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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
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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.
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−
723
A.B. Fadhil et al. Fuel 210 (2017) 721–728
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.%
724
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.%
725
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.
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
1
From Ref. [44].
2
From Ref. [46].
726
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.
727
A.B. Fadhil et al. Fuel 210 (2017) 721–728
References addition of diesel, safflower oil esters and additives. Ind Crops Prod
2012;36:267–70.
[27] Costa JF, Almeida MF, Alvim-Ferraz MCM, Dias JM. Biodiesel production using oil
[1] Valente OS, Pasa VMD, Belchior CRP, Sodre JR. Physical–chemical properties of from fish canning industry wastes. Energy Convers Manage 2013;74:17–23.
waste cooking oil biodiesel and castor oil biodiesel blends. Fuel 2011;90:1700–2. [28] Fadhil AB, Abdulahad WS. Transesterification of mustard (Brassica nigra) seed oil
[2] Fadhil AB, Al-Tikrity ET, Albadree MA. Transesterification of a novel feedstock, with ethanol: purification of the crude ethyl ester with activated carbon produced
Cyprinuscarpio fish oil: influence of co-solvent and characterization of biodiesel. from de-oiled cake. Energy Convers Manage 2014;77:495–503.
Fuel 2015;162:215–23. [29] Bindhu CH, Reddy JRC, Rao BVSK, Ravinder T, Chakrabarti PP, Karuna MSI, et al.
[3] Abd Rabu R, Janajreh I, Honnery D. Transesterification of waste cooking oil: process Properties and evaluation of biodiesel from Sterculia foetida seed oil. J Am Oil Chem
optimization and conversion rate evaluation. Energy Convers Manage Soc. 2012;89:891–6.
2013;65:764–9. [30] AOAC International 2000 Official Methods of Analysis of AOAC International 17th
[4] Ali LH, Fadhil AB. Biodiesel production from spent frying oil of fish via alkali-cat- edition Gaithersburg, MD: AOAC International.
alyzed transesterification. Energy Sour Part A 2013;35:564–73. [31] Faccini CS. Uso de Adsorventes na Purificaço de Biodiesel de Oleo de Soja [dis-
[5] Boffito DC, Pirola C, Galli F, Di Michele A, Bianchi CL. Free fatty acids esterification sertation]. Porto Alegre (RS): Universidade Federal do Rio Grande do Sul; 2008.
of waste cooking oil and its mixtures with rapeseed oil and diesel. Fuel [32] Pisarello ML, Dall-Csta BO, Veizaaga NS, Querini CA. Volumetric method for free
2013;108:612–9. and total glycerin determination in biodiesel. Ind Eng Chem Res 2010;49:8935–41.
[6] Fadhil AB. Evaluation of apricot (Prunus armeniaca L.) seed kernel as a potential [33] Krisnangkura K. A simple method for estimation of cetane index of vegetable oil
feedstock for the production of liquid bio-fuels and activated carbons. Energy methyl esters. J Am Oil Chem Soc 1986;63:552–3.
Convers Manage 2017;133:307–17. [34] Lin CY, Li RJ. Fuel properties of biodiesel produced from the crude fish oil from the
[7] Fadhil AB, Aziz AM, Altamer MH. Biodiesel production from Silybum marianum L. soapstock of marine fish. Fuel Process Technol 2009;90:130–6.
seed oil with high FFA content using sulfonated carbon catalyst for esterification [35] Fadhil AB, Ahmed KM, Dheyab MM. Silybum marianum L. seed oil a novel feedstock
and base catalyst for transesterification. Energy Convers Manage 2016;108:255–65. for biodiesel production. Arab J Chem 2017;10:S683–90.
[8] Morshed M, Ferdous K, Khan MR, Mazumder MSI, Islam MA, Uddin MT. Rubber [36] Sahoo PK, Das LM. Process optimization for biodiesel production from Jatropha,
seed oil as a potential source for biodiesel production in Bangladesh. Fuel Karanja and Polanga oils. Fuel 2009;88:1588–94.
2011;90:2981–6. [37] Suppalakpanya K, Ratanawilai SB, Tongurai C. Production of ethyl ester from crude
[9] Fadhil AB, Aziz AM, Altamer MH. Potassium acetate supported on activated carbon palm oil by two-step reaction with a microwave system. Fuel 2010;89:2140–4.
for transesterification of new non-edible oil, bitter almond oil. Fuel [38] Kumar D, Kumar G, Singh PCP. Fast, easy ethanolysis of coconut oil for biodiesel
2016;170:130–40. production assisted by ultrasonication. Ultrason Sonochem 2010;17:555–9.
[10] Al-dobouni IA, Fadhil AB, Saeed IK. Optimized alkali-catalyzed transesterification [39] Wu X, Leung DYC. Optimization of biodiesel production from camelina oil using
of wild mustard (Brassica juncea L.) seed oil. 2016;38(15):2319–25. orthogonal experiment. Appl Energy 2011;88:3615–24.
[11] Nehdi IA, Sbihi HM, Al-Resayes SI. Rhazya stricta Decne seed oil as an alternative, [40] Yang J, Caldwell D, Corscadden K, Lib QSHJ. An evaluation of biodiesel production
non-conventional feedstock for biodiesel production. Energy Convers Manage from Camelina sativa grown in Nova Scotia. Ind Crops Prod 2016;81:162–8.
2014;81:400–6. [41] Ong HC, Silitonga AS, Masjuki HH, Mahlia TMI, Chong WT, Boosroh MH.
[12] Fadhil AB, Saeed IK, Saeed LI, Altamer MH. Co-solvent ethanolysis of chicken Production and comparative fuel properties of biodiesel from non-edible oils:
waste: optimization of parameters and characterization of biodiesel. Energy Sour Jatropha curcas, Sterculia foetida and Ceiba pentandra. Energy Convers Manage
Part A 2016;38(19):2883–90. 2013;73:245–55.
[13] Stojkovic IJ, Miladinovic MR, Stamenkovic OS, Bankovic IB, Povrenovic DS, [42] Al-Hamamre Z, Jehad Y. Parametric study of the alkali catalyzed transesterification
Veljkovic VB. Biodiesel production by methanolysis of waste lard from piglet of waste frying oil for Biodiesel production. Energy Convers Manage
roasting over quicklime. Fuel 2016;182:454–66. 2014;79:246–54.
[14] Cunha Jr. AC, Feddern V, De Pra MC, Higarashi MM, Abreu PG, Coldebella A. [43] Charoenchaitrakool M, Thienmethangkoon J. Statistical optimization for biodiesel
Synthesis and characterization of ethylic biodiesel from animal fat wastes. Fuel production from waste frying oil through two-step catalyzed process. Fuel Process
2013;105:228–34. Technol 2011;92:112–8.
[15] Carvalho AKF, Da Rós PCM, Teixeira LF, Andrade GSS, Zanin GM, de Castro HF. [44] Rashid U, Anwar F, Knothe G. Evaluation of biodiesel obtained from cottonseed oil.
Assessing the potential of non-edible oils and residual fat to be used as a feedstock Fuel Process Technol 2009;90:1157–63.
source in the enzymatic ethanolysis reaction. Indus Crops Prod 2013;50:485–93. [45] Anwar F, Rashid U, Ashraf M, Nadeem M. Okra (Hibiscus esculentus) seed oil for
[16] Meller E, Green U, Aizenshtat Z, Sasson Y. Catalytic deoxygenation of castor oil over biodiesel production. Appl Energy 2010;87:779–85.
Pd/C for the production of cost effective biofuel. Fuel 2014;133:89–95. [46] Amania MA, Davoudi MS, Tahvildari K, Nabavia SM, Davoudi MS. Biodiesel pro-
[17] Cesar ADS, Batalha MO. Biodiesel production from castor oil in Brazil: a difficult duction from Phoenix dactylifera as a new feedstock. Ind Crops Prod 2013;43:40–3.
reality. Energy Policy 2010;38:4031–9. [47] Jamil F, Al-Muhtaseb AH, Al-Haj L, Al-Hinai MA, Hellier P, Rashid U. Optimization
[18] Danlami JM, Arsad A, Zaini MAA. Characterization and process optimization of of oil extraction from waste ‘‘Date pits” for biodiesel Production. Energy Convers
castor oil (Ricinus communis L.) extracted by the soxhlet method using polar and Manage 2016;117:264–72.
non-polar solvents. J Taiwan Inst Chem Eng 2015;47:99–104. [48] Silva TA, de Assunco RMN, Vieira AT, de Oliveira MF, Batista ACF. Methylic and
[19] Ogunniyi DS. Castor oil: vital industrial raw material. Bioresour Technol ethylic biodiesels from pequi oil (Caryocar brasiliense Camb.): production and
2006;97:1086–91. thermogravimetric studies. Fuel 2014;136:10–8.
[20] Saez-Bastante J, Pinzi S, Jiménez-Romero FJ, Luque de Castro MD, Priego-Capote F, [49] Alexandre ECF, Silveira EV, de Souza Castro CF, Sales JF, de Oliveira LCS, Viana LH,
Dorado MP. Synthesis of biodiesel from castor oil: silent versus sonicated methy- et al. Synthesis, characterization and study of the thermal behavior of methylic and
lation and energy studies. Energy Convers Manage 2015;96:561–7. ethylic biodiesel produced from tucumã (Astrocaryum huaimi Mart.) seed oil. Fuel
[21] Fadhil AB, Ahmed AI. Production and evaluation of biodiesel from mixed castor oil 2015;161:233–8.
and waste chicken oil. Energy Sour Part A 2016;38(14):2140–7. [50] Ullah K, Ahmad M, Sofia Qureshi FA, Qamar R, Sharma VK, Sultana S, et al.
[22] Dantas MB, Albuquerque AR, Soledade LEB, Queiroz N, Maia AS, Santos IMG, et al. Synthesis and characterization of biodiesel from Aamla oil: a promoting non-edible
Biodiesel from soybean oil, castor oil and their blends. J Therm Anal Calorim oil source for bioenergy industry. Fuel Process Technol 2015;133:173–82.
2011;106:607–11. [51] Fadhil AB, Ali LH. Alkaline-catalyzed transesterification of Silurus Triostegus Heckel
[23] Farias RMC, Conceicao MM, Candeia RA, Silva MCD, Valter J, Fernandes JR, et al. fish oil: optimization of transesterification parameters. Renew Energy
Evaluation of the thermal stability of biodiesel blends of castor oil and passion fruit. 2013;60:481–8.
J Therm Anal Calorim 2011;106:651–5. [52] El-Mashad HM, Zhang R, Roberto J, Avena B. A two-step process for biodiesel
[24] Plentz Meneghetti SM, Meneghetti MR, Serra TM, Barbosa DC, Wolf CR. Biodiesel production from salmon oil. Biosyst Eng 2008;99:220–7.
production from vegetable oil mixtures: cottonseed, soybean, and castor oils. [53] Santana GCS, Martins PF, de Lima da Silva N, Batistella CB, Maciel Filho R, Wolf
Energy Fuels 2007;21:3746–7. Maciel MR. Simulation and cost estimate for biodiesel production using castor oil.
[25] Barbosa DC, Serra TM, Plentz Meneghetti SM, Meneghetti MR. Biodiesel production 2010;8(8):626–32.
by ethanolysis of mixed castor and soybean oils. Fuel 2010;89:3791–4.
[26] Thomas TP, Birney DM, Auld DI. Viscosity reduction of castor oil esters by the
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