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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 appropri-
ate 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.
application of various low-value oils to biodiesel pro- costless oil. The recycling of UFO imparts value to
duction by comparing these factors and their effects. waste cooking oil and also reduces the load for waste
This would result in the appropriate selection of feed treatment.
oils to maximize biodiesel productivity. First, the typi- CPO and CJO were obtained from Malaysia and
cal low-value oils were characterized in terms of fatty Thailand, respectively. UFO was obtained from a com-
acid composition and the contents of undesirable im- pany treating used oil in Japan (Someya Shouten Ltd.).
purities, which were the two main factors used for iden- 1.2 Feed pretreatment
tifying low-value oils. Then, these oils were pretreated The effects of the principal impurities, which are
under various conditions and subsequently transesterified phospholipids, free fatty acids, and water, in low-value
to investigate the influences of impurities on the re- oils are briefly summarized in Table 2. These impuri-
quired pretreatment and the corresponding biodiesel ties would not only contaminate the biodiesel product
purities and yields. Finally, the feed oils in which a but also waste the catalyst. Further, they would reduce
sufficient amount of the impurities were removed by the product purity and yield because of one or more
pretreatment were transesterified under varying opera- effects, as explained in the table. Therefore, feed pre-
tion conditions; then, the various oils and the effects treatment (FP) involving dephosphorization (DP), dea-
of the above-mentioned conditions on the production cidification (DA), and dehydration (DH) was required
performance were compared. to appropriately remove phospholipids, free fatty ac-
ids and water, respectively, before transesterification.
1. Experimental Various combinations of DP, DA, and DH were car-
ried out in the study on feed pretreatment.
1.1 Low-value oils DP was carried out first during the FP because of
Table 1 lists the low-value oils selected as feed the drawback of phospholipids (a-1 and c-1-3 in Table
oils in this study. The oils were crude palm oil (CPO), 2), which affected not only the transesterification but
crude jatropha oil (CJO), and used frying oil (UFO). also the other pretreatments. The conditions of DP are
The merits of CPO are the comparatively higher scale listed in Table 3(a). Phosphoric acid (H 3 PO 4) was
of production and lower price than other commodity added to the feed oil, which was heated up to 343 K to
vegetable oils. CJO is superior because of its inedibil- enable the conversion of non-hydratable phospholipids
ity, i.e., no demand for its use in food. Further, jatropha to water-soluble phosphatidic acid. Then, sodium hy-
plants are also drought-resistant perennial plants that droxide (NaOH) was added to neutralize the phosphoric
grow well in even poor soil. UFO is considered as a acid. This was followed by washing with deionized
215
Table 2 Effects of impurities, fatty acid composition, and operating factors on biodiesel production
Factor Effect
a-1. Phospholipid c-1, c-2, c-3
a-2. Free fatty acid b-1
a-3. Water b-1, b-2
a-4. Fatty acid carbon chain length More b-2 (if chain is shorter), more c-6 (if chain is shorter)
a-5. Alcohol amount for transesterification More c-7
a-6. Alkaline-catalyst amount for transesterification More b-2
water to dissolve the hydratable phospholipid and 1.3 Transesterification and biodiesel purification
phosphatidic acid. The water phase was separated from The conditions of transesterification are shown in
oil phase by centrifugation. Table 4. The feed oil was CPO, CJO, or UFO; pre-
Next, DA, for which the conditions are listed in treatment was carried out in some cases (see Tables 1
Table 3(b), was carried out. The free fatty acid in the and 3). Methanol was selected as an alcohol. An alka-
oil was converted to oil-insoluble soap by neutraliza- line catalyst was used in transesterification because it
tion with excess NaOH. The soap was also produced was the most conventional method with a fast reaction
by the saponification of triglyceride occurring simul- rate and requiring mild operating conditions. The al-
taneously with neutralization. The soap was then re- kaline catalyst was NaOH. The molar ratio of metha-
moved by centrifugation. Subsequently, deionized nol and the mass ratio of NaOH relative to the feed oil
water was added to dissolve the soap and finally sepa- were varied systematically, as specified in Table 4. Ac-
rated from the oil by centrifugation. The deacidifica- cording to a previous study (Sinthupinyo et al., 2008),
tion temperature was set high enough at 353 K to pre- the feed oil composition, i.e., fatty acid carbon chain
vent the emulsification, which interferes with the sepa- length (a-4), amount of alcohol (a-5), and amount of
ration of soap from the oil. catalyst (a-6) also influence the biodiesel production,
DH was the last step in the FP, as water con- as observed from Table 2. The reaction was carried out
taminated the oil in the previous pretreatments, in a 50 × 10–6 m3 flask, which was equipped with a
dephosphorization and deacidification. The conditions reflux condenser and temperature-controlled oil bath.
of DH are summarized in Table 3(c). The water was After the oil was heated to a specified temperature in
removed from the oil by adsorption using magnesium the reactor, the mixture of methanol and NaOH at the
sulfate (MgSO4), and the oil was subsequently filtered same temperature was added to the oil. Transesterification
to remove magnesium sulfate crystals (Tapasvi et al., involved a set of simultaneous reactions, and this re-
2004). This DH method was selected because it was a action system was heterogeneous throughout the whole
convenient and effective method on the laboratory reaction, and hence, this system was constantly and
scale. Other physical dehydration methods such as va- vigorously well mixed by a magnetic stirrer and left to
porization may be more suitable for the large-scale stand for 1 h, which would enable the reaction to
biodiesel plant from the financial point of view. progress sufficiently. During the reaction, nitrogen gas
was purged inside to avoid moisture contamination and uct were determined by analyses using a gas chromato-
oxidation by air. graph (G-3000, Hitachi Ltd.) with a 30 m × 0.25 mm i.d.
After transesterification, the biodiesel and glyc- capillary column coated with a 0.25 µm thick layer of
erol phases were separated from each other by using a 5% diphenyl–95% dimethylpolysiloxane (TC-5, GL Sci-
decantation funnel. The methanol, soaps, and glycerol ence Inc.) and a flame ionization detector equipped with
were removed from the oil phase by washing with warm chromato-integrator (D-2500, Hitachi Ltd.). In the case
water at approximately 333 K (mass ratio of approxi- of feed oil analysis, the triglycerides in the feed oil
mately 0.2 to the biodiesel phase); this was followed should first be converted into the methyl ester form
by drying over magnesium sulphate and filtering to (Umezawa et al., 1997) to enable analysis by using the
remove the solid drying agent (Tapasvi et al., 2004). gas chromatograph. From these compositions, the av-
Lastly, the biodiesel phase was analyzed to determine erage molar masses of the free fatty acid and triglycer-
the methyl ester content. ide could be calculated.
1.4 Analysis The phosphorus content in the oil was determined
The fatty acid chain compositions in the feed oil that by using an inductively coupled plasma spectrometer
was not subjected to feed pretreatment and biodiesel prod- (SPS7800 Series, Seiko Instruments Inc.); the acid
Transesterification
Feed oil Low-value oil with or without pretreatment
(see Tables 1 and 3)
Mass of feed oil, F1 [g] 15
Alcohol Methanol
Molar ratio of alcohol relative to feed oil, ral [—] 3–9
Catalyst Sodium hydroxide (NaOH)
Mass ratio of catalyst relative to feed oil, Rcat [—] 0.005–0.015
Temperature [K] 333
Time [h] 1
Biodiesel purification
Mass ratio of deionized water* relative to biodiesel phase [—] 0.2
Mass ratio of dehydrating agent (MgSO 4) relative to biodiesel phase [—] (proper quantity)
value was examined by titration according to ASTM and TE, respectively. Since the feed pretreatment and
D 664, and the water content was measured by using a transesterification were separately studied in the batch
Karl-Fisher titrator (758 KFD Titrino Metrohm Ltd.). experiment, F1 was a fraction of FDH. Accordingly, the
denominator of YTE was F1 and not FDH. The overall
2. Results and Discussion yields of oils in terms of F0 after DA, YOA,DA, and DH,
Y OA,DH, were represented by
2.1 Characterization of low-value oils
The mass fraction of fatty acid i in the low-value YOA,DA = FDA/F0 (5)
oils, xi,0, the contents of phosphorus, xP,0, free fatty acid,
xFFA,0, and water, xW,0, are summarized in Table 1 to- YOA,DH = FDH/F0 (6)
gether with the previous results (Azam et al., 2005;
Maycock, 1987; Çetinkaya and Karaosmanoglu, ˘ 2004). YOA,TE = [FTE/(F1/FDH)]/F0 (7)
All the oils contained fatty acid chains mainly in C16
(palmitic) and C18 (stearic, oleic, linoleic). CPO had = Y OA,DH·Y TE (8)
more C16 chains than CJO and UFO. The compositions
obtained in this study were almost the same as those in As it was difficult to recover all of the biodiesel phase
previous results. The highest contents of phosphorous, during the filtration of MgSO4 after drying, the mass
free fatty acid (FFA), and water were found in CJO. of the biodiesel phase just after washing with water
The FFA content in UFO was much lower than the con- and before drying was measured and substituted for
tents in CPO and CJO. FTE. In previous studies, it was reported that the emul-
2.2 Influence of impurities in the feed oil and feed sification occurred in the washing step due to soap and
pretreatment di- and mono-glyceride, which act as emulsifiers in
The following variables were assigned to indicate the biodiesel phase; hence, the values of yields shown
the biodiesel productivity and quality in this study. here might be higher than the exact values. The me-
The respective yields of oils in dephosphorization, thyl ester purity in the biodiesel product obtained by
Y DP , deacidification, Y DA , dehydration, Y DH , and TE, xME,TE, was calculated as
transesterification, YTE, were defined as
xME,TE = xMy,TE + xPa,TE + xS,TE + xO,TE + xL,TE (9)
Y DP = FDP/F0 (1)
where the mass fractions of the respective methyl es-
Y DA = FDA/FDP (2) ters 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 over-
Y DH = FDH/FDA (3) all yield after TE, YOA,ME,TE, were determined as
where F0 and F1 are the masses of the feed oils to be YOA,ME,TE = xME,TE·YOA,TE (11)
pretreated and transesterified, respectively; FDP, FDA,
FDH, and FTE are the masses of oils after DP, DA, DH,
Dehydration
x P,DH [—] 9.0 × 10–6 (=x P,0) 5.8 × 10–6 2.7 × 10–6 6.7 × 10–6 2.6 × 10–6
x FFA,DH [—] 0.051 (=xFFA,0) 0.054 0.0010 0.0010 0.0010
x W,DH [—] 0.0047 (=xW,0) 0.0008 0.0125 0.0008 0.0009
Y DH (Y OA,DH) [—] 1 (1) 0.94 (0.83) 1 (0.63) 0.94 (0.69) 0.96 (0.63)
Dehydration
x P,DH [—] 40 × 10–6 (=xP,0) 9.4 × 10–6 3.1 × 10–6 13 × 10–6 2.9 × 10–6
x FFA,DH [—] 0.11 (=x FFA,0) 0.12 0.0013 0.0013 0.0014
x W,DH [—] 0.023 (=xW,0) 0.0009 0.0185 0.0008 0.0009
Y DH (Y OA,DH) [—] 1 (1) 0.95 (0.75) 1 (0.45) 0.94 (0.61) 0.91 (0.41)
Thus, YME,TE and YOA,ME,TE are increased by increasing xP,DH = 6.7 × 10–6, 13 × 10–6, and 6.2 × 10–6 for CPO,
Y TE, YOA,TE, or xME,TE. CJO, and UFO, respectively. DH, namely, adsorption
The effects of performing feed pretreatment (FP) by MgSO4, did not result in a reduction in phospho-
in terms of the reduction in the impurities for each type rous or FFA content. The water content increased by
of feed oil are presented in Table 5. DP, DA, and DH DP and DA, and hence, DH was necessary when DP
resulted in a reduction in the mass fraction of phos- and/or DA required despite the water content in the
phorous, xP,DH, to less than 10 × 10–6, a reduction in original feed oil being considerably low. The contents
that of free fatty acid (FFA), xFFA,DH, to 0.0015, and a of phosphorous and FFA were also decreased by
reduction in that of water, xW,DH, to 0.001; for all feed transesterification and biodiesel purification. When the
oils. DP did not result in a reduction in the FFA con- water content in the feed oil to be transesterified, xW,DH,
tent, while phosphorus was removed by DA; even when was high, that in the biodiesel product, xW,TE, was high,
DP was not carried out, the phosphorous content was although dehydration was carried out during biodiesel
reduced from xP,0 = 9 × 10 –6, 40 × 10–6, and 8.9 × 10–6 to purification.
Dehydration
xP,DH [—] 8.9 × 10–6 (=x P,0) 5.7 × 10–6 2.6 × 10–6 6.2 × 10–6 2.6 × 10–6
xFFA,DH [—] 0.0062 (=xFFA,0) 0.0073 0.0011 0.0011 0.0011
xW,DH [—] 0.0072 (=xW,0) 0.0008 0.011 0.0008 0.0008
YDH (Y OA,DH) [—] 1 (1) 0.96 (0.86) 1 (0.86) 0.97 (0.93) 0.95 (0.82)
On the other hand, the FP also resulted in the loss Y ME,TE values were extremely low, and xME,TE did not
of feed oils, which differed with the type of feed oil, meet the biodiesel standard, 0.965 (EN14214) in the
as seen from the different oil yields across all cases, as case of CPO and UFO. On the other hand, when DP,
listed in Table 5. Whereas the yields in DP, YDP, for DA, and DH were carried out (full feed pretreatment,
CPO and UFO were almost constant at 0.9, that for FFP), the Y ME,TE values were improved for all the feed
CJO was lower (approximately 0.75). This may be a oils. The overall yields of methyl ester, Y OA,ME,TE, were
consequence of emulsification with a relatively high also improved because of the increases in YTE and xME,TE,
content of phospholipid in CJO. In the case of CPO in spite of the feed oil loss due to pretreatment as men-
and CJO, where the FFA content was high, DA resulted tioned above. When DP was not carried out, the xME,TE
in the lowest yield (Y DA) among DP, DA, and DH be- and Y ME,TE values for all the feed oils were almost the
cause of the saponification (c-5 by b-2 in Table 2). YDA, same as those in the case of FFP; the YOA,DH and YOA,ME,TE
which was indicated by the FFA content, decreased in values were the highest. This indicates that DP is not
the following order: UFO, CPO, and CJO; in other the essential unit in this study; rather, DP caused an
words, the required amount of NaOH was larger and unnecessary loss of feed oil due to emulsification.
the saponification occurred to a greater degree. When When DA was not carried out, Y TE, xME,TE, and YME,TE
the feed oil contains a high amount of FFA, DA car- for all the feed oils were relatively low, and the yield
ried out by using an acid is preferable to that carried decreased in the following order: UFO, CPO, and CJO;
out by using an alkali (Freedman et al., 1984); never- in particular, for CJO, the biodiesel phase could not be
theless, a feasibility study in which the production obtained as it was in the case without FP. These results
yield, chemical consumption, and rate of production were attributed to the presence of FFA in the oils and
are considered must be carried out to select the appro- its content, as listed in Table 2. The FFA (a-2) is neutral-
priate feed pretreatment. The yields in DH, Y DH, were ized with an alkaline catalyst during transesterification
around 0.95 for all the feed oils. The overall yields (b-1), which results in soap formation (b-3) and loss of
after dehydration, YOA,DH, when DP, DA, and DH were the catalyst (c-4); the soap formation leads to foaming
all carried out, decreased in the following order: UFO, with gas (c-1), emulsification (c-2), and solubilization
CPO, and CJO; this is identical to the case of Y DA. of the alkyl ester product into the glycerol phase (c-3);
The importance of DP, DA, and DH in biodiesel the foaming and the catalyst loss result in a low reac-
production was examined in terms of the influence of tion rate, i.e., low purity and low yield; as the emulsi-
impurity contents in the oils after pretreatments on the fication makes phase separation difficult, the yield
yields and purities for all the feed oils, as listed in Ta- becomes low, and the yield is lowered also by the solu-
ble 5. When FP was not carried out, the biodiesel phase bilization. Water content of just x W,DH = 0.0185 and
could not be obtained because of the stable emulsifi- 0.011 in CJO and UFO obviously reduced Y TE and
cation in the reactor in the case of CJO. The Y TE and Y ME,TE, and a water content of just xW,DH = 0.0125 in
Fig. 2 Effects of alcohol (methanol) and catalyst (NaOH) ratios relative to feed oil in transesterification (ral and Rcat, respec-
tively) 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 biodiesel product, YTE, in the case of CPO was lower
to the soap formation by OH – (a-3, b-1-2, c-1-5 in Ta- than the yield in the case of the others since the C16
ble 2). Among the three kinds of oils, the reduction in content in CPO was higher (see Table 2) (Azam et al.,
Y TE, xME,TE, and Y ME,TE due to water was greatest in the 2005). Overall, the YTE values varied with ral, and the
case of CPO. The C16 content in CPO was higher than maximum YTE was observed at the moderate r al in the
the C16 contents in the other feed oils; as a result, the range considered in this study. This is because while
saponification tended to occur more easily in CPO (see methanol promoted the transesterification, its excess
Table 2). Thus, the water contamination of the feed oil amount dissolved the produced methyl esters into the
that resulted in saponification had the most significant glycerol phase (a-5 and c-7 in Table 2). YTE decreased
effect in the case of CPO. with increasing Rcat in the range considered in this study
2.3 Influence of fatty acid composition in the feed as a result of increased saponification (a-6, b-2, b-3,
oil and amounts of alcohol and catalyst in and c-1-5 in Table 2). The overall yields, YOA,TE, were
transesterification lower than Y TE, and they decreased in the following
The mass fractions of impurities in the feed oils order: UFO, CPO, and CJO; the overall yields were
were standardized by full feed pretreatment, and they given according to the degree of feed oil loss in the
did not influence the biodiesel production thereafter. FP, as discussed in the previous section. In some runs,
The effects of the amounts of methanol and so- YTE exceeded unity; this is attributed to the emulsifica-
dium hydroxide, r al and Rcat, on the biodiesel yields, tion of water in the oil when washing the biodiesel
Y TE and YOA,TE, are shown in Figure 1. The yield of the product, as mentioned above.