Fuel Processing Technology 104 (2012) 271280

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Fuel Processing Technology

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Development of a novel process for biodiesel production from palm fatty acid
distillate (PFAD)
Hyun Jun Cho, Jin-Kuk Kim, Seok Won Hong, Yeong-Koo Yeo
Department of Chemical Engineering, Hanyang University, Haengdang-dong, Sungdong-gu, Seoul, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: A novel process for the non-catalytic esterication of PFAD (palm fatty acid distillate) has been developed
Received 26 November 2011 through theoretical modeling and experimental studies. The detailed reaction kinetics and effect of reaction
Received in revised form 8 May 2012 temperature on the performance of processes are fully analyzed. Distillation is employed to purify palm bio-
Accepted 19 May 2012
diesel product produced from the reactor, and it has been demonstrated that biodiesel product from the de-
Available online 12 June 2012
veloped process meets European standard of EN 14214, while 91.2% of biodiesel product yield was obtained.
Keywords:
Process modeling and simulation of the developed process with the production capacity of 8000 tyr 1, have
Biodiesel been made, which allows to carry out rigorous techno-economic analysis for evaluating cost-effectiveness of
Non-catalytic esterication the proposed process and comparing it with those of other processes. The estimated capital cost of a new pro-
Palm fatty acid distillate cess is $1.63 10 6 which requires 20.7% more than that of the alkali-catalyzed process, but 22.4% less than
Design that of the supercritical process. For total manufacturing cost, a new process is estimated to be about 25%
Economic analysis cheaper than the other two processes. Under the current market situations, the developed process has com-
petitive relative payback years and break-even prices, against the other two processes, which clearly shows
the competitiveness of the proposed process.
2012 Elsevier B.V. All rights reserved.

1. Introduction
In general, biodiesel, fatty acid methyl ester (FAME), is efciently
produced from the transesterication of vegetable oil or animal fats
or from esterication of fatty acids with short chain alcohols in the
presence of homogeneous or heterogeneous alkali- and/or acid-
based catalysts [1]. Among the catalytic processes, alkali-catalyzed
transesterication reaction is much faster than acid-catalyzed trans-
esterication and is popular in commercial production [2,3]. But,
alkali-catalyzed transesterication is suitable only for biodiesel pro-
duction from feedstock containing low level of free fatty acid (FFA),
such as rened vegetable oils. For achieving efcient reactions of al-
kaline transesterication, the feedstock should contain no more
than 1 wt.% FFA [4]. If the FFA level is too high, the soap generated
during the transesterication inhibits the separation of glycerol
from the methyl esters, and, after the reaction, emulsion formation
occurred during the water wash, which results in signicant product
yield loss and poor quality of FAME product [5]. Therefore, some low
quality feedstock which is unrened and much cheaper than the re-
ned oil, such as used cooking oils(27% FFA), animal fats(530%),
palm fatty acid distillate(PFAD, 8595%) and trap grease (100%), is
denitely unattractive for alkaline transesterication processes.
Corresponding author. Tel.: + 82 2 2220 0488; fax: + 82 2 2220 4007.
E-mail address: ykyeo@hanyang.ac.kr (Y-K. Yeo).
Recently, heterogeneous acid catalysts have been more widely fa-
vored over homogeneous ones since they are more separable and thus
easier to recover. Especially there have been various studies on indepen-
dent transesterication and/or esterication processes without requiring
homogeneous alkali-catalyzed transesterication, based on the heteroge-
neous catalysts [613]. However, processes employing heterogeneous
catalysts have not been widely commercialized. Competitiveness of
those processes may be improved by the increase of stability of catalysts
during long-term operation and by the application of efcient treat-
ment methods for wastes generated during the catalyst-regenerating
process.
There have been only a few studies on non-catalytic esterication
and/or transesterication reactions which lead to much simpler puri-
cation and environmentally-friendly processes [1416]. Diasakou et
al. [14] investigated the non-catalytic thermal transesterication of
soybean oil with methanol and its reaction kinetics. Kusdiana and
Saka [15] reported the effects of molar ratio of reactants and reaction
temperature on the catalyst-free transesterication of rapeseed oil
and proposed a simple method for the analysis of reaction kinetics.
In addition to the work, Saka and co-workers have had specialized
studies in the reaction conditions and kinetics of the supercritical bio-
diesel production process [1719]. Yujaroen et al. [16] investigated
the effects of temperature, molar ratio of methanol to fatty acid
(FA) components and water content in the feed on the esterication
of palm fatty acid distillate (PFAD). Most of these studies were con-
ducted under pressurized conditions, i.e., supercritical or subcritical
conditions of methanol. However, these processes mentioned above

0378-3820/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2012.05.022
272 H.J. Cho et al. / Fuel Processing Technology 104 (2012) 271280
are not easily applicable to actual production of biodiesel, due to sig-
nicantly high production and capital costs required. In addition,
these processes are operated under severe operating conditions,
such as high pressure, high temperature and high molar ratio of
methanol, in which uncertain safety and potential hazard issues
should be carefully managed.
In the present work, a novel method for the non-catalytic esteri-
cation of fatty acids, especially, PFAD (palm fatty acid distillate), is de-
veloped. From the kinetic study on the non-catalytic esterication of
PFAD, values of activation energy and frequency factor for the reac-
tion were determined as well. Meanwhile, PFAD, used as raw material
of the esterication reaction in this work, is a byproduct being inevi-
tably generated in the purication process of palm oil renery, and so
the price of PFAD is much cheaper than other rened oils which are
major feed stocks for most of current biodiesel plants. The process
for the non-catalytic single-step esterication of PFAD proposed in
this work is readily applicable to actual biodiesel production and
can be one of the most competitive processes due to its simplicity, ex-
cellent reaction yield and use of low-priced feedstock.
Besides these technical advantages, economic feasibility is becom-
ing more and more important in the context of the industrial uptake
of the proposed technology for biodiesel production in future. Studies
had been conducted to evaluate economics of various technologies
available for biodiesel production in which a wide range of economic
criteria have been employed, and different design options and feed-
stocks had been considered.
Haas et al. [20] presented a comprehensive economic study of the
alkali technology for a 33.1 kt/yr plant which produces biodiesel from
crude degummed soy oil using alkali-catalyzed transesterication
technology. They conclude that the total capital cost is of the order
of $11.35 10 6 while soy oil cost accounts for 88% of the unit produc-
tion cost. Steady state simulations are performed with the process
simulator AspenPlus, which is based on experimental results carried
out by Freedman et al. [21,22].
Zhang et al. [23,24] presented an economic study of a biodiesel pro-
duction plant with a capacity of 8 kt/yr using waste cooking oils as a raw
material. They compared four different available production technolo-
gies and concluded that the alkali-catalyzed transesterication features
signicantly lower total capital investment. Their simulation of alkali-
catalyzed transesterication process was based on experimental results
done by Freedman et al. [21,22]. They further concluded that, based on
after-tax rate of return and break-even price of biodiesel, the acid-
catalyzed processes were economically a competitive alternative to
the alkali process for biodiesel production. Sensitivity analysis of differ-
ent processes for biodiesel production showed that plant capacity, the
price of waste cooking oil and the price of biodiesel were the major fac-
tors affecting the economic feasibility of the biodiesel production. They
used HYSYS for solving the pertinent material and energy balances.
Harding et al. [25] also used AspenPlus to simulate production
processes that use either inorganic or biological catalysis for the pro-
duction of biodiesel by the transesterication of rapeseed oil. They
evaluated environmental impacts of the processes considered, and
concluded that the enzymatic production route is environmentally
more favorable as expected.
Marchetti et al. [26] compared the economics of alkali-catalyzed,
acid-catalyzed and solid resin-catalyzed processes for producing ap-
proximately 36 kt/yr of biodiesel from spent oils containing 5% of
free fatty acids. SuperPro Designer was used for the simulation
with which raw material cost is the most important contribution to
the unit production cost (which is estimated to be around $0.50.52/kg)
for all the cases. The alkali-catalyzed based process appeared to be the
most economically attractive alternative followed by the heterogeneous
catalyst based process.
West et al. [27] compared the economics of four different tech-
nologies for producing biodiesel, namely, homogeneous alkali cata-
lyst processes, homogeneous acid catalyst processes, heterogeneous
catalyst processes and supercritical processes. For a production capacity
of 8 kt/yr, they concluded that the heterogeneous catalytic process is
the most economically attractive process and at the same time the
least complex. All other processes appeared not to be protable.
Marchetti and Errazu [28] compared the economics of a biodiesel
plant that operates at supercritical conditions with the economics of
biodiesel plants that use classical catalytic production routes, and all
protability indicators are worse for the plant that operates at super-
critical conditions, due to higher operating costs involved in the su-
percritical plant which can partially be attributed to the high
pressure (7.0 MPa) and high temperature (200 C) of operation of
the reactor(s).
van Kasteren and Nisworo [29] evaluated the cost of biodiesel pro-
duction using supercritical methanol with waste cooking oil as the
raw material. Using the experimental results of Cao et al. [30], they
analyzed the economic competitiveness of the supercritical process
and compared it to the result of Zhang et al. [23,24], in which the eco-
nomic feasibility of alkali- and acid-catalyzed BDF processes is compared.
Lim et al. [31] designed the supercritical process for biodiesel pro-
duction considering actual experimental data as well as the unwanted
residue, and it was one of studies made for the processes based on su-
percritical conditions which has not been fully attempted in past. The
supercritical process and their own experimental data were described
and, then, the economic performance of the supercritical process using
three different operating conditions was analyzed and compared to
the alkali-catalyzed process [24].
For the current study, experimental study was established for the
production of biodiesel from PFAD, based on the non-catalytic esteri-
cation method, while process modeling was carried out with
AspenPlus, which provides costing basis for economic analysis.
The techno-economic performance of the proposed process and its
cost-effectiveness was compared with two processes, namely, alkali-
catalyzed transesterication process [24] and supercritical process
[32] in order to evaluate the applicability and competitiveness of
the proposed design in practice.
2. Experimental
2.1. Materials
The PFAD feedstock used in experiments originated from Malaysia
and is purchased from Sandakan Edible Oils SDN, BHD. The fatty acid
(FA) content of the PFAD is 87.3% (palmitic 41.6%, oleic 33.5%, linoleic
6.7%, stearic 3.8%, myristic 1.0%, eicosanoic 0.4%, eicosenoic 0.1%, pal-
mitoleic 0.2%) and the rest of the PFAD includes triglycerides 4.5%, di-
glycerides 3.7%, monoglycerides 2.6%, water 1.0% and a small amount
of unknown impurities. The acid value (AV) of the PFAD sample used
in the experiments is 191.37 mg KOH/g. The purity of methanol
which is supplied from SK Chemicals Ltd. exceeds 99.5%.
2.2. Analysis
FA content in samples is determined using the gas chromatogra-
phy by mixing internal standard materials with samples. Typical re-
agents and apparatus used in the analysis of samples are listed in
Table 1.
The analysis method used to determine concentration of FA is
based on internationally approved EN 14103:2003 (Fat and oil deriv-
atives fatty acid methyl esters (FAME) determination of ester and
linolenic acid methyl ester contents), which has been modied in this
work as follows. The method starts with the dissolution of hep-
tadecanoic acid in n-heptane to give 100 mg/ml of the internal stan-
dard solution which is injected into the vial charged with 100 mg of
sample by the amount of 200 L through a syringe. Then, 100 L of
N,O-bis(trimethylsilyl)triuoroacetamide (BSTFA) is added, which is
then followed by the silylation for 10 min in the oven kept at 60 C.
 H.J. Cho et al. / Fuel Processing Technology 104 (2012) 271280
Table 1
Reagents and apparatus used in this study.
Heptadecanoic acid (internal standard of fatty acid: >99.5%, Tokyo Chemical
Industry Co., Ltd.)
N,O-Bis(trimethylsilyl)triuoroacetamide (BSTFA) (reagent grade, Sigma-Aldrich Co.)
n-Heptane (analytical grade: >99.9%, SK Chemicals Ltd.)
Methylene chloride (analytical grade: >99.9%, SK Chemicals Ltd.)
Gas chromatography system (Agilent 6890N with FID detector)
Gas chromatography column (Agilent, 122-5731, DB-5ht 30 m)
The FA content of the feed (C) is measured by the gas chromatography.
The results represented in %(w/w) are calculated by Eq. (1).
AAFI C FI  V FI
C   100%:
AFI m is terminated when the target reaction time is reached.
Where A is the sum of peak areas of various FA components, AFI
is the peak area of heptadecanoic acid, CFI is the concentration of hep-
tadecanoic acid solution (mg/mL), VFI is the volume of heptadecanoic
acid solution fed into the sample (mL), and m is the mass of the sam-
ple (mg). As for the gas chromatography column the non-polar col-
umn (Agilent, 122-5731, DB-5ht 30 m) was chosen which is resistant
to high temperatures and is suitable for analysis of FA content.
The acid value was measured according to the procedures and
methods described in EN 14104:2003 (fat and oil derivatives fatty
acid methyl esters (FAME) determination of acid value).
2.3. Reaction
Fig. 1 shows the experimental apparatus employed in this work.
The reactor (1) is designed to perform semi-batch reactions. After
the reactor is charged with reactants, methanol is fed into the bot-
tom of the reactor via the methanol feed pump (2). Bubbles in the
reactor are diminished and dispersed into the liquid phase by the
impeller (3). The reactor is heated by the external jacket heater
(4) and the internal temperature and RPM of the impeller are maintained
as constant values by the controller (5). The excess methanol, water pro-
duced during the reaction and the small amount of FA and FAME compo-
nents vaporized and dispersed with water are condensed in the
condenser (7) and collected in the receiver (8). Sampling is performed
through the sampling line (13) with periodic sampling time. The sample
Fig. 1. Schematic diagram of the semi-batch reaction system for non-catalytic esterica-
tion.1: Reactor (internal volume: 2 L), 2: methanol feed pump, 3: impeller, 4: electrical heat-
er jacket, 5: temperature and RPM controller, 6: motor, 7: condenser, 8: receiver, 9: pressure
regulator, 10: nitrogen charging line, 11: thermocouple, 12: pressure gauge, 13: sampling
line, 14: cooler(double jacketed), 15: chiller.
273
is transported to cooler (14) and cooled rapidly well below to 50 C in
order to prevent the loss of low boiling components such as methanol
and water by ashing.
The PFAD feed used in the present work is in solid state at room
temperature. Thus the feed heated over 50 C is liqueed. The reactor
is pressurized up to reaction pressure (0.85 MPa) by the injection of
nitrogen gas after a specic amount of the feed (860 g) is charged
into the reactor. Agitation begins when the temperature reaches
60 C followed by subsequent heating up to reaction temperature.
When the temperature of the reactor rises to the specic reaction tem-
perature, methanol is fed into the reactor with the rate of 2.4 g/min.
The reactor temperature and the speed of the impeller are maintained
constant throughout the reaction. The samples taken with constant
sampling time are cooled below to 50 C by the cooler. The reaction
1
Water produced during the reaction is vaporized and removed
from the reactor so that the reaction rate is improved and the forward
reaction is further prevailed for this equilibrium reaction. It is impor-
tant for FAMEs and FAs not to be vaporized in order to minimize un-
necessary loss. Fig. 2 shows the vapor pressures of water, methyl
palmitate, methyl oleate, palmitic acid and oleic acid which are typi-
cal FA and FAME components with respect to temperature. Most of
water exists in vapor phase, while FAs and FAMEs are hardly vapor-
ized in present experimental conditions. In this work reaction behav-
ior related to the changes in reaction temperature was analyzed for
the identication of the reaction kinetics. Fig. 2 shows the \reaction
conditions used in the present work.
2.4. Purication
It was proposed to set a purication process based on batch distilla-
tion systems up, in order to verify whether crude FAME produced from
the proposed reaction can be puried to meet the internationally-
approved product quality standard or not, as shown in Fig. 3. The
crude FAME was distilled at a very low pressure less than 0.133 kPa at
the higher part of the column, while the temperature of batch distilla-
tion was regulated below 250 C to avoid undesired reaction.
3. Modeling
To assess the technological feasibility and to obtain material and
energy balances for a preliminary economic analysis, complete pro-
cess modeling of the biodiesel process adopting non-catalytic esteri-
cation of PFAD was performed. Despite some expected differences
between a process modeling and actual operation, process simulators
are commonly used to provide reliable information on process oper-
ation, owing to their vast component libraries, comprehensive
Fig. 2. Vapor pressure of each component and reaction conditions used in this work.
(methyl palmitate: calculated by Antoine equation [33], others: calculated by
AspenPlus).
274 H.J. Cho et al. / Fuel Processing Technology 104 (2012) 271280
Fig. 3. Schematic diagram of the distillation system for purication of crud FAME.1: kettle,
2: heating jacket, 3: thermometer, 4: hot plate, 5: packed column, 6: condenser, 7: receiver,
8: vacuum.
thermodynamic packages and advanced computational methods.
AspenPlus 2006 (ASPEN Tech, Cambridge MA) was used to con-
duct the modeling.
The rst step in developing the process model was selecting the
chemical components for the process, as well as a thermodynamic
model. Additionally, unit operations and operating conditions, plant
capacity and input conditions must all be selected and specied.
AspenPlus library contained information for the following compo-
nents used in the modeling: methanol, water, oleic acid, methyl oleate
and triolein. PFAD was simply represented by the mixture of triolein
Fig. 4. AspenPlus model for BD production by non-catalytic esterication of PFAD.
(11.7%), oleic acid (87.3%), and water (1.0%), based on the composition
of PFAD in the experimental work. Accordingly, methyl-oleate, also avail-
able in the AspenPlus component library, was taken as the product of
the esterication reaction. A considerable difference was observed be-
tween the value of vapor pressure of triolein from the physical property
library of AspenPlus and that of triolein estimated from the experi-
ment, and therefore, vapor pressure data provided by Appostolakou et
al. [34] was adopted for thermodynamic calculation in the study.
Owing to the presence of polar compounds such as methanol and
water in the process, the Wilson thermodynamic/activity model with
the RedlichKwong equation of state was selected for use as the property
package for the modeling. Since some binary interaction parameters for
vaporliquid equilibrium were not available in the software databanks,
they were estimated using the UNIFAC group method in AspenPlus.
Plant capacity for the non-catalytic esterication process was specied
at 8000 t/yr biodiesel (the same as in other 2 cases).
Fig. 4 shows the owsheet for a biodiesel production process
which is composed of a non-catalytic esterication of PFAD, FA/
FAME recovery (distillation), product purication (distillation) and
methanol recovery (distillation) using AspenPlus. PFAD (FEED-P1,
P2, P3) and methanol (FEED-M1, M2, M3, M4) were used as raw ma-
terials. PFAD was pumped up to reach the reaction pressure using a
pump (PUMP1) and preheated to the reaction temperature through
a heat exchanger (HEATER1). Recovered unreacted methanol is mixed
with fresh methanol at MIXER1, which is evaporated (EVAPORAT) and
transferred back to the reactor. The modeling of a reactor is based on
the reaction condition in the experiment, and the continuous reactor
employed takes liquid PFAD (FEED-P2) feed from the upper part of the
reactor, which is counter-currently contacted with vapor methanol
(FEED-M4) supplied from the lower part of the reactor. The RadFrac sim-
ulation module available in AspenPlus was used to model and simu-
late reactive distillation, by using kinetic parameters for a non-catalytic
esterication of PFAD veried from the experimental study and as-
suming 10 stages and 3 h of reaction duration for the column. The
reboiler (HEATER2) is employed to provide the heat required for
endothermic reaction. Top vapor product from the reactor includes
 H.J. Cho et al. / Fuel Processing Technology 104 (2012) 271280 275

unreacted methanol, water produced from the reaction and FA/
FAME. FA/FAME is recovered from the column (REC-COL) and ret-
urned to the reactor, while the light components (i.e. methanol
and water) are further processed in the column to recover metha-
nol. Five theoretical stages is taken for REC-COL (RadFrac). FAME-
rich bottom liquid product from the reactor is puried in the distil-
lation column (BDCOL). The RadFrac column simulation module is
applied for the rigorous simulation of MEOH-COL, under atmospher-
ic pressure and with 20 theoretical stages, and the reux ratio is ad-
justed to meet the required purity of methanol which is pure
enough to be recycled to the reactor. The bottom product from
MEOH-COL, mainly water, is discharged as wastewater. Also, The
RadFrac is employed to simulate the distillation column (BDCOL)
which puries crude FAME, bottom product from the reactor. Due
to high boiling point of FAME, the column is operated at very low
operating pressure less than 1.5 kPa, and 20 theoretical stages are
used. The reux ratio is adjusted to satisfy the specication of bio-
diesel set by the European Standard EN 14105. The nal product
is obtained from the top distillate stream of the column, and resi-
due, mainly, triglyceride, is discharged from the bottom of the
column.
4. Economic analysis
Economic analysis was performed on the process for non-catalytic
esterication of PFAD using the method of Turton et al. [35] and
economic comparison is made with costing data given from Lim
et al. [31]. The plant capacity of each process was assumed to be
the same: 8000 t/yr and 8000 operating h/yr. The equipment size
of each process unit was estimated based on the pump power,
heat exchanging area, uid volume, and the ow rate, calculated
by an AspenPlus model and on the method of Apostolakou et
al. [34]. Especially, distillation column sizing is done with the func-
tionality of tray sizing (or pack sizing) available in the RadFrac cal-
culation module of AspenPlus.
According to Turton et al. [35], to estimate the total capital cost in-
cluding direct cost and indirect cost, the bare module equipment cost,
CBM, was calculated for each equipment.
0
C BM C p F BM :
Index) of 394 is applied. The total manufacturing cost was estimated
from the mass balance, heat duty, price of chemicals, the utility costs
and cost of operating labor [35].
As mentioned earlier, total manufacturing cost and prot is heavi-
ly inuenced by raw material cost, raw material used in the process
considered by Lim et al. [31] is rapeseed oil (RSO), which is different
to PFAD used in the proposed process. Also, the nal products for both
cases are not the same. Therefore, in this study, raw material and
product sale costs are averaged over the last 4 years between 2007
and 2010, which are used in the economic analysis, as given in
Table 2. For other chemical prices and operating costs for utilities
used in the process, the same cost information given in Lim et al.
[31] is applied, as also shown in Table 2.
5. Results and discussion
5.1. Reaction kinetics
In order to estimate the extent of reaction, we employed the con-
version of FA within PFAD given in Eq. (6) as an indicating index.


C FA;0 C FA;t
Xt  100%: 6
C FA;t
Here, Xt is the conversion of FA at time t and CFA,t and CFA,0 are concen-
trations of FA at reaction time t and initial time, respectively (mol/ml).
With the reaction pressure and methanol feed rate being kept
constant as 0.85 MPa and 2.4 g/min respectively, the conversions
and changes in acid value according to reaction temperature are
shown in Fig. 5. The region representing 90180 min range in
Fig. 5(b) is enlarged as shown in Fig. 5(c). The reaction temperature
adopted in this work is much higher than the boiling point of water
( 173 C at 0.85 MPa) produced during the reaction. Therefore,
water is removed effectively from the reaction system and conse-
quently backward reaction is inhibited. In short, a very fast forward
reaction can be achieved even without using any catalysts. As
shown in Fig. 5(c), at the reaction temperature above 250 C, the re-
action is completed in 180 min and we can see that the resultant bio-
2 diesel products satisfy required criterion (AV b 0.5). It is observed that

The purchase cost for base conditions, C 0p, is calculated by Eq. (3).
Table 2
Prices of raw materials, chemicals, utilities and products.
0 2
log10 C p K 1 K 2 log10 A K 3 log10 A : 3
Year Raw material Product

K1, K2 and K3 are constants to the equipment type and A is the pa- PFADa RSOb PFAD/RSO PBDc RBDd PBD/RBD
($/t) ($/t) (%) ($/t) ($/t) (%)
rameter for the capacity or the size of the equipment. The bare mod-
ule cost factor, FBM, the function of operating pressure and the 2007 563 961 59 849 1210 70
2008 501 1330 38 1158 1528 76
construction materials is calculated by Eq. (4).
2009 442 867 51 773 937 83
2010 718 1015 71 967 1062 91
F BM B1 B2 F M F P : 4
Avg. 556 1043 53 937 1184 79
Chemicals and utilities [31]
B1 and B2 are constants depending on the equipment type, and FM
is the material factor decided by the equipment type. Stainless steel Item Price

was used for the reactor (REACTOR), the FA recovering column Glycerol (pharmaceutical) 1200 ($/t)
(REC-COL), units relating to feed preheating (PUMP1, HEATER1), Methanol 180 ($/t)
NaOH 4000 ($/t)
and the reboiler for reactor (HEATER2). Carbon steel was chosen for
H3PO4 340 ($/t)
the rest of the units as the main construction material. FP is the pres- Cooling water $0.007/m3
sure factor given by the following Eq. (5). Electricity $0.062/kW h
Low-pressure steam $7.78/GJ
2
log10 F p C 1 C 2 log10 P C 3 log10 P : 5 High pressure steam $19.66/GJ
Waste treatment chemicals (liquid) 150 ($/t)
a
C1, C2 and C3 are constants depending on equipment type and P is PFAD: MPOB export price (http://econ.mpob.gov.my/economy/EID_web.htm).
b
RSO (rapeseed oil).
pressure. The actual values for Ki, Bi and Ci were borrowed from the c
PBD (palm biodiesel).
literature [35]. For having a fair comparison with cost presented in d
RBD (rapeseed biodiesel): average of Reuter daily commodity price (http://
Lim et al. [31], the same CEPCI (Chemical Engineering Plant Cost www.reuters.com/nance/commodities).
276 H.J. Cho et al. / Fuel Processing Technology 104 (2012) 271280

balances for FA, the reaction rate can be represented as Eq. (7).

dC FA
kf C FA C MeOH kr C FAME C H2 O : 7
dt

Here, CFA, CFAME, CMeOH and CH2O are concentrations of fatty acid
(FA), fatty acid methyl ester (FAME), methanol, and water, respec-
tively (mol/ml), and kf and kr are the rate constants for forward reac-
tion and for reverse reaction (ml/mol min). Reaction conditions
adopted in the present study aims the continuous removal of water
from the reaction system. Therefore the reverse reaction can be
ignored and Eq. (7) can be reduced to Eq. (8).

dC FA
kf C FA C MeOH : 8
dt

Moreover, since excess methanol is fed into the reaction system as

in the case of Joelianingsih et al. [5], CMeOH can be regarded as con-
stant and Eq. (8) may be rewritten in terms of CFA in Eq. (9).

dC FA
kf C FA : 9
dt

Then, the reduced rate constant kf of the forward reaction is given

by Eq. (10).
!
C FA;t
ln kf t: 10
C FA;0

Table 3 summarizes rate constants at different reaction tempe-

ratures obtained by substituting with the results of experiments car-
ried out at constant pressure (0.85 MPa) and methanol feed rate
(2.4 g/min) while varying reaction temperature into Eq. (10). Results
of Joelianingsih et al. [5] are also shown for comparison. From Table 3,
it can be seen that rate constants kf from the present study are about 4
times greater than those obtained by Joelianingsih et al. [5]. High rate
constants from the present study seem to be caused by the large
methanol concentration at 0.85 MPa, which is about 20 times greater
than that measured at atmospheric pressure. Concentrations of FA
and FAME computed by substituting rate constants in Table 3 into
Eq. (9) are shown in Fig. 6 with measured values. It can be seen that
computational results agree well with experimental results. There-
fore, rate constants obtained from the present study and the reduced
model given by Eq. (9) have some guiding signicance to describe the
reaction mechanism.
The rate constant kf satises Arrhenius Eq. (11).
Fig. 5. Effects of temperature on reaction. (a): conversion of FA, (b) and (c): acid values
measured (230290 C, 0.85 MPa, methanol feed rate: 2.4 g/min).
Ea
lnk f lnA : 11
RT

the acid value is not decreased down to 0.5 at 230 C even in 240 min. Fig. 7 displays relationship between temperature and kf given in
It is believed that the acid value is lowered below 0.5 when 99.6% of Table 3. It can be seen that the results are well tted by Arrhenius
FA in the feed is converted. As far as the authors know, so far, there equation. The activation energy is 17.74 kJ/mol and the frequency fac-
are no published results that achieved desired target (AV b 0.5) tor is 2.12 min 1. From comparison with values by Joelianingsih et al.
using only single stage esterication reaction for 120180 min with [5], it appears that the frequency factors are about the same, while the
or without catalysts. Even under supercritical or subcritical condi- activation energy by Joelianingsih et al. (24.8 kJ/mol) is a little larger
tions [13,16], the AV criterion of biodiesel was not achieved by the
single-stage reaction using strong acid catalyst such as sulfuric acid
Table 3
[36] or heterogeneous catalyst [13]. The main reason for those Comparison of rate constants (present study: 0.85 MPa, Joelianingsih et al. [5]:
methods seems to be the lack of effective elimination of water from 101.3 kPa).
the reaction system. Comparing to other reaction methods developed
Present study Joelianingsih et al. [5]
so far, the proposed reaction system consisting of single-stage with-
out catalyst can easily be commercialized and is promising due to T (C) kf (min 1) R2 T (C) kf (min 1)
its cost effective characteristics. 230 0.0299 0.954 200 0.0052
The non-catalytic esterication reaction performed in the semi- 250 0.0375 0.974 225 0.0073
batch reaction system can be regarded as a homogeneous reversible 270 0.0405 0.966 250 0.0095
290 0.0481 0.961
reaction. Assuming the 1st order reaction and considering mass
 H.J. Cho et al. / Fuel Processing Technology 104 (2012) 271280 277

than the value obtained from the current study. This means that the
non-catalytic reaction is accelerated as temperature increases.

5.2. Product quality

As can be seen in Table 4, biodiesel product, which was produced

through the non-catalytic esterication from PFAD and the purica-
tion by distillation, meets all the required specication of EU's stan-
dard EN 14214. Especially, the level of impurities, for example, tri-,
di-, and mono-glyceride, is considerably lower than the required
level, and the product quality is superior in terms of CSF (Cold Soak
Filterability), which great attention has been being paid to in US.
This clearly supports the applicability of the proposed process in in-
dustrial practice. Product yield from the proposed manufacturing
scheme is measured as 91.2 wt.% (product/PFAD).

5.3. Modeling results

Table 5 presents operating conditions based on the reaction condi-

tion (290 C, 0.85 MPa, FA:Methanol = 1:4.8 (molar)) from the exper-
iment and composition of streams involved in the owsheet, which
are obtained from simulation developed from this study, and Fig. 4
shows energy requirement for various unit operations consuming
external heating or cooling. From the composition of biodiesel
product (BDF) in Table 5, the produced product has more than
96.5% of ester, and less than 0.2% of methanol, and less than 0.1%
of triglyceride, which meets the standard of EN 14214. The simula-
tion is carried out to have 91.2% of product yield. From Fig. 4, com-
pared to energy requirements of the supercritical processes of He et
al. [32] reported in Lim et al. [31], it should be noted that energy
required for pumping is signicantly reduced as only 1.2% of overall
energy required for the proposed process is needed for driving two
pumps.

5.4. Analysis of the process competitiveness in economic aspects

Results of comparison for overall capital cost, which are based on

the methodology of Turton et al. [35], are given in Table 6. The
novel process proposed in this paper requires capital investment of
$1.63 10 6, which is 20.7% more than that of alkali-catalyzed process
[24], but 22.4% less than that of supercritical process [32]. This costing
can be contributed by the fact that operating pressure of the proposed
process lies between extremely high pressure of supercritical process
and relatively low pressure of alkali-catalyzed process. Although the
developed process is relatively simple and the number of units in-
volved in the owsheet is comparatively less than other conventional
processes, reaction rate is slow and hence a large size for the reactor is
necessary. It has been analyzed that reactor cost is around half of total

Fig. 6. Concentrations of FA and FAME: comparison between computational results

(based on the 1st-order model) and experimental results (a) 230 C, (b) 250 C,
(c) 270 C, and (d) 290 C.

Fig. 7. Arrhenius plot for the esterication of PFAD (0.85 MPa, methanol feed rate:
2.4 g/min).
278 H.J. Cho et al. / Fuel Processing Technology 104 (2012) 271280

Table 4 Table 6
Results of quality analysis for typical biodiesel product considered in the present work. Comparison of capital cost.

Property Test-method Units Limit Results ($106) The Lim et al. [31]
present
Ester content EN 14103 % (m/m) Min. 96.5 97.2 Alkali-catalyzed [24] Supercritical [32]
work
Water content EN ISO 12937 mg/kg Max. 500 45
Total contamination EN 12662 mg/kg Max. 24 8 Reactor 0.48 0.29 0.48
Oxidation stability, 110 C EN 14112 h Min. 6.0 8.7 FAME recovering column 0.03
Acid value EN 14104 mg KOH/g Max. 0.50 0.32 Neutralization 0.02
Iodine value EN 14111 g Iodine/100 g Max. 120 43 Methanol distillation column 0.06 0.14 0.16
Methanol content EN 14110 % (m/m) Max 0.20 b0.01 Washing distillation column 0.10
Monoglyceride content EN 14105 % (m/m) Max 0.80 b0.01 FAME rening column 0.17 0.16 0.21
Diglyceride content EN 14105 % (m/m) Max. 0.20 b0.01 Heat exchangers 0.19 0.00 0.13
Triglyceride content EN 14105 % (m/m) Max. 0.20 b0.01 Pumps 0.05 0.05 0.17
Free glycerine EN 14105 % (m/m) Max. 0.02 b0.01 Others 0.05 0.11
Total glycerine EN 14105 % (m/m) Max. 0.25 b0.01 Total bare module cost, CBM 0.98 0.81 1.26
Group I metals (Na + K) EN 14108 mg/kg Max. 5.0 b1 Contingency fee, CCF = 0.18CBM 0.18 0.15 0.23
Group II metals (Ca + Mg) EN 14538 mg/kg Max. 5.0 b1 Total module cost, 1.16 0.96 1.49
Phosphorus content EN14107 mg/kg Max. 10.0 b1 CTM = CBM + CCF
CFPP EN116 C Report + 15 Auxiliary facility cost, 0.26 0.22 0.34
Cold soak lterability ASTM D7501 s Max. 360 106 CAC = 0.27CBM
Fixed capital cost, 1.42 1.17 1.83
CFC = CTM + CAC
Working capital cost, 0.21 0.18 0.27
bare module cost, and this is one of the key factors to increase the
CWC = 0.15CFC
total capital cost. Total capital cost, 1.63 1.35 2.10
Manufacturing cost for the developed process is $8.59106/yr, which CTC = CFC + CWC
is about 25% less than the alkali-catalyzed process ($11.43106/yr) and
the supercritical process ($11.25106/yr) (Table 7). Main reason for
this is that the cost of raw material PFAD is only 53% of that of rapeseed to produce biodiesel under any processes considered in this paper.
oil (RSO) used in the other two processes selected for comparison, as This strongly indicates that governmental support, for example, tax
shown in Table 2. For the other two processes compared in this study, benets, is to be introduced if industrial uptake of biodiesel technol-
there is an economic gain by selling glycerol ($0.73106/yr for alkali- ogy is desired under current economic environment.
catalyzed process and $1.02106/yr for supercritical process) and an ad- It should be noted that there are uncertainties in the economic
ditional cost for waste disposal is needed in the developed process. How- costing made in this study, and this should be taken into account if
ever, raw material is signicantly cheaper for the proposed process, which further detailed evaluation is needed. However, the relative values
can not only compensate any economic decit or disadvantage associated or the differences among these results are of importance for evaluat-
with waste disposal, but also ensures considerably high economic return ing the competitiveness of the processes. Two economic measures are
for the proposed process although its sale of glycerol is not possible. Fig. 8 suggested for this study to evaluate cost-effectiveness of processes
illustrates economic advantage using PFAD in terms of total manufactur- considered in this study.
ing cost, compared to the other two processes, and the proposed process The rst index considered is the ratio between the difference of
is an economically viable option as long as the price ratio of PFAD to RSO is total capital cost (TCC) and the difference of prot before tax (PBT),
below 82%. Considering the highest purchase cost of PFAD is 71% of that of which indicates how quickly the difference of capital investment is
rapeseed oil over the last 4 years (20072010) as can be seen in Table 2, returned, relative to the reference process. As given in Eq. (12), total
this cost trend is expected to be maintained for the future which clearly capital cost (TCC) and prot before tax (PBT) of alkali-catalyzed pro-
justify the development of the new proposed process as it demands con- cess [24] are taken as a reference cost, as TCC of alkali-catalyzed pro-
siderably lower total manufacturing expenditure. The residue generated cess is the smallest among three processes considered.
from the developed process mainly consists of inert components during
the reaction including triglyceride and byproducts which originated TCC of compared process  TCC of the alkali process
PT dtcc : 12
from PFAD, and therefore, it would be acceptable for fuel, for example, PBT of compared process  PBT of the alkali process
for the boiler. If this is the case, another economic gain can be obtained
from the proposed process, because, currently, expenditure related to The calculated PTdtcc for supercritical process and the proposed
waste disposal and relevant management is estimated to be about 3% of process is given in Table 8, which clearly demonstrates that the pro-
overall manufacturing cost. posed process has economic advantage as additional capital cost ex-
Overall prot in Table 8 is calculated from average product selling penditure associated with the proposed process, can be recovered
price of biodiesel given in Table 2 and overall manufacturing cost signicantly faster than supercritical process. The extra capital invest-
given in Table 7, which clearly shows that it is not economically viable ment needed for the proposed process, compared to capital investment

Table 5
Stream table for the process of the present work.

Stream FEED-P3 FEED-M4 RX-BOT4 BDF RESIDUE R-MEOH WWT

Temp. (C) 310 290 312.3 55 277 50 110.2

Press. (MPa) 1.10 1.10 0.86 0.0013 0.0053 0.10 0.21
Flow (kg/h) 1097 636 1137.7 1000.2 133.7 510 85.3
Comp. (wt frac.)
Methanol 0.0000 0.9984 0.0037 0.0004 0.0000 0.9980 0.1548
Water 0.0100 0.0016 0.0000 0.0000 0.0000 0.0020 0.8447
Oleic acid 0.8730 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000
Methyl oleate 0.0000 0.0000 0.8835 0.9990 0.0447 0.0000 0.0005
Triolein 0.1170 0.0000 0.1128 0.0006 0.9552 0.0000 0.0000
 H.J. Cho et al. / Fuel Processing Technology 104 (2012) 271280 279

Table 7 Table 8
Comparison of manufacturing cost. Comparison of prots and competitiveness for three processes considered in the pre-
sent work.
($106/yr) The Lim et al. [31]
present The Lim et al. [31]
Alkali-catalyzed [24] Supercritical [32]
work present
Alkali-catalyzed [24] Supercritical [32]
work
Direct manufacturing cost
Oil/PFAD feedstock 4.88 8.78 8.69 Prots ($106/yr)
Methanol 0.18 0.17 0.17 Revenue 7.48 9.47 9.47
Catalysts and solvents 0.00 0.32 0.00 Expenses 8.59 11.43 11.25
Operating labor 0.61 0.58 0.62 Prot before tax 1.11 1.96 1.78
Supervisory and clerical Labor 0.09 0.09 0.09 Payout time
The difference of TCC, 0.28 0 0.75
Utility costs ($106)
Steam 0.41 0.09 0.31 The difference of PBT, 0.85 0 0.18
Electricity 0.00 0.02 0.09 ($106/yr)
Cooling water 0.00 0.01 0.00 PTdtcc, (yr) 0.33 4.13
Waste disposal 0.26 0.01 0.05 Break even price ($/t)
Maintenance and repair 0.07 0.07 0.11 Break-even prices 1074 1429 1406
Operating supplies 0.01 0.01 0.02 Minimum subsidy requireda 139 245 222
Laboratory charges 0.09 0.09 0.09 a
Minimum subsidy required = break-even price of product price of product aver-
Patents and royalties 0.20 0.20 0.20
aged in 20072010.
Indirect manufacturing cost
Overhead 0.47 0.44 0.49 It should be noted that the selling price of biodiesel is not steady
Local taxes 0.02 0.02 0.03
over time because the selling price of biodiesel in the market is obvi-
Insurance 0.01 0.01 0.01
Depreciation 0.14 0.12 0.18 ously and heavily dependent on that of petro-diesel produced from
petroleum-based rening and prices of raw materials for the biodiesel
General expense production, mainly vegetable oils, are highly uctuating according to
Administrative costs 0.12 0.11 0.12
the productivity of crop and demand in the market. Care must be
Distribution and selling Cost 0.68 0.68 0.67
Research and development 0.34 0.34 0.33
taken to interpret the outcome of economic analysis carried out in
Total production cost 8.59 12.16 12.27 this work, as uncertainties in the prices of raw material and biodiesel
Glycerol credit () 0.00 0.73 1.02 product denitely affect, especially, the calculation of operating cost-
Total manufacturing cost 8.59 11.43 11.25 ing and prot. It has been analyzed how costs of raw material and
biodiesel product inuence overall economics of the processes con-
sidered in this work. This sensitivity is schematically represented in
Fig. 9, which shows prot before tax for each year using price of
for the alkali-catalyzed process, can be returned within 4 months of op- raw material and biodiesel product for 4 years (20072010).
eration, and prot from the proposed process after 4 months can be $1.2 million prot is observed for the proposed process under the
obtained more rapidly than the alkali-catalyzed process. market condition of 2008, and the proposed process has a far more
Another economic criteria introduced in this work is break-even prot or less loss than the other two processes compared. It can be
prices for biodiesel production, and its results are shown in Table 8, summarized that the proposed process is better in terms of process
in which it can be seen that break-even price for the proposed process economics under typical market situation.
is the lowest. Also, the minimum subsidy required for each process to
avoid any prot loss is also given in Table 8, based on price of biodie-
sel which is the averaged value for 4 years (20072010). From the ob- 6. Conclusions
servation such that the break-even price and minimum subsidy
required for the proposed process is the lowest among three schemes Experimental study together with theoretical modeling work has
studied in this paper, it is the most economically acceptable solution been carried out to develop a novel process for the non-catalytic es-
for potential users in future to employ the new process rather than terication of PFAD, of which major unit operations include non-
the other two processes if there are nancial supports or tax credits catalytic single-step reaction for the esterication of PFAD, distillation
from government or relevant authorities. for methanol recovery and distillation for biodiesel purication.

Fig. 8. Sensitivity analysis for the total manufacturing cost according to the change in Fig. 9. Prot before tax for various processes during 4 years (20072010).(NCE: non-
the price ratio of PFAD to RSO. (NCE: non-catalytic esterication (this work), ACT: catalytic esterication (this work), ACT: alkaline-catalyzed transesterication [24],
alkaline-catalyzed transesterication [24], SCT: supercritical transesterication [32]). SCT: supercritical transesterication [32]).
280 H.J. Cho et al. / Fuel Processing Technology 104 (2012) 271280
From an experimental study for investigating reaction kinetics, ef-
fects of reaction temperature are analyzed and reaction rate constants
are determined by the 1st-order model of FA concentration. Further
experimental study has been carried out to improve the purity of bio-
diesel product produced from the reactor and to check whether the
produced biodiesel product can meet various specications of EU
standard EN 14214.
Based on experimental results from lab-scale reactor and distilla-
tion process, the overall owsheet has been modeled and simulated
with AspenPlus, which provides the basis for techno-economic cost-
ing made in this paper. Two performance indices (i.e. relative payback
time and break-even prices) have been calculated to understand eco-
nomic performance of the proposed process by comparing it with
other two biodiesel processes, from which the proposed process has
a clear economic advantage by having lower payback time, and
more prot or less loss under typical market conditions.
The main features of the proposed process are the employment of
single-step reaction without catalyst and the direct use of PFAD, as raw
material, of which the cheap price makes the process competitive over
other processes. For this reason, the proposed process can be readily
commercialized and be a promising one in the biodiesel industry.
Acknowledgments
This work was supported by Korea Research Foundation Grant
funded by the Korean Government (2010-0007152) and in part by
Manpower Development Program for Energy & Resources supported
by the Ministry of Knowledge and Economy (MKE).
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