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Article history:
Received 4 January 2007
Accepted 12 July 2008
Available online 10 September 2008
An overow system for continuous esterication of palm fatty acid distillate (PFAD) using an economical
process was developed using a continuous stirred tank reactor (CSTR). Continuous production compared
to batch production at the same condition had higher product purity. The optimum condition for the
esterication process was a 8.8:1:0.05 molar ratio of methanol to PFAD to sulfuric acid catalyst, 60 min of
residence time at 75 C under its own pressure. The free fatty acid (FFA) content in the PFAD was reduced
from 93 to less than 1.5%wt by optimum esterication. The esteried product had to be neutralized with
10.24%wt of 3 M sodium hydroxide in water solution at a reaction temperature of 80 C for 20 min to
reduce the residual FFA and glycerides. The components and properties of fatty acid methyl ester (FAME)
could meet the standard requirements for biodiesel fuel. Eventually the production costs were calculated
to disclose its commercialization.
2008 Elsevier Ltd. All rights reserved.
Keywords:
Biodiesel
Palm fatty acid distillate (PFAD)
Continuous esterication
Economical process
1. Introduction
Biodiesel is renewable clean bio-energy as it can be produced
from vegetable oils and has no sulfur content. The quality of biodiesel is similar to diesel fuel; thus it becomes a promising alternative to diesel fuel [1].
At present, the main drawback for the commercialization of
biodiesel is its higher cost than petroleum-based diesel. The high
cost of biodiesel is due to its being produced mostly from expensive
high-quality virgin oil with a low content of free fatty acid (FFA)
[2,3]. A way of reducing biodiesel cost is to use less expensive
feedstock containing high FFA, recycled or waste oils and by
products of the rening vegetable oils. With feedstock having high
FFA, biodiesel production is processed in two steps. The rst step is
to reduce the FFA content of the oil by esterication. The second
step is transesterication, which converts the triglyceride portion
of the oils to mono-alkyl ester and glycerol [47].
Esterication is an acid-catalyzed chemical reaction involving
FFA and alcohol which yields fatty acid alkyl ester and water (H2O).
Methanol is the most commonly used alcohol because of its low
cost and high reactivity as compared to longer-chain alcohols [2,8].
Biodiesel production in the presence of enzyme catalysts can achieve satisfactory ester yield under mild conditions. However, the
process is costly and needs longer reaction times and higher catalyst concentrations. For example, the enzymatic production of
1060
Table 1
Fatty acid proles of PFAD
Table 2
Independent variables and levels of L9(34) for Taguchi method
Fatty acid
Formula
Structure
%wt
C14H28O2
C16H32O2
C18H36O2
C20H40O2
14:0
16:0
18:0
20:0
1.0
45.6
3.8
0.3
16:1
18:1
20:1
24:1
0.2
33.3
0.2
0.6
18:2
18:3
7.7
0.3
alkaline-catalyzed transesterication process. Consequently, esterication was operated. All chemicals including methanol (99.5%),
sulfuric acid (98%), and sodium hydroxide (99%) are of commercial
grade.
2.2. Experimental design
Continuous production using an overow process was simply
carried out under mild conditions, low reaction temperatures (65,
70 and 75 C) that made the system pressure slightly higher than
the atmospheric pressure. This process requires an uncomplicated
apparatus which is easily constructed and low cost. The
experiments were designed by the Taguchi method [13]. With
a three-level-four-factor array, L9(34), nine experiments were
investigated as shown in Table 2. Molar ratio of methanol to PFAD
(R), reaction temperature (T), reaction time (t) and catalyst amount
(S) were selected as independent variables.
2.3. Batch experiments
To save time and expenses the optimum condition for the batch
experiment was used as the initial condition for continuous
1
2
3
4
5
6
7
8
9
T (min)
R (mole/mole)
S (%wt)
65
65
65
70
70
70
75
75
75
60
90
120
60
90
120
60
90
120
5.7:1
7.2:1
8.8:1
7.2:1
8.8:1
5.7:1
8.8:1
5.7:1
7.2:1
0.92
1.83
2.75
1.83
0.92
2.75
1.83
2.75
0.92
Fig. 1. A schematic diagram of a continuous unit for biodiesel production from PFAD using an economical process.
1061
Table 3
Batch process yields of FAME from PFAD in comparison with continuous process
yields
Process
Batch
Continuous
Fig. 2. FAME content obtained from a Taguchis experimental condition (Table 2) for
deciding the initial condition used in the continuous process.
separating funnel and then allowed to settle into two phases. The
soap phase that formed in the neutralization reaction was
removed. The FAME phase was washed with water at 6080 C,
allowed to settle and heated to evaporate residual water.
2.4. Continuous experiments
The continuous experiments contain two processes: (1) an
esterication process, which is carried out in a continuous stirred
tank reactor (CSTR) and (2) a purication process, where FAME was
puried to meet the standard requirements for biodiesel fuel. A
schematic diagram of the continuous experiments is shown in Fig. 1.
2.4.1. Esterication
On the basis of the results from Section 2.3.1, the reaction
operating parameters were set to a 8.8:1 molar ratio of methanol to
PFAD, a 0.05:1 molar ratio of H2SO4 to PFAD, a reaction temperature
of 75 C under its own pressure (about 133 kPa) for residence time
of 60 min.
Fresh methanol (2.3 kg/h), recycled methanol (6.5 kg/h) and
H2SO4 (0.16 kg/h) were mixed rst and pumped into a 22.4 L
CSTR. PFAD was fed into the CSTR after being heated to 75 C.
The mixture was mixed at a constant stirring rate of 400 rpm.
After that, the product mixture overowed to the cooling water
Esterication
Purication
% Yield
% FAME
% Yield
% FAME
99
97
93.9
97.3
94.4
94
99.6
99.7
Table 4
Operating costs for the annual production of 72,000 kg of biodiesel from PFAD in this
study
Description
Cost
(baht)
Annual
use
Annual cost
(baht/year)
Unit cost
(baht/kg)
Raw materials
PFAD
Methanol
Sulfuric acid
Sodium hydroxide
Subtotal raw materials
11/kg
19/kg
8/kg
19/kg
76,464 kg
20,115 kg
1404 kg
756 kg
841,100
382,199
11,232
14,364
1,248,895
17.34
Utilities
Electricity
Charcoal
Process water
Subtotal utilities
1/kga
3.4/kg
0.012/L
72,000
9853
1037
82,890
1.15
Labor
Operating
Gross production cost
Fig. 3. FAME and glycerides content in the neutralized product using the 3 M NaOH
H2O solution at 80 C under atmospheric pressure for 15 min.
200/day
2898 kg
86,400 L
72,000
1.00
1,403,612
19.50
1062
Table 5
Properties of PFAD biodiesel in comparison with others
Properties
Unit
PFAD
biodiesela
Rubber seed
oil biodiesel
Mahua
biodiesel
Soy soapstock
biodiesel
Diesel
Biodiesel standards
ASTM D6751-02
Density at 15 C
Viscosity at 40 C
Flash point
Pour point
Water content
Ash content
Carbon residue
Acid value
kg/m3
mm2/s
C
C
%
%
%
mg KOH/g
879
4.87
180
14
0.03
0.007
0.07
0.33
874
5.81
130
8
NA
NA
NA
0.118
880
3.98
208
6
0.04
0.01
0.20
0.41
885
4.302
169
NA
<0.01
0.02
0.01
0.05
850
2.60
68
20
0.02
0.01
0.17
0.35
870900
1.96.0
130
15 to 10
0.03
0.02
0.80
PFAD biodiesel from neutralization with 10.24%wt of 3 M NaOHH2O solution at 80 C for 20 min.
1063
[5] Veljkovic VB, Lakicevic SH, Stamenkovic OS, Todorovi ZB, Lazic ML. Biodiesel
production from tobacco seed oil with a high content of free fatty acids. Fuel
2006;85:26715.
[6] Wang Yong, Ou Shiyi, Liu Penzhen, Xue Feng, Tang Shuze. Comparison of two
different processes to synthesize biodiesel by waste cooking oil. Journal of
Molecular Catalysis A: Chemical 2006;252(12):10712.
[7] Shashikant VG, Hifjur R. Process optimization for biodiesel production from
mahua (Madhuca indica) oil using response surface methodology. Bioresource
Technology 2006;97:37984.
[8] Warabi Y, Kudiana D, Saka S. Reactivity of triglycerides and fatty acids of
rapeseed oil in supercritical alcohols. Bioresource Technology 2004;91:
2837.
[9] Royon D, Daz M, Ellenrieder G, Locatelli S. Enzymatic production of biodiesel
from cotton seed oil using t-butanol as a solvent. Bioresource Technology
2006;98:64853.
[10] Zheng S, Kates M, Dube MA, McLean DD. Acid-catalyzed production of biodiesel from waste frying oil. Biomass and Bioenergy 2006;30:26772.
[11] Di Serio M, Tesser R, Dimiccoli M, Cammarota F, Nastasi M, Santacesaria E.
Synthesis of biodiesel via homogeneous Lewis acid catalyst. Journal of
Molecular Catalysis A: Chemical 2005;239(12):1115.
[12] He H, Wang T, Zhu S. Continuous production of biodiesel fuel from vegetable
oil using supercritical methanol process. Fuel 2007;86:4427.
[13] Peace GS. Taguchi methods. 2nd ed. The United States of America: AddisonWesley Publishing Company; 1993.
[14] Michael J. Improving the economics of biodiesel production through the use of
low value lipids as feedstocks: vegetable oil soapstock. Fuel Processing Technology 2005;86:108796.