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Biodiesel production by transesterication of duck tallow with methanol on alkali catalysts

Kyong-Hwan Chunga, Jin Kima,b, Ki-Young Leea,c,
a

Center for Functional Nano Fine Chemicals, Chonnam National University, Gwangju 500-757, Republic of Korea Department of Advanced Chemicals Graduate School, Chonnam National University, Gwangju 500-757, Republic of Korea c Department of Applied Chemical Engineering & The Research Institute for Catalysis, Chonnam National University, Gwangju 500-757, Republic of Korea
b

art i cle info

Article history: Received 8 February 2008 Received in revised form 12 April 2008 Accepted 17 April 2008 Available online 6 June 2008 Keywords: Biodiesel Duck tallow Transesterication Alkali catalyst

ab st rac t
Duck tallow was employed as a feedstock for the production of biodiesel by transesterication with methanol. The content of fatty acid methyl ester (FAME) was evaluated on various alkali catalysts during transesterication. The composition and chemical properties of the FAME were investigated in the raw duck tallow and the biodiesel products. The major constituent in the biodiesel product was oleic acid. The FAME content was 97% on KOH catalyst in the reaction. It was acceptable for the limit of European biodiesel qualities for BD100. Acid value, density, and kinematic viscosity of the biodiesel products also came up to the biodiesel qualities. & 2008 Elsevier Ltd. All rights reserved.

1.

Introduction

When biodiesel is produced from rened edible oils, feedstock cost contributes more than 70% to the cost of biodiesel [1]. Recently, because of a rapid increase of the price of vegetable feedstocks for biodiesel fuels, it has been considered to employ other inexpensive oil as a feedstock for biodiesel fuels. The use of inexpensive, non-edible feedstock and the utilization of by-products in the biodiesel production may signicantly reduce the cost of biodiesel. Animal fats, the byproducts obtained from roasting, can be used as a feedstock for biodiesel production. The use of methyl esters of beef tallow (BTME) as a diesel fuel had been investigated [25]. Hanna et al. [6] highlighted

the occurrence of crystallization in BTME and the fuel properties. Ma et al. [7] asserted that mixing is very important for the transesterication of beef tallow, because melted beef tallow and a sodium hydroxidemethanol solution are immiscible. However, biodiesel production by transesterication of other animal fats has been rarely studied in comparison with that from vegetable oils. In the present study, duck tallow was employed as a feedstock for biodiesel production in transesterication with methanol. Biodiesel production was conducted on alkali catalysts in the transesterication of duck tallow with methanol. Fatty acid methyl ester (FAME) content in the biodiesel product was evaluated with various reaction conditions. The composition of methyl esters and chemical

Corresponding author at: Department of Applied Chemical Engineering & The Research Institute for Catalysis, Chonnam National University, Gwangju 500-757, Republic of Korea. Tel.: +82 62 530 1843; fax: +82 62 530 1819. E-mail address: likeu21@hanmail.net (K.-Y. Lee). 0961-9534/$ - see front matter & 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.biombioe.2008.04.014

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properties of FAME were also investigated in the product and raw duck tallow.

2.
2.1.

Materials and methods

Materials

Duck tallow was obtained from the roasting of a duck meat in a restaurant. Methanol was purchased from Aldrich (99%). Potassium hydroxide (Ducksan, 98%), sodium hydroxide (Ducksan, 98%), and sodium methoxide (TCI, 98%) were employed as the alkali catalysts in the reaction.

sponding to A for blank titration (ml), and W is the mass of the sample (g). Kinematic viscosity of the produced biodiesel was measured according to ASTM D 445 [8]. The test was conducted by measuring the time required for a volume of liquid to ow under gravity through a Cannon-Fenske-style glass capillary tube used commonly for ASTM D 445. The density of the products was dened from specic gravity (gspec) and reference density (dref). The equation for the density (d) is dened as d dref gspec. Specic gravity was measured using a hydrometer.

2.2.

Transesterication of duck tallow with methanol

3.

Results and discussion

Transesterication of duck tallow with methanol over the catalysts was carried out by a batch-type reactor equipped with a mechanical stirrer and a water-cooled condenser. The reactants were charged, and then were stirred in a 500 ml round bottom ask. The speed of stirring was maintained at 600 rpm. The composition of the products was analyzed by a gas chromatograph (GC; Shimadzu, 9A) equipped with a capillary column (HP-1, i.d.: 0.32 mm, length: 50 m, lm thickness: 0.17 mm) and a FID detector.

2.3.

Analysis

The conversion of duck tallow to biodiesel was calculated as a molar ratio of produced FAME per feedstock. The FAME content (Yester) in the product was measured by GC analysis according to the EN 14103 test method [8]. At rst, a standard (STD) solution was prepared as 10 mg/ml of methyl heptadecanoate (C17:0) with heptane solution. The numbers in parenthesis signify the number of carbon atoms and the unsaturated centers (double bond). The sample (250 mg) was added to 5 ml of STD solution. The mixed sample with STD solution was analyzed by GC. The FAME content was determined from the following equation: P A As Cs Vs 100 (1) Yester % As m P where A is summation of GC peak areas of methyl esters (C14:0C24:1), As is the GC peak area of methyl heptadecanoate (internal STD), Cs is the concentration of STD solution (10 mg ml1), Vs is volume of STD solution (5 ml), and m is the amount of sample (250 mg). The acid value was determined according to ASTM D 664 by potentiometric titration [8]. The sample was dissolved in a mixture of toluene and isopropanol. The sample was titrated potentiometrically with alcoholic potassium hydroxide. The meter readings are plotted dened inections in the resulting curve. The acid value was the quantity of base, expressed as mg KOH g1 of sample, required to titrate the sample to a specied end point. The acid value was calculated according to the following equation [8]: Nacid 56:1 MA B=W (2)

where Nacid is the acid value, M is the concentration of KOH (mol l1), A is the volume of KOH used to reach the end point corresponding to basic buffer (ml), B is the volume corre-

Fig. 1 shows the FAME content on KOH catalyst with various reaction conditions. The basic reaction conditions were xed as 65 1C of reaction temperature, 1 wt% of loading amount of catalyst to the duck tallow, 3 h of reaction temperature, and 6:1 molar ratio of methanol to feedstock. The FAME content to the reaction conditions was 97% on KOH catalyst. The high content of FAME was obtained at 5585 1C of reaction temperature as shown in Fig. 1(A). The reactivities of transesterication were high in the reaction temperatures. The variation of the FAME content with different loading amounts of KOH catalyst is shown in Fig. 1(B). The high content of FAME was exhibited at 1 wt% of KOH catalyst loading to the feedstock. While the loading amount of catalyst exceeded more than 1 wt%, the FAME content decreased reversely. The effect of methanol addition was evaluated with the FAME content on KOH catalyst (Fig. 1(C)). When methanol was added according to the stoichiometry of the reaction as 3:1 molar ratio of methanol to triglyceride, the FAME content was 75%. The FAME content was increased signicantly to 97% in 6:1 molar ratio of methanol to feedstock. However, the FAME content decreased with the increase in methanol injection. The FAME content with reaction time is represented in Fig. 1(D). The FAME content reached at equilibrium after 3 h. The FAME content exceeded 80% even for 1 h reaction. Table 1 lists the fatty acid composition of feedstock and biodiesels produced by transesterication of duck tallow with methanol at 65 1C. The duck tallow feedstock mainly consisted of oleic acid and linoleic acid. The biodiesel produced by transesterication on various alkali catalysts was composed mainly of oleic acid and palmitic acid. It was dened that the linoleic acid in the feedstock disappeared mostly after the reaction. The composition of oleic acid and palmitic acid increased signicantly after the reaction. The reactivities and chemical properties of the products after separation of methanol and glycerol are listed in Table 2. The conversion of duck tallow was about 80% on KOH and sodium methoxide catalysts. It is about 10% lower than that of vegetable oil on the same alkali catalyst [9]. However, the conversion is enough to use as a biodiesel fuel. It can be suggested that the duck tallow is more available as a feedstock for biodiesel fuel than vegetable oils, since it has a competitive price compared to the vegetable oils. The FAME content was obtained as 97.1% on KOH catalyst. The result is acceptable for the limit of European biodiesel

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157

FAME content (%)

100 80 60 40 20 0 50 60 70 80 90 Reaction temperature (C)

100 80 60 40 20 0 0 0.5 1 1.5 2 Loading amount of KOH (g)

FAME content (%)

100 80 60 40 20 0 0 5 10 15 20 Methanol/duck tallow molar ratio (-)

100 80 60 40 20 0 0 2 4 6 Reaction time (h)

Fig. 1 FAME content on KOH catalyst with various reaction conditions: (A) FAME content with variation of reaction temperature. (B) FAME content with variation of catalyst loading amount. (C) FAME content with different molar ratio of methanol to feedstock. (D) FAME content with reaction time. Other basic reaction conditions were xed as 65 1C of reaction temperature, 0.5 g of catalyst loading, 3 h of reaction temperature, and 6:1 molar ratio of methanol to feedstock.

Table 1 Fatty acid composition of duck tallow and biodiesels produced using various alkali catalystsa FAME Feedstock After reaction on KOH catalyst
0.8 24.2 0.3 72.5 2.2

After reaction on NaOH catalyst

0.7 26.0 0.3 71.5 1.5

After reaction on CH3NaO catalyst

0.7 25.8 71.9 1.6

% Myristic (C14:0)b % Palmitic (C16:0) % Palmitoleic (C16:1) % Stearic (C18:0) % Oleic (C18:1) % Linoleic (C18:2) % Linolenic (C18:3) % Arachidic (C20:0)

17.0 4.0 59.4 19.6

a The reaction conditions: loading amount of catalyst 1 wt% to the feedstock, molar ratio of methanol to feedstock 6:1, reaction temperature 65 1C, reaction time 3 h. b Numbers in parentheses signify the number of carbon atoms and the unsaturated centers (double bond).

qualities for BD100 [8]. The acid value of the feedstock was 0.56 mg KOH g1 before the reaction. After the reaction with methanol, the acid value reduced to 0.20 and 0.24 mg KOH g1 on KOH catalyst and sodium methoxide catalyst, respectively. The acid value of the biodiesel was also acceptable for the

limit of European biodiesel qualities. Density and kinematic viscosity of the products were improved to the limits of European biodiesel qualities (EN 14214). Especially, the kinematic viscosity was signicantly enhanced in comparison with that of raw duck tallow.

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Table 2 Chemical properties of feedstock and biodiesel produced by transesterication of duck tallow with methanola Property Feedstock After reaction on KOH catalyst
79.7 97.1 0.20 864 5.5

After reaction on NaOH catalyst

62.3 81.3 0.48 748 6.0

After reaction on CH3NaO catalyst

79.3 83.6 0.24 887 5.8

Conversion (%) FAME content (%) Acid value (mg KOH g1) Density (kg m3) Kinematic viscosity (mm2 s1)
a

0.56 908 35.7

The reaction conditions: loading amount of catalyst 1 wt% to the feedstock, molar ratio of methanol to feedstock 6:1, reaction temperature 65 1C, reaction time 3 h.

4.

Conclusion
[2]

The production of biodiesel from duck tallow was evaluated by transesterication with methanol on alkali catalysts. The FAME content in the product was obtained as 97% on KOH catalyst at 65 1C. The major constituent of the biodiesel product was 72% oleic acid. The oleic acid and palmitic acid increased signicantly after the reaction. The content of methyl ester in the biodiesel product came up to the limit of European biodiesel qualities for BD100. After the reaction with methanol, the acid value reduced to 0.2 mg KOH g1 on KOH catalyst. The acid value, density, and kinematic viscosity of the biodiesel product were improved to the European biodiesel qualities.

[3] [4]

[5]

[6]

Acknowledgment
We greatly acknowledge the nancial support of Post BK21 program.
R E F E R E N C E S

[7]

[8] [9]

fatty acid esters from vegetable oils. Journal of the American Oil Chemists Society 2004;81:839. Ali Y, Eskridge KM, Hanna MA. Testing of alternative diesel fuel from tallow and soybean oil in Cummins N14-410 diesel engine. Bioresource Technology 1995;53:24354. Ali Y, Hanna MA. Physical properties of tallow ester and diesel fuel blends. Bioresource Technology 1994;47:1314. Ali Y, Hanna MA, Borg JE. Optimization of diesel: methyl tallowate: ethanol blend for reducing emissions from diesel engine. Bioresource Technology 1995;52:23743. Ali Y, Hanna MA, Cuppett SL. Fuel properties of beef tallow and soybean oil esters. Journal of the American Oil Chemists Society 1995;72:155764. Hanna MA, Ali Y, Cuppett SL, Zhang D. Crystallization characteristics of methyl tallowate and its blend with ethanol and diesel fuel. Journal of the American Oil Chemists Society 1996;73:75963. Ma F, Clements LD, Hanna MA. The effect of mixing on transesterication of beef tallow. Bioresource Technology 1999;69:28993. Van Gerpen J, Shanks B, Pruszko R, Clements D, Knothe G. Biodiesel analytical methods. NREL/SR-510-36240, 2004. Kim HJ, Kang B-S, Kim M-J, Park YM, Kim D-K, Lee J-S, et al. Transesterication of vegetable oil to biodiesel using heterogeneous base catalyst. Catalysis Today 2004;93:31520.

[1] Haas MJ, Scott KM, Marmer WN, Foglia TA. In situ alkaline transesterication: an effective method for the production of