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7th International Conference on Environment and Industrial Innovation IOP Publishing
IOP Conf. Series: Earth and Environmental Science1234567890
67 (2017) 012021 doi:10.1088/1755-1315/67/1/012021
Utilization of eggshell waste as low-cost solid base catalyst for
biodiesel production from used cooking oil
N P Asri1*, B Podjojono1, R Fujiani1 and Nuraini1
1
Chemical Engineering Department, Faculty of Engineering,, WR. Supratman University,
Surabaya, Indonesia, 601191. *corresponding author:
[email protected] Abstract. A solid CaO-based catalyst of waste eggshell was developed for biodiesel
production from used cooking oil. The waste eggshell powder was calcined in air at 900º C for
4 h to convert calcium species in the eggshells into active CaO catalysts. The characterization
of CaO catalyst was done by XRD and BET analysis. The CaO catalyst was then introduced
for transesterification of used cooking oil (UCO) for testing of its catalytic activity. The
experiment was conducted in batch type reactor that consists of three-neck glass equipped by
reflux condenser and magnetic stirrer. Before tranesterification process, the UCO was treated
by coconut coir powder in order to reduce the free fatty acid content. The result showed that
the catalyst was potentially use for transesterification of used cooking oil into biodiesel with
relatively high yield of 75.92% was achieved at reaction temperature, reaction time, molar ratio
UCO to methanol and catalyst amount of 65°C, 7 h, 1:15 and 6%, respectively.
1. Introduction
The energy consumption has increased every year in line with the increase in human population. This
increase occurred in various sectors including transportation, power generation, industry and
households. Until now, the world's energy needs are supplied by fossil fuels. By 2030, it is estimated
that the increase in energy consumption reaches 53%, so that the oil reserves expected to be exhausted
within the next 41-63 years [1]. In addition, the use of fossil fuels continuously, causing environmental
impacts such as the increase of CO2 emissions that result in accelerated of global warming, air
pollution and other environmental issues. The rapid depletion of fossil fuels and the increasing energy
needs has encouraged each country to make savings and conducting various studies to obtain
renewable fuels. Biodiesel is a renewable fuel that can be used as a substitute for diesel fuel.
Biodiesel is mono alkyl ester derived from many sources such as vegetable oils, animal fats or used
cooking oil. The main factors affecting the cost of biodiesel production is the raw material and the
type of catalyst used. In 2012, cooking oil demand in Indonesia is estimated to reach more than 4.7
million tons. After use, the cooking oil will undergo changes in chemical composition and contain
carcinogenic compounds. Therefore, the used cooking oil is no longer worthy to be used for food
processing. The abundant and availability of used cooking oil can be used as an alternative raw
material for the manufacture of biodiesel [2]. Typically, biodiesel was produced through the
transesterification process using homogeneous acid / alkaline catalyst [3], [4], [5] that usually called
conventional process. This process is fast and efficient, for example more than 95% conversion is
achieved at 60°C in 1 h of reaction time. However, it has many disadvantages including the formation
of side products such as soaps [6], [7], [8], the complicated separation of the product with the catalyst
[3]. In addition, the alkaline waste that formed in large enough quantities also requires a complicated
separation process. This separation process requires considerable energy and the increasing of costs
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7th International Conference on Environment and Industrial Innovation IOP Publishing
IOP Conf. Series: Earth and Environmental Science1234567890
67 (2017) 012021 doi:10.1088/1755-1315/67/1/012021
production [7], [9]. Those problems can be mitigated by replacing homogeneous catalysis with solid
catalyst. The use of solid acid catalysts in biodiesel production has been studied primarily from
transition metal oxides such as zirconia and titanium oxide [9], [10]. The main obstacle of use of acid
catalysts requires long reaction times and high reaction temperatures [9], [11]. Solid base catalyst such
as calcium oxide [12], magnesium oxide [13], alkali alumina [14], hydrotalcite [15], zeolite [16] seems
to be a promising strategy to substitute acid catalyst, but most of them use of synthetic chemicals that
are relatively expensive.
This study developed a solid CaO-based catalyst of eggs shell for the production biodiesel from used
cooking oil. The purpose of this study is to utilize CaO contained in the eggshell into a solid catalyst
instead of homogeneous catalysts that will influence decreasing of biodiesel production costs, so the
price of biodiesel can compete with diesel oil. Eggshell has a small porosity and high of CaCO 3
content that is indispensable in the industry of biodiesel [17]. Components of the eggshell include
calcium carbonate (94%), magnesium carbonate (1%), calcium phosphate (1%), and other organic
materials (4%). Based on the pore structure and content of CaCO3, eggshell provides opportunities for
development as heterogeneous catalysts [18].
Utilization of this catalyst is expected to provide a solution to obtain a feasibility study of biodiesel
production process that is effective and efficient and reduce environmental pollution. The study was
conducted in the scale laboratory includes several stages, namely preparation of catalysts, catalyst
characterization, and testing catalyst activity to determine the best operating conditions include
amount of catalyst and reaction time.
2. Materials and Methods
2.1. Materials
Waste cooking oil was found from local street food vendors in Surabaya, East Java. The physical and
chemical characteristics of UCO were analyzed using several methods based on the procedure
described elsewhere [2]. The free fatty acid (FFA) content of 4.4946% was analyzed based on
American Oil Chemist (AOCS) official Method (Ca 5a-71, 1993). Meanwhile, its density and water
content of 0.9219 g/cm3 and 0.78%, respectively were analyzed based on ISO 662 – 1089. FAME
standards and internal standards of chromatographic grade were obtained from Sigma–Aldrich
(Switzerland). Technical grade of methanol was purchased from local supplier Bratacho-Chem.
Meanwhile eggshell was collected from the local bakeries in Surabaya, East Java, Indonesia.
2.2. Catalyst preparation and characterization
At first, the eggshells being crushed into small chips, then soaked and rinsed thoroughly several times
with hot water to remove the impurities and other interference materials. The clean eggshell chips
dried at 110°C for 24 h in the dry oven. The dried chips eggshells then powdered and sieved to the size
of qualifying on 100 mesh and retained on 200 mesh. Calcination process was performed in the
muffle furnace at 900°C for 4 h under static air. Surface area analysis of the catalyst was examined
using Brunauer-Emmett-Teller (BET) methods. Sample was degassed at 105 °C prior to analysis and
the adsorption of N2 was measured at -196 °C. Meanwhile, X-ray diffraction (XRD) was measured by
XPert MPD using Cu Ka radiation. The prepared catalyst from eggshell was assigned as ES-CaO, and
then kept in a desiccator in the presence of silica gel in order to avoid water and CO2 contacting with
the catalyst.
2.3. Transesterification process
In this research, the collected UCO was pre-treated based on the procedure described elsewhere [2],
[8]. First, the collected UCO was filtered to remove the food residues or the suspended particulate
matters, and then it was heated at 100-105ºC for 30 minutes to remove the excess of water content.
Further, UCO was treated by adsorption process using coconut coir powdered (CCP) (wt.% to the
UCO) to reduce the FFA content of the UCO. It has been stated in the last work [2] that the optimum
amount of CCP is 7% (wt.% to the UCO), therefore it was used for treating UCO in this work. The
treated UCO was analyzed to determine its final FFA content, and then it was ready subjected for
transesterification process using ES-CaO catalyst.
2
7th International Conference on Environment and Industrial Innovation IOP Publishing
IOP Conf. Series: Earth and Environmental Science1234567890
67 (2017) 012021 doi:10.1088/1755-1315/67/1/012021
Transesterification process was conducted in batch type reactor consists of three neck glass, equipped
with reflux condenser and magnetic hot plate stirrer. The reaction was carried out at 65ºC and molar
ratio of UCO to methanol 1:15. Meanwhile, the amount of catalyst and reaction time were varied of 3-
7% (wt.% o oil) with 1% of range and 2-7 h with range of 1 h, respectively. The amount of ES-CaO
catalyst, methanol, and treated UCO were measured and introduced into the reactor, and allowed to
keep a while until the reaction temperature of 65°C was reached. The reaction mixtures were stirred
thoroughly at constant speed using magnetic stirrer. After desired duration time was reached, the
reactor was cold down and the reaction mixtures were withdrawn at room temperature. The mixtures
were filtered to separate the catalyst from the liquid phase. The liquid phase was introduced into a
separation funnel where the glycerine was decanted, and then the excess methanol was recovered
using a rotary evaporator. Biodiesel concentration was analysed by a gas chromatograph GC-14B
(Shimadzu) equipped with a flame ionization detector and a capillary column HP-Innowax (30 m × id
0.25 mm, 0.25 μm). Helium was used as the carrier gas throughout the whole experiment. Biodiesel
analyses can be used to calculate the yield of biodiesel (%) defined as Equation 1 [19]
( ) (1)
Where, w of ab means weight of actual biodiesel was calculated from weight of biodiesel produced
(mg) in the experiment multiple by weight % of FAME in the sample. Meanwhile, W of oil is weight
of oil (mg) used in the experiment.
3. Result and Discussion
3.1. Characterization of ES-catalyst
The specific surface area prepared ES-CaO catalyst of 125.927 m²g-1 was obtained using BET
methods. This result is much higher than that crab shells catalyst of 13 m2 g-1 that was stated by Boey
et al. (2009) [20]. Meanwhile, mud clam shell and commercial CaO have the surface area of 68.57 and
62.91 m2 g-1, respectively [21].
Counts
Kulit Telur Kalsinasi 3gr
600
400
200
10 20 30 40 50 60 70 80
Position [°2Theta] (Copper (Cu))
Figure 1. XRD patterns of eggshell (ES-CaO) catalyst calcined at 900°C
X-ray diffraction (X-RD) patterns of ES-CaO was depicted by figure 1. XRD results revealed that the
composition of uncalcined eggshell mainly consisted of calcium–magnesium carbonate (CaCO3–
MgCO3) with the absence of CaO peak (the figure was not shown). This result confirm with the
composition of eggshell that mostly consisted by CaCO3 (94%). However, for the calcined catalyst at
900°C (figure 1), CaCO3 completely converted into CaO and release the CO2 gas. The narrow and
high intense peaks of the calcined catalyst showed the well crystalline structure of the catalyst that
mainly consisted of the active ingredient CaO.
3.2. Effect of reaction variable on yield of biodiesel
The yield of biodiesel was affected by many factors, such as the type triglyceride, type of catalyst used,
reaction temperature, molar ratio of oil to methanol, catalyst amount or reaction time. Therefore, the
3
7th International Conference on Environment and Industrial Innovation IOP Publishing
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67 (2017) 012021 doi:10.1088/1755-1315/67/1/012021
effect of reaction variables was studied in the presence of ES-CaO solid base catalyst. In this work we
focused on the influence of the catalyst amount used and the reaction time on yield of biodiesel.
There are 2 keys parameter including free fatty acid and moisture content that are determining the
viability of vegetable oils to be used in transesterification process [2], [22]. Water content will
accelerate the hydrolysis reaction and simultaneously reduce the amount of ester formation [23]. To
achieve 90% yield of biodiesel, then water content of triglyceride that used in the transesterification
process not more than 0.5% [24]. Moreover, it was known that higher free fatty acid contents will lead
to formation of soap and water. If free fatty acid content more than 3%, the homogeneous base catalyst
is not suitable for the transesterification reaction [2], [24].
The UCO that was used in this work contained 4.4946% (wt. %) free fatty acid (FFA). In order to
reduce the FFA content of the UCO, it was treated by adsorption process using 7% of coconut coir
powder [2]. Coconut coir is one of the agricultural waste products often used as adsorbent in
wastewater treatment [25]. Due to its availability and its abundant in the environment, make it to be a
good source used in the adsorption process [2], [25]. The nature of coconut coir dust such as good
structural stability, high water absorptivity and high porosity enhance its effectiveness as adsorptive or
ion exchange capacities. Its composition includes lignin, cellulose, pentosan and ash were 36.15, 33.61,
29.27 and ash 0.61% (wt. % of dry basis), respectively [26]. After adsorption process, the FFA content
of UCO was determined using AOCS method. The result showed its FFA content decrease into
0.2079%. Furthermore, the treated used cooking oil is ready for the transesterification process.
3.2.1. Effect of catalyst amount on yield of biodiesel
Investigating the influence of catalyst amount on yield of biodiesel the experiments were performed in
varied catalyst amount of 3-7% with range of 1% (wt.% to UCO) under constant stirring speed using
reaction temperature, reaction time and molar ratio of UCO to oil at 65 ºC, 1 hr and 1:15, respectively.
Figure 2 shows the influence of catalyst amount on yield of biodiesel. As depicted by figure 1, the
amount of catalyst was significantly influence on yield of biodiesel. Yield of biodiesel increases with
increasing the amount of catalyst. Without the presence of catalyst, no biodiesel was formed (data
yield of biodiesel using 0 % catalyst amount was not shown in the figure).
Figure 2. Effect of amount of ES-CaO catalyst on yield of biodiesel
In contrary, yields of biodiesel linearly increase with the increasing the amount of catalyst at 3 up to
6%. It is strongly evidence that the presence of catalyst affected the reaction rate [2]. In this work, the
maximum yield of biodiesel of 5.62% was found at 7% catalyst amount of ES-CaO. However, at
catalyst loading amount of 6-7% there is no increased significantly on yield of biodiesel. Therefore,
for the economic point of view, 6% amount of catalyst was decided as the optimum condition, and it
was selected for further studies.
4
7th International Conference on Environment and Industrial Innovation IOP Publishing
IOP Conf. Series: Earth and Environmental Science1234567890
67 (2017) 012021 doi:10.1088/1755-1315/67/1/012021
3.2.2. Effect of reaction temperature on yield of biodiesel
Evaluating the influence of reaction time on yield of biodiesel on transesterification of UCO using ES-
CaO catalyst, the experiments were conducted by varying time of reaction from 1 to 7 h with range of
1 h. Meanwhile, the others conditions were kept constant, at 65ºC, molar ratio treated UCO to
methanol of 1:15, and amount of catalyst of 6% (wt. % to UCO).
Figure 3. Effect of reaction time (h) on yield of biodiesel (%)
Figure 3 depicted that yield of biodiesel significantly increased with increasing of the time of reaction.
In 1 h of reaction, yield of biodiesel was low, because it is a heterogeneous reaction and the fact that
mass transfer is slow in the earlier of reaction. Huaping et al. (2006) reported the similar result [27].
After one up to 6 h, yield of biodiesel linearly increase from 5.54 up to 72.05%. At reaction time of 6
up to 7 h, biodiesel yields were gradually increased from 72.05 to 75.92 %. It seems that the
equilibrium condition was achieved at 7 h with highest yield of 75.92%. It proved that the yield of
biodiesel increased up to certain of reaction time. Refaat et al. (2008) and Asri et al. (2013) stated the
similar statement [19], [28]. Therefore, the reaction time of 7 h was decided as the optimum reaction
time on transesterification of used cooking oil into biodiesel using ES-CaO catalyst.
4. Conclusion
Calcium oxide (CaO) solid base Catalyst has been successfully prepared from eggshell waste by
calcination process at high temperature (900° C). The eggshell waste (ES-CaO) catalyst has been
introduced to transesterification process of used cooking oil with refluxed methanol. The high content
of free fatty acid in used cooking oil reduced using 7% (wt.% to UCO) of coconut coir powder. The
transesterification reaction was carried out under constant stirring speed at 65 ºC and molar ratio of
UCO to methanol 1:15. The result shown, that the amounts of catalyst and reaction time have
significant effect on yield of biodiesel. The high enough biodiesel yield of 75.92% was obtained using
6% of catalyst amount within 7 h of reaction time. It proved that the eggshell waste catalyst seems to
be very promising for producing biodiesel from used cooking oil. However, the activity of the eggshell
catalyst should be improved to achieve the higher biodiesel yield (>95%) in a shorter time of reaction.
Therefore, the study of developing and engineering of CaO solid base catalyst derived from shell
waste is still need to be encouraged to enhance the efficiency of biodiesel production from used
cooking oil.
5. References
[1] Kiakalaieh A T, Amin N A S, and Mazaheri H 2013 A review on novel processes of biodiesel
production from waste cooking oil Applied Energy 104 683–710
[2] Asri N P, Puspitasari D A, Poedjojono B, and Suprapto 2015a Pre-treatment of waste frying oils
for biodiesel production Modern Applied Science 9 7 99-106
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67 (2017) 012021 doi:10.1088/1755-1315/67/1/012021
[3] Freedman, B, Butterfield RO, and Pryde EH 1986 Transesterification kinetics of soybean oil J
American Oil Chemists Society 63 1375-80
[4] Canakci M 2007 The potential of restaurant waste lipids as biodiesel feedstocks Bioresource
Technology 98 1 183–190.
[5] Asri N P, Machmudah S, Wahyudiono W, Suprapto S, Budikarjono K, Roesyadi A, and Goto
M 2013a Non catalytic transesterification of vegetables oil to biodiesel in sub-and
supercritical methanol: a kinetic’s study Bulletin of Chemical Reaction Engineering &
Catalysis 7 3 215-223
[6] Ilgen O, Akin A N 2008 Development of alumina supported alkaline catalyst used for biodiesel
production Jourrnal of Turkey 33 281–287
[7] Zabeti M, Daud W H A M, and Aroua M K 2009 Activity of solid catalysts for biodiesel
production: A review Fuel Processing Technology 90 770-777
[8] Asri N P, Poejojono B, Puspitasari D A, Suprapto S, and Roesyadi A 2015b Biodiesel
production using double promoted catalyst CaO/KI/ -Al2O3 in batch reactor with refluxed
methanol Springer Procedding in Energy, Energy System And Management Germany
Springer Verlag, ch 15
[9] Furuta S, Matsuhashi H and Rata K 2006 Green diesel fuel production with solid amorphous-
zirconia catalyst in fixed bed reactor Biomass And Bioenerg 30 870-873
[10] Jitputti J, Kitiyanan B, Rangsunvigit P, Bunyakia K, Attnatho L and Jenvanipanjakul P 2006
Transesterification of kernel oil and crude coconut oil by different solid catalysts Chemical
Engineering Journal 116 61-66
[11] Marchetti J M, Miguel V U and Errasu A F 2007 Heterogeneous esterification of oil with high
amount of free fatty acids Fuel 86 906–910
[12] Granados M L, Poves M D Z, Alonso D M , Mariscal R, Galisteo F C, Moreno-Tost R,
Santamarí a J and Fierro J L G 2007 Biodiesel from sunflower oil by using activated calcium
oxide Applied Catalysis B: Environmental 73 317–26
[13] Wang Y, Zhu S, He H and Liu X 2007 Transesterification of soybean oil to biodiesel using SrO
as a solid base catalyst Catalayst Communication 8 1107-11
[14] Xie W and Li H 2006 Alumina supported potassium iodide as a heterogeneous catalyst for
biodiesel production from soybean oil J Molecular Catalysis A: Chemical 255 1-9
[15] Kim M J, Park S M, Chang D R and Seo G 2010 Transesterification of triacetin, tributryin, and
soy bean oil with methanol over hydrotalcite with different water content Fuel Process
Technology 91 618-24
[16] Noiroj K, Intarapong P, Luengnaruemitchai A and Jai-In S 2009 A comparative study of
KOH/Al2O3 and KOH/NaY catalyst for biodiesel production via transesterification from
palm oil Renewable Energy 34 1145–50
[17] Empikul, V N, Krasae P, Puttasawat B, Yoosuk B, Chollacoop N and Faungnawakij K 2010
Waste shell of mollusk and egg as biodiesel production catalyst Bioresource Technology 101
3765-67
[18] Stadelman, W J 2000 Eggs and egg products. In: Francis, F.J. (Ed.) Encyclopedia of Food
Science and Technology 2nd Ed. New York John Wiley and Sons 593–599
[19] Asri N P, Machmudah S, Wahyudiono W, Suprapto S, Budikarjono K, Roesyadi A and Goto
M. 2013b Palm oil transesterification in sub and supercritical methanol with heterogeneous
base catalyst Chemical Engineering and Processing: Process Intensification 72 63-67
[20] Boey P L, Maniam G P, and Hamid S A 2009 Biodiesel production via transesterification of
palm olein using waste mud crab (Scylla serrata) shell as a heterogeneous catalyst
Bioresource Technology 100 6362–68
[21] Ismail S, Ahmed A S, Anr R, and Hamdan S 2016 Biodiesel production from castor oil by using
calcium oxide derived from mud clam shell Journal of Renewable Energy Article ID
5274917, 8 pages
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[22] Gashaw A and Teshita A 2014 Production of biodiesel from waste cooking oil and factors
affecting its formation: A review International Journal of Renewable and Sustainable
Energy 3 5 92-98
[23] Leung D Y C and Guo Y 2006. Transesterification of neat and used frying oil: Optimization for
biodiesel production. Fuel Processing Technology 87 10 883–90
[24] Gnanaprakasam A, Sivakumar V M, Surendhar A, Thirumarimurugan M, and Kannadasan T
2013 Recent strategy of biodiesel production from waste cooking oil and process influencing
parameters: A review. Hindawi Publishing Corporation Journal of Energy, 10 pages
[25] Okafor P C, Okon P U, Daniel E F, Ebenso E E 2012. Adsorption capacity of coconut (Cocos
nucifera L.) shell for lead, copper, cadmium and arsenic from aqueous solutions
International Journal Electrochemical Science 7 12354 –12369
[26] Etim U J, Umoren S A and Ednok U M 2012 Coconut coir dust as a low adsorbent for the
removal of cationic dye from aqueous solution Journal of Saudi Chemical Society
[27] Huaping Z, ZongbinW, Duan Shjie CY, Yuangxiong C, Ping Z, Xiaohua L and Zongqiang M.
2006 Preparation of biodiesel catalyzed by solid super base of calcium oxide and its refining
process Chinese Journal Of Catalyses 27 5 391-96
[28] Refaat A A, Attia N K, Sibak H A, El Sheltawy S T and El Diwani I 2008 Production
optimization and quality assessment of biodiesel from waste vegetable oil International
Journal of Environmental Science and Technology 5 1 75-82
6. Acknowledgments
The authors would like gratitude to Directorate of Research and Community Services, Directorate
General of higher education, the Ministry of Research Technology and Higher Education of Republic
Indonesia, for the financial support through the research grant in the fiscal year of 2017.
