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Fuel 210 (2017) 721–728

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Fuel
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Full Length Article

Biodiesel production from mixed non-edible oils, castor seed oil and waste MARK
fish oil

Abdelrahman B. Fadhila, , Emaad T.B. Al-Tikrityb, Mohammed A. Albadreeb
a
Industrial Chemistry Researches Laboratory, Department of Chemistry, College of Science, University of Mosul, Mosul, Iraq
b
Department of Chemistry, College of Science, Tikrit University, Salahaldeen, Iraq

A R T I C L E I N F O A B S T R A C T

Keywords: Biodiesel production from non-edible oils is one of the effective approach to reduce cost of production, and solve
Castor seed oil and waste fish oil part of the obstacles facing the availability of the traditional raw materials. The present investigation explores
Mixed non-edible oils biodiesel production from mixed non-edible oils, castor seed oil (CSO) and waste fish oil (WFO). Different blends
Biodiesel of WFO and CSO (10:90–50:50% WFO:CSO w/w) were implemented and evaluated in order to select the optimal
Fuel properties evaluation
blend that possesses properties closer to those of conventional raw oils that were used for biodiesel production.
Analysis of biodiesel
The equivalent blend (50:50% WFO:CSO w/w) was found to be the optimal blend; thus, it was transesterified
with methanol to produce fatty acid methyl ester. Effect of the operating and processing variables, such as the
type and the concentration of the catalyst, methanol to oil molar ratio, reaction temperature, reaction time, and
the rate of stirring were thoroughly investigated. The results revealed that the optimal conditions for synthesis of
biodiesel were 0.50 wt% KOH, 8:1 methanol to oil molar ratio, 32 °C reaction temperature, 30 min of reaction,
and 600 rpm rate of stirring. Under these conditions, biodiesel with a yield of 95.20 ± 2.5% w/w was obtained.
1
HNMR spectroscopy was used to assure the conversion of the oils blend to biodiesel. Based on 1HNMR spec-
troscopy results, conversion of mixed CSO and WFO into biodiesel was 97.74%. The fuel properties of the
resulting biodiesel were within the acceptable limits prescribed by ASTM D 6751. Furthermore, biodiesel from
the said blend, have low viscosity and density comparing to those of CSO biodiesel. In conclusion, the proposed
oils blend may be a profitable feedstock source, and easy way to improve biodiesel properties that synthesized
from CSO.

1. Introduction seed oil, due to it is not suitable for human consumption and thus it
does not compete with food crops, its high content of oil which amounts
Biofuel which is made up by mono-alkyl-esters of long chain fatty 50% in addition to the high oil yields which could reach about 1188 kg
acids, derived from triglycerides (vegetable oils or animal fat) is known oil per hectare annually. Furthermore, the castor plant does not ne-
as biodiesel (BD). It can be used as a partial or total substitute of petro cessitate a great deal of maintenance or high quality water and it can
diesel in compression ignition engines or for electricity generation. grow in marginal soils. On these basis, castor oil is an attractive low
Transesterification process which involves the exchange of the glycerin cost feedstock for BD production [16].
in the triglycerides molecule by the alkyl group of the utilized alcohol The castor (Ricinus communis) plant can be found worldwide. It is
which is mainly methanol or ethanol in the presence of either an acid wild grown in many tropical and sub-tropical countries without special
catalyst or a base catalyst [1,2]. care, because it can tolerate very different climate conditions. However,
Many edible and non-edible feedstocks were utilized for BD pro- the castor plant agriculture have been increased in several countries,
duction. Nonetheless, availability and cost of the oil feedstock restrict such as Brazil, China and India [17]. The oil extracted from the castor
the BD production. Therefore, non-edible oil feedstocks, such as waste bean seed has more than 700 uses in the field of; plastics, cosmetics,
cooking oils [3–5], lipids from food waste [2,4], non-edible vegetable manufacturing of biodiesel, lubricants and medicine [1,2]. Moreover,
oils [6–11] and waste animal fats [2,12–15] were utilized as cheaper due to its high viscosity, it becomes a prime candidate as additive for
feedstocks for BD production were reported so as to decrease the pro- diesel fuel to increase the lubricity of the latter. India is the largest
duction cost of BD. Among non-edible oils that has been received more world producer and exporter of castor oil, with about 70% of the total
attention as a feedstock for BD production is castor (Ricinus communis) exports, followed by China 15%, Brazil 8% and Thailand 1%, whereas


Corresponding author.
E-mail addresses: abdelrahmanbasil@yahoo.com (A.B. Fadhil), emaad_bakir@yahoo.com (E.T.B. Al-Tikrity).

http://dx.doi.org/10.1016/j.fuel.2017.09.009
Received 8 June 2017; Received in revised form 22 August 2017; Accepted 4 September 2017
0016-2361/ © 2017 Elsevier Ltd. All rights reserved.
A.B. Fadhil et al. Fuel 210 (2017) 721–728

pour point values. Nevertheless, BD from animal fats might be used


Nomenclature
100% pure fuel in boilers for heat generation or mixed with other raw
materials, even improving some fuel characteristics [2,27,28].
BD biodiesel
Waste fish oil which can be obtained from discarded parts of fish is a
FAME fatty acid methyl esters
suitable feedstock for BD production due to it can be obtained with
CSO castor seed oil
huge amounts in addition to its very low kinematic viscosity value
WFO waste fish oil
which could produce a BD fuel with a kinematic viscosity lower than
CN cetane number
those reported in literature for biodiesels form various animal fats and
HHV higher heating value
vegetable oils [2]. Nonetheless, blending of CSO with WFO to produce
SV saponification value
BD fuel with properties conformed to those prescribed by ASTM stan-
IV iodine value
dards has not yet been reported in the literature to best of the authors
knowledge.
Production of BD from mixed CSO and WFO through base-catalyzed
countries such as USA, Russia and Japan are the major importers [18].
transesterification with methanol is the main target of the present in-
According to the National Supply Company, in Brazil, the production of
vestigation. Different blends of CSO and WFO were prepared and their
castor bean fruit reached 137.1 thousand tons in the 2005/2006 har-
properties were evaluated to select the optimal oils blend that is having
vest, and castor oil may become the main resource of oil for biodiesel
properties closer to those reported for oils used in BD synthesis.
production in Brazil. In Iraq, the castor plant has widely planted in
Optimization of transesterification parameters of the optimal oils blend
addition to its presence naturally. Southern and central Iraq comprise
were optimized. The fatty acid composition of the CSO, WFO and their
more areas where castor is grown. Nevertheless, the castor plant can
equivalent blend was determined. In addition, The 1H NMR spectro-
also be found in northern Iraq, such as Nineveh Governorates, Sala-
scopy was used to monitor the conversion of the said blend to BD and to
haldeen Governorates and Erbil Governorates. Unfortunately, ex-
determine the quality of the resulting BD as well. The fuel properties of
ploitation of castor bean oil for industrial application is limited so far,
the obtained biodiesel were determined following the ASTM standards.
and it is mainly produced for medical purposes.
The CSO has a unique chemical structure in comparison to other
2. Experimental
vegetable oils due to it mainly consists of Ricinoleic acid, which is
characterized by containing a hydroxyl group on carbon-12, which
2.1. Materials and reagents
made it the highest polarity vegetable oil. In addition, the high polarity
of CSO made it possess the highest viscosity and density compared to
The castor seeds were collected from the lands located in the city of
remaining vegetable oils. The kinematic viscosity of CSO is
Mosul, Nineveh Governorates, while the fish waste was collected from
(226 mm2 s−1) at 40 °C, while the kinematic viscosity values of most
fish Slaughterhouse located in Salahaladeen Governorates during the
vegetable oils are between 27 and 54 mm2 s−1 at the same temperature
summer of 2013. Methanol (98.0%), Analytical grade isopropyl alcohol
[19,20]. Accordingly, the kinematic viscosity of the BD produced from
(99.8%), n-hexane (96%), anhydrous sodium sulfate (Na2SO4 99%),
the CSO is much greater than those of conventional biodiesels, and thus
iodine (pellets), acetone, and diethyl ether were purchased from BDH
must be blended with other less viscosities diesel fuels (biodiesels or
(UK). Chloroform, potassium hydroxide (KOH, pellets), sodium hydro-
petro diesel fuel) to lessen its properties to the acceptable limits
xides (NaOH, pellets), sodium methoxide (CH3ONa) and sodium eth-
[21–26]. Blending of BD from the CSO with those of lower viscosities
oxide (CH3CH2ONa) were obtained from Fluka (Germany).
biodiesels was widely reported in literature. Meneghetti et al. [24]
studied transesterification of blends of the CSO with cotton seed and
2.2. Preparation of feedstocks
soybean oils, and obtained maximum yield of BD using a blend that
contains 25% soybean oil and 75% CSO. Barbosa et al. [22] in-
The castor seeds were cleaned and oven-dried at 50 °C for 24 h to be
vestigated transesterification of mixed CSO and soybean oil with
ground later by an electrical grinder. The oil was extracted by n-hexane
ethanol and reported that the yield of BD increased with decreasing
in a Soxhlet extractor for 10 h, followed by distillation under vacuum
CSO content. Besides, the viscosity of BD from the blends reduced with
using a rotary evaporator to separate the oil from the solvent. The
decreasing CSO content. Production of BD from an equivalent blend of
obtained oil was dried over anhydrous sodium sulfate to eliminate the
CSO and waste chicken oil was investigated by Fadhil and Ahmed [21].
residual moisture, filtered and finally kept in a sealed container at 5 °C
They prepared various blends of CSO and waste chicken oil, and found
for further assessment and use. The yield of the oil was calculated, on
that the equivalent blend was the optimal feedstock for BD synthesis.
dry bases [9,10].
Finally, Blending CSO esters with safflower methyl and ethyl esters
Discarded parts of Cyprinus carpio fish (head, tails, backbones, fatty
exhibited similar reduction in viscosity [23].
layer and skin) were used as source for fish oil. Extraction of fish oil was
Production of BD from waste animal fats is cheaper than that pro-
conducted following procedure given elsewhere [2]. In brief, the fish
duced from vegetable oils, due to animal waste are greatly generated
waste was transferred to a 1 L conical flask and heated by means of a
with huge amounts from slaughter houses and other meat processing
boiled water bath. The resulting fish oil was placed into a separating
industries. In addition, recovery of oils or fats from waste animal fats is
funnel and left for 24 h for water separation, followed by filtration and
cheaper than the production of oils from vegetable oils. As a result, use
finally drying over anhydrous sodium sulfate. The pure fish oil was kept
of waste animal fats is a significant means for solving the high pro-
in a dark place for subsequent assessment and use.
duction cost of BD and to decreases environmental impacts caused by
their incorrect management, due to such raw materials adds value to
2.3. Preparation and characterization of CSO, WFO and their blends
the wastes, which otherwise need to be further eliminated.
Furthermore, huge quantities of animal wastes are generated and their
The CSO and WFO were mixed and utilized in BD production.
use as animals feed has been strongly decreased, due to the possibility
Different blends of CSO and WFO (10, 20, 30, 40 and 50% CSO:WFO w/
of transmission of severe animal disease. BD from animal fats has higher
w) were prepared through mixing CSO with WFO using a mechanical
calorific value and cetane number due to their high level of saturated
stirrer for 30 min to obtain homogeneous mixture. Later on, several
fatty acids. On the other hand, BD from animal fats has several dis-
physical and chemical properties of the parent oils and their blends
advantages including less stability to oxidation, due to the absence of
including the density at 15.5 °C, the kinematic viscosity at 40 °C, flash
natural antioxidants in addition to the its higher cold filter plugging and
point, the acid value, the refractive index and the pour point were

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A.B. Fadhil et al. Fuel 210 (2017) 721–728

measured as per ASTM standards test methods in order to select the (ASTM D 5002), kinematic viscosity (ASTM D 445), flash point (D93),
acquired blend. saponification value (ASTM D5555-95), the refractive index (D1747 –
The fatty acids composition of the CSO, WFO and their optimal 09), the cloud and pour points (ASTM D 2500) and the acid value
blend were determined using gas chromatography (GC, Perkin Elmer, (ASTM D664) were evaluated as per the ASTM standard procedures,
Auto system GLX, Shelton, U.S.A.) equipped with a Supelco SP™-2380 while Hanus method was followed for measuring the iodine values of
(30 m × 0.25 mm i.d., 0.25 µm film thickness) column equipped with the resulting BD [30]. AOCS Cc 17-95 was followed to determine the
flame ionization detector (FID) [28]. The average molecular weight (g/ soap content in the prepared biodiesels [31], while Pisarello et al. [32]
mol) of the oils was determined by a weighted average method utilizing method was applied to determine the free and total glycerin contents in
the fatty acid composition. the BD. The cetane number (CN) of the prepared BD was calculated by
based on the saponification value (SV) and the iodine value (IV) of the
2.4. Transesterification of mixed CSO and WFO with methanol samples using the following formula [33]:
5458
CN = 46.3 + −0.225 × IV
The oils blend (100 g) was placed in a three neck round-bottomed SV
flask (500 mL), fitted with mechanical stirrer, condenser, thermostat,
The higher heating value (HHV) of fatty acid alkyl esters was cal-
and sampling outlet. A known amount of freshly prepared methylic
culated following equation is given by Krisnangkura [33]:
solutions of the catalyst salts, NaOH, KOH or CH3ONa was then added
to the oils blend. Afterward, the mixture was refluxed with stirring at HHV = 49.43−[0.041 (SV ) + 0.015 (IV )]
600 rpm for a specific reaction time. After the reaction was over, the
Each property was measured in triplicate and the results were pre-
reaction products were transferred to a separating funnel and left
sented as the mean ± standard deviation (SD).
overnight to obtain two distinct phases. The lower layer (glycerin) was
separated and discarded, while the upper layer (methyl esters) was
3. Results and discussion
distilled under vacuum using a rotary evaporator to recover excess al-
cohol, followed by washing with distilled water to remove impurities,
3.1. Properties and analysis of the oils
such as residual methanol, soaps, catalyst and glycerin. Finally, the
methyl esters were dried over anhydrous sodium sulfate to dispose of
The oil contents of the castor seed and Cyprinus Carpio fish waste
any traces of leftover water [2,9]. Column chromatography method
were found to be 51.72 and 76.0% w/w, respectively, which are much
which was suggested by Bindhu et al. [29] was utilized to determine the
higher than those documented from other vegetable seeds [9,10] and
ester content on the purified biodiesel. The BD yield was calculated as
fish waste [34]. As a result, the CSO and WFO are promising feedstocks
follow [6]:
for BD production. As shown in Table 1, the density, the kinematic
Weight of the purified BD× FAME content (%) viscosity, the flash point, the acid value and the refractive index of the
BD yield (%) = × 100
Total weight of mixed oils used (g) CSO have been significantly reduced with increasing the WFO content
in the prepared blends. This finding is ascribed to the lower density,
kinematic viscosity, flash point, acid value and the refractive index of
2.5. Analysis and properties evaluation of biodiesel WFO in comparison to the CSO.
It can be seen from Table 1 that the fatty acid composition of the
A Varian (Palo Alto, CA, USA) V NMR spectrometer operating at raw oils has been markedly altered after blending. The ricinoleic acid
400 MHz proton Nuclear Magnetic Resonance spectrophotometer content of the CSO has reduced from 78.03% to 6.76% after blending
(1HNMR) was used to calculate the conversion (%) of the said blend to with WFO. On the other hand, contents of palmitic and stearic acids of
BD. Samples (approximately 150 µL) were diluted in 500 µL of deut- WFO have also changed after blending with the CSO. These achieve-
erated chloroform (CDCl3). ments could be ascribed to a possible chemical reaction between hy-
Properties of the produced fatty acid methyl esters including density droxyl groups of the ricinloeic acid and the free fatty acids of WFO and/

Table 1
Properties and fatty acids profile of CSO, WFO and mixed CSO + WFO.

Property CSO WFO Blend 90 + 10 Blend 80 + 20 Blend 70 + 30 Blend 60 + 40 Blend 50 + 50

Density @ 15.5 g/mL 0.9983 0.9190 0.9693 0.9640 0.9583 0.9558 0.9514
Kinematic Viscosity@ 40 °C mm2/s 205.11 23.20 109.48 91.87 68.68 57.49 39.88
Flash Point °C 244 220 208 211 213 215 217
Acid Value mg KOH/g oil 0.80 0.70 0.65 0.61 0.57 0.55 0.51
Refractive index@20 °C 1.4770 1.4685 1.4750 1.4710 1.4620 1.4530 1.4520
Pour Point °C < −10 6 8− 6− 4− 2− 1−

Fatty acids profile of CSO, WFO and mixed CSO + WFO

Fatty acid composition CSO WFO CSO + WFO (50:50% w/w)

C14 – 0.46 0.90


C16 1.88 18.55 16.19
C16:1 – 4.69 6.73
C18 2.48 6.80 5.63
C18:1 6.22 56.56 46.49
C18:2 8.76 8.67 11.62
C18:3 0.64 0.93 1.73
C20 – 0.08 0.11
C20:1 0.65 1.96 2.01
Ricinoleic acid 78.03 – 6.76
Others 1.34 1.30 1.79

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or due to the dilution effect. This could also be the reason behind the methyl esters yield, and that 32 °C was the optimal reaction tempera-
reduction in the values of CSO properties after blending with WFO. ture because it gave highest yield of methyl esters (95.22 wt%).
Nevertheless, obtaining maximum yield of BD at a relatively low re-
3.2. Biodiesel production from an equivalent blend of CSO and WFO action temperature (32 °C) is a very important finding, as far as the cost
of the production is concerned. As shown in Fig. 3, reaction tempera-
As shown in Table 1, the acid value of mixed CSO and WFO is much tures higher than 32 °C favor the side reaction, i.e. part of the esters may
lower than those published for other non-edible oils, such as Silybum converted to soap (saponification reaction) leading to decreases the BD
marianum L. seed oil (13.6–20 mg KOH/g) [7,35] and karanja seed oil yield [10,11,27]. Hence, 32 °C was chosen as an optimal reaction
(6.04 mg KOH/g) [36]. Accordingly, the said blend is a suitable feed- temperature.
stock for BD production through direct base- catalyzed reaction which The influence of reaction duration on the methyl ester yield was
in turn results in lower cost of production due to it does not need to a investigated by conducting the transesterification reaction at various
pre-treatment step, namely an acid esterification process which is a durations (15, 30, 45, 60, 75 and 90 min) as depicted in Fig. 4. In all
necessary step to produce BD from other non-edible oils, such as Si- experiments, other parameters were kept at their optimal values. It was
lybum marianum L. seed oil [7,35] and karanja seed oil [36]. Therefore, observed that the highest methyl ester yield (95.20 wt%) was obtained
parameters affecting the transesterification process, such as the catalyst at a duration of 30 min. However, durations greater than 30 min re-
type and concentration, methanol to oil molar ratio, reaction tem- sulted in lower methyl ester yield, due to the hydrolysis of some the
perature, reaction time, and rate of stirring were thoroughly in- formed methyl esters, resulting in lower yield of the methyl esters
vestigated. [28,35]. As a result, the optimal reaction duration was set as 30 min.
Fig. 1 displays effect of the catalyst type and concentration on the Transesterification process is induced by the stirring rate due to the
BD yield. On this account, transesterification of the said blend different intact area between the oil and the catalyst solution, and the reaction
was conducted using various alkali catalysts (KOH, NaOH and CH3ONa) become faster as the mixing increases [37,38]. Therefore, stirring speed
with different concentrations (0.25–1.25% w/w of oil), while other was varied from 300 rpm to 900 rpm at intervals of 100 rpm, while
parameters were kept constant at 6:1methanol: oil molar ratio, 32 °C other parameters were kept at their optimal values. It was observed that
reaction temperature, 600 rpm agitation rate and 30 min reaction time. phase change had occurred at different rate of stirring. At lower rate of
It was noticed that the lower concentrations of the alkali catalysts stirring (300 rpm), a little phase changes formation was observed and
(0.25 wt%) led to an incomplete reaction and thus gave a lower BD the yield of the methyl esters was at lowest level (85.44% w/w) as
yield. The BD yield increased and reached maximum at 0.50 wt% using shown in Fig. 5. Whereas, the increase in the rate of stirring the phase
any of the tested catalysts. It was also found that KOH was the best change formation was more clear, and the yield of BD increased to
alkali catalyst due to it produced maximum yield of BD (92.45% w/w) maximum (95.20%) at a stirring rate of 600 rpm. These findings were
in comparison to other catalysts, which is in accordance with many attributed to the facts that increases the rate of stirring promotes
literatures published elsewhere [10,11,35]. The variation in the yield, homogeneity of the reactants and, hence, resulting in higher conver-
among different alkali catalysts, may be attributed to their variation in sion. Nevertheless, at high rate of stirring more than 600 rpm, the BD
the strength of alkalinity. Nevertheless, increasing KOH concentration yield decreased as a result of the hydrolysis of some of BD causing soap
more than 0.50 wt% decreased the BD yield due to the saponification formation. These findings were also reported by other authors [37,38].
reaction and resulting in low yield of BD [27,35]. Therefore, KOH at a
concentration of 0.50% w/w of oil was chosen as a type of catalyst and
the optimal concentration, respectively. 3.3. Comparison of results with other published studies
Transesterification reaction is greatly influenced by alcohol to oil
molar ratio. Accordingly, number of experiments were carried out using In order to assess the above results, transesterification results of
different methanol to oil blends molar ratio in the range of 3:1–10:1 as mixed CSO and WFO with methanol were compared with those of other
shown in Fig. 2 with keeping the other factors fixed at 0.50 wt% KOH, studies as listed in Table 2. In the present study, 0.50 KOH wt% was the
32 °C reaction temperature, a reaction time of 30 min and 600 rpm. The best concentration due to it resulted in maximum yield of BD from the
results indicate that maximum yield of BD (95.20% w/w) was obtained said blend. Transesterification reaction of S. marianum oil [29] and
at 8:1 methanol to oil molar ratio. As can be seen from Fig. 2, any camelina sativa oil [39,40] with methanol needed higher KOH con-
further increase in methanol to oil molar ratio reduced the BD due to centration to yield the maximum conversion. However, amount of KOH
the fact that solubility of glycerin in the methyl esters phase increases required for maximum conversion of the said blend to BD was lower
with increasing molar ratio of methanol, which in turn makes separa- than those of other studies. Regarding effect of methanol to oil mole
tion of glycerin from the methyl esters harder. Moreover, higher me- ratio, the present study showed that the highest yield of BD from mixed
thanol to oil molar ratio may cause the equilibrium reaction to proceed CO and WFO was achieved at 8:1 methanol to oil molar ratio which is
backward and recombine with the methyl esters to form mono-glycer- comparable to those published for S. marianum oil [29] and camelina oil
ides, leading to decrease in the yield of BD [10,28,35]. Therefore, 8:1
95
was established as the optimal methanol to oil molar ratio.
93
The reaction temperature plays a vital role on the transesterification
91
Yield of FAME, wt.%

reaction rate, yield conversion, and the cost of BD production.


Therefore, it is necessary to optimize the reaction temperature to obtain 89
maximum yield with less energy consumption. It was reported that 87
selecting the optimal reaction temperature for transesterification de- 85
pends on the chemical composition of the raw oil feedstock, and the 83 KOH
type of utilized alcohol [2]. Therefore, different experiments were ac- 81
CH3ONa
complished by conducting transesterification of the said blend at dif- 79
ferent temperatures (25, 32, 45, 55, 60, 65 and 70 °C) whilst other 77 NaOH
variables were fixed at 0.50% KOH w/w of oil, 8:1 methanol to oils
75
blend molar ratio, 30 min reaction time and 600 rpm rate of stirring. It 0.25 0.45 0.65 0.85 1.05 1.25 1.45
was observed that transesterification of the mixture with methanol at alkali catalyst concentration, wt.%
room temperature resulted in good yield of the methyl esters (88.68 wt
Fig. 1. Effect of catalyst type and concentration on methyl esters yield.
%). However, further increase in the reaction temperature increased the

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A.B. Fadhil et al. Fuel 210 (2017) 721–728

100 production cost of BD from the said blend will be less, due to maximum
BD yield was obtained at milder reaction conditions compared with
Yield of FAME, wt.%

95
other alternative processes and feedstocks. Nevertheless, the variation
90 in the required optimal conditions to produce maximum yield of BD
among various raw oils could be attributed to many factors, such as the
85
acid values of raw oils utilized in the production of BD, the reactivity of
80 the utilized base catalyst and mode of heating (conventional, micro-
wave, or sonication) employed during the transesterification process.
75
3.4. Fuel properties evaluation
70
3 4 5 6 7 8 9 10 11
Methanol:oil molar ratio Fuel properties of BD obtained from mixed CSO and WFO are
summarized in Table 3 together with the standards specified in the
Fig. 2. Effect of methanol:oil molar ratio on methyl esters yield. ASTM D6751 as well as the published values of several biodiesels in
literature [44,46]. For comparison, biodiesels from CSO and WFO were
96 individually prepared using the optimal conditions obtained for that
94 produced from the said blend, and their properties were also measured
Yield of FAME, wt.%

and included in Table 3. The ASTM standards have not specified the
92
fatty acid methyl esters content of BD. However, the EN 14214 stan-
90 dards included the ester content of BD. Thus, following the EN 14214
88
standards, the resulting BD has a fatty acid methyl esters content of
(97.66% w/w) which is higher than the specified limit in EN 14214
86 standards (96.50% w/w). The breakup of the fuel injected into the
84 cylinder is affected by the fuel's density. In addition, as the fuel's density
increases, more fuel is injected by mass. Besides, the engine fuel in-
82
25 35 45 55 65 75 jection system is greatly affected by the density and compressibility.
Reaaction temperature, °C Amount of injected fuel, injection timing and injection spray pattern are
directly affected by these parameters [46]. The density of BD produced
Fig. 3. Effect of reaction temperature on methyl esters yield. from the said blend was much lower than that obtained from CSO.
Besides, the density value was also close to those observed for other
96 biodiesels in literature [44,46]. One of the crucial features of the fuel in
an engine is the viscosity of the fuel, due to it plays a significant role in
Yield of FAME, wt.%

94
the fuel spray, mixture formation and combustion process. Further-
92
more, the high viscosity of the fuel impedes the injection process and
90 results in an inadequate fuel atomization [46]. As shown in Table 3, the
88 kinematic viscosity of the BD prepared from mixed CSO and WFO was
lower than that produced from the CSO by around 64.67%. Moreover,
86
the viscosity of the resulting fuel was comparable to those documented
84 for other biodiesels [44,46]. According to ASTM and EN standards, the
82 standard amount of viscosity for BD is 1.9–6 mm2/s and 3.5–5 mm2/s,
15 25 35 45 55 65 75 85 95 respectively. As a result, BD prepared from the said blend has a better
Reaction Time, minutes injection and atomization when compared to BD prepared from CSO.
The reduction in the acid value of the said blend after transesterifica-
Fig. 4. Effect of reaction time on methyl esters yield.
tion process was by around 88.23%. Besides, the acid value of the re-
sulting biofuel is much lower than that published for biodiesel from
96
cotton seed oil [44]. The quality of BD is affected by its cold flow
94 properties. The poor cold flow ability of BD is associated with a delay
Yield of FAME, wt.%

start-up and low-temperature operability problems under cold weather


92 conditions which could mainly be happened as a result of crystals for-
mation of and solid precipitates at low temperatures. The pour point is
90
one of the important variables that is typically used evaluate the cold
88 flow properties of BD [47]. It is well known that biodiesels from animal
fats have higher pour point than vegetable oils biodiesels, due to the
86 latter have higher unsaturated fatty acids level than the former. How-
ever, BD produced from the said blend has a pour point value of
84
300 400 500 600 700 800 900 1000 −2.0 °C. Such a value could be a good indicator that the BD is suitable
Rate of stirring, rpm for use in some cold weathers such as those prevailing in north Iraq in
winter. Besides, the pour point of the prepared BD was much lower than
Fig. 5. Effect of rate of stirring on methyl esters yield.
those reported for biodiesels from cotton seed oil [44] and palm oil
[46]. The saponification values refers to the presence of short chains in
[39], but much lower than those reported for Sterculia foetida oil [41], alkyl groups in fatty acids present in BD [45,47]. The saponification
WCO [3,42] and the esterified WCO [43]. value of the resulting BD was lower than those measured for biodiesels
A reaction temperature of 32 °C and a duration of 30 min were the from CSO and WFO individually. This finding indicates that BD from
optimal reaction temperature and time, respectively for methanolysis of mixed oils has higher molecular weight and higher length chains of
said blend, which are much lower than those reported in Table 2 for hydrocarbon in alkyl groups of the fatty acids present in BD than bio-
many other vegetable oils. In addition, such achievement means that diesels from the parent oils. The iodine value is used as a measure of the

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A.B. Fadhil et al. Fuel 210 (2017) 721–728

Table 2
Comparison of transesterification result of mixed CSO + WFO with those of other oils.

Feedstock Catalyst% w/w Methanol/oil molar ratio Temperature, (°C) Time (minutes) BD yield, (wt%) Ref.

Mixed CSO + WFO 0.50 KOH 8:1 32 30 95.20 This study


WCO 1.0 NaOH 12:1 60 120 95.0 [3]
R. stricta oil 1.0 NaOH 6:1 60 120 97.20 [11]
S. marianum oil 1.50 KOH 8:1 60 20 95.75 [35]
Camelina sativa oil 1.25 KOH 8:1 40 40 96 [39]
Camelina oil 1.0 KOH 8:1 50 70 95.80 [40]
Sterculia foetida oil 1.0 NaOH 12:1 55 150 93.55 [41]
WCO 1.0 KOH 9.5:1 50 20–40 98.0 [42]
Esterified WCO 1.0 KOH 9.1:1 55 60 90.56 [43]
Cottonseed oil 0.75 CH3ONa 6:1 65 90 96.90 [44]
Okra seed oil 1.0 CH3ONa 7:1 65 120 96.80 [45]

Table 3
Properties of biodiesel produced from mixed CSO + WFO.

Property ASTM EN1 4214 BD from CSO BD from WFO BD from mixed CSO + WFO BD from cotton seed BD from Palm
D6751 oil1 oil2

Yield, wt% – – 93.55 ± 2.0 94.66 ± 1.5 95.20 ± 2.5 96.9 –


Ester Content, wt% – 96.50 91.98 ± 2.0 96.65 97.66 ± 1.5 – –
Density at 15.5 °C 0.9000 0.860–0.900 0.9474 ± 0.0021 0.8788 ± 0.0012 0.8989 ± 0.0001 0.8750 0.8800
Kinematic Viscosity at 40 °C 5.0 3.50–5.0 10.22 ± 0.11 3.45 ± 0.05 3.61 ± 0.03 4.07 5.70
Flash Point, °C 130 120 1.0 ± 158 96 ± 1.0 84 ± 1.0 150 164
Acid Value, mg KOH/g oil 0.50 0.50 0.08 ± 0.001 0.10 ± 0.001 0.06 ± 0.002 0.16 –
Cloud Point, °C – – −3.0 ± 0.50 3.0 ± 0.50 5.0 ± 0.50 7.0 13
Pour Point, °C – – < −10 −1.0 ± 0.50 −2.0 ± 0.50 6.0 –
Refractive Index at 20 °C – – 1.4770 ± 0.0012 1.4444 ± 0.0002 1.4510 ± 0.0002 – –
Saponification value, mg KOH/ – – 186.68 ± 1.50 182.62 ± 1.0 175.24 ± 1.0 – 201.0
g
Iodine value, g I2/100 mg – 120 93.33 ± 1.50 91.55 ± 2.0 91.0 ± 2.0 – 57.0
Cetane Number 47 min 51 min 54.53 55.59 56.97 – 60.0
HHV – – 40.39 40.57 40.88 – 40.33
Total glycerol, wt% 0.24 0.25 0.06 ± 0.02 0.80 ± 0.02 0.01 ± 0.01 0.229 –
Free glycerol, wt% 0.02 0.02 0.0035 ± 0.003 0.0040 ± 0.001 0.0023 ± 0.002 0.015 –
Soap, ppm 5.0 5.0 0.44 ± 0.03 0.87 ± 0.02 0.30 ± 0.01 – –

1
From Ref. [44].
2
From Ref. [46].

Fig. 6. 1H NMR spectra of BD obtained from mixed CSO and WFO.

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A.B. Fadhil et al. Fuel 210 (2017) 721–728

degree of unsaturation of BD. It was reported that the presence of un- considered a successful mean to alter the fuel properties of oil into a
saturated fatty acids in BD is required to certain extent so as to avoid more valuable fuel.
the fuel solidification [46]. It can be seen from Table 3 that the iodine
values of the biodiesels produced from the parent oils as well as their
equivalent mixture were nearly the same. The iodine value of (91 g I2/ 3.6. Cost analysis
100 mg) for BD from the said blend indicates that it is highly resistant
to oxidization. The temperature at which the fuel will start to a flame Iraq is one of the fish producers worldwide due to the presence of
when it comes in contact with fire is called the flash point is. It is an huge water patch represented by Tigris and Euphrates rivers, Hawizah
important feature for a fuel from the safety point of view during storage marsh as well as the presence of lakes and seasonal floods (with a
and forwarding. It also relates to the fuels volatility which is an im- flooded area of 15,000–20,000 km2). The fish wealth in Iraq represents
portant fuel feature for an engine’s starting and warming [46]. It was an important resource of food security. Grypus Barbus, Barbus luteus
found that BD prepared from mixed CSO and WFO has a very low flash Heckel, Hypophthalmicthyes molotrix and Silurus triostegus Heckel are the
point compared to BD prepared from the CSO individually, which could main types that can be fishing in these rivers and marshes [2,51].
be attributed to the presence of WFO in the oil blend. It can be seen Moreover, fish breeding ponds are another source for fish production.
from Table 3 that the flash point of BD prepared from the WFO was These ponds are distributed south, middle and north of the country.
much lower than that measure for BD from CSO, but closer to that Such a huge production of fish produces massive amounts of wastes
measured for BD prepared from the said blend. This variation could be which are either disposed as waste or may be used as a manure. Due to
ascribed to the varied chemical composition of the raw oils. The diesel the huge consumption of Cyprinus Carpio fish which its waste was used
fuel quality, especially for the combustion quality can be measured in as a source of oil in the present investigation, Salahaldeen Governorate
term of the cetane number which also measures readiness of the fuel to alone contains more than 500 fish breeding ponds, each has an area of
auto-combustion when it is injected into the engine. The structure of 2.5 acres, and each acre produces an average of four tons of fish an-
fatty acids in BD affects its combustion quality [46,47]. The cetane nually (average weight of mature fish is 2 kg). As a result, the average
number of the fuels was calculated following Krisnangkura’s method amounts of production for this fish reached nearly 10,000 tons an-
which is included in the standard range of EN and ASTM. The cetane nually. It was calculated that 25% of that fish is proposed as a waste,
number of the fuels ranged from 54.53-56.97. Besides, the cetane which means that 2500 tons of waste are produced, and the oil content
number of the biodiesels were lower than that published for BD from of this fish waste was found to be ∼76.0% w/w. In consequence, 1900
palm oil [46] due to the fact that BD from palm oil has higher saturated tons of fish oil can be recovered from Cyprinus Carpio fish waste [2].
fatty acid content which its presence with high level in an oil will raise However, the overall cost of BD production from Cyprinus Carpio fish
its cetane index. The contents of total glycerin, free glycerin, and soaps was estimated to be (0.65 $/L) taking in the consideration the cost of
of BD produced from the said blend conformed to ASTM D 6751 and EN the feedstock, used chemicals (methanol, KOH, drying agent, power,
14214 standards. These findings assure the high purity level of the etc.) and energy requirements [2], which is lower than the production
produced fuels. cost of BD from salmon fish oil which was stated to be (1.116 $/L) [52].
This variation in the price may attributed to the two-step process of BD
3.5. Analysis of biodiesel from mixed CSO and WFO production from salmon oil which needed about double the price of
chemicals and other requirements. As regard the production cost of BD
1 from CSO, it was estimated that production of 1 kg of BD from CO in
H NMR spectroscopy was utilized by many researchers for mon-
itoring transesterification reaction as well as to determine the conver- Brazil amounts 0.92 $ without glycerin purification [53], which higher
sion of an oil to its fatty acid alkyl esters [48–50]. Hence, the obtained than the production cost of BD from Cyprinus Carpio fish. Consequently,
methyl esters were analyzed using 1HNMR spectroscopy to assure the blending of CSO with WFO will reduce the production cost of BD from
conversion of the mixed CSO and WFO to its fatty acid methyl esters. As CSO individually.
shown in Fig. 6, many peaks which relate to the aliphatic hydrogens
(3.3–0.4 ppm), methoxy group (3.6 ppm) and the region of olefin hy-
drogens (near 5.3 ppm) were observed in the resulting BD. However, 4. Conclusion
the presence of a singlet near (3.60 ppm) relates to the methoxy group
and a characteristic intense peak at (2.24 ppm) which relates to the α- Fatty acid methyl esters (biodiesel) were successfully prepared from
carbonyl methylene groups confirmed the presence of methyl esters in mixed non-edible oils, CSO and WFO. The oils blend was transesterified
the BD sample. As 1H NMR can also be used to quantify the conversion with methanol in the presence of an alkali catalyst, and the results re-
of vegetable oil in methyl esters by transesterification reaction; the vealed that 50/50 w/w CSO:WFO was the acquired mixture. Base-cat-
relevant signals chosen for integration were those of methoxy group in alyzed transesterification of the mixture with methanol was optimized,
the methyl esters at 3.60 ppm and of the -carbonyl methylene groups and the highest yield (95.20 wt% and a purity of 97.66% w/w) was
protons at 2.24 ppm. The equation that was used to quantify the yield produced using 0.50% KOH w/w, 8:1 methanol to oils blend molar
of transesterification is: ratio, 32 °C reaction temperature, 30 min of reaction, and 600 rpm rate
of stirring. The 1H NMR spectroscopy confirmed the conversion of the
2AMe
Conversion (%) = × 100 blend to their fatty acid methyl esters with a conversion of 97.74%. The
3ACH2
measured properties of the biodiesel were conformed to ASTM D 6751
where, standards indicating suitability of the obtained fuel for diesel engines. It
was concluded that using mixed oils system reduces the required re-
AMe = integration value of the methoxy protons of the methyl es- action temperature to give maximum conversion, which in turns re-
ters. duces cost of the production of biodiesel.
ACH2 = integration value of α-carbonyl methylene protons.

The percentage conversion of triglycerides to corresponding methyl Acknowledgment


esters by above equation was found to be 97.74%% which is quite in
good agreement with the practically observed yield of 95.20 ± 2.5%. The authors would like to express their thanks to Tikrit University,
This finding demonstrate the merits of transesterification process to College of Science, Chemistry Department for supporting this research
convert triglycerides into its corresponding methyl esters, and may work.

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A.B. Fadhil et al. Fuel 210 (2017) 721–728

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