Research Paper

Journal of Chemical Engineering of Japan, Vol. 43, No. 2, pp. 214223, 2010

Factors Influencing the Use of Various Low-Value Oils in Biodiesel

Production
Patima S INTHUPINYO, Hiroaki HABAKI
and Ryuichi EGASHIRA
Department of International Development Engineering,
Graduate School of Science and Engineering,
Tokyo Institute of Technology, 12-1, O-okayama-2-chome,
Meguro-ku, Tokyo 152-8550, Japan

Keywords: Biodiesel Production Process, Low-Value Oils, Crude Palm Oil, Crude Jatropha Oil, Used Frying
Oil
Various low-value oils, namely, crude palm oil (CPO), crude jatropha oil (CJO), and used frying oil
(UFO), were investigated by comparing them as feed oils used in biodiesel (BD) production, with the
objective of clarifying the effects of various factors that influence the feed oil characteristics on the
required feed pretreatment (FP), operating conditions in transesterification, and the obtained biodiesel
yield and purity. First, the low-value oils were characterized in terms of fatty acid compositions and the
contents of undesirable impurities. All the feed oils contained mainly C 16 and C18 fatty acid chains, and
the content of C16 in CPO was higher than the contents of C 16 in the other feed oils. The highest contents
of impurities, namely, a phospholipid, free fatty acid (FFA), and water were found in CJO. Then, the
feed oils were pretreated under various conditions and subsequently transesterified to convert triglycerides
to BD in the methyl ester form. The BD productivity and quality could be improved by proper feed
pretreatment; deacidification and dehydration were particularly effective. Alkali deacidification is not
appropriate for treating CJO since significant oil loss was observed during neutralization of FFA in
deacidification. Lastly, the pretreated oils whose impurity contents were sufficiently low were
transesterified under varying operating conditions. CPO gave a relatively lower yield but higher purity
than the other oils because of the higher C16 content in the feed oil, which had a negative effect on yield
but increased the purity in the BD product. For all feed oils, the purity of the obtained BD met the
standard for BD purity, and the transesterification yields were improved by carrying out the appropriate FP, as well as adjusting the amounts of alcohol and catalyst in transesterification according to the
type of feed oil. The obtained results can be applied to select the appropriate feed oils and maximize BD
productivity in the BD production from various low-value oils.

Introduction
Biodiesel is one of the most popular alternative
fuels in the energy business because of its biodegradability, low sulfur content, high cetane number, etc.
(Vicente et al., 2004). Moreover, since the biodiesel
system is carbon neutral, the introduction of this
system can dramatically reduce carbon emission. However, although biodiesel was commercialized more than
ten years ago, its market share is still insufficient for it
to substitute of petroleum-based diesel fuel. This is
mainly due to two constraints: the high cost of biodiesel
production, especially that of oil for feedstock, as concluded in a previous study (Krawczyk, 1996; Connemann
and Fisher, 1998) in which the cost of feed oil constituted approximately 7095% of the total biodiesel production cost, and the insufficient supply of feed oil for
Received on May 22, 2009; accepted on October 22, 2009.
Correspondence concerning this article should be addressed to
R. Egashira (E-mail address: regashir@ide.titech.ac.jp).
Partly presented at the 72nd Annual Meeting of the Society of
Chemical Engineers, Japan at Kyoto, March, 2007.

214

biodiesel production. The oil imbalance resulting from

using food oil as biodiesel feedstock also has been
raised as a global economic concern. Effective ways
to overcome these problems would be to utilize several types of low-value oils, including supplemented
untreated edible, inedible, and used oils, as the
feedstock for biodiesel production, as well as to improve productivity in order to use such feed oils effectively.
Low-value oils have a variety of properties and
contain various kinds of impurities, which are undesirable and should be removed by appropriate pretreatment. Indeed, a few studies on the characterization and
comparison of oils (Rice et al., 1998; Alcantara et al.,
2000) have been carried out, and there is no concrete
report on the influence of the differences among oils
on the required feed pretreatment, operating conditions,
obtained biodiesel purity, yield, etc.; this knowledge
is necessary to develop a new process involving the
use of a combination of such oils.
The objective of this study was to clarify the relationship between various factors that influence the
Copyright 2010 The Society of Chemical Engineers, Japan

Table 1

Low-value oils and their principal characteristics

Remarks

Origin
Mass fraction of myristic acid (C14:0), xMy,0 []
Mass fraction of palmitic acid (C16:0), xPa,0 []
Mass fraction of stearic acid (C18:0), x S,0 []
Mass fraction of oleic acid (C18:1), x O,0 []
Mass fraction of linoleic acid (C18:2), xL,0 []
Average molar mass of triglyceride [gmol1]
Average molar mass of free fatty acid [gmol1]
Mass fraction of phosphorus, xP,0 []
Acid value [mg-KOHg-oil 1]
Mass fraction of free fatty acid, xFFA,0 []
Mass fraction of water, xW,0 []

Crude palm oil

Crude jatropha oil

Used frying oil

Edible
High production scale
Low price

Inedible
Drought-resistant
Perennial
Growable in poor soil

Costless

Malaysia

Thailand

Japana

0.11
0.35
0.046
0.42
0.17
853
272

(0.011b)
(0.44 b)
(0.045 b)
(0.39 b)
(0.10 b)
(840b)
(267b)

9.0 106
11
0.051
0.0047

0
0.10
0.14
0.43
0.26
875
279

(0.014c)
(0.16c)
(0.097c)
(0.41c)
(0.32c)
(866 c)
(276 c)

40 106
22
0.11
0.023

0
0.077
0.040
0.34
0.54
875
279

(0.0023d)
(0.12d)
(0.038d)
(0.31d)
(0.51d)
(866d)
(276d)

8.9 106
1.2
0.0062
0.0072

Someya Shouten Ltd.

Maycock (1987)
c
Azam et al. (2005)
d
etinkaya and Karaosmanoglu
(2004)
b

application of various low-value oils to biodiesel production by comparing these factors and their effects.
This would result in the appropriate selection of feed
oils to maximize biodiesel productivity. First, the typical low-value oils were characterized in terms of fatty
acid composition and the contents of undesirable impurities, which were the two main factors used for identifying low-value oils. Then, these oils were pretreated
under various conditions and subsequently transesterified
to investigate the influences of impurities on the required pretreatment and the corresponding biodiesel
purities and yields. Finally, the feed oils in which a
sufficient amount of the impurities were removed by
pretreatment were transesterified under varying operation conditions; then, the various oils and the effects
of the above-mentioned conditions on the production
performance were compared.
1.

Experimental

1.1 Low-value oils

Table 1 lists the low-value oils selected as feed
oils in this study. The oils were crude palm oil (CPO),
crude jatropha oil (CJO), and used frying oil (UFO).
The merits of CPO are the comparatively higher scale
of production and lower price than other commodity
vegetable oils. CJO is superior because of its inedibility, i.e., no demand for its use in food. Further, jatropha
plants are also drought-resistant perennial plants that
grow well in even poor soil. UFO is considered as a

costless oil. The recycling of UFO imparts value to

waste cooking oil and also reduces the load for waste
treatment.
CPO and CJO were obtained from Malaysia and
Thailand, respectively. UFO was obtained from a company treating used oil in Japan (Someya Shouten Ltd.).
1.2 Feed pretreatment
The effects of the principal impurities, which are
phospholipids, free fatty acids, and water, in low-value
oils are briefly summarized in Table 2. These impurities would not only contaminate the biodiesel product
but also waste the catalyst. Further, they would reduce
the product purity and yield because of one or more
effects, as explained in the table. Therefore, feed pretreatment (FP) involving dephosphorization (DP), deacidification (DA), and dehydration (DH) was required
to appropriately remove phospholipids, free fatty acids and water, respectively, before transesterification.
Various combinations of DP, DA, and DH were carried out in the study on feed pretreatment.
DP was carried out first during the FP because of
the drawback of phospholipids (a-1 and c-1-3 in Table
2), which affected not only the transesterification but
also the other pretreatments. The conditions of DP are
listed in Table 3(a). Phosphoric acid (H 3 PO 4) was
added to the feed oil, which was heated up to 343 K to
enable the conversion of non-hydratable phospholipids
to water-soluble phosphatidic acid. Then, sodium hydroxide (NaOH) was added to neutralize the phosphoric
acid. This was followed by washing with deionized

215

Table 2

Effects of impurities, fatty acid composition, and operating factors on biodiesel production

(a) Primary effects

Factor

Effect

a-1.
a-2.
a-3.
a-4.
a-5.
a-6.

c-1, c-2, c-3

b-1
b-1, b-2
More b-2 (if chain is shorter), more c-6 (if chain is shorter)
More c-7
More b-2

Phospholipid
Free fatty acid
Water
Fatty acid carbon chain length
Alcohol amount for transesterification
Alkaline-catalyst amount for transesterification

(b) Secondary effects

Factor

Effect

b-1. Neutralization with OH

b-2. Saponification with OH
b-3. Soap formation

b-3, c-4
b-3, c-4, c-5
c-1, c-2, c-3

(c) Final effects on biodiesel production

Factor

Effect

c-1.
c-2.
c-3.
c-4.
c-5.
c-6.
c-7.

Low purity and yield

Low yield
Low yield
Low purity and yield
Low yield
Higher purity (if chain is shorter)
Lower purity and yield

Foaming with gas (low reaction rate)

Emulsification (difficulty in phase separation)
Solubilization of alkyl ester product into glycerol phase
Loss of alkaline-catalyst (low reaction rate)
Losses of glyceride and alkyl ester product
Dissolution of mono- and di- glycerides in glycerol phase
Dissolution of alkyl ester into glycerol phase

water to dissolve the hydratable phospholipid and

phosphatidic acid. The water phase was separated from
oil phase by centrifugation.
Next, DA, for which the conditions are listed in
Table 3(b), was carried out. The free fatty acid in the
oil was converted to oil-insoluble soap by neutralization with excess NaOH. The soap was also produced
by the saponification of triglyceride occurring simultaneously with neutralization. The soap was then removed by centrifugation. Subsequently, deionized
water was added to dissolve the soap and finally separated from the oil by centrifugation. The deacidification temperature was set high enough at 353 K to prevent the emulsification, which interferes with the separation of soap from the oil.
DH was the last step in the FP, as water contaminated the oil in the previous pretreatments,
dephosphorization and deacidification. The conditions
of DH are summarized in Table 3(c). The water was
removed from the oil by adsorption using magnesium
sulfate (MgSO4), and the oil was subsequently filtered
to remove magnesium sulfate crystals (Tapasvi et al.,
2004). This DH method was selected because it was a
convenient and effective method on the laboratory
scale. Other physical dehydration methods such as vaporization may be more suitable for the large-scale
biodiesel plant from the financial point of view.

1.3 Transesterification and biodiesel purification

The conditions of transesterification are shown in
Table 4. The feed oil was CPO, CJO, or UFO; pretreatment was carried out in some cases (see Tables 1
and 3). Methanol was selected as an alcohol. An alkaline catalyst was used in transesterification because it
was the most conventional method with a fast reaction
rate and requiring mild operating conditions. The alkaline catalyst was NaOH. The molar ratio of methanol and the mass ratio of NaOH relative to the feed oil
were varied systematically, as specified in Table 4. According to a previous study (Sinthupinyo et al., 2008),
the feed oil composition, i.e., fatty acid carbon chain
length (a-4), amount of alcohol (a-5), and amount of
catalyst (a-6) also influence the biodiesel production,
as observed from Table 2. The reaction was carried out
in a 50 106 m3 flask, which was equipped with a
reflux condenser and temperature-controlled oil bath.
After the oil was heated to a specified temperature in
the reactor, the mixture of methanol and NaOH at the
same temperature was added to the oil. Transesterification
involved a set of simultaneous reactions, and this reaction system was heterogeneous throughout the whole
reaction, and hence, this system was constantly and
vigorously well mixed by a magnetic stirrer and left to
stand for 1 h, which would enable the reaction to
progress sufficiently. During the reaction, nitrogen gas

216

JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

Table 3

Conditions of feed pretreatments (FP)

(a) Dephosphorization (DP, removal of phospholipid)

Oil
Mass of oil, F0 [g]

Low-value raw oil (given in Table 1)

50

Phospholipid solubilization
Mass ratio of H3PO4a relative to oil []
Temperature [K]

0.001
343

H3PO4 neutralization
Mole ratio of NaOHb relative to added H3PO4 []

Washing
Mass ratio of deionized waterc relative to oil []

0.03

(b) Deacidification (DA, removal of free fatty acid)

Oil
Mass of oil [g]

Low-value raw oil (given in Table 1);

Oil after dephosphorization
50; Mass of oil after dephosphorization, FDP

Free fatty acid neutralization

Mole ratio of NaOHd relative to free fatty acid in oile []
Temperature [K]
Time [h]

1.15
353
0.083

Washing
Mass ratio of deionized waterc relative to deacidified oil [g]

0.15

(c) Dehydration (DH, removal of water)

Oil

Low-value oil (given in Table 1);

Oil after dephosphorization; oil after deacidification

Mass of oil [g]

50;
Mass of oil after dephosphorization, FDP;
Mass of oil after deacidification, FDA

Mass ratio of MgSO 4 relative to oil []

(proper quantity)

Added as an aqueous solution in which the mass fraction was 0.0085

Added as an aqueous solution in which the mass fraction was 0.001
c
Prepared by Di-Pak, Milli-Di, Millipore Corp.
d
Added as an aqueous solution in which the mass fraction was 0.095
e
Determined on the basis of mass fraction of free fatty acid in low-value feed oil before pretreatment
b

was purged inside to avoid moisture contamination and

oxidation by air.
After transesterification, the biodiesel and glycerol phases were separated from each other by using a
decantation funnel. The methanol, soaps, and glycerol
were removed from the oil phase by washing with warm
water at approximately 333 K (mass ratio of approximately 0.2 to the biodiesel phase); this was followed
by drying over magnesium sulphate and filtering to
remove the solid drying agent (Tapasvi et al., 2004).
Lastly, the biodiesel phase was analyzed to determine
the methyl ester content.
1.4 Analysis
The fatty acid chain compositions in the feed oil that
was not subjected to feed pretreatment and biodiesel prodVOL. 43 NO. 2 2010

uct were determined by analyses using a gas chromatograph (G-3000, Hitachi Ltd.) with a 30 m 0.25 mm i.d.
capillary column coated with a 0.25 m thick layer of
5% diphenyl95% dimethylpolysiloxane (TC-5, GL Science Inc.) and a flame ionization detector equipped with
chromato-integrator (D-2500, Hitachi Ltd.). In the case
of feed oil analysis, the triglycerides in the feed oil
should first be converted into the methyl ester form
(Umezawa et al., 1997) to enable analysis by using the
gas chromatograph. From these compositions, the average molar masses of the free fatty acid and triglyceride could be calculated.
The phosphorus content in the oil was determined
by using an inductively coupled plasma spectrometer
(SPS7800 Series, Seiko Instruments Inc.); the acid
217

Table 4

Conditions of transesterification (TE) and biodiesel purification

Transesterification
Feed oil

Low-value oil with or without pretreatment

(see Tables 1 and 3)
15
Methanol
39
Sodium hydroxide (NaOH)
0.0050.015
333
1

Mass of feed oil, F1 [g]

Alcohol
Molar ratio of alcohol relative to feed oil, ral []
Catalyst
Mass ratio of catalyst relative to feed oil, Rcat []
Temperature [K]
Time [h]
Biodiesel purification
Mass ratio of deionized water* relative to biodiesel phase []
Mass ratio of dehydrating agent (MgSO 4) relative to biodiesel phase []

0.2
(proper quantity)

*Prepared by Di-Pak, Milli-Di, Millipore Corp.

value was examined by titration according to ASTM

D 664, and the water content was measured by using a
Karl-Fisher titrator (758 KFD Titrino Metrohm Ltd.).
2.

Results and Discussion

2.1 Characterization of low-value oils

The mass fraction of fatty acid i in the low-value
oils, xi,0, the contents of phosphorus, xP,0, free fatty acid,
xFFA,0, and water, xW,0, are summarized in Table 1 together with the previous results (Azam et al., 2005;
Maycock, 1987; etinkaya and Karaosmanoglu,
2004).
All the oils contained fatty acid chains mainly in C16
(palmitic) and C18 (stearic, oleic, linoleic). CPO had
more C16 chains than CJO and UFO. The compositions
obtained in this study were almost the same as those in
previous results. The highest contents of phosphorous,
free fatty acid (FFA), and water were found in CJO.
The FFA content in UFO was much lower than the contents in CPO and CJO.
2.2 Influence of impurities in the feed oil and feed
pretreatment
The following variables were assigned to indicate
the biodiesel productivity and quality in this study.
The respective yields of oils in dephosphorization,
Y DP , deacidification, Y DA , dehydration, Y DH , and
transesterification, YTE, were defined as

and TE, respectively. Since the feed pretreatment and

transesterification were separately studied in the batch
experiment, F1 was a fraction of FDH. Accordingly, the
denominator of YTE was F1 and not FDH. The overall
yields of oils in terms of F0 after DA, YOA,DA, and DH,
Y OA,DH, were represented by
YOA,DA = FDA/F0

(5)

YOA,DH = FDH/F0

(6)

YOA,TE = [FTE/(F1/FDH)]/F0

(7)

= Y OA,DHY TE

(8)

As it was difficult to recover all of the biodiesel phase

during the filtration of MgSO4 after drying, the mass
of the biodiesel phase just after washing with water
and before drying was measured and substituted for
FTE. In previous studies, it was reported that the emulsification occurred in the washing step due to soap and
di- and mono-glyceride, which act as emulsifiers in
the biodiesel phase; hence, the values of yields shown
here might be higher than the exact values. The methyl ester purity in the biodiesel product obtained by
TE, xME,TE, was calculated as
xME,TE = xMy,TE + xPa,TE + xS,TE + xO,TE + xL,TE

Y DP = FDP/F0

(1)

Y DA = FDA/FDP

(2)

Y DH = FDH/FDA

(3)

Y TE = FTE/F1

(4)

where F0 and F1 are the masses of the feed oils to be

pretreated and transesterified, respectively; FDP, FDA,
FDH, and FTE are the masses of oils after DP, DA, DH,
218

(9)

where the mass fractions of the respective methyl esters in the product are xMy,TE, xPa,TE, xS,TE, xO,TE, and x L,TE.
The yield of methyl esters in TE, Y ME,TE, and the overall yield after TE, YOA,ME,TE, were determined as
YME,TE

= xME,TEYTE

YOA,ME,TE = xME,TEYOA,TE

(10)
(11)

JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

Table 5

Effects of pretreatments of feed oil on impurity removals and biodiesel production

(a) Crude palm oil

Pretreatment

DP, DH

DP, DA

DA, DH

DP, DA, DH

Dephosphorization
Y DP []

0.88

0.86

0.89

Deacidification (mass of NaOH used was 0.43 g)

Y DA (Y OA,DA) []
1 (1)

1 (0.88)

0.73 (0.63)

0.73 (0.73)

0.74 (0.66)

Dehydration
x P,DH []
x FFA,DH []
x W,DH []
Y DH (Y OA,DH) []

5.8 106
0.054
0.0008
0.94 (0.83)

2.7 106
0.0010
0.0125
1 (0.63)

6.7 106
0.0010
0.0008
0.94 (0.69)

2.6 106
0.0010
0.0009
0.96 (0.63)

4.1 106
0.0398
0.00030
0.85 (0.70)
0.84
0.71 (0.59)

2.4 106
0.0011
0.015
0.87 (0.55)
0.92
0.80 (0.51)

4.3 106
0.0010
0.00030
0.97 (0.67)
0.99
0.96 (0.66)

2.4 106
0.0010
0.00030
0.96 (0.61)
1
0.96 (0.61)

9.0 106 (=x P,0)

0.051 (=xFFA,0)
0.0047 (=xW,0)
1 (1)

Transesterification (ral = 6, Rcat = 0.01)

x P,TE []
5.9 106
x FFA,TE []
0.0417
x W,TE []
0.00030
0.76 (0.76)
Y TE (Y OA,TE) []
0.79
x ME,TE []
Y ME,TE (Y OA,ME,TE) []
0.60 (0.60)
(b) Crude jatropha oil
Pretreatment

DP, DH

DP, DA

DA, DH

DP, DA, DH

Dephosphorization
Y DP []

0.79

0.75

0.75

Deacidification (mass of NaOH used was 0.91 g)

Y DA (Y OA,DA) []
1 (1)

1 (0.79)

0.60 (0.45)

0.65 (0.65)

0.60 (0.45)

Dehydration
x P,DH []
x FFA,DH []
x W,DH []
Y DH (Y OA,DH) []

9.4 106
0.12
0.0009
0.95 (0.75)

3.1 106
0.0013
0.0185
1 (0.45)

13 106
0.0013
0.0008
0.94 (0.61)

2.9 106
0.0014
0.0009
0.91 (0.41)

0 (0)

0 (0)

2.7 106
0.0011
0.015
0.93 (0.42)
0.98
0.91 (0.41)

11 106
0.0011
0.0003
0.98 (0.60)
0.99
0.97 (0.59)

2.5 106
0.0011
0.0003
1 (0.41)
0.99
0.99 (0.41)

40 106 (=xP,0)
0.11 (=x FFA,0)
0.023 (=xW,0)
1 (1)

Transesterification (ral = 6, Rcat = 0.01)

x P,TE []

x FFA,TE []

x W,TE []
0 (0)
Y TE (Y OA,TE) []
x ME,TE []

0 (0)
Y ME,TE (Y OA,ME,TE) []

Thus, YME,TE and YOA,ME,TE are increased by increasing

Y TE, YOA,TE, or xME,TE.
The effects of performing feed pretreatment (FP)
in terms of the reduction in the impurities for each type
of feed oil are presented in Table 5. DP, DA, and DH
resulted in a reduction in the mass fraction of phosphorous, xP,DH, to less than 10 106, a reduction in
that of free fatty acid (FFA), xFFA,DH, to 0.0015, and a
reduction in that of water, xW,DH, to 0.001; for all feed
oils. DP did not result in a reduction in the FFA content, while phosphorus was removed by DA; even when
DP was not carried out, the phosphorous content was
reduced from xP,0 = 9 10 6, 40 106, and 8.9 106 to
VOL. 43 NO. 2 2010

xP,DH = 6.7 106, 13 106, and 6.2 106 for CPO,

CJO, and UFO, respectively. DH, namely, adsorption
by MgSO4, did not result in a reduction in phosphorous or FFA content. The water content increased by
DP and DA, and hence, DH was necessary when DP
and/or DA required despite the water content in the
original feed oil being considerably low. The contents
of phosphorous and FFA were also decreased by
transesterification and biodiesel purification. When the
water content in the feed oil to be transesterified, xW,DH,
was high, that in the biodiesel product, xW,TE, was high,
although dehydration was carried out during biodiesel
purification.
219

Table 5

(continued)

(c) Used frying oil

Pretreatment

DP, DH

DP, DA

DA, DH

DP, DA, DH

Dephosphorization
YDP []

0.90

0.89

0.90

Deacidification (mass of NaOH used was 0.051 g)

YDA (YOA,DA) []
1 (1)
1 (0.90)

0.96 (0.86)

0.96 (0.96)

0.95 (0.86)

Dehydration
xP,DH []
xFFA,DH []
xW,DH []
YDH (Y OA,DH) []

5.7 106
0.0073
0.0008
0.96 (0.86)

2.6 106
0.0011
0.011
1 (0.86)

6.2 106
0.0011
0.0008
0.97 (0.93)

2.6 106
0.0011
0.0008
0.95 (0.82)

4.2 106
0.0015
0.0002
0.87 (0.75)
0.98
0.85 (0.73)

2.3 106
0
0.015
0.91 (0.78)
0.99
0.91 (0.78)

4.8 106
0.0010
0.0002
1 (0.92)
0.99
0.99 (0.92)

2.3 106
0.0010
0.0002
1 (0.82)
1
0.99 (0.81)

8.9 106 (=x P,0)

0.0062 (=xFFA,0)
0.0072 (=xW,0)
1 (1)

Transesterification (ral = 6, Rcat = 0.01)

xP,TE []
6.1 106
xFFA,TE []
0.0038
xW,TE []
0.0004
0.82 (0.82)
YTE (YOA,TE) []
0.87
xME,TE []
YME,TE (Y OA,ME,TE) []
0.71 (0.71)

On the other hand, the FP also resulted in the loss

of feed oils, which differed with the type of feed oil,
as seen from the different oil yields across all cases, as
listed in Table 5. Whereas the yields in DP, YDP, for
CPO and UFO were almost constant at 0.9, that for
CJO was lower (approximately 0.75). This may be a
consequence of emulsification with a relatively high
content of phospholipid in CJO. In the case of CPO
and CJO, where the FFA content was high, DA resulted
in the lowest yield (Y DA) among DP, DA, and DH because of the saponification (c-5 by b-2 in Table 2). YDA,
which was indicated by the FFA content, decreased in
the following order: UFO, CPO, and CJO; in other
words, the required amount of NaOH was larger and
the saponification occurred to a greater degree. When
the feed oil contains a high amount of FFA, DA carried out by using an acid is preferable to that carried
out by using an alkali (Freedman et al., 1984); nevertheless, a feasibility study in which the production
yield, chemical consumption, and rate of production
are considered must be carried out to select the appropriate feed pretreatment. The yields in DH, Y DH, were
around 0.95 for all the feed oils. The overall yields
after dehydration, YOA,DH, when DP, DA, and DH were
all carried out, decreased in the following order: UFO,
CPO, and CJO; this is identical to the case of Y DA.
The importance of DP, DA, and DH in biodiesel
production was examined in terms of the influence of
impurity contents in the oils after pretreatments on the
yields and purities for all the feed oils, as listed in Table 5. When FP was not carried out, the biodiesel phase
could not be obtained because of the stable emulsification in the reactor in the case of CJO. The Y TE and

Y ME,TE values were extremely low, and xME,TE did not

meet the biodiesel standard, 0.965 (EN14214) in the
case of CPO and UFO. On the other hand, when DP,
DA, and DH were carried out (full feed pretreatment,
FFP), the Y ME,TE values were improved for all the feed
oils. The overall yields of methyl ester, Y OA,ME,TE, were
also improved because of the increases in YTE and xME,TE,
in spite of the feed oil loss due to pretreatment as mentioned above. When DP was not carried out, the xME,TE
and Y ME,TE values for all the feed oils were almost the
same as those in the case of FFP; the YOA,DH and YOA,ME,TE
values were the highest. This indicates that DP is not
the essential unit in this study; rather, DP caused an
unnecessary loss of feed oil due to emulsification.
When DA was not carried out, Y TE, xME,TE, and YME,TE
for all the feed oils were relatively low, and the yield
decreased in the following order: UFO, CPO, and CJO;
in particular, for CJO, the biodiesel phase could not be
obtained as it was in the case without FP. These results
were attributed to the presence of FFA in the oils and
its content, as listed in Table 2. The FFA (a-2) is neutralized with an alkaline catalyst during transesterification
(b-1), which results in soap formation (b-3) and loss of
the catalyst (c-4); the soap formation leads to foaming
with gas (c-1), emulsification (c-2), and solubilization
of the alkyl ester product into the glycerol phase (c-3);
the foaming and the catalyst loss result in a low reaction rate, i.e., low purity and low yield; as the emulsification makes phase separation difficult, the yield
becomes low, and the yield is lowered also by the solubilization. Water content of just x W,DH = 0.0185 and
0.011 in CJO and UFO obviously reduced Y TE and
Y ME,TE, and a water content of just xW,DH = 0.0125 in

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Fig. 1

Effects of alcohol (methanol) and catalyst (NaOH) ratios relative to the feed oil in transesterification (ral and Rcat,
respectively) on biodiesel yields, YTE and Y OA,TE: (a) crude palm oil (CPO); (b) crude jatropha oil (CJO); (c) used
frying oil (UFO)

Fig. 2

Effects of alcohol (methanol) and catalyst (NaOH) ratios relative to feed oil in transesterification (ral and Rcat, respectively) on the methyl ester purity in biodiesel product, x ME,TE: (a) crude palm oil (CPO); (b) crude jatropha oil (CJO);
(c) used frying oil (UFO)

CPO reduced Y TE, xME,TE, and Y ME,TE; this is attributed

to the soap formation by OH (a-3, b-1-2, c-1-5 in Table 2). Among the three kinds of oils, the reduction in
Y TE, xME,TE, and Y ME,TE due to water was greatest in the
case of CPO. The C16 content in CPO was higher than
the C16 contents in the other feed oils; as a result, the
saponification tended to occur more easily in CPO (see
Table 2). Thus, the water contamination of the feed oil
that resulted in saponification had the most significant
effect in the case of CPO.
2.3 Influence of fatty acid composition in the feed
oil and amounts of alcohol and catalyst in
transesterification
The mass fractions of impurities in the feed oils
were standardized by full feed pretreatment, and they
did not influence the biodiesel production thereafter.
The effects of the amounts of methanol and sodium hydroxide, r al and Rcat, on the biodiesel yields,
Y TE and YOA,TE, are shown in Figure 1. The yield of the
VOL. 43 NO. 2 2010

biodiesel product, YTE, in the case of CPO was lower

than the yield in the case of the others since the C16
content in CPO was higher (see Table 2) (Azam et al.,
2005). Overall, the YTE values varied with ral, and the
maximum YTE was observed at the moderate r al in the
range considered in this study. This is because while
methanol promoted the transesterification, its excess
amount dissolved the produced methyl esters into the
glycerol phase (a-5 and c-7 in Table 2). YTE decreased
with increasing Rcat in the range considered in this study
as a result of increased saponification (a-6, b-2, b-3,
and c-1-5 in Table 2). The overall yields, YOA,TE, were
lower than Y TE, and they decreased in the following
order: UFO, CPO, and CJO; the overall yields were
given according to the degree of feed oil loss in the
FP, as discussed in the previous section. In some runs,
YTE exceeded unity; this is attributed to the emulsification of water in the oil when washing the biodiesel
product, as mentioned above.
221

Fig. 3

Effects of alcohol (methanol) and catalyst (NaOH) ratios relative to feed oil in transesterification (ral and Rcat, respectively) on methyl ester yields, Y ME,TE and Y OA,ME,TE: (a) crude palm oil (CPO); (b) crude jatropha oil (CJO); (c) used
frying oil (UFO)

Figure 2 depicts the effects of ral and Rcat on the

methyl ester purity in the biodiesel product, xME,TE. The
xME,TE value in the case of CPO was higher than the
corresponding values in the case of others; this was
attributed to the higher fraction of C16. As mentioned
in Table 2(a-4), during transesterification, a small
number of anions of diglyceride and monoglyceride
with the shorter chain that remained in the biodiesel
phase could dissolve to a greater degree in the glycerol/aqueous phase than could those with the longer
chain (more c-6); therefore, the content of impurities
in the case of CPO was lower. The x ME,TE value increased with r al and Rcat and became higher than 0.99
when r al and Rcat were equal to or greater than 6 and
0.01, respectively.
The effects of ral and Rcat on the methyl ester yields,
Y ME,TE and Y OA,ME,TE, are presented in Figure 3. The
YME,TE values for CJO and UFO were higher than the
value for CPO. As YME,TE was a function of YTE and xME,TE
given by Eq. (10), even though the xME,TE value was the
highest for CPO, the most significant factor that lowered the Y ME,TE for CPO was Y TE. The highest Y ME,TE was
obtained at r al = 6, Rcat = 0.005 for CPO and r al = 6, Rcat
= 0.01 for CJO and UFO. The overall yield, Y OA,ME,TE,
was lower than YME,TE and decreased in the following
order: UFO, CPO, and CJO; this is identical to the results of Y TE and YOA,TE.
The effects of r al and Rcat on Y TE, xME,TE, and Y ME,TE
varied with the type of oil because the tendency of soap
formation and dissolvability of mono- and di-glycerides in the glycerol phase varied with the carbon chain
length of the fatty acid in the oil. For this reason, a
different oil would require different ral and Rcat for obtaining its maximum YTE, xME,TE, and YME,TE. For example, the shorter carbon chain would require higher ral
and lower Rcat to accommodate the transesterification instead of soap formation.

Conclusion

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JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

C16 and C18 chains were the two main fatty acid
groups in the low-value oils studied. The content of
C16 in crude palm oil was higher than the contents in
crude jatropha oil and used frying oil. A phospholipid,
free fatty acid, and water were studied as the main
impurities, and their highest contents were found in
crude jatropha oil. The fatty acid compositions and
impurity contents in the feed oils were two main factors that influenced the required feed pretreatment,
operating conditions in transesterification, and
biodiesel yield and purity. Feed pretreatment was successfully carried out to remove the impurities from the
feed oils; in particular, deacidification as well as dehydration were effective pretreatments to improve the
biodiesel productivity and achieve the biodiesel quality standard. Alkali deacidification is not suitable for
oils that contain a large amount of free fatty acid, such
as crude jatropha oil, because the oil loss in feed pretreatment increased with the free fatty acid content in
the oils. The yield and purity in the case of crude palm
oil were lower and higher than those in the case of the
other oils, respectively, since the yield decreased and
purity increased with increasing C16 content in the feed
oil. The yield and purity would be improved by adjusting the operating conditions, such as the amounts
of alcohol and catalyst, appropriately for each oil type.
These techniques and obtained results were useful for
the selection of the feed oils and maximization of
biodiesel productivity when the various kinds of lowvalue oils were utilized in a biodiesel production system.
Acknowledgment
We would like to thank Someya Shouten, Ltd., Sumida, Tokyo,
for providing used frying oil.

Nomenclature
F
=
R cat
=
=
r al
xi
=
Y
=
=
YOA

mass of oil
mass ratio of catalyst relative to oil
molar ratio of alcohol relative to oil
mass fraction of component i
yield of oil in operation
overall yield of oil

<Subscript>
0
=
1
=
al
=
cat
=
DA
=
DH
=
DP
=
FFA
=
i
=
L
=
ME
=
My
=
O
=
OA
=
P
=
Pa
=
S
=
TE
=
W
=

feed oil to be pretreated

feed oil to be transesterified
alcohol
catalyst
deacidification
dehydration
dephosphorization
free fatty acid
component i
linoleic acid
methyl ester in total
myristic acid
oleic acid
overall (based on feed oil to be pretreated)
phosphorus
palmitic acid
stearic acid
transesterification and purification
water

[g]
[]
[]
[]
[]
[]

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VOL. 43 NO. 2 2010

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