TRANSPORTATION BIOFUELS WITH

IMPROVED COLD PROPERTIES BY THERMAL

CRACKING OF WASTE FISH OIL
S.M. Sadrameli and M. Maghami

Process Engineering Department, Faculty of Chemical Engineering, Tarbiat Modares University, Tehran,
Iran.

ABSTRACT: Waste fish oil (WFO) is a byproduct of fishmeal plants processes. There are some
drawbacks in direct use of this oil in industries due to its impurities, high acidity and sanitary problems.
Conversion of this oil by transesterification to biodiesel and thermal cracking process to the liquid
transportation fuel could solve the environment treats which caused by dispose of this oil. It also
introduces a new source of renewable energy. However, thermal cracking of crude vegetable oil has
some drawbacks such as biofuel production yield with high water content, coke formation, and
production of undesired side reactions that produces poisonous gases like acrolein which is very
harmful to the human health. Biodiesel from WFO is also an environmental friendly alternative liquid
transportation fuel that can be used in diesel engines without major modifications but due to its high
cold properties it has a limit of being used only in the moderate and hot climate regions. The scope of
this research work is to produce a transportation liquid fuel with improved cold properties using thermal
cracking of waste fish methyl esters. Analysis of the products results show that the cloud points
decreased from 7 °C to -12 °C and the pour point improved from -2 °C to -24°C for the fuels produced
from methyl esters thermal cracking. It is also shown that the produced fuel has a similar distillation
curve to the refinery diesel which proves that the hydrocarbons contents of both are in the same range.
The results also indicate that increasing the temperature and retention time of the reaction enhances
the yield of the light liquid products. The properties of the produced liquid fuel with improved cold
properties are in agreement with F class diesel in EN590 standard.

Keywords: Waste fish oil, transesterification, cold properties, thermal cracking, and liquid fuel

1. INTRODUCTION

Biofuels are environmental friendly alternative liquid transportation fuels that received a huge
attention worldwide due to the consumption increase and depletion of the fossil fuels and their
environmental impacts. They are processed from biomass-based materials via different chemical routes
as shown in Figure 1. Biodiesel is one of the most common types of biofuels which is produced from
transesterification of triglycerides from vegetable oils and animal fats. Using biodiesel as a neutral
carbon dioxide and zero Sulphur content products instead of petro diesel helps the atmospheric CO2
recycling and does not contribute to the greenhouse effect [1,2,3]. The main feedstock for the
production of biodiesel is crop oil seeds. Food security concern and price of such raw materials usually

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are the main difficulty for the scale up of biodiesel production systems due to the fact that edible oils
such as soybean and canola are the main sources of biodiesel nowadays. By using less expensive
feedstocks for biodiesel production such as waste oils, up to 25% reduction in production cost could be
obtained and it does not interfere to the food security [4,5,6]. According to the economic analysis, the
costs of biodiesels produced from corn oil, waste chicken fat and waste fish oil were 1.62 €, 1.40 € and
1.13 €, respectively [7]. In some studies the mixture of waste oil and vegetable oil has been
recommended to reach the higher methyl ester contents in the final product [8]. However, methyl ester
contents of biodiesel which has been produced using fresh and waste oils such as waste fish oil,
chicken and animal fats has not reached to the ASTM standard limits especially for the cold properties
and therefore more optimization studies need to be performed in this area [9]. Biodiesel produced from
the transesterification of triglycerides also has stability limitations. This problem causes the formation of
heavier compounds that are solids and causes excessive plugging of the fuel inside the fuels system of
the diesel engines
Fish product wastes are one of the main organic sources that can contribute to the environmental
pollution. Waste fish oil (WFO) is a byproduct of fishmeal plant which cannot be used as a food or
industrial raw materials [10-11].

Renewable Sources

Geothermal Biomass Tidal

Wind Solar
Triglycerides
Lignocellulose Triglycerides Amorphous Sugars

Thermal Cracking Transesterification

Bio-Oil Biodiesel

Figure 1. Renewable resources and biofuel production root from biomass

The world production of fishery products was 154 million tones in year 2011 from which 130.8 MT/y
has been used for human food and 40-65% of that converted to waste [12]. Therefore, it is a suitable
source for the biodiesel production due to its lower price in comparison to other feedstock used for such
renewable fuel and sustainable availability. The biodiesel produced from the waste fish oil has also
some advantages over other feedstock such as high cetane number, and more lubricity which makes it
comparable and suitable in comparison to other feedstocks [13]. Table 1 shows the comparison
between the compositions and some physical properties of waste cooking oil and waste fish oil methyl
esters with refinery diesel fuel. The results indicate that the higher carbon number contents in waste fish
oil methyl esters (WFOMEs) cause the viscosity to be the highest between other fuels. The higher
oxygen contents of the two methyl esters also decrease the heating values of the fuel in comparison to
the petro diesel.

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Table1. Elemental contents and some physical properties of waste cooking oil and WFO methyl esters in comparison
with refinery diesel [14, 15]

Properties Waste cooking oil ME WFO methyl Diesel No. 2

esters
Carbon content, wt.% 78.07 80.01 87.17
Hydrogen content, wt.% 12.25 12.75 12.76
Nitrogen content, wt.% 0.05 0.05 0.07
Oxygen content, wt.% 9.63 7.19 0.0
Heating value, MJ/kg 40.1 41.4 46.2
Cetane No. 48.1 50.9 53.2
C20-C22, wt.% 1.99 37.3 -
Specific gravity 0.870 0.860 0.830
Viscosity at 40 oC, Cst 4.7 7.2 3.4

Fast pyrolysis of WFO in a continuous pilot plant reactor at 525 oC has been performed by Wiggers
et al. [16, 17]. The experimental run has been performed under steady state condition with 10 kg of
biomass as a feed at flow rate of 3.2 kg/hr. The cracking products have been distilled in three phases of
gas, liquid and solid. The analysis of the products phases shows 72-73% liquid in which 35% are light
like gasoline and 34% heavy liquids very similar to diesel.
Assessment of liquid bio-oil produced from waste fish fat by catalytic cracking and utilization of the
fuel and some other fuels in a diesel engine of 4.5 kW at 1500 rpm has been tested by Geo Varuvel et
al. and Mrad et al. [18,19]. Their experimental results indicate that higher brake thermal efficiency has
been achieved using neat bio-oil over other tested fuels. Emission gases such as NOx, HC, CO and PM
were also reported to be higher with undistilled bio-oil in comparison with neat bio-oil and PM, CO and
HC emissions decreased for bio-oil over diesel. They finally concluded that bio-oil from catalytic
cracking of waste fish fat can be an acceptable substitution of refinery diesel for diesel engines.
Recently, production of liquid fuels and activated carbon from WFO as one of the non-edible oils has
been performed by Abdelrahman B. Fadhil et al. [20]. The oil has been extracted from the waste fish
meal and tranesterified to biodiesel using methanol and ethanol. The remaining solids from the oil
extraction with particle size of 0.25 mm then were pyrolized in a laboratory fixed bed reactor at 500 oC
and 60 minutes reaction time for the production of bio-oil. The maximum yield of the bio-oil was 57.13%.
The bio-char obtained from the pyrolysis has also been used for the production of activated carbon via
steam activation method.
As mentioned before some of the main drawbacks of using vegetable oils as raw materials for the
production of biofuels via thermal cracking are low yield, production of coke, and some undesired and
toxic materials such as acrolein. In the present study thermal cracking of waste fish oil methyl esters
have been used for the first time as an innovative alternative technique for the production of a
transportation liquid fuel similar to the refinery diesel with improved cold properties. Waste fish oil has
been converted to methyl esters in two steps process (esterification/transesterification). At first
esterification process has been applied to remove the oil free fatty acids (FFAs). The esterified oil has
then been used for the biodiesel production using design of experiments with 33 full factorial methods.
Effects of temperature, methanol to oil molar ratio, MR and catalyst concentration including their
interactions have been studied. The waste fish oil methyl esters (WFOMEs) finally has been cracked
thermally in a fixed bed continuous reactor and the products have been purified and analyzed for the
final use applications.

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2. MATERIALS AND METHODS

2.1 Materials

The list of materials used in the experimental part except WFO which has been purchased from one
of the fishmeal plants in Semnan, Iran is shown in Table 2. The fatty acid compositions of the WFO
were analyzed using a gas chromatography (GC) analyzer (Claus 580 GC model, Perkin Elmer Co.,
USA). The inert temperature of GC was 250 oC and helium gas (purity 99.99%) with 1 ml/min flow used
as a mobile phase. The GC results are shown in Fig. 2.

Table 2. Materials used in the thermal cracking of WFO methyl esters

Material Chemical Formula Brand Name

Ethanol C2H5OH (99.5 wt.%) Merck
Sulfuric acid H2SO4 (98 wt.%) Merck
Potassium KOH (84 wt.%) Merck
hydroxide CH3OH (99.5 wt.%) Merck
Methanol KI (99.9 wt.%) Merck
Sodium Na2S2O7 (99.5 Merck
thiusulphate wt.%) Dr. Mojalali Co.,
Dichloromethane (CH2OH)2CHOH Iran Merck
Glycerin C3H7OH (99.9 wt.%) Merck
Propanol (99.5 wt.%) Dr. Mojalali Co.,
Starch CH3COOH (99.9 Iran
Acetic acid wt.%)

Figure 2. Gas Chromatography results for the WFO

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2.2 WFO properties

WFO physico-chemical properties such as acidity, FFA content, water content, density, viscosity,
and fatty acid compositions have been measured. For measuring the acidity and free fatty acid contents
of WFO 1gr of the oil solved in 10 ml isopropanol and then titrated by KOH 0.1M (5.61 mgKOH in 1 ml
ethanol) in the presence of phenolphthalein as indicator. Acidity was mg KOH which has been used for
titration of 1 gr oil and FFA content has been calculated 5.07% according to equation 1.

Where V is KOH solution volume (lit), C is solution molarity (0.1 mole/lit), M is WFO molecular weight
(gr/mole) and m is WFO weight (gr). The physical properties and chemical compositions of WFO are
listed in Table 3. Measured FFA content of 5.07% was not suitable for alkali catalyzed
transesterification because of the soap formation and FFA removal is essential [11, 14]. For maximizing
FFA removal of WFO, esterification has been done during 1hr, in the presence of 1% acid sulfuric
catalyst and methanol to oil molar ratio of 9 and 60°C. The amount of FFA content of oil has been
reduced from 5.07% to 0.3% after esterification reaction.

Table 3. Physical properties and chemical compositions of WFO

Property Unit Compositions wt.%

Acidity mg KOH/g Oil 10.5 C14:0 2.07
FFA content % 5.07 C15:0 4.04
Water content % wt./wt. 0.05 C16:0 22.7
Density g/cm3 0.88 C16:1 6.37
Viscosity cP 40.5 C18:0 6.48
oC
Flash point 173 C18:1 3.31
Color - Dark brown C18:2 32.3
C18:3 5.7
C20:1 1.24
C22:0 1.95
C22:5 0.52
C22:6 0.69
Ricinoloic 5.63

2.3 Biodiesel production

For the biodiesel production two steps (esterification/transesterification) process was applied.
Because of the high FFA content of the oil and for avoiding the soap formation during the base catalyst
transesterification, at the first step free fatty acids have been removed by acid esterification during 1hr
reaction. Esterified oil then was used in the transesterification reaction. During the experiments the
magnetic stirring speed was fixed at 700 rpm and all of the experimental runs have been performed in
one hour reaction time. For avoiding methanol evaporation during the experiments, maximum
temperature in all runs has been set to 60 °C.
The production steps are as follows:
- Due to the high contents of FFA in WFO esterification of the oil has been performed using
H2SO4 catalyst
- 100 g of the esterified oil has been preheated to the reaction temperature
- Dissolve KOH in methanol (99.5%)
- Preheating of methanol and catalyst to the reaction temperature and adding to the preheated oil

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 - Mixing the materials at 700 rpm in one hour
Experimental design has been performed according to 33 full factorial design procedures which are
shown in Table 4. Design Expert software (Stat-Ease Inc., USA) applied for the experimental design
analysis and modeling. Yield of the reaction and experimental parameters relationship have been
measured and explained by the third order polynomial model. After each experiment glycerin and
biodiesel have been separated and biodiesel phase has been washed by acidified water and distillated
water for removing methanol, glycerin and catalyst from the biodiesel phase. Wet biodiesel has been
dried at 105°C in an oven for 1hr to remove the remaining moisture content. Dried biodiesel sample
then analyzed by GC for the methyl ester content. For the yield estimation after each reaction, FAMEs
content of product was measured. The reaction yield is defined as a ratio of the methyl ester amounts
(gr) to the crude WFO (gr) in each experiment.

Table 4. Experimental design range of parameters, conditions and biodiesel yield

Run A: Catalyst, wt./wt.% B: Temp., °C C: MR FAME, % Yield, %

1 0.5 40 3 67 56.62
2 1 40 3 75 66.75
3 1.5 40 3 74 63.64
4 0.5 50 3 77 66.22
5 1 50 3 79 69.13
6 1.5 50 3 81 61.97
7 0.5 60 3 77 67.76
8 1 60 3 82 71.34
9 1.5 60 3 80 65.20
10 0.5 40 6 70 62.65
11 1 40 6 82 73.80
12 1.5 40 6 80 68.96
13 0.5 50 6 78 69.42
14 1 50 6 84 76.86
15 1.5 50 6 82 65.60
16 0.5 60 6 82 72.98
17 1 60 6 88 79.20
18 1.5 60 6 85 64.60
19 0.5 40 9 73 64.97
20 1 40 9 89 78.00
21 1.5 40 9 76 63.08
22 0.5 50 9 78 66.30
23 1 50 9 84 69.72
24 1.5 50 9 77 60.83
25 0.5 60 9 75 63.75
26 1 60 9 85 70.55
27 1.5 60 9 75 54.75

2.4 Thermal Cracking of methyl esters

The cold flow properties, and chemical stability of the methyl esters produced from transesterification
of WFO are the two limitations of the fuel that decreases its applications and recognition in the
marketplace. A relatively high freezing temperature of biodiesel commonly and routinely experienced in
many countries during the cold season.
There are some techniques to improve the cold flow properties of biodiesel such as winterization
[21], adding suitable additives [22] and changing the molecular structure of the methyl esters but there

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are some drawbacks in the above techniques for the improvements of cold flow properties of the fuel.
One of the most common methods for such improvement is chemical formula modification using thermal
and catalytic cracking of methyl esters in which the molecules of the methyl esters are converted the
lower chain hydrocarbons such as alkanes, alkenes and aromatics. The biodiesel produced by
transesterification also does not have the standard purity which is 96%. This problem is very common
for the waste cooking oil [23]. To overcome this problem WFO is mixed with other vegetable oils such
as palm or frying oils [24].

2.4.1 Experimental setup

The experimental setup for the thermal cracking process is composed of a fixed bed continuous
reactor electrically heated in a fully controlled furnace with dimensions of 450 mm diameter and 550 mm
length manufactured by ATRA (an Iranian furnace manufacturer located in Tehran) and a condenser
using cold water at 10 oC for separating the non-condensable gases from the liquid products as shown
in Fig. 3. The reactor which is fixed inside the electric heater is made of quartz with 20 mm diameter
and 660 mm length from which 450 mm is the effective heated length and has a uniform temperature as
shown in Fig. 4. The outlet gas temperature is measured by a thermocouple and controlled by the
controller. The condensates from the condenser are collected in a jar and the remaining non-
condensable gases are sent to the flare.
A flow of nitrogen is passed through the reactor before the experiment to exit air and oxygen trapped
in the system. The methyl esters then are pumped to the reactor passes through the heated area
(vaporization zone) in which its temperature is controlled by a controller system. All the gaseous
products are passed through the cracking zone and exit to a condenser with 10 oC and the liquid
products are collected in a jar with non-condensable gases which are sent to the flare. Decoking
process is done after each experiment using hot air at 550 oC and the reactor will be cleaned for the
new run.
Thermal cracking products are analyzed offline by a GC model Varian CP-3800. The used column
was Varian capillary column VF-5 MS with 30 m length and 0.25 mm diameter. The injection
temperature was 250 oC with Helium gas of 99.99% at 10 ml/min rate. The properties of produced liquid
fuel such as density, viscosity, flash point, cold properties, distillation curve, and cetane number have
been measured using the standard method as reported by ASTM standards.

2.4.2 Design of experiments for thermal cracking

The main parameters affect the yield of products in the thermal cracking of vegetable oils and their
methyl esters are temperature and residence time as reported by the first author in his previous
research on vegetable oils and their methyl esters thermal cracking at UND [24]. The design of
experiment has been done using Design Expert software. The range of parameters were selected from
the preliminary experimental results as temperature of 425-525 oC and flow rate of 10-30 g/hr to
maintain the required residence time. The experimental design parameters and their ranges are listed in
Table 5. The liquid products has been distilled and three different cuts have been collected at different
boiling point namely; below 150 oC, 150-350 oC and above 350 oC.

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 Figure 3. Experimental setup of WFO methyl esters thermal cracking

Liquid Feed

660
50 mm Vaporization
Quart Zone
z
Glass
40 Tube
,
Ø20
mm
30 Cracking
L ( cm )

Zone

20

10

Product exit
0 Zone
100
200
300
400
500
0

T ( ºC )

Vapor
Products

Figure 4. Reactor temperature distribution profile and length of the effective zone

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Table 5. Experimental design parameters with full factorial and the yields

Temperature, Flow Yield 1 Yield 2 Average

o
C rate, 0-150 oC 150-350 oC Yield, wt.%
g/hr
425 10 95.00 92.00 93.50
450 10 92.00 92.50 92.25
475 10 89.80 88.00 88.90
500 10 73.33 71.11 72.22
525 10 64.00 68.00 66.00
425 20 92.46 90.84 91.65
450 20 91.60 89.81 90.71
475 20 86.36 87.00 86.68
500 20 87.67 78.69 78.68
525 20 68.53 66.50 67.52
425 30 97.02 95.00 96.01
450 30 89.17 91.80 90.49
475 30 85.71 89.23 87.47
500 30 85.96 89.81 87.89
525 30 77.05 78.18 77.61

3. RESULTS AND DISCUSSIONS

3.1 Transesterification of WFO

The transesterification results are shown in Table 4. Effect of catalyst concentration (0.5, 1, and
1.5%), temperature (40, 50 and 60 °C) and methanol to oil molar ratio (MR) (3:1, 6:1 and 9:1) on yield of
biodiesel have been determined. The reaction yield changes from 54.75% to 79.2%. The increase in the
reaction yield was not linear for variables which could be shown the interactions between variables. For
finding the variables interactions ANOVA analysis has been applied. Based on the ANOVA analysis,
quadratic model has been used to explain parameter interactions. The ANOVA table results are given in
Table 6. It observes that the model is highly significant. Coefficient of determination for this model is R2
= 0.9531 and shows good agreement between predicted and experimental values. It could be noted that
the results with p-value < 0.05 are significant. It shows that all parameters affect the transesterification
reaction and their interactions are also important in biodiesel production. Modified cubic polynomial
used for reaction parameter and yield relationship modeling. The model explains that increase in
catalyst concentration has negative effect on the yield of the reaction. It is because of soap formation at
high levels of catalysts. Temperature and MR increase biodiesel yield however there interaction is most
important parameter.

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Table 6. Experimental modeling results and the significance of quadratic modeling parameters for biodiesel
production

Source Sum of df Mean F Value p-value

Squares Square Prob > F
Model 853.0664 12 71.08886 23.68512 < 0.0001 significant
A-catalyst 30.55527 1 30.55527 10.18029 0.0065 significant
B-Temp 21.54615 1 21.54615 7.178665 0.0180 significant
C-MR 20.35042 1 20.35042 6.780275 0.0208 significant
AB 82.0587 1 82.0587 27.34001 0.0001 significant
AC 22.88041 1 22.88041 7.623208 0.0153 significant
BC 97.98368 1 97.98368 32.64583 < 0.0001 significant
A2 424.4807 1 424.4807 141.4269 < 0.0001 significant
B2 0.226852 1 0.226852 0.075582 0.7874 Non-signif
C2 141.9769 1 141.9769 47.30333 < 0.0001 significant
A2C 24.71747 1 24.71747 8.235273 0.0124 significant
AB2 9.589344 1 9.589344 3.194941 0.0955 significant
BC2 14.00007 1 14.00007 4.66449 0.0486 significant
Residual 42.01981 14 3.001415
Cor Total 895.0862 26

F-value of 32 for MR-temperature interaction shows that it is possible to reach higher yields at low
temperatures with increasing alcohol to oil molar ratio. 78% yield (@ 40°C, MR: 9) which is comparable
with maximum yield (79.2 % at 60°C, MR: 6). The reaction temperature is very important due to the side
reactions such as formation of soap at higher temperatures [28].
3.2 Thermal Cracking results

The results reported in the literature from the previous researchers on the thermal cracking of
vegetable oils and their methyl esters [21] show that the main two parameters affect the yield of the
products were reaction temperature and flow rate to the reactor. Therefore these two parameters have
been selected for the analysis in the design of experiment. Table 7 lists the range of parameters used in
the design of experiment and the obtained yields of products at two distillation temperature ranges
called yield 1 and yield 2 and the average yield values. The products have been distilled in two ranges
of boiling temperatures. The main products of distillation with boiling point range of 150-350 oC is the
modified biodiesel with properties very similar to refinery diesel. The physical properties of the modified
biodiesel at different reaction temperature and flow rates are indicated in Table 8. The optimum points
were at reaction temperature of 525 oC with a flow of 20 g/hr to the reactor.

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Table 7 Full factorial results of the DOE analysis for thermal cracking of WFOMEs

Temperature, Flow Yield 1, % Yield 2, % Average

o
C rate, g/hr (B.P.<150 (150<B.P.<35 Yield, %
o
C) 0
425 10 95.00 92.00 93.50
450 10 92.00 92.50 92.25
475 10 88.0 88.0 88.90
500 10 73.33 71.11 72.22
525 10 64.00 68.00 66.00
425 20 92.46 90.84 91.25
450 20 91.60 89.81 90.71
475 20 86.36 87.00 86.68
500 20 78.67 78.69 78.68
525 20 68.53 66.50 67.52
425 30 97.02 95.00 86.01
450 30 89/17 91.80 90.49
475 30 85.71 89.23 87.47
500 30 85.96 89.81 87.89
525 30 77.05 78.18 77.61

Table 8. Physical properties of products from thermal cracking of WFOME (B.P. of 150-350 oC)

Temperature Flow Density, Viscosity, Acidity, Cloud Pour

oC rate, kg/m3 cP mgKOH point, Point, oC
g/hr /g oil oC

425 10 860 5.62 1.45 0 -6

450 10 866 4.20 1.22 -2 -9
475 10 860 4.04 2.00 -2 -9
500 10 860 4.09 2.00 -5 -15
525 10 854 3.68 1.40 -10 -24
425 20 868 5.33 2.10 1 -6
450 20 868 4.23 1.40 -2 -9
475 20 868 3.83 1.60 -3 -9
500 20 860 3.83 1.85 -5 -12
525 20 856 3.89 2.00 -6 -18
425 30 870 5.17 2.44 -1 -6
450 30 872 4.75 1.20 -1 -9
475 30 864 4.20 1.60 -2 -12
500 30 866 4.33 1.70 -5 -15
525 30 860 4.17 2.00 -6 -18

The yields of WFO methyl esters cracking at different temperatures and flow rates are shown in
Fig. 5. As illustrated from the figure at lower flow rates which corresponds to the higher residence time
in the reaction the yields of gas and lower components increases. The inverse effects will be shown at
the higher flowrates. The yield of heavy cut or diesel has been decreased from 73% at 425 oC to 57.5%
at 525 oC as expected. The increase in light products is also clearly shown in the figure. The yields of
light products have been decreased from 11.54% to 4.84% at 500 oC with increasing the flowrate from
10 to 30 g/hr. The yields of heavy cuts (> 350 oC) are also decreased with increasing the temperature
as seen in the figure.

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 Table 9 shows the temperature points of different distillation volume for the methyl ester cracking
products. As indicated in the table at higher cracking temperature light materials have been increased
with lower liquid products. The same trend is shown at higher residence time inside the reactor. The
comparison of the distillation curve between refinery diesel, WFO biodiesel, and cracking products of
WFO methyl esters are illustrated in Fig. 6. As shown from the figure the distillation curve of cracking
products is very similar to the refinery diesel which indicate that the hydrocarbon contents of both fuels
are comparable.

Table 9. The temperature points of different distillation volume for the ME cracking results

Biodiesel 0-150 oC 150-350 oC

Temperature Flow 10% 50% 90% 10% 50% 90%
(oC) (g/hr) (oC) (oC) (oC) (oC) (oC) (oC)
425 10 150 150 150 220 325 350
450 10 60 110 150 180 280 310
475 10 60 100 120 190 300 330
500 10 66 100 150 180 305 330
525 10 60 110 150 180 305 330
425 20 100 140 150 240 330 339
450 20 60 100 150 240 315 340
475 20 53 100 145 240 320 338
500 20 65 100 150 230 320 338
525 20 65 100 145 230 310 338
425 30 61 69 140 240 334 339
450 30 65 110 150 240 325 341
475 30 60 100 150 240 320 340
500 30 65 100 150 240 330 338
525 30 65 105 150 230 310 338

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 Figure 5. Product yields for different cuts from thermal cracking WFO methyl esters

Figure 6. Distillation curves for the refinery diesel, WFO methyl esters, and cracking products of WFO and its
methyl esters

CONCLUSIONS

The following conclusions can be drawn from this part of the research work:
- The analysis of WFO shows that there are more than 30 fatty acids in the structure of
triglyceride from which more than 50% are unsaturated fatty acids. The oil also contains 5.07% FFA that
affects the yield of biodiesel production and has to be esterified by acidic catalyst. The product of the
esterification reaction at optimum conditions of 60 oC and alcohol to oil ration of 9 has only 0.3% FFA.
- The product of esterification reaction has been used for the biodiesel production with optimum
conditions of 700 rpm, catalyst of 1%, alcohol to oil ratio of 6, reaction time of one hour, and
temperature of 55 oC. The yield of product was 79.87% with methyl esters contain of 90%.
- Due to the high cold properties of the biodiesel (Cloud point = 7 oC) the product of
transesterification has been cracked thermally at 525 oC and flow rate of 20 g/h from which the cloud
point has been improved to -12 oC.

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 - The distillation curve and other fuel properties of the methyl esters cracking products are very
close to the refinery diesel which proves the similarity of the hydrocarbon contents of the products with
refinery diesel. The final products of the cracking and distillation processes can be used as a liquid fuel
for diesel engine at cold climate regions.

ACKNOWLEDGEMENTS

The research grant from Tarbiat Modares University is gratefully acknowledged.

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