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Article history: Biodiesel (BD) is commonly produced from rened vegetable oils by alkali-catalyzed methanolysis. Unre-
Received 17 July 2008 ned vegetable oils are economically attractive but not suitable for alkali catalysis because of their high
Received in revised form 11 April 2009 content of free fatty acids (FFAs). Novozym 435 (immobilized Candida antarctica lipase B), which accepts
Accepted 11 April 2009
both FFA and oil as substrates, was, therefore, employed to convert unrened palm oil to BD. Three
Available online 21 April 2009
different methanolysis methods, namely, t-butanol mediated system (method-1), LiCl solution based
controlled release system for methanol (method-2) and solvent-free system with three successive addi-
Keywords:
tions of methanol (method-3), were compared. The optimal methanol to oil molar ratios in the method-1,
Biodiesel
Novozym 435
-2 and -3 are 6:1, 3:1 and 3:1, respectively. BD yield at an optimal methanol concentration reaches 9192%
Unrened palm oil after 10, 20 and 24 h in the method-1, -2 and -3, respectively. BD yield remains the same over ve repeated
Method cycles in the method-1, while it drops to 68 and 71% by the fth cycle in the method-2 and -3, respectively.
Methanolysis The results show that the method-1 is the most effective for production of BD from a low cost feedstock
like unrened palm oil.
2009 Elsevier B.V. All rights reserved.
2.1. Materials
Corresponding author. Fax: +65 63166182. Rened palm oil, oleic acid (99%), Novozym 435 (Candida
E-mail address: talukder@ices.a-star.edu.sg (Md.M.R. Talukder). antarctica lipase B immobilized on acrylic resin), LiCl and t-
1381-1177/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.molcatb.2009.04.004
Md.M.R. Talukder et al. / Journal of Molecular Catalysis B: Enzymatic 60 (2009) 106112 107
Fig. 1. Novozym 435 activity at different methanol to oil molar ratio. Reaction condi-
tions: 10 g unrened palm oil, 0.4 g lipase (Novozym 435), methanol to LiCl solution
ratio 7:3 (v/v), volume of methanolLiCl solution was varied according to methanol
to oil molar ratio, 10 ml t-butanol, reaction time 2 h, temperature 40 C and shaking
speed 190 rpm. Methanol is added by single addition.
Fig. 4. Effect of added oleic acid on Novozym 435 activity. Reaction conditions: 10 g
unrened palm oil, methanol to oil molar ratio 3:1 (with t-butanol or LiCl solution Fig. 6. Comparison of esterication of oleic acid and transesterication of triolein
system) and 1:1 (solvent-free system), methanol to oleic acid molar ratio for all in t-butanol. Reaction conditions: 20 ml oleic acid (0.15 M) or triolein (0.05 M),
methods 1:1, amount of Novozym 435 was varied according to 4 wt.% of total sub- methanol to oleic acid molar ratio 1:1, methanol to triolein molar ratio 3:1, Novozym
strates (oil plus oleic acid), 10 ml t-butanol, 2.3 ml methanolLiCl solution mixture 435 of 0.0340.035 g (4 wt.% of oleic acid or triolein), temperature 40 C and shaking
(7:3, v/v), reaction time 2 h, temperature 40 C and shaking speed 190 rpm. speed 190 rpm.
110 Md.M.R. Talukder et al. / Journal of Molecular Catalysis B: Enzymatic 60 (2009) 106112
Fig. 8. Biodiesel yield at molar excess of methanol. Reaction conditions are the same
Fig. 7. Time course methanolysis of unrened palm oil at molar equivalent of as those in Fig. 7 except reaction time was 10, 20 and 24 h for the method-1, -2 and
methanol (i.e. methanol to oil molar ratio 3:1). Reaction conditions: 10 g unrened -3, respectively. For the method-3, 1/3 molar equivalent of methanol was added at
palm oil, 0.4 g Novozym 435, 10 ml t-butanol, 2.3 ml methanolLiCl solution mixture 0 h and the rest is added by two successive additions of equal volume of methanol
(7:3, v/v), temperature 40 C and shaking speed 190 rpm. For the method-1 and -2, at 4 and 15 h.
methanol was added by single addition while for the method-3, it was added by
three successive additions of 1/3 molar equivalent of methanol at 0, 4 and 10 h. methanol deactivates Novozym 435 in the method-3, and decreases
BD yield.
Fig. 12. Effect of added -carotene content in rened and unrened palm oils
on Novozym 435 activity. 10 g rened or unrened palm oils, 0.4 g Novozym 435,
methanol to oil molar ratio 6:1 (with t-butanol, 10 ml) and 1:1 (without t-butanol),
temperature 40 C, reaction time 2 h and shaking speed 190 rpm.
Fig. 10. Methanolysis of rened and unrened palm oils in t-butanol mediated
is one of the enzyme inhibitory substances. In absence of t-butanol
system (method-1). Reaction conditions: 10 g rened or unrened palm oil, 0.4 g
Novozym 435, methanol to oil molar ratio 6:1, 10 ml t-butanol, temperature 40 C and exogenous phospholipid, Novozym 435 activity with unrened
and shaking speed 190 rpm. palm oil is 2.02 (g BD/h/g lipase), less than half of that with rened
palm oil (4.65 g BD/h/g lipase). The addition of t-butanol increases
the activity from 2.02 to 9.25 g BD/h/g lipase, close to that with
3.6. Comparison of rened and unrened palm oils as biodiesel
rened palm oil (10.25 g BD/h/g lipase). This result suggests that
feedstock
t-butanol reduces the inhibitory effect of phospholipids.
One of the unique characteristics of unrened palm oil is its
Since method-1 is most effective in terms of reaction efciency
high content of carotenoids (0.050.07 wt.%), which impart the
and Novozym 435 recycling, this method was chosen for the com-
orangered colour to palm oil [26]. 8090% of palm oil carotenoids
parison of rened and unrened palm oils as biodiesel feedstocks.
are - and -carotenes in the ratio of 2:1 [27]. The effect of -
The time course methanolysis of rened and unrened palm oils
carotene on Novozym 435 activity is thus worth to investigate.
with methanol to oil molar ratio of 6:1 were shown in Fig. 10. The
Carotenes content in unrened palm oil used in this study is
ultimate BD yield with rened (93% after 8 h) and unrened (92%
0.04 wt.%. Fig. 12 shows that Novozym 435 activity remains the
after 10 h) palm oils are almost the same but the methanolysis of
same over -carotene (added) concentrations of 0.010.1 wt.%,
rened palm oil progresses faster. In addition to FFA and water con-
indicating that carotene is possibly inert to Novozym 435.
tent, rened and unrened palm oils also differ in phospholipids
content. Phospholipids are the main components of oil gum, which
increases viscosity and reduces mass transfer. Since this gummy 4. Conclusions
component is removed during rening, the methanolysis of rened
palm oil progresses faster. To better understand the phospholipids Three different methanolysis methods using Novozym 435 as a
effect, Novozym 435 activity at different phospholipids concentra- biocatalyst for converting unrened palm oil to BD were investi-
tions in rened and unrened palm oils was investigated. gated. Compared with the method-2 and 3, the method-1 is more
Gum (as phospholipids) content in unrened palm oil effective in minimizing methanol deactivation of Novozym 435. The
(0.020.1 wt.%) [22,23] is generally much lower than that in other inhibitory effects of phospholipid and water on Novozym 435 activ-
oils such as soybean (1.52.1 wt.%) [24] and rapeseed (1.01.5 wt.%) ity were signicantly reduced by the method-1. The presence of FFA
[25]. Phospholipids content in unrened palm oil used in this study and carotene in palm oil showed a negligible effect on Novozym
is 0.05 wt.%. Fig. 11 shows that Novozym 435 activity decreases with 435 activity. It has been demonstrated that BD yields with rened
the increase in phospholipids content, indicating that phospholipid and unrened palm oils are almost the same. This study shows
that Novozym 435 can successfully convert unrened palm oil to
biodiesel and the method-1 is the best. The results reported in this
paper are useful for production of biodiesel from vegetable oils with
high content of free fatty acids, water and phospholipids.
Acknowledgement
References
[8] J.W. Chen, W.T. Wu, J. Biosci. Bioeng. 95 (2003) 466469. [18] T. Samukawa, M. Kaeda, T. Matsumoto, K. Ban, A. Kondo, Y. Shimada, H. Noda,
[9] L. Li, W. Du, D. Liu, L. Wang, Z. Li, J. Mol. Catal. B: Enzym. 43 (2006) 5862. H. Fukuda, J. Biosci. Bioeng. 90 (2000) 180183.
[10] V. Dossat, D. Combes, A. Marty, Enzym. Microb. Technol. 25 (1999) 194200. [19] G. Bell, A.E.M. Janssen, P. Halling, Enzym. Microb. Technol. 20 (1997) 471477.
[11] M.M.R. Talukder, K.L.M. Beatrice, O.P. Song, S. Puah, Energy Fuels 22 (2008) [20] G.V. Chowdary, S.G. Prapulla, Process Biochem. 38 (2002) 393397.
141144. [21] A. Marty, V. Dossat, J.S. Condoret, Biotechnol. Bioeng. 56 (1997) 232237.
[12] Y. Luo, G. Wang, Y. Ma, D. Wei, J. Chem. Technol. Biotechnol. 81 (2006) [22] S.H. Goh, S.L. Tong, P.T. Gee, J. Am. Oil Chem. Soc. 61 (1984) 15971600.
18461848. [23] S. Arora, S. Manjula, A.G.G. Krishna, R. Subramanian, Desalination 191 (2006)
[13] W. Du, Y. Xu, J. Zeng, D. Liu, Biotechnol. Appl. Biochem. 40 (2004) 187190. 454466.
[14] Y. Watanabe, Y. Shimada, A. Suguhara, Y. Tominaga, J. Mol. Catal. B: Enzym. 17 [24] E.F. Sipos, B.F. Szuhaj, in: Y.H. Hui (Ed.), Baileys Industrial Oil and Fat Products,
(2002) 151155. vol. 2, 5th ed., John Wiley, New York, 1996, pp. 497601.
[15] J. Mendham, R.C. Denney, J.D. Barnes, M. Thomas, Vogels Textbook of Quanta- [25] N.A.M. Eskin, B.E. Mcdonald, R. Przybylski, L.J. Malcolmson, R. Scarth, T. Mag, K.
tive Chemical Analysis, 6th ed., Pearson Education, Harlow, England, 2000. Ward, D. Adolph, in: Y.H. Hui (Ed.), Baileys Industrial Oil and Fat Products, vol.
[16] M. Holcapek, P. Jandera, J. Fischer, B. Prokes, J. Chromatogr. A 858 (1999) 1331. 2, 5th ed., John Wiley, New York, 1996, pp. 195.
[17] S. Tamalampudi, M.M.R. Talukder, S. Hama, T. Numata, A. Kondo, H. Fukuda, [26] D. Darnoko, M. Cheryan, J. Am. Oil Chem. Soc. 83 (2006) 365370.
Biochem. Eng. J. 39 (2008) 185189. [27] E.O. Farombi, G. Britton, Food Chem. 64 (1999) 315321.