Preparation and characterizaton of CaO nanoparticle for biodiesel production

Jharna Gupta and Madhu Agarwal

Citation: AIP Conference Proceedings 1724, 020066 (2016); doi: 10.1063/1.4945186
View online: http://dx.doi.org/10.1063/1.4945186
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PREPARATION AND CHARACTERIZATON OF CaO

NANOPARTICLE FOR BIODIESEL PRODUCTION
1

Jharna Gupta1,b), and Madhu Agarwal1,a)

Department of Chemical Engineering, MNIT, Jaipur, 302017, India

a)
Corresponding author: madhunaresh@gmail.com
b)
onlinejharna@gmail.com

Abstract. Nanoparticle of CaO from calcium Nitrate (CaO/CaN) and Snail shell (CaO/SS) are successfully synthesized
by method as described in the literature and used as an active and stable catalyst for the biodiesel production. These
catalysts are characterized by Fourier-transform infrared spectra (FT-IR), X-ray diffraction (XRD), and thermal
gravimetric analysis (TGA). The average crystalline size in nanometer was also calculated by DebyeScherrer equation.
The performance of the CaO/CaN and CaO/SS were tested for their catalytic activity via transesterification process and it
was found that biodiesel yield has been increased from 93 to 96%. The optimum conditions for the highest yield were
8wt% catalyst loading, 65C temperature, 12:1 methanol/oil molar ratio, and 6 h for reaction time. The nano catalyst from
snail shell exhibits excellent catalytic activity and stability for the transesterification reaction, which suggested that this
catalyst would be potentially used as a solid base nano catalyst for biodiesel production. In order to examine the
reusability of catalyst developed from snail shell, five transesterification reaction cycles were also performed.

INTRODUCTION
New renewable sources have been widely studied due to the reduction of petroleum reserves and increase in
environmental and health concerns [1]. As an alternate fuel to conventional crude oil, biodiesel has the possible way
to reduce the dependency on natural resources and greenhouse gas emissions [2].
Biodiesel is usually produced by transesterification or esterification reaction using basic or acidic catalysts such as
NaOH, KOH, H2SO4, HCl etc. This is very common process to speed a reaction between triglycerides and alcohol in
the presence of a catalyst. Methanol and ethanol are preferred due to low cost, polarity, smaller carbon chain, and
their solubility in KOH and NaOH [3]. Homogeneous alkali catalysts such as NaOH and KOH have good catalytic
activity with some disadvantages such as requirement of large quantity of water, high cost of production and
envoirmental problem from liquid waste [4-5].To solve this problem, heterogeneous alkali catalysts is used because
heterogeneous catalysts provides many advantages such as easy to separate from liquid product, non-corrosive, good
catalytic activity and selectivity, longer catalyst life, recyclable and effective. Till now various heterogeneous alkali
catalysts such as Zeolite [6-8], alkali earth metal oxides [9-10], KF/Al2O3 [11-12] and sodium aluminate etc. [13]
have been developed for biodiesel production. These heterogeneous catalyst have also some limitation such as they
required high reaction temperature(>170C),long reaction time (>24 hour) and low catalytic stability with significant
leaching of catalyst components to the deactivation of the catalyst [14]. So the use of nanocatalyst provides higher
catalytic activity due to its nanodimension and morphological structure, easier to separate and reusable, simple
operational procedures, and regenerates of less pollution [15].Among them, CaO is one of widely-used catalysts due
to its highly availability in nature, low cost and high activity [16].Various nanocatalyst have been investigated for
biodiesel production such as Wen et al. investigated KF/Cao nanocatalyst and conclude the max biodiesel yield
found 96.8% at reaction temperature 65C,12:1 of alcohol to oil ratio, 4% w/w catalyst and reaction time 2.5

2nd International Conference on Emerging Technologies: Micro to Nano 2015 (ETMN-2015)

AIP Conf. Proc. 1724, 020066-1020066-10; doi: 10.1063/1.4945186
Published by AIP Publishing. 978-0-7354-1371-9/$30.00

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hour[17]. Madhuvilakku et.al. used TiO2-ZnO mixed oxide nanocatalyst and found 92.2% of FAME conversion in 5
hour at 60C reaction temperatures with 6:1 methanol to oil molar ratio and 200 mg catalyst loading[25].
The present research work reports the preparation of CaO nanoparticle by using chemicals and waste snail shell
and then compared with each other in terms of yield and properties for the production of biodiesel from soybean oil.
The produced nanoparticles characterized using, and X-Ray Diffraction (XRD), thermo Gravimetric Analysis
(TGA) and Fourier Transform Infrared Spectroscopy (FTIR).The effect of catalyst concentration, oil to methanol
ratio, reaction time and reusability was also investigated.

EXPERIMENTAL SECTION
Materials
Snail shells were obtained from Ram Ganga shore in Bareilly, India. Soybean oil was purchased from the local
market .Anhydrous methanol of analytical grade, NaOH, Ca(NO3)2.4H2O and ethylene glycol from Merck limited,
Mumbai India was used in this study.

Characterization of oil
The quality of soybean oil is expressed in terms of the physicochemical properties such as density, acid value,
Kinematic viscosity, saponification value and flash point, fire point etc. These properties of soybean oil (without
further treatment) were determined as per ASTMD6751 Standard which has shown in Table 1.
TABLE 1. physicochemical properties of soybean oil

Properties of soybean oil

Unit

Measured

value

Density
Kinematic viscosity at 40C
Acid value
FFA
Flash point C
Fire point C
Cloud point C
Pour pointC
Saponification value

(gm/ml)
(Cst)
(mg of KOH/gm of oil)
%

C
(mg of KOH/gm of oil)

0.8444
16.55
1.12
0.56
260
275
-2
-3
196

Molecule weight
Ester value
% of glycerol

(gm/mol)
(mg)
-

863.60
194.88
10.65

Catalyst preparation
The CaO nanoparticle from calcium nitrate (CaO/CaN) and snail shell (CaO/SS) were synthesized by method as
described in the literature [18]. For preparation of Cao/CaN nanoparticle, a mixture of ethylene glycol (12 ml) and
Ca(NO3)2. 4H2O (6 g) was added to NaOH (1 g) and the solution continuous stirred at room temperature for 10 min;
the gel solution was kept about 5 h at static state. Afterwards, it was washed using water and dried under vacuum
drying. Finally, the prepared CaO nanoparticle was calcinated at 700C for 3 h. For CaO/SS nanoparticle, the snail
shells were washed with tap water three to four times for removing dust,impurities and any other unwanted material,
and subsequently dried at 120C for 10 h. After drying, shells were pulverized in a grinder. Snail shell powder as

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CaCO3 source was used instead of Ca(NO3)2.4H2O by method described in literature [18] for preparing CaO/SS
nanoparticle.

Catalyst characterization
The thermal stability of catalyst was examined using thermal analyzer STA6000 from room temperature to 900 C
under an inert nitrogen atmosphere and a heating rate of 20 C min-1.In order to determine the crystalline nature , Xray diffraction (XRD) patterns for each catalyst samples were analyzed using XRD (X-Pert pro powder panalytical
instrument).The FTIR spectra were recorded on FTIR spectrometer (Perkin Elmer spectra two) in the range of 400
4000 cm1. The KBr pellet method was used for the sample preparation. The Hammett indicator method was used to
determine the basic strength (H_) and basicity of the samples. Also measured Lewis basicity of solid catalyst by
exchange method in terms of pH with time.

Transesterification reaction procedure

The transesterification reaction was carried out in 250 ml 2 neck round bottom flask equipped with a reflux
condenser, temperature controller and magnetic stirrer. Typically 8 wt%(based on oil weight) catalyst sample was
suspended in methanol (99.5% Analytical Grade). Subsequently the 100 ml soybean oil was added into the flask
under vigorous stirring. The methanol/oil molar ratio was maintained at 12:1 in all runs. After completion of the
methanolysis reaction (6 hour), the catalyst was recovered from the reaction mixture by centrifugation and excess
methanol was recover in distillation unit. When the product was cooled, an oil phase clearly separated from a
glycerol phase. The top oil phase i.e. biodiesel was collected. The percentage of biodiesel yield was defined as
follows:

Yield (%) =




Equation (1)

Characterization of biodiesel
The methyl ester obtained from transesterification were analyzed by using gas chromatograph (Master GC Dani
Instruments, Italy) with DN biodiesel capillary column of length 30 m, I.D. 0.32 mm and film thickness 0.25 m. The
chromatographic conditions included: injector: 240 C, detector: 280 C, column: 100 200 at 40 C min-1, 200232 at 2C
min-1, and 232280 at 30 C min-1. The carrier gas was high purity nitrogen. Mixture of pure methyl esters (C8C24) were
used as standard in the GC.

RESULT AND DISCUSSION

Catalyst characterization
XRD analysis
The XRD pattern of CaO/SS and CaO/CaN nanoparticle has been shown in Figure 1(a) and 1(b) respectively. All
reflection peaks in XRD analysis such as 17.89, 29.34, 34.10, 50.7 for CaO/CaN and 18.03, 29.42 and 33.95 for
CaO/SS can be readily indexed to a pure cubic phase of CaO[18] .The crystallite size diameter (D) of the CaO
nanoparticle has been calculated by the DebyeScherrer equation (D = K/ cos ), where FWHM (full-width at
half-maximum or half-width) is in radian and is the position of the maximum of the diffraction peak. K is the socalled shape factor, which usually takes a value of about 0.9, and is the X-ray wavelength (1.5406 for Cu K)
[28]. The average crystallite size of CaO/CaN and CaO/SS were about 44 nm and 33.42 nm respectively.

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FTIR analysis
Figure 2(a) and 2(b) shows the FT-IR spectrum of CaO/SS and CaO/CaN respectively. The broad peak for CaO/SS
and CaO/CaN at 3643.54 and 3642.2 cm-1 respectively can be attributed to the (OH) stretching vibration. These
peaks indicate the presence of physisorbed water linked to nanoparticle. After calcination at 700C, as shown in
figure 2, the intensity of these bands decreases due to thermal decomposition of CaCO 3 and formation of CaO and
Ca(OH)2 .Band at 1412.35 cm-1 and 1419.15cm-1 for CaO/SS and CaO/CaN respectively shows CaO group[18].
TGA analysis
Figure 3(a) and 3(b) reveals the thermo-gravimetric analysis (TGA) curves of CaO/SS and CaO/CaN respectively,
obtained in nitrogen atmosphere at the intermediate rate of 20C per minute respectively. The CaO/CaN nanoparticle
calcined at 700C shows two mass losses in figure 3(b) .The first mass loss in the range 414.83-523.27C is due to
the removal of Ca(OH)2 and the second loss in the temperature range 646.45-800.36C is attributed to the
decomposition of CaCO3 to CaO and CO2 along with some loss of inorganic impurities. The loss weight of two
events is 15.32% and 11.30% respectively [20]. TGA curve of CaO/SS as shown in figure 3(a) also display two loss
weight peaks at 362.45-480.28C and 704.39-822.96oC, corresponding to the crystal water loss (6.3%) and sintering
of the performed compound (25.42%) respectively. The result of thermal analysis suggests that best calcination
temperature of CaO/SS and CaO/CaN are in the range of 700-850C and 650-815C respectively.

FIGURE 1 XRD analysis (a) CaO/SS (b) CaO/CaN .

FIGURE 3 TGA analysis (a) CaO/SS (b) CaO/CaN.

FIGURE 2. FTIR analysis (a) CaO/SS (b) CaO/CaN.

FIGURE 4 Basicity determinations in terms of pH.

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Basicity determination
Hammett indicator method was used for quantitative determination of basicity. 50 mg of sample was shaken with
5 ml volume of a methanol solution and 2-3 drops Hammett indicator and left to equilibrate for 2 h after which
further color changes were observed. This indicates that the basic strength of the catalyst is stronger than the
indicator used. When the solution produces no color change, the basic strength of the catalyst is weaker than that of
indicator used. After color change, the sample solution was titrated with a methanol solution of benzoic acid (0.1N)
for determine the leachable basicity(potentially soluble basicity). Hammett indicators included dimethyl yellow (H_
= 3.3), neutral red (H_ = 6.8) bromthymol (H_ = 7.2), phenolphthalein (H_ = 9.8), indigo carmine (H_ = 12.2), 2,4
dinitro aniline(H_= 15.0), 4-chloride-2nitroaniline(H_ = 17.2) and nitroaniline (H_ = 18.4).Table 2 shows the base
strength and total basicity of the catalyst. After observation, CaO/CaN showed lower base strength in the range of
9.8< H_<17.2 which is in good agreement with literature [4] and the base strength of CaO/SS catalyst was in the
range of 9.8< H_<18.4 which could be considered as a strong basic catalyst for transesterification reaction.

Catalyst

TABLE 2- Basicity of solids

Basic strength
(H_)

Total basicity
(mmoles/gm)

CaO/CaN
CaO/SS

9.8< H_<17.2
9.8< H_<18.4

11.23
13.45

Measurement of Lewis basicity

Exchange method was used for determining the Lewis basicity of solid catalyst. The number of catalytically Lewis
basic sites of the catalyst was determined by the process described in literature[19] in which a pH electrode (range
from 0-14 pH with a resolution of 0.01 pH) was introduced in 20 ml of benzoic acid 0.005M standardized solution,
until no pH variation were observed i.e. pH=3. About 1 gm of the catalyst fresh sample was added and pH measured
as a function of time for 1 hr. As shown in figure 4, the pH evolution as a function of time has been represented for
the different catalyst prepared in this research work. In this figure, it was observed that for CaO/SS, the rate of
basicity neutralization is very high and after 25 min, no pH changes were found for this catalyst. And for CaO/CaN,
the basic sites reaction with benzoic acid is slower.

Optimization of reaction conditions on the transesterification of soybean oil

Influence of amount of catalyst
The effect of the amount of catalyst on biodiesel yield was investigated by varying the load from 2 to 10 wt% as
shown in figure 5(a) .The reaction was carried out at 65C for 6 hour with a methanol to oil molar ratio of 12:1. It
was found that the yield of biodiesel was initially increased from 55% to 93% for CaO/CaN and 62% to 96% for
CaO/SS with amount of catalyst was increased from 2 to 8 wt.% and a slight fall in the conversion was observed at
10 wt.%. At higher catalyst loads, the reaction mixture may become more viscous which resists the mass transfer in
the liquidliquidsolid system and hence, results in the decline of biodiesel yield. The catalytic activity of our
catalyst was compared with that of other similar catalyst (Table 3).

Influence of methanol/oil molar ratio

The effect of methanol to oil ratio on biodiesel yield was investigated at a 8 wt.% of catalyst , reaction temperature
of 65C and reaction time of 6 hour Figure 5(b). According to the stoichiometry of transesterification reaction, 3 mol
of methanol is required for each mole of triglyceride. However in practice, a higher methanol to oil molar ratio than
the stoichiometry is needed to drive the reaction for completion and production of more methyl esters. As indicated

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in Figure 5(b), methanol to oil molar ratio was varied in the range of 3:115:1 and biodiesel yield was increased
from 50% to 93% for CaO/CaN and 56-96% for CaO/SS with an increase in the methanol to oil molar ratio from 3:1
to 12:1. It was also observed that there was no significant improvement in the methyl ester formation between the
alcohol to oil ratio of 12:1 and 15:1.
Influence of time
Figure 5(c) depicts the effect of reaction time on methyl ester conversion. The yield increased significantly from
80% to 93% for CaO/CaN and 84%-96% for CaO/SS as the reaction time was increased from 2-10 hr and the
conversion decreased slightly for the operation beyond 6hr. This is due to the fact that the longer reaction time
resulted in the hydrolysis of esters and caused more fatty acids to form soap. Thus from the influence of parameters
on transesterification, it was found that a 8wt.% catalyst (based on oil weight), methanol to oil molar ratio of 12:1,
reaction temperature of 65C and reaction time of 6 hour are required to obtain a max biodiesel yield of 93% for
CaO/CaN and 96% for CaO/SS.

(a)

(b)

(c)
FIGURE 5- The effect of catalysts loading, methanol-to-oil ratio, and reaction time of transesterification reactions of soybean oil
by using CaO/CaN and CaO/SS catalyst (a) Effect of catalyst wt.% on biodiesel yield(methanol to oil ratio =12:1, temperature =
65C, time = 6hour) (b) Effect of methanol to oil molar ratio on biodiesel yield(catalyst loading=8wt%, temperature = 65C, time
= 6hour) (c ) Effect of time on biodiesel yield(methanol to oil ratio =12:1, temperature = 65C, catalyst loading=8wt% )

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TABLE 3. Comparison of various nano catalysts for transesterification reaction

Nano Catalyst

Experimental conditions
Catalyst loading (wt%)
Oil: Methanol

Yield (%)

References

Time
(hour)

KF/CaO
TiO2-ZnO
Copper dopped ZnO
KF/CaO-Fe3O4
CsCa/SiO2TiO2
MgAl hydrotalcite

4
200 mg
10
1
2
5

12:1
6:1
10:1
12:1
12:1
30:1

2.5
5
1
3
2
4

<96%
92.2
97.18
95%
98%
93.4

17
22
23
24
25
26

Sulfated Zirconia

40

40:1

27

CaO/CaN

12:1

96%
conversion
93

CaO/SS

12:1

96

Current
work
Current
work

Reusability of the catalyst

From economic point of view, the reusability the catalyst is of great importance for industrial application. As shown
in figure 6, the recyclability efficiency of the calcined CaO/CaN and CaO/SS was investigated by performing the
transesterification steps for several runs. To evaluate the reusability, the supernatant biodiesel and glycerol layers
were discharged and the solid catalyst was left in the flask under the optimum conditions. Same amount of fresh
soybean oil and methanol was added into the flask and performed transesterification reaction again. The catalytic
activity of calcined CaO/CaN and CaO/SS decreased sharply with in 5 runs from 93% reduced to 81% and 96% to
90% respectively as shown in figure 6. Because the catalyst particle was crushed by strong stirring and the powder
like small particles were discharged with supernatant glycerol, no further experiments were conducted.

FIGURE 6 recyclability study

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Biodiesel characterization
Properties of Biodiesel produced from soybean oil were analyzed .These properties of soybean biodiesel were
compared as per ASTM D6751 Standard [20] which has shown in Table 4.
TABLE 4. Properties of soybean biodiesel
Properties

Density
Kinematic viscosity
at 40C
Acid value
Cloud point
Pour point
Flash point

Unit

Soybean biodiesel from

CaO/CaN

Soybean biodiesel from

CaO/SS

ASTMD6751
Standard

(gm/ml)
(Cst)

0.888
5.582

0.879
4.921

0.860-0.900
1.9-6.0

(mg of KOH/gm
of oil)

0.49

0.46

0.50

9
3
150

6
-3
163

-3 to 12
-15 to 10
130-170

GC analysis
The chromatogram of soybean biodiesel shows the presence of derivates of linoleic acid (C18:2), oleic acid (C18:1),
steraic acid (C18:0), palmitic acid (C16:0) and linolenic acid (C18:3) as shown in figure 6. The chromatogram of
biodiesel obtained from soybean oil confirmed the formation of methyl esters. The identified components of the
biodiesel are found matching with the standard graph. This data are according with the literature [21].

FIGURE-7 GC analysis of biodiesel from soybean oil

CONCLUSION
CaO/CaN and CaO/SS were tested as solid base nanocatalyst in transesterification of soybean oil in batch reactor
systems. The prepared solid basic catalyst was characterized by XRD, FT-IR and TGA. The characterization results
show that the CaO/SS nanocatalyst exhibits stronger basicity than that of CaO/CaN nanocatalyst. This modification
process enhances the basicity and catalytic ability of the catalyst. The catalyst showed the highest yield 96% for
transesterification reaction at 65C, 12:1 methanol to oil ratio, 6 hour with 8 wt% catalysts loading. The reusability
of the catalyst was moderate and future studies focusing on regeneration and enhancing the reusability of the catalyst
are recommended.

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