Materials and Structures (2018) 51:115

https://doi.org/10.1617/s11527-018-1243-7 (0123456789().,-volV)
(0123456789().,-volV)

ORIGINAL ARTICLE

Eggshell waste to produce building lime: calcium oxide

reactivity, industrial, environmental and economic
implications
Eduardo Ferraz . José A. F. Gamelas . João Coroado . Carlos Monteiro .
Fernando Rocha

Received: 3 May 2018 / Accepted: 23 August 2018 / Published online: 3 September 2018
Ó RILEM 2018

Abstract Eggshells wastes are produced in huge
amounts worldwide. The recycling or valorization of
this waste, which otherwise is usually disposed in
landfills, represents an opportunity within a circular
economy perspective. In the present work, the poten-
tial of chicken eggshell waste to produce calcitic lime
was explored. After collection from an industry
supplier, the waste was thoroughly characterized for
its mineralogical, chemical, and thermal properties.
The material was calcined at 1000 °C, and the
obtained calcium oxide was evaluated for its reactivity
in wet slaking tests. Comparison was made with
commercial limestone used as reference. It was found
E. Ferraz  J. Coroado
Techn&Art R&D Unit, Polytechnic Institute of Tomar,
Quinta do Contador, Estrada da Serra, 2300-313 Tomar,
Portugal
e-mail: ejmoferraz@ipt.pt
J. A. F. Gamelas (&)
CIEPQPF R&D Unit, Department of Chemical
Engineering, University of Coimbra, Pólo II. R. Sı́lvio
Lima, 3030-790 Coimbra, Portugal
e-mail: jafgas@eq.uc.pt
that the calcium oxide from eggshell waste belonged
to the most reactive class (R5—60 °C within 10 min),
the same of the calcium oxide from limestone.
However, different times were obtained to reach
60 °C (25 s and 4:37 min:s) and for 80% of the
reaction (28 s and 5 min) for calcium oxide from
limestone and eggshell waste, respectively. The lower
reactivity of calcium oxide from eggshell waste was
related to its larger size particles with smoother
surfaces and lower specific surface area in comparison
to limestone calcium oxide. Industrial, environmental
and economic implications concerning the use of this
waste to produce lime were also evaluated. The
eggshell waste could be all consumed at an industrial
scale in Portugal allowing for approximately 2.6%
partial substitution of limestone in a lime factory.
Keywords By-product  Quicklime  Wet slaking 
Hydration rate  Induction periods  Colour
1 Introduction

C. Monteiro
Egg-laying female animals of many different species,
CaCO3 - Conservação do Património Artı́stico, Lda, Vale including birds, reptiles, amphibians and fishes are
Cabrito - Madalena, 2305-441 Tomar, Portugal kept throughout the world to produce eggs that are
eaten by humankind since ancient times. Nowadays,
F. Rocha
Geobiotec R&D Unit, Department of Geosciences,
egg from chicken or hen (Gallus gallus domesticus,
University of Aveiro, Campus Universitário de Santiago, Linnaeus, 1758) represents a global mass production
3810-193 Aveiro, Portugal
115 Page 2 of 14
industry, and other worldwide choices for consump-
tion are quail, duck, goose, turkey and ostrich eggs.
Bird eggs consist of an eggshell (biomineralized
protected material), eggshell membrane, albumen
(white) and vitellus (yolk). An eggshell is constituted
by a three-layered structure: cuticle, spongeous and
lamellar layer. The cuticle layer represents the outer-
most surface composed mainly by proteins. Spon-
geous and lamellar layers form a matrix constituted by
protein fibres bonded to calcium carbonate crystals.
The eggshell is generally composed by 94 wt% of
calcium carbonate, 1 wt% of calcium phosphate,
1 wt% of magnesium carbonate and 4 wt% of organic
matter [1]. Two thin eggshell membranes constituted
mainly by collagen, alkynes, alkanes, amines, and
amides of proteins and carboxylic acids [2] exist
between the eggshell and the albumen. The eggshell
waste is composed by the three layers and the two
membranes.
Quina et al. [3] and Oliveira et al. [4] collected
some technological options for recycling eggshell as
raw material in food additives for human and animal
feed, soil amendment, cosmetics and biomaterials
composites, and in operating supplies, such as, catalyst
and sorbent applications. Pliya and Cree [5] reported
the use of chicken eggshell waste as limestone filler in
a Portland cement mortar. The role and performance
of eggshell membrane in engineering applications was
reviewed by Park et al. [2], and Baláž [6] made a
compilation on the eggshell membrane as a platform
for applications in materials science.
Calcined chicken eggshell waste, as source of
calcium oxide, has been studied for some applications:
catalyst in biodiesel production [7], green synthesis
[8], CO2 sorbent [9], mortar based on eggshell lime
[10], polyethylene composite [11], transesterification
[12], thermoluminescence [13], and many others.
The calcium carbonate present in the eggshell can
be transformed into calcium oxide, afterwards into
calcium hydroxide (calcitic lime), and finally used as
binder (construction material) on a mortar.
Limestone, as the most common georesource of
CaCO3 (calcite), is submitted to thermal decomposi-
tion (heating) between 950 and 1000 °C on a process
called calcination (or lime-burning) to liberate the
CO2 and convert the CaCO3 into CaO (quicklime).
Quicklime is very unstable at ambient pressure and
temperature. To minimize this constraint, it must be
combined with water, on a process called slaking or
Materials and Structures (2018) 51:115
hydration, and transformed into Ca(OH)2 (port-
landite). In ‘‘dry slaking’’, quicklime is slaked with
just enough water to obtain the hydrated lime in
powder form. In ‘‘wet slaking’’, the hydrated lime is
obtained in suspension form. When the suspension
settles, it is obtained a clear supernatant solution (lime
water) saturated with Ca(OH)2 colloidal particles and
dissolved Ca2? and OH- ions.
To evaluate the reactivity of a lime in wet slaking
process, the temperature, in the reaction of mixing
quicklime with water, is measured as a function of
time, thus providing the wet slaking curve. The wet
slaking curves have been used by Frank [14], Potgieter
et al. [15], Hogewoning et al. [16], Ferraz et al. [17],
and others to study de hydration behaviour of calcium
oxide from various origins.
The general wet hydration mechanism of quick-
lime was stated by several authors [18–24]. This
mechanism stipulates two ‘‘retardant periods’’ during
the wet slaking. Briefly, first the consumption of
CaO occurs with the formation of thin layers of
Ca(OH)2 on the surface of the CaO crystals. This
transformation is controlled by the diffusion of Ca2?
and OH- ions in the solid–liquid interface from the
solution onto the CaO reacting surface. Also, some
Ca(OH)2 dissolves providing Ca2? and OH- to the
solution. The speed of the diffusion directly affects
the first retardant period. Then, a second retardant
period occurs in which the precipitation of Ca(OH)2
from the supersaturated liquid phase occurs. The
duration of these ‘‘induction periods’’ depends much
on the lime reactivity.
In Portugal, according to the FAO [25] official data,
the average annual production of chicken eggs has
been 131318 t, for the years between 2012 and 2016.
The potential amount of eggshell waste is 15758
t/year, considering as * 12 wt% the content of
eggshell waste (eggshell plus membrane) in chicken
egg with an average mass of * 61 g/egg. The
industrial row of pasteurized and derivative egg
products is constituted by four (two medium and two
small-sized) enterprises which produce chicken pas-
teurized liquid egg, white and yolk, boiled egg, peeled
egg, egg in spray, and other egg derivatives. The
process for obtaining the referred products generates
chicken eggshell waste, that is classified as animal by-
product [26] in category 3 [27].
The present research aimed at finding a sustainable
solution for the recycling/valorization of eggshell
Materials and Structures (2018) 51:115
waste, by exploring its potential to produce calcitic
lime. The recycling will transform the eggshell waste
into a high value-added eco-binder construction
product and reduce the problems associated to waste
deposition in landfill. Additionally, it will contribute
to the reduction of the exploitation of georesources,
commonly associated to the industrial production of
lime.
2 Materials and methods
The industrial chicken eggshell waste (shell plus
membrane) used in this work was provided by a
factory located in Portugal producing pasteurized
liquid eggs and boiled eggs. A commercial limestone,
collected from an industrial rock plant, was used as
reference material.
The weight ratio of the eggshell waste to the total
egg was determined in household eggs (A category
and M class). The water content of the corresponding
household eggshell waste was evaluated by gravime-
try after drying the waste at 105 ± 5 °C. For the
industrial eggs, this value was taken from the litera-
ture [28].
The industrial eggshell waste was dried at
105 ± 5 °C (Memmert UF 110), crushed in a porce-
lain mortar, milled in a tungsten grinder (Retsch RMO
100) for 3 min and sieved at 38 lm.
The powders were characterized by mineralogical
analysis using X-ray diffraction (XRD), chemical
analysis by X-ray fluorescence (XRF) spectrometry,
thermogravimetric analysis (TGA), differential scan-
ning calorimetry (DSC), Fourier Transform Infrared-
Attenuated Total Reflection (FTIR-ATR) spec-
troscopy, and Raman spectroscopy, following previ-
ously published methodologies [17].
The eggshell waste was calcined at 1000 °C with
2 h soak time in a Nabertherm N 100/H laboratory
kiln. The quicklime was milled in a porcelain roller
ball mill during a maximum of 30 min.
The specific surface area of the quicklime samples
was determined by N2 adsorption at 77 K in a
Micromeritics ASAP 2000 instrument, using the
BET theory. Samples were previously treated in a
vacuum at room temperature before analysis. The
morphology of the particles was evaluated by field
emission scanning electron microscopy (FESEM) in a
Carl Zeiss Merlin microscope, in secondary electron
Page 3 of 14 115
mode. An acceleration voltage of 2 kV and working
distance of 6.6 mm were used. Samples were previ-
ously sputter-coated with gold using an Edwards EXC
120 turbo vacuum pump controller coupled with a
Huttinger PFG 1500 DC generator for direct current
sputtering. The thickness of the gold layer was
approximately 25–30 nm.
The quicklime powder, previously sieved under
250 lm, was submitted to the wet slaking reactivity
test according to NP EN 459-2 standard. The exper-
imental description of the wet slaking test is detailed
elsewhere [17]. This reactivity test measures the
temperature increase in the reaction of mixing quick-
lime with water as a function of time, enabling to
obtain the wet slaking curve. Additionally, the time
necessary to reach a threshold temperature (60 °C or
50 °C) allows to set the reactivity class of the calcined
material. The slaking reaction of the quicklime is
assumed to be 100% complete when is reached the
maximum temperature of the test (T0 maximum).
Tmaximum (°C) represents the maximum temperature
of the reaction and is calculated from the maximum
temperature reached during the test (T0 maximum), as
follows in Eq. 1:
Tmaximum ¼ ð1:1  T0 maximumÞ  2 ð1Þ
The reactivity of the quicklime may also be
reported as the time (tu) required for the reaction to
be 80% complete. The temperature (Tu) at which the
reaction is 80% complete is calculated using the Eq. 2,
where T0 (°C) is the initial temperature of the test:
Tu ¼ ð0:8  T0 maximumÞ þ ð0:2  T0Þ ð2Þ
After calculating the Tu value, the tu value is
obtained directly from the wet slaking curve.
The free water content and the expansion behaviour
were evaluated on the suspensions obtained after the
wet slaking test, according to NP EN 459-2 standard.
Hydrated lime powder samples were obtained after
drying (105 ± 5 °C) the lime suspensions.
This material was submitted to fundamental char-
acterization and to colour evaluation measurements
[17]. The colour results expressed in CIE L*a*b*
colour space were calculated with the data of four
replicates.
115 Page 4 of 14
3 Results and discussion
3.1 Characterization of the eggshell waste
The decomposition of the organic matter present in the
wet eggshell waste emanates an intense odour, that
was somewhat noticed during the drying stage.
The X-ray diffraction patterns of the eggshell and
the commercial limestone, with the identification of
Fig. 1 X-ray diffraction patterns of the raw and lime materials from eggshell and limestone
Materials and Structures (2018) 51:115
the main crystalline phases, are presented in Fig. 1.
The mineralogical composition of the eggshell and the
commercial limestone is similar. Commercial lime-
stone was mainly composed by calcite, as expected,
and vestigial dolomite. Calcite was the only mineral
identified in eggshell.
The XRF spectroscopy data of the major elements
(Table 1, expressed in the oxide form) showed, for
both materials, the prevalence of Ca (54–55 wt%)
Materials and Structures (2018) 51:115 Page 5 of 14 115

Table 1 XRF data (major elements) of the raw and lime materials from eggshell and limestone
Sample CaO MgO Na2O K2O SiO2 Al2O3 Fe2O3 MnO TiO2 P2O5 SO3 LOI
(wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%)

Raw 55.25 0.38 0.04 0.01 0.20 0.12 0.06 nd nd 0.01 0.06 43.88
limestone
Raw 53.51 0.66 0.12 0.03 0.02 0.01 nd nd nd 0.30 0.55 44.79
eggshell
Lime 81.73 1.25 0.09 0.04 0.22 0.11 0.17 nd nd 0.01 0.16 16.24
Eggshell 76.77 0.86 0.10 0.03 0.07 0.02 nd nd nd 0.33 0.18 21.65
lime
LOI loss on ignition, nd not detected

corroborating the dominant presence of calcite iden-
tified by XRD. The commercial limestone had
0.4 wt% of Mg that is related with the vestigial
dolomite identified by XRD. In eggshell, the magne-
sium (0.7 wt%), sulphur (0.6 wt%) and phosphorus
(0.3 wt%) contents are probably associated to impu-
rities in the lattice, or even present in the organic
phase. No mineral containing these elements was
detected by XRD.
The loss on ignition values were 43.9 wt% for
limestone and 44.8 wt% for eggshell, mainly related
with the CO2 release from calcite (in limestone and
eggshell) and dolomite (limestone) identified by XRD.
For eggshell, loss on ignition also includes the release
of organic matter present in the shell structure.
As for the minor elements (Appendix, Table 4), the
most noticed ones were chlorine in eggshell (184 ppm)
and strontium in both limestone (101 ppm) and
eggshell (98 ppm).
The thermogravimetric (TG and DTG) and differ-
ential scanning calorimetry (DSC and DDSC) plots of
the raw materials samples are presented in Fig. 2 and
in Appendix, Fig. 6, respectively. The weight loss
(Table 2) for eggshell occurred in three steps. The first
step up to * 125 °C could be attributed to the release
of residual adsorbed moisture (0.6 wt%). The second
step between * 125 and * 650 °C corresponding to
a weight loss of 4.4 wt% is attributed to the release of
organic matter present in the eggshell waste (shell plus
membrane). This value is in accordance with the value
of 4 wt% reported previously by Rivera et al. [1]. On
the other hand, the exothermic peak at * 357 °C
observed in the DSC expresses the thermal decompo-
sition of the organic matter. As expected for calcium
carbonate-based materials, the main weight loss, due
to the thermal degradation of calcium carbonate to
calcium oxide with the release of CO2, occurred from
* 650 8C to * 900 °C: 41.5 wt% for eggshell and
43.9 wt% for limestone; this corresponded to an
intense endothermic reaction. The theoretical CaCO3
content was calculated as 99.8 wt% for limestone and
94.4 wt% for eggshell (Table 2). The total weight loss
(20–1000 °C) was of 44.2 wt% and 46.6 wt%, for
limestone and eggshell, respectively, being these
values in reasonable agreement with the LOI values
obtained by XRF.
Figure 3 shows the FTIR spectra of the raw
materials. The spectra of the limestone and eggshell
(previously dried at 105 °C) were reasonably similar
showing three high-intensity bands at 1392/1396, 872
and 712 cm-1 corresponding to the asymmetric
stretching (m3), out-of-plane bending (m2) and in-plane
bending (m4), respectively, of the carbonate groups.
Two low-intensity bands at 2514 and 1795 cm-1 were
also observed, due to harmonic vibrations (2m2 ? m4
and m1 ? m4, respectively) of the fundamental modes
[29]. For the eggshell raw material two additional
bands at 1647 and 1085 cm-1 were observed. The
broad band at 1647 cm-1 can express the presence of
carbonyl groups (–C=O stretching) associated to
amides [30] present in the membranes of eggshell.
The band at 1085 cm-1 could be attributed to
asymmetric stretching of phosphate groups [31].
The Raman spectra of both the natural eggshell and
limestone (Appendix, Fig. 7) showed bands at 155 and
280 cm-1 (translational lattice vibrations), 711 cm-1
(m4), 1085 cm-1 (m1), 1435 cm-1 (m3) and 1747 cm-1
(m1 ? m4), which confirm the presence of calcite
115 Page 6 of 14 Materials and Structures (2018) 51:115

Fig. 2 Thermogravimetric
(TG) plot and derivative
curve (DTG) for the raw
eggshell and limestone

Table 2 Weight losses in the thermogravimetric analysis and CaCO3 content for the raw eggshell and limestone
Sample Weight loss CaCO3 (wt%)
Moisture (wt%) Organic matter (wt%) CO2 (wt%) Total (wt%)
20–125 °C 125–650 °C 650–900 °C 20–1000 °C

Raw limestone 0.1 0.1 43.9 44.2 99.8

Raw eggshell 0.6 4.4 41.5 46.6 94.4

Fig. 3 FTIR spectra of the

raw and lime materials from
eggshell and limestone
Materials and Structures (2018) 51:115
[29, 32]. Within the region of 4000–1800 cm-1 (not
presented in Appendix, Fig. 7) no bands were
observed in the spectra of any of the analysed
materials.
3.2 Wet slaking behaviour of the calcium oxide
from eggshell waste
Samples of eggshell waste and limestone were
calcined at 1000 °C. An incipient blasting, inside the
laboratory kiln, was noted during the calcination of the
eggshell waste.
Previously to the wet slaking experiments, the
calcium oxide samples were characterized for their
morphology and specific surface area. Figure 4 shows
the FESEM microphotographs of CaO samples
obtained after calcination of the CaCO3 materials at
1000 °C for 2 h. The results revealed that depending
on the origin, the particles differed significantly in
size, shape and agglomeration. In general, it can be
observed that CaO from eggshell (Fig. 4b) presents
particles with larger size than CaO from limestone
(Fig. 4a). CaO from eggshell presents rounded crys-
tals with smooth and wavy surfaces (Fig. 4d) by
opposition to crystals with irregular shape and rough
Fig. 4 FESEM micrographs of the calcium oxide particles from limestone and eggshell at 5000 (a and b, respectively) and 20,000
(c and d, respectively) magnifications
Page 7 of 14 115
and angular surfaces in the case of CaO from
limestone (Fig. 4c). CaO particles from eggshell show
higher agglomeration, revealing the merge of individ-
ual units into an interconnected skeleton structure.
The general absence of pores for both samples is
observed.
The BET specific surface area values of the
calcined materials were 5.2 and 1.4 m2/g, for calcium
oxide from limestone and calcium oxide from egg-
shell, respectively. These results agree with FESEM
microphotographs, with the lower size and less
agglomerated particles of CaO from limestone show-
ing a higher BET surface area.
It should be noted that the fresh quicklimes easily
react with atmospheric CO2 in the cooling process
inside the kiln, or during the further milling and
sieving stages, as proven by FTIR-ATR and XRD,
producing therefore residual amounts of calcium
carbonate in the calcined samples.
The calcined eggshell and calcined limestone
samples, after milled and sieved, were submitted to
wet slaking to obtain the wet slaking curves (Fig. 5)
and the reactivity parameters (Table 3) of each
calcium oxide material.
115 Page 8 of 14 Materials and Structures (2018) 51:115

Fig. 5 Wet slaking curves

of the calcined eggshell and
calcined limestone

Table 3 Wet slaking parameters and free water for the calcined eggshell and calcined limestone
Sample t60 Reactivity T’maximum Tmaximum Tu, 80% tu, 80% Free water
(min:s) class (°C) (°C) reaction (°C) reaction (min:s) (wt%)

Limestone CaO 00:25 R5 76.6 82.3 65.3 00:28 72.0

Eggshell CaO 04:37 R5 76.2 81.9 65.0 05:00 73.1
t60 time to reach 60 °C, T’maximum maximum temperature reached during the slaking process, Tmaximum maximum temperature
reached during the slaking process corrected using Eq. 1, Tu, 80% reaction temperature at which the slaking process is 80%
complete, calculated by Eq. 2, tu, 80% reaction time required for the slaking process to be 80% complete, obtained by the wet curve

The resulting suspensions reached the threshold
temperature of 60 °C for R5 and R4 reactivity class.
As expected, CaO from limestone showed a faster
slaking time (60 °C in 25 s), which classifies this
material on the class of the most reactive materials,
that is R5 class (reach 60 °C up to 10 min). The CaO
from eggshell was also classified on R5 class, but with
a slaking time at 60 °C much higher (04:37 min:s)
than that obtained for CaO from limestone. Concern-
ing the duration of the plateau temperature there was
no significant difference between the two tested
materials, as well as, for the cooling stage of the
suspensions (not drawn in Fig. 5). The difference
between the calcined limestone and calcined eggshell
for the parameters Tmaximum (0.4 °C) and Tu, 80%
reaction (0.3 °C) was negligible. Another important
fact was related with the tu parameter: for the CaO
from limestone the slaking reaction was 80% complete
in 28 s, but the CaO from eggshell required more time,
5:00 min.
It was not detected the formation of any kind of
lumps during the slaking of calcium oxide from
eggshell. Previously, it was claimed that the presence
of Mg in the raw carbonate material could give rise to
that behaviour [17, 33], but in the present case,
0.7 wt% of magnesium, as determined by XRF, did
not promote the formation of lumps.
Potgieter et al. [33] also proposed that the increas-
ing addition of magnesium oxide to limestone contin-
uously reduces the reactivity of the lime produced with
the admixtures. In the present work, the natural
eggshell has a Mg content higher than the natural
Materials and Structures (2018) 51:115
limestone (0.7 and 0.4 wt%, respectively) and the
calcined eggshell presented lower reactivity than the
calcined limestone. It is very likely that the presence of
larger particles in the calcium oxide from eggshell,
with ca. 4 times lower specific surface area, con-
tributes to its lower reactivity. Additionally, their
agglomerated structure and smoother surface can be
an evidence of some sintering process, which could
affect negatively the wet slaking reactivity. Other
specific parameters of the samples’ surface physical-
chemistry such as the surface energy, acid–base
character, among others, can also influence the wet
slaking reactivity. This will be addressed in forth-
coming studies, where surface sensitive tools will be
used to probe differences between calcium oxides
obtained from calcination of different raw materials.
The slaking behaviour of the calcined eggshell was
completely different from that of the calcined lime-
stone. The calcium oxide from limestone exhibits a
slaking curve with ‘‘line’’ pattern by opposition to a
‘‘S’’ pattern of the calcium oxide from eggshell
(Fig. 5). The hydration rate of the calcined materials
is influenced by the two induction periods underlying
the slaking process. As previously reported [17], the
slaking of the CaO from limestone is developed in one
step, with a very high hydration rate (97.7 °C/min)
from 00:00 to 00:30 min:s. In this case, it is not
evidenced the manifestation of any induction period in
the slaking curve. On the other hand, the calcined
eggshell presented lower hydration rate than the
calcined limestone. In detail, the hydration rate of
the CaO from eggshell could be divided in three steps
with three distinct rates. The first with a value of
20.1 °C/min (from 00:00 to 00:30 min:s), the second
with a value of 4.2 °C/min (from 00:30 to
03:00 min:s) and the last with a value of 11.6 °C/
min (from 03:00 to 05:30 min:s). It must be noted that
the hydration rate in the second segment has the lowest
value, which could be an indicator of the first
induction period. It is less evident the discrimination
of the second induction period in the wet curve, since it
can occur at a later stage of the hydration process but
in parallel with the first one. However, for CaO from
eggshell, the hydration rate in the third segment
presented lower value when compared with that of the
first segment, which could be an evidence of the
second induction period. If this second induction
period did not occur, the hydration rate for the first and
third segments of the wet curve would be similar.
Page 9 of 14 115
It should be remarked that for calcined limestones
and dolomites, the rapid slaking is not necessarily the
most desirable, because other variables will affect the
real performance of the lime when used in a mortar
system [34]. In this context, future work focused on
the formulation of mortars with lime from eggshell,
and on the evaluation of their mechanical properties
will have to be done.
It was not noted any important variation in the
thickening of the suspensions during the slaking of the
calcium oxide samples, namely after reaching the
temperature of 60 °C.
The suspensions obtained after the wet slaking test
presented similar free water content, of 72 and 73 wt%
for CaO from limestone and eggshell, respectively
(Table 3). The free water content upper to 70 wt%
classifies these suspensions as milk of lime, according
to NP EN 459-1 standard. This is a consequence of
having been used a 1:4 (w/w) proportion of CaO:water
for carrying out the reactivity test.
Concerning the expansion test, it was not observed
expansion cracks in the cylindrical test specimens
moulded with the lime slurries and subsequently dried
at 150 °C.
3.3 Characterization of the hydrated lime powder
from eggshell waste
A subsample of the lime suspension was dried to
obtain a hydrated lime in the form of powder, that was
submitted to mineralogical, chemical, FTIR and
colour characterization to evaluate its own quality.
The limes were mainly composed by portlandite, as
expected, with vestigial contents of calcite (Fig. 1).
Calcite rose from the inevitable carbonation of these
materials occurring first in the suspension, during the
wet slaking test, and then in the drying process. Traces
of a phase containing phosphate were detected in the
lime from eggshell. For the two limes, traces of
brucite, [Mg(OH)2], were also detected, formed by the
hydration of vestigial MgO present in the calcined
materials.
The chemical analysis (major elements) of the lime
materials by XRF (Table 1) showed a Ca content of 82
and 77 wt% for lime from limestone and lime
from eggshell, respectively, related with the presence
of portlandite as main phase, and calcite as vestigial
phase. The Mg content (1.3 wt% for lime from
limestone and 0.9 wt% for lime from eggshell) was
115 Page 10 of 14
in line with the brucite traces identified by XRD
(Fig. 1). The P content (0.3 wt%) present in the lime
from eggshell can be associated to the phosphate-
containing phase identified by XRD. The loss on
ignition values were 16 wt% for lime from limestone
and 22 wt% for lime from eggshell, which are related
to the dehydroxylation of portlandite (and brucite in a
minor extent) and to the decarbonation of calcite.
The FTIR spectra of the limes (Fig. 3) showed the
characteristic band of portlandite at 3639 cm-1 (OH
vibration). Band of carbonate groups from calcite, as
contaminant phase, at 872/875 cm-1 (m2) was also
present. The m4 bending band was also observed as a
very weak band at 713 cm-1 in the spectrum of lime
from eggshell, confirming the low content of the newly
formed calcite. The broad band within the
1400–1500 cm-1 region had several peak compo-
nents, fact that could indicate the presence of several
types of carbonate, besides the carbonate in calcite (m3
band). Additionally, in the spectrum of lime from
eggshell (Fig. 3), a weak band at 1093 cm-1 was
observed, probably related with the phosphates pres-
ence already mentioned. In the OH stretching vibra-
tion region, for the two lime samples, besides the
strong band at 3639 cm-1 related to portlandite [35], a
weak band at 3693 cm-1 occurred, ascribed to brucite
[36], both minerals identified by XRD.
The lime from limestone presented the following
colour coordinates: L* = 97.39, a* = - 0.02,
b* = 1.21; and the lime from eggshell: L* = 98.51,
a* = - 0.01, b* = - 0.03. The shift to the green
(a* \ 0) was negligible for both materials. The lime
from limestone showed a slight deviation to the yellow
(b* [ 0) by opposition to the lime from eggshell that
showed a negligible deviation to the blue (b* \ 0).
The lime from eggshell showed a white tonality
superior that of the lime from limestone used as
reference material.
4 Industrial, environmental and economic
implications
In Portugal, a lime factory can reach an average
production of 920 t/day of quicklime. To do this, it
must be supplied with approximately 1643 t/day of
limestone. The amount of eggshell waste produced in
Portugal of 43.2 t/day (average between 2012 and
2016) represents approximately 2.6 wt% the
Materials and Structures (2018) 51:115
consumption of limestone in the lime factory. If
taking into consideration only the eggs forwarded for
industrial processing, by considering for that the
‘‘processing factor’’ of 0.24 [37], the obtained value
for industrial eggshell waste is 10.4 t/day. In this
scenario, this could represent around 0.6 wt% of the
limestone used in the factory.
The industrial eggshell waste has costs around 130
€/t, for a maximum delivery distance of 160 km,
which cover operation expenses to treat (centrifuga-
tion and fragmentation), store (maximum 2 days),
load, transport and deposit in appropriated landfill.
This type of elimination has the consequent ecological
and economic constraints. The costs related with the
exploitation and transport of limestone (30/120 mm
grain size), from the quarry to the lime factory, were
estimated to be around 6–8 €/t, for a maximum
delivery distance of 100 km.
The water content present in the household eggshell
waste (* 9 wt%) or in the industrial eggshell waste
(* 15% wt% [28]) will not be a critical parameter
regarding the control of the industrial calcination
conditions, since, in general, the portuguese lime
factories have installed parallel-flow kilns, which
allow a previous drying of the raw material, before its
calcination.
Recycling the eggshell waste in the manufacture of
lime has some benefits, such as: reduce the waste
disposal costs, which are likely to rise due to the
landfill tariff; extend the landfill life, helping to
conserve the countryside; conserve the environment,
promoting a rational exploitation of limestone, a non-
renewable resource.
The slight blasting of the eggshell waste that occurs
during de calcination could be a constraint at industrial
scale. Another disadvantage could be related with the
decomposition of the organic matter (4.4 wt%) present
in the eggshell waste during the industrial calcination
stage, which would promote an expected increase in
the volatile organic compounds emissions. The man-
ifestation of intense and/or malodorous odour, related
with the decomposition of the organic matter, during
the storing of the waste in the lime factory, can be
minimized with the addition of an odour inhibitor (e.g.,
enzymatic agent). The lime factory must be legally
authorized to the management of this type of waste and
needs to make the necessary industrial lay-out adap-
tation to receive, store and manipulate the waste
concerning hygiene and safety conditions.
Materials and Structures (2018) 51:115
Although the present study showed that the quick-
lime from eggshell waste was less reactive than the
quicklime from limestone, it is not expected that the
mixture of eggshell waste and limestone would highly
reduce the quality of the final produced lime, since the
eggshell waste would be combined at the process in a
small proportion relatively to limestone (\ 3%). This
would allow for the total consumption of the eggshell
wastes produced in Portugal without predictable loss
of the quality of lime. In addition to the application in
the construction industry, which is the scope of the
present work, other potential applications can be
envisaged for eggshell lime, namely in the iron and
steel industry, chemical industry, environmental pro-
tection and agriculture.
Recycling the eggshell waste in the production of
an ecological binder material, contributes, at the same
time, to a sustainable construction.
Finally, all this process increases private and public
companies’ awareness, as well as that of governmental
institutions for sustainable waste elimination, and
could be an opportunity within the context of the
development of a circular economy.
5 Conclusions
The present work aimed at valorizing eggshell waste
by exploring its potential to produce calcitic lime. The
characterization of eggshell waste (after previous
drying at 105 °C) showed it to be composed of calcite
(* 94 wt%), with a minor amount of organic matter
and phosphates.
It was found that the quicklime obtained from
calcination of eggshell waste at 1000 °C belonged to
the most reactive class (R5), the same of calcium oxide
from limestone. However, the wet slaking pattern with
‘‘S’’ design for CaO from eggshell waste was
completely different from the ‘‘line’’ design developed
in the wet slaking of the CaO from limestone. Also, the
time to reach 60 °C and the time for 80% of the
reaction was much higher for the calcium oxide from
Page 11 of 14 115
eggshell waste. This distinct behaviour could be
partially related with differences in the morphology
and specific surface area of the calcium oxide
particles. Larger size particles with smoother surfaces
for calcium oxide from eggshell waste, induced a
lower reactivity in wet slaking, in comparison to
limestone calcium oxide.
The hydrated lime powder from the eggshell waste
obtained after drying the slurry at 105 °C did not
present any physico-chemical constraint and had a
white tonality superior that of the hydrated lime
powder obtained from the commercial limestone used
as reference.
The use of eggshell waste in an industrial process of
lime production enables some opportunities: (i) val-
orization of eggshell waste in the construction indus-
try, which otherwise would be commonly disposed in
landfill; (ii) rationalization of natural limestone
exploitation, by incorporating a small amount (max-
imum 2.6 wt%) of eggshell waste in the process; and
(iii) and probably the most important, an interesting
perspective within the circular economy context
associated to the economic, environmental and soci-
etal advantages.
Acknowledgements The authors are grateful to Derovo -
Derivados de Ovos, S.A. (Pombal, Portugal) and VAC Minerais,
S.A. (Rio Maior, Portugal) for the supply of industrial chicken
eggshell waste and commercial limestone, respectively. This
research was supported by Sistema de Incentivos à Investigação
e Desenvolvimento Tecnológico through Quadro de Referência
Estratégica Nacional (QREN) and by Geobiotec R&D Unit
(UID/GEO/04035/2013) financed by the Fundação para a
Ciência e a Tecnologia (FCT).
Compliance with ethical standards
Conflict of interest The authors declare no competing finan-
cial interest.
Appendix
See Table 4, Figs. 6, 7.
115 Page 12 of 14 Materials and Structures (2018) 51:115

Table 4 XRF data (minor elements) of the raw and lime materials from eggshell and limestone
Raw material Lime
Limestone Eggshell Limestone Eggshell

Cl (ppm) nd 184 185 82

Sc (ppm) 9 9 8 9
Cr (ppm) 7 3 8 9
Mn (ppm) 27 nd 61 nd
Co (ppm) 8 nd nd nd
Ni (ppm) nd nd nd 4
Cu (ppm) 11 16 12 6
Zn (ppm) 3 3 nd nd
Se (ppm) nd 1 nd nd
Br (ppm) nd 2 1 nd
Rb (ppm) 4 3 3 2
Sr (ppm) 101 98 160 124
Y (ppm) 1 nd 3 nd
Mo (ppm) 2 2 2 2
Cs (ppm) 9 nd nd 7
La (ppm) 15 10 11 17
Ce (ppm) 31 32 46 41
Nd (ppm) 16 15 25 26
W (ppm) 11 nd nd nd
Pb (ppm) 9 4 4 7
U (ppm) 3 nd 1 nd
V, Ga, Ge, As, Zr, Nb, Ag, Cd, Sn, Sb, Te, I, nd nd nd nd
Ba, Sm, Yb, Hf, Ta, Tl, Bi and Th (ppm)
nd not detected

Fig. 6 Differential
scanning calorimetry (DSC)
plot and derivative curve
(DDSC) for the raw eggshell
and limestone
Materials and Structures (2018) 51:115
Fig. 7 Raman spectra of
the raw eggshell and
limestone
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