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Biokim I PDF
Biokim I PDF
Department of Chemical Engineering, Faculty of Chemistry, Complutense University, 28040 Madrid, Spain
Received 3 September 2002; received in revised form 6 August 2003; accepted 31 August 2003
Abstract
The most common catalysts for biodiesel production are homogeneous basic catalysts. In the present paper, a comparison is
made of dierent basic catalysts (sodium methoxide, potassium methoxide, sodium hydroxide and potassium hydroxide) for
methanolysis of sunower oil. All the reactions were carried out under the same experimental conditions in a batch stirred reactor
and the subsequent separation and purication stages in a decanter. The analytical methods included gas chromatography and the
determination of fat and oil conventional parameters. The biodiesel purity was near 100 wt.% for all catalysts. However, near 100
wt.% biodiesel yields were only obtained with the methoxide catalysts. According to the material balance of the process, yield losses
were due to triglyceride saponication and methyl ester dissolution in glycerol. Obtained biodiesel met the measured specications,
except for the iodine value, according to the German and EU draft standards. Although all the transesterication reactions were
quite rapid and the biodiesel layers achieved nearly 100% methyl ester concentrations, the reactions using sodium hydroxide turned
out the fastest.
2003 Elsevier Ltd. All rights reserved.
Keywords: Biodiesel; Fatty acid methyl esters; Methanolysis; Transesterication; Sunower oil; Basic catalyst
1. Introduction
Biodiesel is dened as fatty acid methyl or ethyl esters
from vegetable oils or animal fats when they are used as
fuel in diesel engines and heating systems. In this context,
biodiesel shows the following general advantages: (1) An
alternative to petroleum-based fuel, which implies lower
dependence on crude oil foreign imports. (2) Renewable
fuel, helping to achieve the EU renewable energy target (12% of total energy output to consist of renewable
energy by 2010) (European Commission, 1997). (3) A
favourable energy balance. (4) A reduction in greenhouse
gas emissions in line with the Kyoto Protocol agreement.
(5) Lower harmful emissions, which is very advantageous
in environmentally sensitive areas such as large cities and
mines. (6) Biodegradable and non-toxic fuel, being benecial for reservoirs, lakes, marine life and other environmentally sensitive places. (7) The use of agricultural
surplus, as agreed in the European Agricultural Policy
regulations, which can also help to improve rural eco*
0960-8524/$ - see front matter 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2003.08.014
298
C H2
C
O
C
O
CH
C H2
C H2 OH
O
100 Kg
3 C H3OH
3R
C H3 + C H OH
C H2OH
11 Kg
100 Kg
11 Kg
high content of free fatty acid. Conversely, the saponication side-reaction only takes place when the catalyst
is potassium or sodium hydroxide, because they contain
the necessary hydroxide group (OH) for this reaction.
However, the basic methoxides only have the hydroxide
ion as an impurity. In this sense, they do not produce
soap through trygliceride saponication (Fr
ohlich and
Rice, 1995a).
Likewise, the soap formation can also be avoided by
using an acid catalyst. In addition, the acids catalyse the
free fatty acid esterication to produce fatty acid methyl
esters, increasing the biodiesel yield. Nevertheless, the
acid-catalysed transesterication is much slower than
the basic catalysed reaction and also needs more extreme
temperatures and pressure conditions (Freedman et al.,
1984; Schwab et al., 1987).
More recently, there has been an increase in the development of heterogeneous catalysts to produce fatty
acid methyl esters, because their utilisation in the transesterication reaction greatly simplies and economises
the post-treatment of the products (separation and purication). Besides, the use of heterogeneous catalysts does
not produce soaps through free fatty acid neutralisation
and triglyceride saponication. However, the heterogeneous catalysed reaction also requires extreme reaction
conditions, while the methyl ester yield and the reaction
time are still unfavourable compared to the alkali catalysts (Vicente et al., 1998).
In most studies, the triglyceride conversion rate, the
changes in product composition during reaction or some
of the quality parameters of biodiesel are calculated.
However, only Fr
ohlich and Rice (1995a, 2000) has
dealt with other relevant aspects of the process such as
biodiesel phase yield after the post-treatment stage and
the inuence of the side-reactions on the biodiesel yield.
According to Fr
ohlich, there could be two possible
sources of yield loss in triglyceride transesterication,
namely the dissolution of the methyl ester in the glycerol
phase and the saponication of the triglyceride. The
yield and yield losses can be evaluated through a material balance of the process.
In the present paper, a comparison is made of different basic catalysts for transesterication of sunower
oil. The study is focused on all the above-mentioned
aspects: biodiesel purity and yield, the material balance
of the process, biodiesel quality and changes in product
composition over time.
2. Methods
2.1. Materials
To prepare biodiesel by basic catalysed transesterication, rened sunower oil was obtained from Olcesa
(Cuenca, Spain). The free fatty acid content of the oil
299
300
Table 1
Eect of the catalyst on the biodiesel purity and yield
Catalyst
Sodium hydroxide
Potassium hydroxide
Sodium methoxide
Potassium methoxide
Biodiesel
purity (wt.%)
99.70
99.75
99.72
99.65
99.71 0.04
99.69
99.80
99.80
99.74
99.76 0.05
99.70
99.69
99.72
99.75
99.72 0.03
99.40
99.50
99.65
99.53
99.52 0.10
Biodiesel
yield (wt.%)
86.33
86.67
87.00
86.71
86.71 0.28
91.67
91.67
91.33
92.00
91.67 0.27
99.17
99.33
99.83
99.00
99.33 0.36
98.33
98.50
98.33
98.67
98.46 0.16
301
Table 2
Material balance of the process
Catalyst
Sodium hydroxide
Potassium hydroxide
Sodium methoxide
Potassium methoxide
85.08
85.15
85.22
85.32
85.19 0.10
90.54
90.00
89.67
90.10
98.62
98.78
98.99
98.16
98.64 0.35
97.20
97.66
97.49
97.82
97.54 0.27
Triglyceride
saponication (1)
(molar%)
5.42
5.66
5.66
5.87
5.65 0.18
3.33
3.45
3.48
3.60
3.46 0.11
0.01
0.07
0.05
0.01
0.04 0.03
0.19
0.08
0.10
0.18
0.13 0.05
Methyl ester in
glycerol (2)
(molar%)
6.07
6.03
6.09
5.97
6.04 0.05
2.86
3.07
3.09
2.98
3.00 0.11
0.07
0.12
0.13
0.12
0.11 0.03
0.33
0.48
0.45
0.46
0.43 0.07
11.49
11.70
11.75
11.84
11.69 0.15
6.18
6.53
6.57
6.58
6.46 0.19
0.09
0.19
0.18
0.13
0.15 0.05
0.52
0.56
0.55
0.64
0.56 0.05
3.43
3.15
3.03
2.84
3.11 0.25
3.28
3.48
3.76
3.23
3.44 0.24
1.29
1.02
0.83
1.70
1.21 0.38
2.28
1.78
1.96
1.54
1.89 0.31
Biodiesel yield
(molar%)
90.1 0.36
molar yield losses stemming from triglyceride saponication and methyl ester dissolution in the glycerol phase.
The results, which include the repetitions, the arithmetical averages and the standard deviations, are presented in Table 2. All the calculated standard deviations
were very low. As expected, the yield losses in the reactions with sodium or potassium methoxides were
slight, 0.15 and 0.56 molar%, respectively. However,
when sodium or potassium hydroxide was the catalyst,
there were yield losses due to triglyceride saponication
and methyl ester dissolution in the glycerol phase. As a
result of the lower sodium hydroxide molecular weight
in comparison with the corresponding weight of the
potassium hydroxide, more soaps were produced during
the saponication with sodium hydroxide, 5.65 molar%,
than with potassium hydroxide, 3.46 molar%. This, in
turn, involved an increase in the methyl ester proportion
in the glycerol to 6.04 molar%, when sodium hydroxide
Table 3
Material balance of the process
Catalyst
Catalyst concentration (wt.%)
Biodiesel yield (molar%)
Triglyceride saponication (1) (molar%)
Methyl ester in glycerol (2) (molar%)
Total loss (1) + (2) (molar%)
Loss not accounted for (molar%)
Temperature 65 C, methanol:sunower oil molar ratio 6.
Sodium hydroxide
Potassium hydroxide
1
85.19 0.10
5.65 0.18
6.04 0.05
11.69 0.15
3.11 0.25
1.5
90.6 0.30
5.15 0.21
2.18 0.10
7.33 0.13
2.07 0.15
302
Table 4
Quality control of biodiesel
Catalyst
Sodium
hydroxide
Monoglyceride
content (wt.%)
Diglyceride
content (wt.%)
Triglyceride
content (wt.%)
Bonded
glycerol (wt.%)
Free glycerol
(wt.%)
Total glycerol
(wt.%)
Acid value
(mg KOH/g)
Iodine value
(mg I2 /g)
Potassium
hydroxide
Sodium
methoxide
Potassium
methoxide
EU Draft
standard
prEN 14214
German
standard
DIN51606
US standard
NBB/ASTM
0.295 0.042
0.24 0.053
0.285 0.026
0.48 0.103
Max. 0.8
Max. 0.5
n.d.
n.d.
n.d.
n.d.
Max. 0.2
Max. 0.3
n.d.
n.d.
n.d.
n.d.
Max. 0.2
Max. 0.3
0.076 0.011
0.062 0.014
0.074 0.007
0.124 0.027
Max. 0.2
0.0033 0.0006
0.0032 0.0002
0.0040 0.0008
0.0042 0.0004
Max. 0.02
Max. 0.01
6 0.02
0.0793 0.0107
0.0652 0.0135
0.0780 0.0063
0.1280 0.0270
Max. 0.25
Max. 0.2
6 0.24
0.033 0.004
0.0085 0
0.007 0.001
0.0500 0.002
Max. 0.5
Max. 0.5
Max. 120
Max. 115
128.1 0.7
127.7 0.9
128.5 0.7
128.1 0.8
100
100
80
Sodium hydroxide
Potassium hydroxide
Sodium methoxide
Potassium methoxide
60
40
80
Methyl Ester
Concentration
(% wt)
Methyl Ester
Concentration
(% wt)
303
60
40
20
20
0
0
20
40
60
Fig. 2. Change in methyl ester concentration during transesterication. Temperature 65 C, methanol:sunower oil molar ratio 6,
catalyst 1 wt.%.
0
0
10 15 20 25 30 35 40 45 50 55 60
Time (minutes)
Fig. 3. Change in methyl ester concentration during transesterication. Temperature 65 C, methanol:sunower oil molar ratio 6.
304
Product
Concentration
(% wt)
8
7
6
5
4
3
2
1
0
0
20
40
60
4. Conclusions
The following conclusions can be drawn from this
study. When the four catalysts were used, the methyl
ester concentrations were near 100 wt.%. High biodiesel
purities are important for biodiesel applications since
residual monoglyceride, diglyceride and triglyceride can
cause serious problems in diesel engines. Biodiesel yields
after the separation and purication steps were higher
than 98 wt.% for the methoxide catalysts, because the
yields losses due to triglyceride saponication and
methyl ester dissolution in glycerol were negligible.
Acknowledgements
This work has been funded by the Comisi
on Inteministerial de Ciencia y Tecnologa from Spain (Project CICYT QUI96-0907).
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