 8 73 6 126 1

EN 590 820845 2.04.5 Min 51 Max 50 Min 55 Max 200 1

882 4.5 41,901 52 131.1 7 78 2 111 1

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26.0

D. Altparmak et al. / Bioresource Technology 98 (2007) 241246

Torque (Nm)

22.0

18.0

14.0 1600

1800

2000 D2

2200

2400 2600 Engine Speed (rpm) 60% TOME

2800 70% TOME

3000

3200

3400

50% TOME

Fig. 2. Engine torque at full load.

8 7

Power (kW)

6 5 4 3 1600

1800

2000 D2

2200

2400 2600 Engine Speed (rpm) 60% TOME

2800

3000

3200

3400

50% TOME

70% TOME

Fig. 3. Engine power at full load.

350

Specific fuel consumption (g/kWh)

300

250

200 1600

1800

2000 D2

2200

2400 2600 Engine speed (rpm)

60% TOME

2800
70% TOME

3000

3200

3400

50% TOME

Fig. 4. SpeciWc fuel consumption at full load.

engine speeds. This can be attributed to the oxygen content of biodiesel. The results indicated that lower CO concentrations in exhaust gases could be obtained with blended fuels at all engine speeds (Fig. 5). Similar results have been reported by other researchers (Antolin et al., 2002; Silva et al., 2003). This is due to the higher cetane number of blended fuels,

leading to an increase in combustion eYciency. CO concentrations with blended fuels were 15% to 38.9% lower than those with diesel fuel. Instability of NOx formation was seen at both low and high engine speeds. However, higher NOx concentrations in exhaust gas were obtained with all blended fuels between 2200 and 3200 rpm (Fig. 6). NOx concentration

D. Altparmak et al. / Bioresource Technology 98 (2007) 241246

2500 2000

245

CO (ppm)

1500 1000 500 0 1600

1800

2000

2200 D2

2400 2600 Engine speed (rpm) 60% TOME

2800

3000

3200

3400

50% TOME

70% TOME

Fig. 5. CO emissions at full load.

2000

1500 NOx (ppm)

1000

500

0 1600

1800

2000 D2

2200

2400 2600 Engine speed (rpm) 60% TOME

2800

3000

3200

3400

50% TOME

70% TOME

Fig. 6. NOx emissions at full load.

4.0

Smoke opacity (K factor 1/m)

3.0

2.0

1.0

0.0 1600

1800

2000

2200 D2

2400 2600 Engine speed (rpm) 50% TOME

2800

3000 70% TOME

3200

3400

60% TOME

Fig. 7. Smoke opacity of exhaust gas at full load.

was increased up to 30% depending on the amount of TOME. This was probably because of the higher nitrogenous compounds content and better combustion of blended fuels. These results are similar to the results of previous researchers (Purcell et al., 1996; Usta et al., 2005; Durbin, 2000).

The measured opacity of exhaust gas is in fact an indication of PM. Compared with the diesel fuel, lower smoke opacity was obtained with blended fuels at about maximum torque speeds (Fig. 7). Amongst the blended fuels, lower opacity was obtained with 30% D270% TOME, especially at middle and higher engine speeds. The maximum reduction

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D. Altparmak et al. / Bioresource Technology 98 (2007) 241246 Dorado, M.P., Ballesteros, E., Arnal, J.M., Gomez, J., Lopez, F.J., 2003. Exhaust emission from a diesel engine fuelled with transesteriWed waste olive oil. Fuel 82, 13111315. Drew, J., Propst, M., 1981. Tall Oil. Pulp Chemicals Association, New York. Dunn, R.O., 2002. Low-temperature Xow properties of vegetable oil/cosolvent blend diesel fuels. Journal of the American Oil Chemists 79 (7), 709715. Durbin, T.D., 2000. EVect of biodiesel, biodiesel blends, and asynthetic diesel on emission from light heavy-duty diesel vehicles. Environmental Science Technology 34 (3), 349355. Feng, Y., Wong, A., Monnier, J., 1993. Chemical composition of tall oilbased cetane enhancer for diesel fuels. First Biomass Conference of the Americas: Energy, Environment, Agriculture and Industry, p. 15. Jacoby, W.A., Robert, C., Siddharth, U., 2003. Conversion of Rosin Acid Fraction of Crude Tall Oil into Fuels and Chemicals. [100]-Oxygenated Fuels. American Institute of Chemical Engineers, USA. Kalligeros, S., Zannikos, F., Stournas, S., Lois, E., Anastopoulos, G., Teas, C., Sakellaropoulos, F., 2003. An investigation of using biodiesel/ marine diesel blends on the performance of a stationary diesel engine. Biomass and Bioenergy 24, 141149. Klass, L.D., 1998. Biomass for Renewable Energy, Fuels, and Chemicals. Academic Press, USA. Knothe, G., Matheaus, A.C., Ryan, T.W., 2002. Cetane number of branch and straight-chain fatty esters determined in an ignition quality tester. Fuel 82, 971975. Ma, F., Hanna, M.A., 1999. Biodiesel production: a review. Bioresource Technology 70, 115. Nogueira, J.M.F., 1996. Crude tall-oil components. Separation Science and Technology 31 (17), 23072316. Purcell, D.L., McClure, B.T., McDonald, J., Basu, H.N., 1996. Transient testing of soy methyl ester fuels in an indirect injection compression ignition engine. JAOCS 73 (3), 381388. Rakopoulos, C.D., 1992. Comparative performance and emission studies when using olive oil as a fuel supplement in DI and IDI diesel engines. Renewable Energy 2 (3), 327331. Sharma, R.K., Bakhshi, N.N., 1991. Upgrading of tall oil to fuels and chemicals over HZSM-5 catalyst using various diluents. The Canadian Journal of Chemical Engineering 69, 10821086. Silva, F.N., Prata, A.S., Teixeira, J.R., 2003. Technical feasibility assessment of oleic sunXower methyl ester utilization in diesel bus engines. Energy Conversion and Management 44, 28572878. Solantausta, Y., Nylund, N., Westerholm, M., Koljonen, T., Oasmaa, A., 1993. Wood-pyrolysis oil as fuel in a diesel-power plant. Bioresource Technology 46, 177188. Tyson, K.S., 2004. Biodiesel handling and use guidelines, report of national renewable energy laboratory. NREL/TP-580-3004 US, pp. 13. Usta, N., ztrk, E., Can, ., Conkur, E.S., Nas, S., on, A.H., Can, A.., Topu, M., 2005. Combustion of biodiesel fuel produced from hazelnut soapstock/waste sunXower oil mixture in a diesel engine. Energy Conversion and Management 46, 741755. Van Gerpen, J., 2005. Biodiesel processing and production. Fuel Processing Technology 86, 10971107.

of opacity value of 31.25% was obtained with 30% D270% TOME fuel at 2600 rpm. 4. Conclusions Blended fuels can be used as alternative fuels in conventional diesel engines without any major modiWcation. Low sulphur and aromatic contents are advantages of tall oil fatty acid methyl esterdiesel fuel blends. At high engine speeds, torque and engine power output increased by 6.1% and 5.9%, respectively, with blended fuels. However, there were no signiWcant torque and power diVerences between the D2 and biodiesel (blended fuels) at low engine speeds. At low engine speeds, speciWc fuel consumption increased with blended fuels depending on the amount of tall oil methyl ester. But, relative to diesel fuel, speciWc fuel consumption for blended fuels did not increase signiWcantly at higher engine speeds. Tall oil methyl esterdiesel fuel blends had the advantages of decreasing CO emissions (up to 38.9%), low sulphur content and higher cetane number. Acknowledgements This study was supported both by the State Planning Organization of Turkey under Project No. 2001 K 120590 and by Gazi University, Research Project No. 07/2003-13. References
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