TALENTA CEST II 2019 IOP Publishing

IOP Conf. Series: Materials Science and Engineering 801 (2020) 012047 doi:10.1088/1757-899X/801/1/012047

The utilization of chicken bones as heterogeneous catalyst

(CaO) in the production of fatty acid ethyl ester from crude
palm oil by using ethanol as solvent

Mersi Suriani Sinaga*, Pontius Pardede and Ermawati

Department of Chemical Engineering, Faculty of Engineering, Universitas Sumatera
Utara, Medan, Indonesia, 20155

*
E-mail: [email protected]

Abstract. Fatty acid ethyl ester is one of the most potential alternative energy because it is
renewable and environmentally friendly. Fatty acid ethyl ester is usually made by
transesterification using heterogeneous alkali catalyst. Chicken bones ash (CaO) is
heterogeneous alkali catalyst which is non-corrosive and environmentally friendly. It can also
be separated easily from the product by filtration and less removal problem than homogeneous
catalyst. This catalyst was made by grinding and calcination the chicken bones. Others
variables used in this research were the dosage of the catalyst, molar ratio of ethanol to crude
palm oil and reaction temperature. The best yield of the fatty acid ethyl ester was 90.052% at
the condition of 17:1 ethanol to crude palm oil molar ratio, 70 oC reaction temperature, 7% of
catalyst (w/w), 7 hours of reaction time and 500 rpm stirring speed.

1. Introduction
This world is going to undergo great energy crisis caused by the limited fossil fuel such as crude oil,
gas and coal [1]. This fossil fuel is categorized as non-renewable source of energy which can not be
produced in a short time after it has been used [2]. Fatty acid ethyl ester is also known, as biodiesel is
one of the most potential alternative energy because it is renewable and environmentally friendly.
Fatty acid ethyl ester is usually produced by transesterification process of oil or fat (vegetable oil or
animal fat) with alcohol to produce fatty acid alkyl ester and glycerol as byproduct [3]. Fatty acid ethyl
ester mixture can be used as ignition compression of diesel machine with or without modification.
Combustion of fatty acid ethyl ester is clearer, easy to use, biodegradable, non-toxic and free of
sulphur and aromatics [4].
Production of CPO in Indonesia is increasing year to year until it reached 24.1 million tons in 2011
and 26.5 million tons in 2012 [5]. CPO contains free fatty acid which can be converted into fatty acid
ethyl ester. This acid is converted to fatty acid ethyl ester by transesterification using alcohol which
makes CPO a good potential raw material in producing fatty acid ethyl ester [6]. The production of
fatty acid ethyl ester from low quality oil is begun with esterification to reduce the free fatty acid
content. The high free fatty acid content is not wanted in transesterification because it can cause soap
formed during the process which resulted lower yield and harder to separate the product [7].
Transesterification of vegetable oil or animal fat by using alcohol with the present of catalyst is the
main process of producing biodiesel. There are a lot of catalyst which can be used, such as alkali

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TALENTA CEST II 2019 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 801 (2020) 012047 doi:10.1088/1757-899X/801/1/012047

catalyst, acid catalyst and enzyme catalyst [8]. Regeneration of homogeneous catalyst after
transesterification is hard and resulted toxic waste. The research of alternative catalyst to substitute
homogeneous catalyst has been done recently and researches has found that heterogeneous catalyst has
some advantages than homogeneous catalyst such as it is easily separated from the product, it can be
reused, low water content and more biodegradable [2].
By considering the description above, further research about producing fatty acid ethyl ester using
chicken bones ash as heterogeneous catalyst is needed to be done to find out more heterogeneous
catalyst which can be used in producing fatty acid ethyl ester and resulted high yield of fatty acid ethyl
ester.
2. Materials and methods
2.1 Raw materials and tools
The main raw materials used in this research are crude palm oil as the material which will be
converted into fatty acid ethyl ester by transesterification and chicken bones as heterogeneous catalyst
to produce fatty acid ethyl ester. The tools used in this research are erlenmeyer, magnetic stirrer, hot
plate, separating funnel, beaker glass, measuring glass, digital scale, stirring rod, thermometer,
furnace, three neck rounded flask and oven.

2.2. Calcination of chicken bones

The chicken bones was collected and boiled for 20 minutes. Then, it was dried under the sun for a few
days. It was crushed by using ball mill and combusted by furnace at 1000oC for 4 hours until it formed
ash. It was sieved by using 100 mesh sieve [9].

2.3. Esterification
150 g of CPO was poured into three neck rounded flask which was equipped by reflux condenser,
thermometer and magnetic stirrer. Methanol was poured into the flask with the ratio of methanol to
CPO at 6:1 and 3% of H2SO4 was added. The reaction temperature was maintained at 60oC for 90
minutes at 250 rpm stirring speed. After the reaction was done, the mixture was poured into separating
funnel and was left until it formed two layers which was methanol at the upper layer and the lower
layer consisted triglyceride, methyl ester, residual free fatty acid and residual catalyst. The lower layer
was separated and washed by 150 ml of aquadest twice. Then, it was dried in the oven at 110 oC until
the mass is constant. The FFA of the oil should be under 5% after esterification then transesterification
can be done.

2.4. Transesterification
5% (w/w) of chicken bones ash was put into a beaker glass and then ethanol was added at the ratio of
13:1 (ethanol to CPO) and was left for 24 hours. Then, CPO was poured into a three necked rounded
flask which was equipped with reflux condenser, thermometer and magnetic stirrer over a hot plate.
The chicken bones ash and methanol mixture was poured into the flask. The mixture was heated by
hot plate until it reached 60oC and the temperature was maintained constant at 500 rpm stirring speed.
After the reaction was finished, the mixture was poured into separating funnel and was left until it
formed two layers. The lower layer, a mixture of the catalyst, ethanol and glycerol, was separated from
the upper layer. The upper layer was washed until it was clean. Then, it was dried by using an oven.
This procedure was repeated for another variable of this research.
3. Result and discussion
3.1. Analysis of crude palm oil as raw material
Gas chromatography was done to find the composition of fatty acid in crude palm oil and to find out
the molecular weight of crude palm oil (in triglyceride form). The figure above shows the composition
of the crude palm oil which can be seen in Table 1.

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TALENTA CEST II 2019 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 801 (2020) 012047 doi:10.1088/1757-899X/801/1/012047

Table 1. Fatty acid composition of CPO (crude palm oil).

Peak Retention Time Component Composition
Number (minute) (% w/w)
1 13.656 Lauric acid (C12:0) 0.1896
2 16.670 Myristic acid (C14:0) 0.8921
3 19.421 Palmitic acid (C16:0) 38.7914
4 19.704 Palmitoleic acid (C16:1) 0.1573
5 21.734 Stearic acid (C18:0) 4.6474
6 22.075 Oleic acid (C18:1) 42.5686
7 22.614 Linoleic acid (C18:2) 11.9100
8 23.352 Linolenic acid (C18:3) 0.3003
9 24.106 Arachidic acid (C20:0) 0.3932
10 24.519 Eicosenoic acid (C20:1) 0.1501
Table 1 shows the composition of unsaturated fatty acid is 55.086% and the composition of saturated
fatty acid is 44.914%. The average molecular weight of CPO free fatty acid is 270.942118 g/mol and
the average molecular weight of CPO triglyceride is 850.982348 g/mol.

3.2. Analysis of free fatty acid in crude palm oil

High level of free fatty acid in crude palm oil can prevent the reaction to happen and it cause soap
formed while transesterification process is done. So that, free fatty acid analysis was done. The free
fatty acid level can be seen in table 2.
Table 2. Free fatty acid level of crude palm oil.
Before esterification After esterification %FFA reduced
1.330 - -
5.141 0.475 90.07
Table 2 shows the FFA of CPO before esterification. The first FFA analysis of the CPO resulted
1.330% and was used in transesterification without esterification. The result was soap formed after the
process. The next FFA analysis of CPO resulted 5.141% and esterification was done to the CPO. The
FFA of the CPO after esterification become 0.475%.
Transesterification is affected by the free fatty acid level of the raw material so that the free fatty acid
level should be as low as possible [1]. Esterification was done to reduce free fatty acid of CPO. The
higher the free fatty acid in CPO will cause the more possibility of soap formed. The soap formed will
cause the separation process is harder to be done and it will increase the viscosity and the separation
cost also [10]. In table 2, we can see that after esterification the free fatty acid reduced was 90.07%.

3.3 The effect of catalyst concentration (%w/w) to fatty acid ethyl ester yield
The concentration of catalyst used in this research was 5%, 6% and 7% (%w/w). The effect of catalyst
concentration to fatty acid ethyl ester yield can be seen in figure 2. The effect of catalyst concentration
to yield at 7 hours of reaction time and different molar ratio can be seen in figure 2. It shows that the
more the chicken bones catalyst used caused the higher the yield obtained. The research which was
done by Yin Tang, et al. (2015) showed that the higher the CaO catalyst used the higher the yield
obtained [11]. Among some catalysts, calcium oxide (CaO) is the most used in producing fatty acid
ethyl ester because it has high alkali, it can react well with the reactant in transesterification, low
solubility and non-toxic.

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TALENTA CEST II 2019 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 801 (2020) 012047 doi:10.1088/1757-899X/801/1/012047

100
90
Yield (%)

80
70
60
50
4 5 6 7 8
Catalyst (%w/w)
13:1 molar ratio 15:1 molar ratio 17:1 molar ratio

Figure 1. The Effect of catalyst concentration (%w/w) to fatty acid ethyl ester yield.
Wu, et al (2013) also did a research by using catalyst in producing biodiesel. But, the main raw
material they used was soybean oil. In this research the concentration of catalyst used was 0.5-5% and
the optimum condition was at 3% of catalyst, 9:1 molar ratio and 65oC temperature reaction which
resulted 95% yield of biodiesel after 3 hours of reaction [12]. Farooq, et al also used chicken bones
(CaO) as catalyst in producing biodiesel by transesterification. However, the main raw material was
used cooking oil and the concentration of catalyst was 1-8%. The optimum yield of the biodiesel
produced was 89.33% at 5% of catalyst, 15:1 molar ratio, 65oC of reaction temperature and 4 hours of
reaction time [9]. Those two researches mentioned above are compared with this research. The
optimum condition of this research wa at 7% of catalyst, 15:1 molar ratio, 7 hours of reaction time and
70oC of reaction temperature and resulted 90.052% yield of fatty acid ethyl ester. It was found that this
research has better result that Farooq, et al. but it produced lower yield of fatty acid ethyl ester than the
research of Wu, et al. because of the concentration of catalyst used, molar ratio, reaction temperature
and reaction time used in this research were higher than Wu, et al. used in their research.

3.4 Effect of temperature to fatty acid ethyl ester yield.

The temperature used in this research were 60, 65 and 70oC. The effect of temperature to yield of fatty
acid ethyl ester is shown in Figure 3 below.

100
90
Yield (%)

80
70
60
50
55 60 65 70 75
Reaction Temperature (oC)

5% catalyst 6% catalyst 7% catalyst

Figure 2. The Effect of temperature to fatty acid ethyl ester yield.

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TALENTA CEST II 2019 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 801 (2020) 012047 doi:10.1088/1757-899X/801/1/012047

Temperature variation is one of the most important variable in producing fatty acid ethyl ester.
Figure 3 shows the effect of temperature to fatty acid ethyl ester yield. It shows that the higher the
temperature used caused the higher the yield of fatty acid ethyl ester obtained. Temperature affects
reaction and result of fatty acid ethyl ester producing. Higher temperature can decrease the viscosity of
oil and increase the reaction. However, if the temperature is higher than the optimum temperature, the
production of fatty acid ethyl ester will decrease. Reaction temperature must be lower than boiling
point of alcohol so that the alcohol does not evaporate [13].
Puneet and Sharma (2016) [14] has done a research on producing biodiesel by using methanol and
ethanol in different temperature variation. It was found that the optimum reaction temperature was
61.3oC at 8.42: molar ratio, 1.21% of catalyst and 2 hours of reaction time which resulted 77.4% yield
of biodiesel [13]. Kaur and Amjad (2013) has also done a research by using Li/CaO as catalyst and
ethanol as solvent in producing biodiesel from cotton seed oil. It was found that the optimum
temperature was at 65oC and at 12:1 molar ratio, 5% of catalyst and 2.5 hours of reaction time. The
yield obtained was 98% [14].
Figure 3 shows that the yield increased as the temperature gets higher. The best condition in this
research was at 70oC, 17:1 molar ratio which resulted 90.052% of fatty acid ethyl ester yield. If this
research is compared with the research by Kaur and Amjad [15] and Puneet and Sharma [14] as
mentioned above, it was found that this research has lower yield than Kaur and Amjad research.
However, the yield of fatty acid ethyl ester in this research is higher than the yield obtained in Puneet
and Shamar research although the time, temperature, catalyst concentration and molar ratio used were
higher than theirs but it resulted the higher yield of fatty acid ethyl ester.
4. Conclusion
Some conclusions can be concluded from this research, they are:
• Esterification is the reaction between fatty acid and alcohol to produce ester. Esterification is a
must done process if the free fatty acid of crude palm oil is high because it will form soap.
• Chicken bones is waste which can be used as heterogeneous catalyst (CaO).
• According to this research, the highest yield was 90.052% at the condition of 7% of catalyst,
17:1 molar ratio and 70oC of reaction temperature.
Acknowledgement
Many thanks to my students for helping me in realizing this research.

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TALENTA CEST II 2019 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 801 (2020) 012047 doi:10.1088/1757-899X/801/1/012047

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