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Potential of Eggshell Waste for Pyrolysis Process

Article  in  Advanced Materials Research · February 2015

DOI: 10.4028/www.scientific.net/AMR.1087.77

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Advanced Materials Research Vol. 1087 (2015) pp 77-80 Submitted: 26.05.2014
© (2015) Trans Tech Publications, Switzerland Revised: 17.07.2014
doi:10.4028/www.scientific.net/AMR.1087.77 Accepted: 13.08.2014

Potential of Eggshell Waste for Pyrolysis Process

ROHAZRINY Rohim1,a, RAZI Ahmad1,b, *, NAIMAH Ibrahim1,c,
NASRUL Hamidin1,d, CHE ZULZIKRAMI Azner Abidin1,e
1
School of Environmental Engineering, Universiti Malaysia Perlis, Kompleks Pusat Pengajian
Jejawi 3, 02600, Arau, Perlis, Malaysia
a
rohazrinyrohim@gmail.com, brazi@unimap.edu.my, cnaimah@unimap.edu.my,
d
nasrulhamidin@unimap.edu.my, ezulzikrami@unimap.edu.my

Keywords: eggshell, calcium oxide, catalyst, pyrolysis, bio-oil

Abstract. The eggshell waste which has potential mineral such as calcium oxide (CaO) was studied
for biomass pyrolysis in a fixed bed reactor. The objective of this study was to characterize the CaO
from waste eggshell and correlated the potential in pyrolysis process. XRF results showed that the
percentage of CaO in raw eggshell was increased in calcined eggshell. Bio-oil product yield
increased by 25.98% by using eggshell waste as a catalyst. CaO from waste eggshell improved the
production of bio-oil in terms of quantity.

Introduction
The production of palm oil products such as crude palm oil and crude palm kernel oil become
largest product in Malaysia. Thus, it contributes highest amount of waste such as empty fruit bunch,
palm kernel shell, trunk, fronds and other waste products, which called as biomass waste [1]. A
palm oil residue amounts to 184.6 million tons in annual production [2]. These wastes are used as
sources to generate energy, however burning of biomass causes environmental damages.
Several researchers have pyrolyzed palm oil waste under various conditions to produce bio-oil
products. Bio-oil is dark brown liquid have high heating value can be used as fuels in boiler, diesel
engines for power generation, or upgraded to produce fuels and bulk chemicals. Pyrolysis process
shows potential for the thermochemical conversion of biomass into liquid fuels because of its higher
yield and quality of liquid oil [3]. Palm kernel shells are one of the palm oil residues which can
produce bio-oil yield in the pyrolysis process. Islam et al. [4] investigated that maximum bio-oil
yield was obtained from pyrolysis of palm kernel shells at a reaction temperature of 500oC with
particle size of 212 – 425 µm, using nitrogen as fluidizing medium.
However, bio-oil is low quality fuels because of its high oxygen and water content. The presence
of oxygen in the bio-oil has a negative effect such as further increasing the corrosion due to its low
pH. The upgrading of bio-oil by catalytic treatment has received increasing consideration. The
catalyst is expected to improve the cracking reactions of the heavy molecules in pyrolysis products
resulting in the production of high yield and high quality of bio-oil. Waste eggshell is expected to
be a catalyst for pyrolysis process. Waste eggshells are considered as one of the solid waste. It has
no economic value and most of it has to be discarded to the landfills without any pretreatment.
Consequently, this can cause high risk to public health and environmental problems. Eggshells have
porosity and contain calcium carbonate (CaCO3) as important element [5].
Besides that, calcium oxide (CaO) can be form from CaCO3 by calcination process. Wei et al. [6]
reported that CaO was the active phase in the eggshells and the calcination temperature must be
above 800oC. CaO from waste eggshell is expected to replace other commercial calcium oxide
which is more expensive and high cost of production. It can reduce oxygen content, which is an
unnecessary compound in the production of bio-oil. The objective of this research is to characterize
CaO from waste eggshells and to study its potential in pyrolysis process.

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78 Current Material Research Using X-Rays & Related Techniques

Methodology
Eggshells were collected from local industries and rinsed several times with water to remove
impurity and interference material. Then, it was dried in the oven at temperature of 100oC for 24
hours. The eggshells were ground with Fritsch Pulverisette 6 Planetary Mono Mill to obtain
homogenize size. Eggshells were analyzed by TGA/DSC 1 Model Mettler Toledo. Raw eggshells
were calcined under nitrogen gas at temperature of 900oC for 1 hour in the tube furnace. Raw and
calcined eggshells were analyzed by XRF model PANalytical miniPAL.
Palm kernel shell was used as biomass material for pyrolysis process. The samples were dried
and separated from physical impurities. The dried palm kernel shell was ground in a rotary cutting
mill and screened into a fraction between 0.6 mm to 1.18 mm in size. The fixed-bed pyrolysis
experiments were performed by using 450oC as a pyrolysis temperature. The product yield was
collected and calculated at the end of pyrolysis process.

Result and Discussion

Calcination temperature. Result from TGA as shown in Fig. 1 showed that there were two distinct
stages of weight losses. The first stage showed the temperature below 640oC and second stage was
between 640oC and 843oC. For the first stage, minor weight loss occurred showed water molecules
were absorbed and loss of organic compound [6]. Major weight loss exhibited on second stage
which occurred at temperature of 843 oC, contributed for 42.2 wt. %,. Loss of carbon dioxide
occurred on this stage [6]. It was due to the conversion of CaCO3 phase to CaO phase [7], which
can be confirmed by XRF result as shown in Table 1. As the weight loss of the sample remains
constant after the temperature 843oC, the suitable temperature for calcination process was 900oC to
ensure complete conversion to CaO.

60

55

50
Weight Loss (mg)

45

40

35

30
0 100 200 300 400 500 600 700 800 900
Temperature (oC)

Fig.1: Weight loss (mg) of raw eggshell analyzed by TGA

Calcium oxide (CaO) content. Table 1 shows the CaO content increased from 98.50% in raw
eggshell to 98.56% in calcined eggshell by XRF analysis. From this result, it showed the CaCO3
had approximately converted to CaO. Besides that, other chemical compositions contain in the
calcined eggshell were MgO (0.69%), Al2O3 (0.1%), CuO (0.027%), SrO (0.051%). Witoon [8]
reported that the percentage of CaO in calcined eggshell was 97.4%, while the percentage of other
 Advanced Materials Research Vol. 1087 79

chemical compositions were 1.63% for MgO, 0.52% for P2O5, 0.26% for SO3, 0.08% for K2O,
0.05% for SrO, 0.02% for Cl, 0.01% for Fe2O3, and 0.01% for CuO. Results showed that CaO was
the most abundant element in the eggshells as the CaCO3 was the main presence in the eggshell.
Small amount of other compositions in the eggshell considered that the waste eggshell could be
natural carbonate-based material [8,9].

Table 1: Chemical compositions of raw and calcined eggshell

Chemical Composition Raw eggshell Calcined eggshell
MgO (%) 0.500 0.690
CaO (%) 98.500 98.560
Al2O3 (%) 0.100 0.100
CuO (%) 0.045 0.027
SrO (%) 0.062 0.051

The effect of catalyst on pyrolysis product. As seen from Table 2, the pyrolysis of palm kernel
produce bio-oil, char, and gas yield. The oil yield was obtained via weighing after the pyrolysis.
With the temperature of 450oC, 19.69% of oil yield were obtained in the absence of catalyst,
however increased by 25.98% by using eggshell waste as a catalyst. While, char and gas yield of
40.05% and 40.25% obtained without catalyst were reduced by 15.13% and 10.84% in catalytic
pyrolysis. It can be explained that the CaO from waste eggshell can increased the oil yield in the
pyrolysis process.

Table 2: Product yield comparison in pyrolysis process

Product yield (%)
Material
Bio oil Char Gas
Without catalyst 19.69 40.05 40.25
With catalyst (20%
45.67 24.92 29.41
waste eggshell)

Conclusion
The conversion of waste eggshell from CaCO3 to CaO was analyzed by TGA and XRF analysis.
After calcination process, most of the composition of the eggshell was transformed to CaO which is
98.56%. Pyrolysis process with eggshell as catalyst increased the production of bio-oil by 25.98%.
CaO from eggshell is expected to be a catalyst for bio-oil production which could lower the
production cost and eco-friendly.

Acknowledgement
The authors wish to acknowledge their appreciation to the School of Environmental Engineering,
Universiti Malaysia Perlis for the use of the facilities and also to RAGS 9018-00069 for the
financial support.
 80 Current Material Research Using X-Rays & Related Techniques

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