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Journal of Cleaner Production 137 (2016) 1432e1438

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Journal of Cleaner Production


journal homepage: www.elsevier.com/locate/jclepro

The environmental sustainability of calcined calcium phosphates


production from the milling of eggshell wastes and phosphoric acid
A.A. Francis*, M.K. Abdel Rahman
Central Metallurgical Research and Development Institute-CMRDI, P.O. Box 87, Helwan, Cairo, Egypt

a r t i c l e i n f o a b s t r a c t

Article history: Industrial waste shells of egg cause environmental and health issues. Diversion of eggshells from landfill
Received 30 March 2016 to a useful product or used in a better way towards the fabrication of marketable/valuable products is of
Received in revised form high economic and ecologic interest. Different structures of calcium phosphates were prepared by
5 August 2016
milling eggshells with different amounts of phosphoric acid (H3PO4) in the presence of gelatin. The
Accepted 5 August 2016
amounts of H3PO4 were varied over wide ranges (2.90 mle8.73 ml), and the impact of such variations on
Available online 6 August 2016
calcined samples was investigated through the characterization of their morphologies by field emission
scanning electron microscopy (FESEM). Long milling time is associated with size reduction of the
Keywords:
Eggshell wastes
eggshell powders. It was demonstrated that addition of 8.73 ml H3PO4 reduced the d50 eggshell particles
Calcium phosphates from ~ 1 mm to 0.96 mm after being milled for 8 h. X-ray diffraction (XRD) has been used to identify the
Morphologies crystalline phases present after milling and also after heat treatment for various times of up to 5 h at
Milling temperatures in the range 700e1200  C. Monetite (CaHPO4) is the characteristic phase of ball-milled
Particle size distributions samples over the whole ranges of phosphoric acid. The thermal treatment applied to the ball-milled
Sustainability samples led to the interaction between the constituents, causing a modification in the proportion of
calcium phosphate structures. At 2.90 and 3.88 ml of H3PO4, both tri-calcium phosphate Ca3(PO4)2 and
hydroxyapatite Ca5(PO4)3OH phases are the major crystalline structures developed at 1000 and 1200  C,
while Ca2P2O7 and Ca3(PO4)2 were mainly the observed phases at lower sintering temperatures. The
present work is establishing a treatment strategy to produce tailor-made calcium phosphate structures
for bio-applications.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction hatcheries and food industries (King'ori, 2011). Considering the


undesirability of dumping in landfill sites and unavailability of
Every day billions of eggshells are being discarded, causing lands as well as the direct costs to the waste producer (handling
serious environmental problems including unpleasant smell, flies, and collection, storage, transport costs, processing, disposal etc.), it
noise and abrasiveness of the eggshell. Several approaches exist to is important to observe that there is a growing demand for wastes
divert eggshell waste typically destined for a landfill, such as soil to be re-used or recycled.
conditioner, fertilizer, additive for animal feed, adsorbents, calcium The properly management of this waste can reduce the risk of
supplement, paper manufacture, and material re-use through microbiological problems and the costs of discard into the envi-
recycling, all having the potential to be more sustainable methods ronment, as well as provide a better source of CaCO3 than limestone
by which to manage solid wastes than via landfill (Christmas and mined from non-renewable sources. Liao et al. (2010) and De Paula
Harms, 1976; Murakami et al., 2007). Industrial waste shells of et al. (2008) have shown that derivatives from eggshell wastes can
egg are excellent source of calcium, which can be used as an be used to effectively remove several heavy metal ions, such as lead,
alternative to calcium carbonate materials to synthesize different cadmium, and copper from aqueous solution. These results may
calcium salts (Boron, 2004; Oliveira et al., 2013). They are waste then be used in conjunction with further work of Ok et al. (2011) on
materials generated from household kitchens, confectionary shops, the use of eggshell wastes as an alternative to CaCO3 for the
immobilization of heavy metals in contaminated soils. The use of
eggshells as a solid catalyst in the conversion of vegetable oil to
* Corresponding author.
methyl esters in biodiesel production has also been evaluated by
E-mail address: adel_francis@hotmail.com (A.A. Francis). Wei et al. (2009).

http://dx.doi.org/10.1016/j.jclepro.2016.08.029
0959-6526/© 2016 Elsevier Ltd. All rights reserved.
A.A. Francis, M.K. Abdel Rahman / Journal of Cleaner Production 137 (2016) 1432e1438 1433

In previous research (Vichaphund et al., 2011), it has been formation and morphology development in this system has not
shown that wollastonite can be obtained from mixtures of eggshell been investigated in a comprehensive manner. Consequently, this
and silica by the microwave assisted solid-state reaction. The work has a particular focus in the development of calcium phos-
application of this technique has reduced the processing temper- phate materials and the tailoring of structure across a range of
ature to 1100  C and time needed (~10 min) to form a-wollastonite. mixing ratios of industrial waste shells of egg and phosphoric acid
Within this context, the work of Boronat et al. (2015) is valuable in in the presence of gelatin as a binding agent to meet the re-
replacing the mineral calcium carbonate by eggshell for developing quirements of any specialized applications.
bio-composite materials. They used a green polyethylene Besides the social and economic benefits for creating new job
biopolymer made from sugarcane ethanol as a bio-composite ma- opportunities and achieving sustainable economic development in
trix and chicken eggshell as filler. It is interesting to note that the food sector, it should be also pointed out that the positive im-
eggshells have been used as a calcium source for the synthesis of pacts of calcium phosphates production from eggshells are the
hydroxyapatite and other calcium phosphates (Rivera et al., 1999; elimination of environmental pollution as a result of microbial
Siva Rama Krishna et al., 2007; Chaudhuri et al., 2013). In recent action and the reduction of noise and unpleasant smells. On the
research, Zhou et al. (2015) reported that the physical and biological other side, knowledge of the relationship between economy and
studies of monetite-based calcium phosphate cements can poten- recycling may be of great importance in steering waste generation
tially be used in bone defect repair. Recently akermanite, known as toward the implementation of cleaner production processes and
promotor for cell proliferation and osteogenic differentiation, was converting waste into industrially viable resources.
synthesized by solegel combustion method using eggshell wastes
as calcium source (Choudhary et al., 2015). Lee and Oh, (2003) re- 2. Experimental procedure
ported the effect of mixing ratios and calcination temperature on
the formation of sinterable hydroxyapatite (HAp) and h-tricalcium The eggshells (EG) were collected from household kitchens and
phosphate (h-TCP) ceramics from recycled eggshells and phos- then crushed to fine powders by using planetary ball mill (Frisch4).
phoric acid. Apart from the application of industrial waste shells of Mixtures of raw eggshell powders (10 g) and phosphoric acid
egg as coating pigments for ink-jet printing (Yoo et al., 2009) or as (commercial grade, 85% H3PO4) in the presence of a constant
CO2 sorbent (Iyer and Fan, 2010), and as a compost for the immo- amount of 1 g gelatin, were prepared by mixing and milling for
bilization of heavy metals (Soares et al., 2015), eggshells can also be different periods in a planetary ball mill. The formulations used
recycled to produce application-oriented products such as calcium throughout this work involve the addition of gelatin as a binder to
phosphate biomaterials. Therefore, industrial waste shells of egg ensure that a workable slurry/mixture is formed. Eggshell slurries
can be efficiently converted to a useful product compared to were prepared by reacting 10 g of fine eggshell powders in the
dumping it as organic waste in landfills, where food processors presence of different contents of phosphoric acid.
have to pay a lot of money to get rid of their waste in landfills. The phosphoric acid content was varied from 2.90 ml to 8.73 ml.
Recycling of eggshell cannot only be seen as key driver to boost The milling process was carried out at solid to ball ratio 1: 10, the
economic performance, but also represents an effective option to size of balls was 2 mm and the rotation speed is 180 rpm. The
safely use the discarded materials, and at the same time reduces mixing ratios of EG(g)/H3PO4(ml) were in the range of 10 g/2.90 ml
risk of microbiological problems as well as the costs of disposal into up to 10 g/8.73 ml. After milling, the slurries were dried at 60  C for
the environment. It is worth stressing that a global and integrated 2 days. The particle size distributions of ball-milled powders and
waste management policy involves a combination of socio- raw eggshell powders were measured by using BT-2001 liquid laser
economic, political, institutional and cultural factors as well as particle size analyzer. The workable temperatures were varied from
environmental and health aspects (Martuzzi et al., 2010; Peter, 700 to 1200  C, and the time was in the range 1e5 h. The crystal-
1996). The world egg production in 2008 is almost estimated at linity of ball-milled and calcined powders was analyzed, as a
62 million tons (FAO, 2009). Since the shell constitutes ~10e11% of function of milling times, amounts of phosphoric acid and tem-
the total egg weight, the waste generated can be calculated as being peratures, by X-ray diffraction (XRD) in a Bruker D8 Advance
around the range 6.2e6.82 million tons per year globally (Boron, diffractometer (Cu Ka radiation). The morphological characteristics
2004). Based on the analysis of the development of egg produc- of calcined eggshell samples at selected temperatures were
tion over the past decades, it is expected that global egg production examined with a field emission scanning electron microscope
will increase from 64.2 million tons in 2010 to 86.8 million tons in (FESEM, Quanta-FEG-250, Holland).
2030 (Windhorst, 2014). In Egypt, about 310 000 tons of egg is
annually produced for the period 2001e2005 (El Nagar and 3. Results and discussion
Ibrahim, 2007). The Eggshells are considered hazardous waste
under EU legislation and companies pay a lot of money dispose of 3.1. Mineralogical compositions
them in landfill sites. According to the Shellbrane Project (2012),
the amount of discarded eggshells in the EU alone was expected to The main composition of the eggshell powder, as analyzed by
amount to 999 000 tonnes in 2015. This project, co-funded by the XRD, is calcium carbonate Fig. 1. The XRD patterns from powder
European Commission through the funding scheme “Research for samples prepared at different mixing amounts of phosphoric acid
the Benefit of SME-s”, had the general objective to develop a in the range of 2.90 mle8.73 ml for a constant milling time of 8 h
method for the industrial-scale separation of avian eggshell and its are shown in Fig. 2. Diffraction lines attributed mainly to calcite
membrane. It also aims at increasing the competitiveness of SME (CaCO3, PDF 88-1808) and monetite (CaHPO4) were observed in all
participants by providing a cost-efficient and sustainable recycling samples. However, the peak intensity of calcite decreases with
solution for eggshell waste management. increasing amounts of H3PO4. At 2.90 ml of H3PO4, small diffraction
There is very little information available in the literature lines belonging to monetite (PDF 70-1425) and brushite (CaH-
regarding the effect of mixing ratios and milling times on the PO4$2H2O, PDF 72-0713) can be observed. By increasing the
particle size distributions of eggshell (Christmas and Harms, 1976; amount of H3PO4 up to 8.73 ml, the monetite became the pre-
Gergely et al., 2010; Lee and Oh, 2003; Rivera et al., 1999; Siva Rama dominant crystalline phase, which indicates the effective role of
Krishna et al., 2007; Zhou et al., 2015). In particular, to the authors’ milling to reach a gradual transformation of eggshells into mono-
knowledge, the influence of heat treatments (700e1200  C) on the calcium phosphate. Based on XRD observations, it can be
1434 A.A. Francis, M.K. Abdel Rahman / Journal of Cleaner Production 137 (2016) 1432e1438

Fig. 1. X-ray diffraction of industrial waste shells of egg, showing the presence of Fig. 4. Particle size distributions of raw eggshells and eggshell powders milled with
calcite. 2.90, 3.88, 5.82 and 8.73 ml of H3PO4 for 1 h.

Fig. 2. X-ray diffraction analyses of ball-milled powders with different amounts H3PO4 Fig. 5. Particle size distributions of raw eggshells and eggshell powders milled with
i) 2.90 ml, ii) 3.88 ml, iii) 5.82 ml, and iv) 8.73 ml for 8 h at room temperature showing 2.90, 3.88, 5.82 and 8.73 ml of H3PO4 for 8 h.
the presence of Calcite (a), Brushite (b), and Monetite (M).

Fig. 6. XRD analyses of calcined powders for 1 h: at i) 800. ii) 1000, and iii) 1200  C
obtained after milling Eggshell powders with 2.90 ml of H3PO4 in the presence of 1 g
Fig. 3. Particle size distributions of raw eggshells and eggshell powders milled with gelation for 2 h at room temperature showing the presence of TCP (labelled X) CPP
5.83 ml of H3PO4 for 1, 2, 4 and 8 h. (labelled C) apatite (labelled Y).
A.A. Francis, M.K. Abdel Rahman / Journal of Cleaner Production 137 (2016) 1432e1438 1435

H3PO4 and then converted into monetite by increasing the tem-


perature to 85e98  C.

3.2. Particle size distributions

Laboratory milling tests generated data that shed the light on


the size distributions of ball-milled products. The data are pre-
sented as cumulative weight percentage following the milling
process for 1, 2, 4 and 8 h. The changes in particles size can be seen
more clearly from the cumulative particle size distribution. The
average median diameter (d50), was chosen to compare the
representative particle sizes of ball-milling products. After milling
the raw eggshell powder (d50 ¼ 1 mm) with 5.82 ml phosphoric acid
for 1 h, the d50 (50% passing size) increased to ~14 mm which means
that an exothermic reaction took place and led to the agglomera-
tion of the eggshell powders. By increasing the milling time up to
8 h, the agglomeration of particles was destroyed and the particle
sizes decreased gradually till reaching 2 mm by 8 h, Fig. 3.
Fig. 7. XRD analyses of calcined powders for 5 h: at i) 800, ii) 1000, and iii) 1200  C
To investigate the extent and progress of reaction between the
obtained after milling 10 g Eggshells with 2.90 ml of H3PO4 in the presence of 1 g
gelation for 2 h at room temperature. C ¼ CaP2O6, Y ¼ Ca5(PO4)3OH, X ¼ Ca3(PO4)2. starting materials, the particle size distributions of ball-milled
powders in the presence of different amounts of H3PO4 and for
various periods were analyzed, Figs. 4 and 5. It has been shown that
concluded that, in the presence of higher amounts of H3PO4, a the 1 h milling with 2.9 ml up to 5.82 ml increased the d50 from 5 to
relatively intense diffraction peaks of monetite are obtained at the 14 mm. However, the d50 dropped to 3 mm by adding 8.73 ml H3PO4,
expense of calcite and brushite. In spite of applying different con- and that's might be attributed firstly to the unreacted or excess of
tents of H3PO4, the change has been just restricted to the pro- H3PO4 that act as dispersing agent and led to the de-agglomeration
portions of the main crystalline phases. It is also necessary to of powders (Asif et al., 2011; Rashchi and Finch, 2000), and sec-
confirm that a complete formation of monetite might be achieved ondly to the high amount of H3PO4 that decomposed the powders
by increasing the milling times. Monetite can be used in powder and released CO2 (Meyssami et al., 1992). The 8 h milling time in the
form in some toothpastes, chewing gums and in food processing presence of 8.73 ml H3PO4 leads to finer powder (d50 ¼ 0.96 mm).
industry as acidity regulator and emulsifier (EUFIC). Brushite
appeared only at low amount of phosphoric acid which meant that 3.3. Ball-milling of EG with H3PO4 for 2 h
calcium diphosphate dihydrate (Brushite) can be transformed into
anhydrous calcium phosphate (Monetite) by adding more phos- To adequately explore the effect of mixing ratios of eggshell/
phoric acid and that's might be attributed to the heat generated H3PO4 on the phase evolution and formation of different structures
during the milling process. It has been reported by Griffith and of calcium phosphates, XRD analyses were carried out on samples
McDaniel (1988), and Martin and Brown (1998) that brushite calcined at various temperatures (800, 1000 and 1200  C) and for
crystals firstly formed from the acid-base reaction of Ca(OH)2 with different periods up to 5 h. Different amounts of H3PO4 are

Fig. 8. Scanning electron micrographs of heat-treated powders at 1000  C (upper images) and 1200  C (bottom images) after milling for 2 h in the presence of 2.90 ml H3PO4.
1436 A.A. Francis, M.K. Abdel Rahman / Journal of Cleaner Production 137 (2016) 1432e1438

introduced to produce various kinds of calcium phosphate after calcination at 800  C, a very small peak of apatite having the
materials. formula Ca5(PO4)3OH is observed, with tri-calcium phosphate
Ca3(PO4)2 as the prominent crystalline phase, Fig. 9. At 1000  C, the
3.3.1. Milling with 2.90 ml H3PO4 apatite Ca5(PO4)3OH phase is well established with Ca3(PO4)2 as the
In the presence of the lesser amount of H3PO4 (2.90 ml), the secondary crystalline phase. Increasing the temperature to 1200  C
diffraction patterns of calcined powders for 1 h at 800, 1000 and leads to the disappearance of the Ca3(PO4)2 phase and its replace-
1200  C after milling for 2 h showed peaks corresponding to tri- ment as the major phase by Ca5(PO4)3OH. The main conclusion to
calcium phosphate [Ca3(PO4)2, PDF 70-2065 TCP] as the major be drawn from the XRD analyses is that the propensity for the
phase and calcium pyrophosphate [Ca2P2O7, PDF 71-21239 CPP] as formation of Ca5(PO4)3OH increases with increasing temperature;
the secondary phase, Fig. 6. By increasing the temperature to 1000 the added 3.88 ml H3PO4 supplies the phosphate necessary for
and 1200  C, the hydroxyapatite phase [Ca5(PO4)3OH, PDF 76-0694 apatite formation. Some diffraction lines belonging to portlandite
HA] begins to appear at the expense of Ca2P2O7 till reaching almost Ca(OH)2 appeared in all figures and that's might be due to the
a 30%/70% mixture of apatite/TCP and the complete disappearance contact of powder samples with the surrounding atmosphere.
of CPP. Nery et al. (1990) used the term of biphasic calcium phos-
phate to describe the bio-ceramic mixture of HA and TCP which
3.3.3. Milling with 5.82 ml & 8.73 ml H3PO4
became available as bone substitute materials for medical appli-
The results of the XRD analyses conducted on samples milled for
cations. The corresponding calcined powders at the same temper-
2 h and calcined in the range 800e1200  C for 1 h are presented in
atures for 5 h showed that the tri-calcium phosphate [Ca3(PO4)2,
Figs. 10 and 11. The effect of temperature for samples containing a
PDF 70-2065 TCP] is the predominant phase in all samples, Fig. 7.
fixed amount of added H3PO4 (5.82 ml) is demonstrated by the
The increase in the calcination time and temperature led to the
patterns in Fig. 10, while Fig. 11 shows the XRD pattern of samples
disappearance of Ca2P2O7 (CPP) and increasing in the relative in-
tensity of apatite till obtaining a mixture of ~50%/50% mixture of
apatite/TCP. It is worthy of note that employing a longer period and
higher temperature increased the crystallinity of both TCP and
Ca5(PO4)3OH. This final result emphasized the potential of pro-
ducing biphasic calcium phosphate from milling eggshell wastes
with 2.90 ml H3PO4, followed by heating at 1200  C for 5 h. Legeros
et al. (2003) reported that the biphasic calcium phosphate
composition depends on the calcium deficiency of the un-sintered
biologic or synthetic apatite and on the sintering temperature.
The morphological features of ball-milled powders with 2.90 ml
H3PO4 heat-treated at 1000  C and 1200  C for 1hr were presented
in Fig. 8. Many macro-sized pores can be observed due to the
emission of carbon dioxide and gelatin. The particles obtained after
treating at 1000  C exhibited finer and cubicelike morphology.
When the temperature rises to 1200  C, the SEM images at high
magnification revealed that particles cohesion increased and firmly
adhered as globular aggregates, and that's attributed to the partial
melting of particles which occurred during the calcination process
at this higher temperature.
Fig. 10. XRD analyses of calcined powders for 1 h: at i) 800, ii) 1000, and iii) 1200  C
obtained after milling Eggshells with 5.82 ml of H3PO4 in the presence of 1 g gelation
3.3.2. Milling with 3.88 ml H3PO4
for 2 h at room temperature. C ¼ CaP2O6, X ¼ Ca3(PO4)2.
With a further increase in the amount of H3PO4 to 3.88 ml and

Fig. 9. XRD analyses of calcined powders for 1 h: at i) 800, ii) 1000, and iii) 1200  C Fig. 11. XRD analyses of calcined powders for 1 h: at i) 800, ii) 1000, and iii) 1200  C
obtained after milling Eggshells with 3.88 ml of H3PO4 in the presence of 1 g gelation obtained after milling 10 g Eggshells with 8.73 ml of H3PO4 in the presence of 1 g
for 2 h at room temperature. Y ¼ Ca5(PO4)3OH, X ¼ Ca3(PO4)2, H ¼ Ca(OH)2. gelation for 2 h at room temperature. C ¼ CaP2O6, Z ¼ Ca4P6O19, d ¼ Ca(PO3)2.
A.A. Francis, M.K. Abdel Rahman / Journal of Cleaner Production 137 (2016) 1432e1438 1437

Fig. 12. Scanning electron micrographs of heat-treated powder at 1000  C after milling for 2 h in the presence of 5.82 ml H3PO4.

the temperature to 1200  C, CaP2O6 is still the main crystalline


phase in all samples irrespective of the calcination temperature.
However, the CaP2O6 peaks decrease in intensity with increasing
temperature. It should be finally pointed out that the amount of
added H3PO4 in the milling stage had an obvious effect on the re-
action degree which was reflected in the XRD results. Fig. 12
depicted the influence of higher amounts of H3PO4 on the
morphology of ball-milled powders with 5.82 ml H3PO4 after
treatment at 1000  C, where the particles showed puzzle-like
shapes. Based on these observations, the amounts of H3PO4 dur-
ing the milling process had an effect on the morphology of powders
heat-treated at various temperatures.
For the sake of comparison, the XRD pattern in Fig. 13 showed
the influence of lower temperature and higher milling time on the
phase development. The predominant phases were CPP and TCP
with some unreacted calcite at 700  C. The micrographs of the
sample calcined at 700  C after milling EG with 5.82 ml H3PO4 for
8 h appear to be significantly different than that of other samples,
Fig. 13. XRD analysis of calcined powders at 700  C for 1 h, obtained after milling Fig. 14. The milling time, heat treatment and the amount of added
Eggshells with 5.82 ml of H3PO4 for 8 h. H3PO4 are dominant factors in controlling the structure and
morphology of calcium phosphate ceramics.
It should be finally pointed out that the general trend has been
containing 8.73 ml of H3PO4 and calcined at the same temperatures. to use eggshell powders as a calcium source for the production of
The patterns in Fig. 10 highlighted that calcium pyrophosphate mono phase hydroxyapatite (Ca10(PO4)6(OH)2) or tri-calcium
(CaP2O6) is the major phase at 800  C, with the appearance of phosphate (Bala zsi et al., 2007; Chaudhuri et al., 2013; Gergely
reasonable quantities of tri-calcium phosphate Ca3(PO4)2 at higher et al., 2010; Lee and Oh, 2003; Rivera et al., 1999; Siva Rama
temperatures. On increasing the amount of H3PO4 to 8.73 ml in the Krishna et al., 2007). Briefly, the waste eggshells in these previous
milling stage, diffraction lines attributed mainly to calcium pyro- works were firstly crushed, and then decomposed to CaO via
phosphate (CaP2O6) and calcium phosphate (Ca4P6O19) are calcination at 900  C to remove any volatile matter, and finally
observed in the sample calcined at the lowest temperature 800  C, reacted with phosphoric acid or phosphate compounds. The dif-
Fig. 11. On increasing the temperature to 1000  C, the calcium py- ference between the calcium phosphate synthesis (HA or TCP) from
rophosphate remains the predominant crystalline phase but a peak the previous studies and the tunable calcium phosphate structures
attributed to calcium phosphate Ca(PO3)2 is observed together with in the current study is that the latter is establishing a special
a decrease in the degree of crystallinity. With a further increase in treatment strategy to produce tailor-made calcium phosphate

Fig. 14. Scanning electron micrographs of heat-treated powder at 700  C after milling for 8 h in the presence of 5.82 ml H3PO4.
1438 A.A. Francis, M.K. Abdel Rahman / Journal of Cleaner Production 137 (2016) 1432e1438

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