252 Int. J. Global Warming, Vol. 2, No.

3, 2010

Utilisation of eggshell membrane as an adsorbent

for carbon dioxide

Arghya Banerjee
Indian Institute of Petroleum,
Mohkampur, Dehradun 248005, Uttarakhand, India
E-mail: arghya_bdelhi@rediffmail.com

Sriparna Panda
Jubilant Oraganosys,
56 Industrial Area,
Nanjangud, Distt. Mysore Karnataka 571 302, India
E-mail: sriparna3@gmail.com

Manojit Sidhantha
Lummus Technology,
Infinity Tower B, 2nd Floor DLF Cybercity,
Phase–II Sector 25A, Gurgaon 122002, India
E-mail: manojit.sidhantha1@gmail.com

Sampa Chakrabarti*, Basab Chaudhuri

and Sekhar Bhattacharjee
Department of Chemical Engineering,
University of Calcutta,
92, Acharya PC Road, Kolkata 700 009, India
Fax: 91 033 2351 9755
E-mail: sampac@vsnl.net
E-mail: sampac.2008@gmail.com
E-mail: basabc@vsnl.net
E-mail: sekharbhatta@gmail.com
*Corresponding author

Abstract: Carbon dioxide (CO2) is a major greenhouse gas responsible for

global warming. This work aims to explore a cheap and easy way for CO2
adsorption from the atmosphere, by using an eggshell membrane. Eggshell
membrane could be used upto four times with intermediate regeneration with
acetic acid solution. Atomic absorption spectrophotometer (AAS) analysed the
amount of CO2 adsorbed as equivalent calcium (Ca) present in calcium
carbonate (CaCO3). An average of 6824 mg CO2 could be adsorbed per g
of eggshell membrane. Scanning electron micrograph (SEM) was used to
analyse the surface morphology of the fresh and regenerated eggshell
membrane.

Copyright © 2010 Inderscience Enterprises Ltd.

 Utilisation of eggshell membrane as an adsorbent for carbon dioxide 253

Keywords: carbon dioxide; adsorption; eggshell membrane.

Reference to this paper should be made as follows: Banerjee, A., Panda, S.,
Siddhanta, M., Chakrabarti, S., Chaudhuri, B. and Bhattacharjee, S. (2010)
‘Utilisation of eggshell membrane as an adsorbent for carbon dioxide’,
Int. J. Global Warming, Vol. 2, No. 3, pp.252–261.

Biographical notes: Arghya Banerjee obtained his BTech (2008, University of

Calcutta) and MTech (2010, IIT Kanpur) in Chemical Engineering.
He is currently working as a Scientist at the Indian Institute of Petroleum,
Dehradun.

Sriparna Panda obtained her BTech in Chemical Engineering from the

University of Calcutta, India, in 2008. She is now working in Jubilant
Organosys Ltd., Mysore, India.

Manojit Sidhantha obtained his BTech in Chemical Engineering from the

University of Calcutta, India, in 2008. He is now working in ABB Lummus,
Gurgaon.

Sampa Chakrabarti received a BTech (1987), an MTech (1989) and a PhD

(2006) in Chemical Engineering from the University of Calcutta. She has
about 11 years of industrial experience in reputed engineering consultancy
organisations of the country and has about 10 years of teaching and research
experiences. She is currently a Reader in the Department of Chemical
Engineering, University of Calcutta. Her research interest is in the area of
environmental remediation and she has about 20 publications in highly rated
international journals and conferences.

Basab Chaudhuri obtained his BTech (1984, University of Calcutta) and PhD
(1989, University of Mumbai) in Chemical Engineering. Engaged in teaching
and research since 1991, he is currently a Professor of Chemical Engineering
and the Registrar of the University of Calcutta. He had worked in the
University of Groningen, The Netherlands, for two years. He was an INSA
visiting scientist in the Chung – Buk National University, South Korea. He has
published over 30 papers in noted journals. He has specialisation in separation
process, catalysis and wastewater treatment.

Sekhar Bhattacharjee received a BTech (1975, University of Calcutta),

MTech (1978, IIT Kanpur) and PhD (2006, University of Pittsburg, USA) in
Chemical Engineering. He has seven years working experience in
internationally reputed consultancy organisations of India and USA. He is
currently a Professor of Chemical Engineering and Dean of the Faculty of
Engineering and Technology in the University of Calcutta. He had been a
Visiting Faculty in the University of Alberta, Canada. He specialises in
chemical engineering thermodynamics, process simulation and environmental
engineering and has published a good number of research papers in
internationally reputed journals.

1 Introduction

Carbon dioxide (CO2), though a Greenhouse Gas (GHG), is a necessary ingredient in the
life cycle of animals and plants (Lindsey, 1993; Pierantozzi, 1993). Combustion of most
254 A. Banerjee et al.

carbon-containing substances produces CO2. Energy utilisation today is based on

combustion of carbonaceous fuels, which are dominated by the three fossil fuels: coal,
petroleum and natural gas. Environmental problems owing to emissions of pollutants
from combustion of solid, liquid and gaseous fuels in various stationary and mobile
energy systems as well as the emissions from manufacturing plants have also become
major global problems involving not only the pollutants such as NOx, SOx and particulate
matter, but also the GHGs such as CO2 and methane (CH4). There are increasing
concerns for global climate change (Levin, 1992; Melillo et al., 1993; Schimel, 1995)
and thus increased interest for reducing the emissions of GHG, particularly CO2 (Paul
and Pradier, 1994; Halmann and Steinberg, 1999; Maroto-Valer et al., 2002; DOE/NETL
Report, 2005). The sources of CO2 emissions include stationary, mobile and natural
sources, as listed in Table 1. Atmospheric CO2 concentration changed only slightly over
the period of 1000 years till 20th century, from 280 ppmv in 1000 to 295 ppmv in 1900
based on Antarctica ice core data (Etheridge et al., 1998; Song, 2006), but increased to
315 ppmv in 1958 and further to 377 ppmv in 2004 based on actual analysis in Hawaii
(Keeling and Whorf, 2005). According to a recent study, about 290 billion tons of carbon
have been released to the atmosphere from the consumption of fossil fuels and cement
production since 1751, but half of these emissions have occurred since the mid-1970s
(Marland et al., 2005).

Table 1 Sources of carbon dioxide emission

Stationary sources Mobile sources Natural sources

Fossil fuel-based electric power Cars and sports utility vehicles Humans
plants
Independent power producers Trucks and buses Animals
Manufacturing plants in industrya Aircrafts Plants and animal decay
Commercial and residential Trains and ships Land emission/leakage
buildings
Flares of gases at fields Construction vehicles Volcano
Military and government Military vehicles and devices Earthquake
facilities
a
Major concentrated CO2 sources include plants for manufacturing hydrogen, ammonia,
cement, limestone and soda ash as well as fermentation processes and chemical oxidation
processes.
Source: Song (2006)

CO2 is an important source of carbon useful for preparation of organic chemicals and
food materials. Therefore, the strategy of CO2 management should stress upon the
utilisation of the captured CO2 for the production of industrially useful and
environmentally safe chemicals as well as alternative fuels (Song, 2006).
Generally, in practice, CO2 is captured by alkali or amine scrubbing for which
disposal of the product is sometimes a problem. Reports are also available for adsorption
of CO2 on to zeolite-type adsorbents (Mao et al., 1993) and photocatalytic reduction of
CO2 to organic compounds like methanol and formaldehyde (Tan et al., 2006; Yang and
Fu, 2003). Such adsorption of CO2 with specially developed adsorbent is generally done
in course of separation and very often leads to the production of a purer form of CO2,
 Utilisation of eggshell membrane as an adsorbent for carbon dioxide 255

but till date it is not cost-effective. This work aims simultaneously at the exploration of a
cheap adsorbent for CO2 and at the disposal of a solid waste like eggshell.

2 Idea behind the process

Eggshell is a typical solid waste from poultry and food industry. In many countries,
it is an accepted practice for eggshells to be dried and used as a source of calcium in
animal feeds. But, nowadays it is not used owing to concerns over the transfer of
pathogens from raw animal by-products. The consumption of egg in India is about
1.6 million tons per annum (www.thepoultrysite.com), which generates a huge amount of
shell as waste. If the biological membrane available from this waste can be used for
adsorption of CO2, it will lead to removal of the GHG from atmosphere to a substantial
extent. A major problem with profitable utilisation of eggshell waste is ensuring the
complete separation of the shell and the membrane. Many methods have been tried to
separate the membrane from the shell completely, as when separated, both items can have
significant value.
Eggshell is typically constituted of three layers – cuticle on the outer surface,
a spongy calcareous middle layer and inner lamellar layer. The second and the third
layers are composed of protein fibres bonded to CaCO3. The porous structure of the
eggshell permits exchange of gas through it. Eggshell membrane stays just below the
shell; there are two layers of membrane – a thick outer layer and a comparatively
thin inner layer. The combined thickness of the two layers of the membrane is about
100 microns. SEM of the eggshell and eggshell membrane are given in Figure 1.

Figure 1 SEM (1000 times magnified) for (a) eggshell and (b) eggshell membrane

It is a common observation that the external membrane of a freshly laid egg is soft and on
being exposed in the atmosphere for a few minutes, the soft membrane becomes a hard
shell, which is due to the formation of CaCO3. When an egg is broken or boiled, the hard
shell containing membrane underneath becomes a waste product. Eggshell has been used
for purification of hydrogen generated for fuel cells (www.physorg.com). Ground
eggshell has also been used for the adsorption of dye (Tsai et al., 2006) or heavy metals
(Otum et al., 2006) from wastewater and CO2 from combustion gases in a fluidised bed
(Ives et al., 2008), but report of using eggshell membrane as an adsorbent for CO2 is not
very common.
256 A. Banerjee et al.

In this research, it has been explored that whether the membrane attached to the hard
shell could be disengaged and used for further uptake of CO2 from air, and whether the
process could be repeated more than once.
It is not easy to recover the membrane lying underneath the hard shell, left behind
after the use of the egg, either in raw, available form or as boiled egg. However, if the
hard shell is exposed to dilute acids, either mineral acid or carboxylic acid, evolution of
CO2 occurs and the membrane gradually disengages from the hard shell.

3 Experimental procedures and materials

Materials
Analytical grade (AR) glacial acetic acid obtained from S.D. Fine Chem., Mumbai, India,
was diluted with distilled water to prepare aqueous acid solutions. Standard calcium
salt solutions for AAS were from E. Merck India, Mumbai. Freshly prepared double
distilled water was used wherever required.
Preparation of the adsorbent membrane
Eggs of hen from poultry were boiled in distilled water at 100°C for 15 min so that the
shell can be easily peeled off from the egg. This is a conventional method for disengaging
eggshell from egg. Support for this method is also available in the works of Pramanpol
and Nitayapat (2006), Sacia (2009). The hard shells were carefully peeled off so that the
membrane could be separated. The membrane was then kept immersed in 55 vol%
(9.7 M) acetic acid (75 mL glacial acetic acid in 55 mL water) for 24 h. The membrane is
now ready for adsorbing CO2 from the ambient air. Decalcification of membrane by
acetic acid or EDTA was suggested by Nys et al. (2004) and Nakano et al. (2003).
It was assumed that all the CaCO3 present in the membrane had been dissolved into
solution as calcium acetate, Ca(CH3COOH)2.
Experimental procedure
In a typical experiment, a known weight of the membrane was exposed to air for
adsorption of CO2. It took about 12 h for the flexible membrane to become hard and the
formation of a hard layer was palpable. An attempt to determine CaCO3 formed by
weighing the membrane did not give reproducible results. It was then thought that the
hard shell formed on the biological membrane would be exposed to aqueous acid solution
again to wash off all CaCO3 deposited on the soft biological membrane and the aqueous
acid would be analysed for its calcium content. The calcium content would then be
correlated with CO2 adsorbed. The only assumption in this method of determination of
CO2 adsorbed is that carbonate deposited on the biological membrane is CaCO3 only and
not any other metal carbonate. Total amount of calcium has been estimated using Varian
AA240 AAS with required dilution against standard calibration curve. Surface
morphology of the membrane was analysed with a Field Emission SEM (FESEM JEOL
Model JSM 6700F).
The piece of membrane sample was then exposed to the atmosphere for 24 h. Area of
the membrane was estimated as 70 cm2 as follows (Narushin, 2005):
 Utilisation of eggshell membrane as an adsorbent for carbon dioxide 257

S = (3.155 – 0.0136 L + 0.0115 B)

where
L = length of egg in cm
B = maximum breadth of egg in cm
S = surface area of egg in cm2.
The piece of membrane was then dipped into an acid solution (Set I) with 70 mL acetic
acid and 55 mL water. It was assumed that calcium dissolved into acetic acid comes
entirely from CaCO3 (produced from the adsorption of CO2 on CaO of the membrane).
Therefore, estimation of total calcium leads to the estimation of adsorbed CO2. The acid
solution was analysed for total calcium content using AAS. The process was repeated
using a 40 vol% (7.1 M), 75 mL glacial acetic acid and 110 mL water (Set II) to note the
influence of concentration of acid.

4 Results and discussions

Table 2 shows the experimental data for the dissolved calcium (that could be correlated
with the adsorbed CO2) from the eggshell membrane. The data shows that the amount of
CO2 adsorbed (Table 2) by the membrane available from a single egg is 1.15 g (average
of Set I and Set II). Average adsorption capacity of the fresh membrane is 6824 mg
CO2/g. It was observed that the membrane could be used up to five times with
intermediate regenerations for adsorbing a considerable amount of CO2. After the fourth
regeneration, in case of Set I, the adsorption capacity was found to decrease to 1608 mg
CO2/g membrane, i.e., 21.1% of its original value. The figure for Set II was 1923.28 mg/g
membrane, i.e., 32% of the original capacity.

Table 2 Amount of carbon dioxide adsorbed

Set I Set II
Conc. of Ca Capacity Conc. of Ca Capacity
Sample Condition (mg/L) (%) (mg/L) (%)
DS0 Fresh membrane 7942.0289 100 6326.7860 100
DS1 Regenerated-1 3826.0869 48 3689.2860 58
DS2 Regenerated-2 3652.1739 45 3546.4290 56
DS3 Regenerated-3 3362.3188 42 3153.5710 49
DS4 Regenerated-4 1681.1594 21 2010.7140 32
Experiments of each set were repeated at least thrice (n = 3) and the standard deviation
was within 5%.

The difference in the concentration of calcium in the two above-mentioned cases may be
attributed to the undissolved CaCO3 with lower acid concentration.
Figure 2 shows the surface morphology of the fresh membrane and the membrane
after the first regeneration. At 500 times magnification, there was no difference observed
on the surface but at 30,000 times magnification, the membrane after regeneration
258 A. Banerjee et al.

appears to be more compact compared with the fresh one. This is the reason for which
adsorption capacity decreased with increased number of regeneration. For both cases,
there were two abrupt decreases in the adsorption capacities after the fourth regeneration.

Figure 2 SEM photograph for the (a) fresh membrane (500 times magnification)
and (b) membrane after first regeneration at different magnifications (30,000 times
magnification)

(a)

(b)

May be due to acid treatment the adsorption sites of the membrane have been destroyed
after the fourth regeneration. EDS analysis (Table 3) shows that there was virtually no
difference between the initial and the membrane after the first regeneration regarding
composition of membrane. A decrease in the calcium content is due to the dissolution of
Ca salt by acetic acid.
If average consumption of eggs in India is 148 million per day (assuming
a population of 1.15 million), then the available membrane surface area is
70 × 148 = 10.36 billion cm2. Therefore, the total quantity of CO2 that can be adsorbed in
India using eggshell membrane is 148 × 106 × 1.15 = 170.2 metric tons.
 Utilisation of eggshell membrane as an adsorbent for carbon dioxide 259

Table 3 EDS analysis data for eggshell membranes

Fresh membrane After first regeneration

Element present Weight percent Element present Weight percent
Carbon 62.81 Carbon 63.35
Oxygen 32.55 Oxygen 31.92
Sulphur 4.63 Sulphur 4.73
Calcium 0.02 Calcium 0.00

5 Conclusion

Eggshell membrane has been used for sequestration of CO2 from atmosphere.
The membrane can be satisfactorily used up to four regenerations though the adsorption
capacity decreases from 6824 mg CO2/g to 1608 mg CO2/g membrane on an average
from fresh to fourth time regenerated membrane. The results are encouraging and point
to a way of capturing CO2 with the help of a waste material like eggshell.
The recovery of membrane by acid treatment that has been practised in the laboratory
process needs to be replaced by a mechanical process in actual scale of operation;
otherwise, the envisaged advantage will not accrue. Moreover, in practice, it is not also
economical to regenerate such waste material till date. The real challenge is to develop
eggshell-like membrane in the laboratory, employing biological techniques, and use the
same for capture of CO2. The study may inspire us to separate the membrane from the
shell mechanically after our daily consumption of egg and to keep the membrane exposed
to atmosphere so that a considerable amount of CO2 may be adsorbed till the process is
developed to an economically viable one.

Acknowledgements

The authors acknowledge Indian Association for Cultivation of Science, Kolkata,

for FESEM and Bose Institute, Kolkata, for AAS.

References
DOE/NETL Report (2005) Carbon Sequestration. Technology Roadmap and Program Plan,
US Department of Energy, National Energy Technology Laboratory.
Etheridge, D.M., Steele, L.P., Langenfelds, R.L., Francey, R.J., Barnola, J.M. and Morgan, V.I.
(1998) ‘Historical CO2 record from the Law Dome DE08, DE08-2, and DSS ice cores
(atmospheric CO2 concentrations, Antarctic ice cores)’, Trends: A Compendium of Data on
Global Change, Obtained through the Internet: http://cdiac.esd.ornl.gov/
Halmann, M.M. and Steinberg, M. (1999) Greenhouse Gas Carbon Dioxide Mitigation: Science
and Technology, Lewis Publishers, Boca Raton, FL, p.568.
260 A. Banerjee et al.

Ives, M., Mundy, R.C., Fennell, P.S., Davidson, J.F., Dennis, J.S. and Hayhurst, A.N. (2008)
‘Comparison of different natural sorbents for removing CO2 from combustion gases,
as studied in a bench-scale fluidized bed’, Energy & Fuels, Vol. 22, No. 6, pp.3852–3857.
Keeling, C.D. and Whorf, T.P. (2005) ‘Atmospheric CO2 records from sites in the SiO air sampling
network’, Trends: A Compendium of Data on Global Change, Carbon Dioxide Information
Analysis Center, Oak Ridge National Laboratory, US Department of Energy, Oak Ridge,
TN, USA.
Levin, S.A. (1992) ‘The problem of pattern and scale in ecology: the Robert H. MacArthur
award lecture’, Ecology, Vol. 73, No. 6, pp.1943–1967.
Lindsey, J.S. (1993) Carbon Dioxide. McGraw-Hill Encyclopaedia of Chemistry, 2nd ed.,
McGraw-Hill, New York, pp.157–159.
Mao, G., Tsuji, M. and Tamaur, Y. (1993) ‘Synthesis and CO2 adsorption features of a
hydrotalcite-like compound of the Mg (super 2+) –Al (super 3+) –Fe(CN)6 (super 4–)’,
Clays and Clay Minerals, Vol. 41, No. 6, pp.731–737.
Marland, G., Boden, T.A. and Andres, R.J. (2005) ‘Global, regional, and national CO2 emissions’,
Trends: A Compendium of Data on Global Change, Carbon Dioxide Information Analysis
Center, Oak Ridge National Laboratory, US Department of Energy, Oak Ridge, Tenn, USA.
Maroto-Valer, M.M., Song, C.S. and Soong, Y. (2002) Environmental Challenges and Greenhouse
Gas Control for Fossil Fuel Utilization in the 21st Century, Kluwer Academic/Plenum
Publishers, New York, p.447.
Melillo, J.M., Mcguire, A.D., Kicklighter, D.W., Moore, B., Vorosmarty, C.J. and Schloss, A.L.
(1993) ‘Global climate change and terrestrial net primary production’, Nature, Vol. 363,
No. 6426, pp.234–240.
Nakano, T., Ikawa, N.I. and Ozimek, L. (2003) ‘Chemical composition of chicken eggshell and
shell membranes’, Poultry Science, Vol. 82, No. 3, pp.510–514.
Narushin, V.G. (2005) Egg Geometry Calculation using the Measurements of Length and Breadth,
Poultry Consultant Office, 35 Lenin Ave. 145-B, Zaporozhye 69035, Ukraine.
Nys, Y., Gautron, J., Garcia-Ruiz, J.M. and Hincke, M.T. (2004) ‘Avian eggshell mineralization:
biochemical and functional characterization of matrix proteins’, C.R. Palevol 3 (General
Palaentology, Palaeobiochemistry), pp.549–562.
Otum, J.A., Oke, I.A., Olariyone, N.O., Adie, D.B. and Okufu, C.A. (2006) ‘Adsorption isotherms
of Pb (II), Ni (II) and Cd (II) ions onto PES’, Journal of Applied Sciences, Vol. 6, No. 11,
pp.2368–2376.
Paul, J. and Pradier, C-M. (Eds.) (1994) Carbon Dioxide Chemistry: Environmental Issues,
Royal Society of Chemistry, Cambridge, UK, p.405.
Pierantozzi, R. (1993) Carbon Dioxide. Kirk-Othmer Encyclopaedia of Chemical Technology,
4th ed., Vol. 5, John Wiley and Sons, New York, pp.35–53.
Pramanpol, N. and Nitayapat, N. (2006) ‘Adsorption of reactive dye by eggshell and its
membrane’, Kasetsart J. (Nat. Sci.), Vol. 40 (Suppl.), pp.192–197.
Sacia, E.R. (2009) Synthesis and Regeneration of Enhanced Eggshell Sorbents for Clean Coal
Applications, BS Thesis, Ohio State University, Ohio, USA.
Schimel, D.S. (1995) ‘Terrestrial ecosystems and the carbon cycle’, Global Change Biol., Vol. 1,
No. 1, pp.77–91.
Song, C. (2006) ‘Global challenges and strategies for control, conversion and utilization of CO2
for sustainable development involving energy, catalysis, adsorption and chemical processing’,
Catalysis Today, Vol. 115, pp.2–32.
Tan, S.S., Zou, L. and Hu, E. (2006) ‘Photocatalytic reduction of carbon dioxide into gaseous
hydrocarbon using TiO2 pellets’, Catalysis Today, Vol. 115, pp.269–273.
 Utilisation of eggshell membrane as an adsorbent for carbon dioxide 261

Tsai, W.T., Yang, J.M., Lai, C.W., Cheng, Y.H., Lin, C.C. and Yeh, C.W. (2006) ‘Characterization
and adsorption properties of eggshells and eggshell membrane’, Bioresource Technology,
Vol. 97, pp.488–493.
Yang, Q.H. and Fu, X.X. (2003) ‘The photocatalyzed reduction of aqueous sodium carbonate
using nano SrFeO3’, Chinese Chemical Letters, Vol. 14, No. 6, pp.649–652.

Websites
Obtained through the internet: http://www.physorg.com/news110038781.html
Obtained through the internet: http://www.thepoultrysite.com/articles/1237/prospects-for-
expanding-egg-consumption