Professional Documents
Culture Documents
Journal of Environmental Management: Amanda Laca, Adriana Laca, Mario Díaz
Journal of Environmental Management: Amanda Laca, Adriana Laca, Mario Díaz
Review
a r t i c l e i n f o a b s t r a c t
Article history: Agricultural wastes are some of the most emerging problems in food industries because of their disposal
Received 31 January 2017 cost. However, it is also an opportunity for the bioeconomy society if new uses for these residual ma-
Received in revised form terials can be found. Eggshells, considered a hazardous waste by UE regulations, are discarded,
24 March 2017
amounting hundreds of thousands of tonnes worldwide. This egg processing waste is a valuable source
Accepted 27 March 2017
material, which can be used in different fields such as fodder or fertilizer production. Additionally, this
residue offers interesting characteristics to be used in other applications, like its employment as an
environment-friendly catalyst. In the present review we provide a global view of eggshell waste uses as
Keywords:
Eggshell waste
catalyst in different processes. According to reviewed researching works, a huge variety of added value
Catalyst products can be obtained by using this catalyst which emphasised the interest of further investigations in
Synthesis order to widen the possible uses of this cheap green catalyst.
Biodiesel © 2017 Elsevier Ltd. All rights reserved.
Syngas
Bioactive compounds
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351
2. Uses of eggshell catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
2.1. Synthesis of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
2.2. Synthesis of hydrogen/syngas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
2.3. Synthesis of dimethyl carbonate (DMC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
2.4. Synthesis of bioactive compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
2.5. Wastewater treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
3. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
http://dx.doi.org/10.1016/j.jenvman.2017.03.088
0301-4797/© 2017 Elsevier Ltd. All rights reserved.
352 A. Laca et al. / Journal of Environmental Management 197 (2017) 351e359
Pore Some recent review papers dealing with uses of eggshell wastes
as a whole or even of specific applications of eggshell membranes
Cuticle
Vertical matrix layer have recently be published (Bala z, 2014; Park et al., 2016; Quina
et al., 2016). Last year, Tan et al. (2015) published a review on the
potential of waste cooking oil-based biodiesel using heterogeneous
Palisade layer catalyst derived from calcined eggshells. In addition, lately Shan
et al. (2016) included in their review, which was related to the
development of Ca-based catalysts for biodiesel production,
Mammillae layer eggshell as one of the waste material that can be employed. How-
Outer membrane ever, eggshell waste can be used as catalyst in many other pro-
Inner membrane cesses. Hence, the present review compiles the studies recently
developed, which show the potential of eggshell wastes to be used
as low cost catalyst in the production of different compounds.
Fig. 1. Schematic illustration of eggshell structure.
2. Uses of eggshell catalysts
methanol/vegetable oil 18:1). These authors compared the perfor- of waste cooking oil. An empirical quadratic regression equation
mance of the CaO catalysts obtained from eggshell, meretrix venus model was used to select the optimum values of the variables
shell and golden apple snail shell. All catalyst exhibited high yields considered (methanol/oil molar ratio 9.15:1, catalyst concentration
(greater than 90%); however, the eggshell catalyst presented the 7.7 wt% and reaction time 75 min). For these conditions the con-
highest value (95%). version to biodiesel was predicted to be 90%, which was in agree-
Biodiesel was produced from Jatropha oil using as catalyst a ment with the real yield value. In a just-published work, Majhi and
mixture of seashell and eggshell in complexation with TiO2. Re- Ray (2016) evaluated the performance of a catalyst derived from
actions were carried out with a methanol/oil molar ratio 20:1 and eggshell in the biodiesel production. The study reported a yield of
10 wt% catalyst at 140e190 C and 60e80 bar, yields of 95% were around 90% using methanol/oil molar ratio of 18:1 and 10 wt%
achieved (Semwal et al., 2011). The same year, Olutoye et al. (2011) catalyst calcined at 950 C.
published a work that employed eggshell modified with magne- Correia et al. (2014) compared the catalytic activities of calcium
sium and potassium nitrates as catalyst for the transesterification of oxide obtained from crab shell and eggshell. Employing natural
palm oil at 65 C. The conditions that achieved the highest yield shells, the conversion from triglycerides (sunflower oil) to methyl
(86%) was 5.3 wt% catalyst, methanol/oil molar ratio of 16:1 and ester was not observed, on the contrary using the calcined catalysts
reaction time 4.6 h. At these conditions, catalyst was reusable for the yields were 83% and 98% for crab shell and egg shell, respec-
three times. tively (methanol/oil molar ratio 1:6e9, catalyst 3 wt%, 60 C). These
Khemthong et al. (2012), demonstrated that, in comparison with results were in accordance to those reported by Viriya-empikul
conventional heating, a significant enhancement for biodiesel et al. (2010). Compared with the calcined crab waste, the higher
synthesis was achieved by using microwaves when a solid CaO content of Ca in the surface of the calcined eggshell justified the
catalyst derived from waste eggshells was employed. A yield above better catalytic performance. It is frequent to find in literature a
96% was reached at the optimal conditions (reaction time 4 min, better behaviour as catalyst of eggshell than other wastes. So, Sinha
microwave power 900 W, methanol/oil ratio 18:1 and catalyst and Murugavelh (2016) reported for the transesterification of waste
15 wt%). cotton cooking oil a yield of 92% with calcined eggshell catalyst,
Furthermore, Navajas et al. (2013) reached a yield of 100% for whereas the yield with pistachio shell was 84% (catalyst 3 wt%,
biodiesel production from used cooking oil using eggshell catalyst methanol/oil molar ratio 9e12:1 and 60 C). In addition, in a work
(60 C, 5 h, methanol/oil ratio 24:1 and 4 wt% catalyst). This work that has just been published (Roschat et al., 2017), rubber seed oil
reported that the surface morphology of the catalyst, a key was successfully employed as substrate to obtain biodiesel using
parameter for the catalyst activity, was determined by the type of waste coral and eggshell catalysts. Eggshell catalyst gave a yield of
eggshell used. More recently, El-Gendy and Deriase (2015) 97% in 180 min, whereas coral catalyst needed a longer time
employed waste eggshells for biodiesel production from a variety (210 min) and more amount of catalyst (100 wt%) to completed the
354 A. Laca et al. / Journal of Environmental Management 197 (2017) 351e359
Table 1
Comparation of eggshell catalyst found in literature.
Biodiesel Oil Wash, dry (100e110 C, overnight-24 h), crush and calcine Wei et al. (2009)
transesterification (200 C-1000 C, 2e4 h). Sharma et al. (2010)
Viriya-empikul et al. (2010)
Khemthong et al. (2012)
Correia et al. (2014)
Chen et al. (2014)
Chavan et al. (2015)
El-Gendy and Deriase (2015)
Reyero et al. (2015)
Tan et al. (2015)
Majhi and Ray (2016)
Sinha and Murugavelh (2016)
Yin et al. (2016)
Roschat et al. (2017)
Treat with 0.005 M HCl (2 h) and calcine (800 C) Cho and Seo (2010)
Wash, dry (110 C, 6 h), mix egg shells and sea shells Semwal et al. (2011)
(1:1 wt) and calcine (550 C, 3 h). Mill with TiO2 and calcine
(550 C, 1 h and 1050 C, 3.5 h). Mix with binder,
pseudoboehmite or g-aluminium oxyhydroxide (3:1 wt)
using 2.5% (v/v) nitric acid and extrude (2.5 mm diameter).
Wash, remove membranes, dry (70 C, overnight), ground Olutoye et al. (2011)
(<1 mm), calcine. Impregnation/co-precipitation with
magnesium and potassium nitrates and calcine (830 C, 4 h).
Wash, dry (120 C, 10 h), crush and sieve (100e150 mm), KF Zeng et al. (2015)
modification-thermal treatment and calcine (800 C, 12 h)
Wash, dry (overnight, 105 C) and crush. Mix with Na2SiO3 Chen et al. (2015a)
solution at pH 8.0. Stir the mixture (500 rpm, 4 h), dry
(100 C, overnight) and calcine (800 C, 4 h)
Sieve dry raw rice husk, wash, filter, dry (105 C) and Chen et al. (2015b)
calcine. Wash the eggshell, dry (105 C, 24 h) and calcine
(800 C, 4 h). Load calcined eggshell onto the ash by wet
impregnation method
Hydrogen/Syngas Methane oxidation Wash with deionized water and calcine (100 C, 4 h) Karoshi et al. (2015)
Wood gasification Remove the membranes, wash and dry. Crush, sieved Taufiq-Yap et al. (2013)
(250 mm), dry and calcine (900 C, 2 h)
Coal gasification Wash and dry (70 C, overnight). Ground and sieved to Fan et al. (2016)
210 mm. Calcine (800 C, 2 h)
Dimethyl carbonate Propylene Wash with deionized water, dry (100 C, 24 h), calcine Gao and Xu (2012)
carbonate and (1000 C, 2 h) and crush.
methanol
transesterification
Bioactive compounds Chromenones Heterogeneous Wash and remove the membranes. Dry (120 C, 1 h). Mill Mosaddegh (2013)
base catalyzed and mix the eggshell powder with CH2Cl2 and place in an
organic synthesis ultrasonic bath (60 Hz, 50 C, 1 h). Filter and dry at room
temperature.
Wash and remove the membranes. Wash and dry at room Mosaddegh and
temperature. Crush and mill by mortar. Hassankhani (2013)
Pyrans Heterogeneous Wash, clean, dry and treat by ball-mill. Mosaddegh et al. (2013)
base catalyzed Wash and remove the membranes. Wash and dry (120 C, Mosaddegh and
organic synthesis 1 h).Mill and calcine (900 C, 1 h). Hassankhani (2014)
Benzylidenepropanedinitrile Knoevenagel Dry (100 C), crush and calcine (900 C, 3 h). Patil et al. (2013)
condensation
Polyhydroquinoline Unsymmetrical Wash and dry (80e90 C, 24 h). Ground by mortar and Morbale et al. (2015)
derivatives Hantzsch calcine (900 C).
condensation
Benzothiazoles Heterogeneous Dry (100 C, 2 h), crush and calcine (900 C, 3 h). Borhade et al. (2016)
base catalyzed
organic synthesis
Lactulose Lactose Wash, dry (105 C, 4e24 h), ground (~5 mm) Montilla et al. (2005)
isomerization Wash, dry (105 C, 12 h), ground and sieved (177 mm) Nooshkam and
Madadlou (2016)
Nanocomposites Reduction of dyes Mix dried powered of eggshell with CuCl2 and/or FeCl3 and Nasrollahzadeh et al. (2016)
in wastewater aqueous extract of Orchis mascula L. in alkaline medium.
Heat (70 C), shake and filter
transesterification under optimum conditions (catalyst 9 wt%, 12/1 catalysts obtained from quail eggshells compared to that obtained
methanol/oil molar ratio and 65 C). with hen eggshells. On the opposite, a recent study (Reyero et al.,
Although most researches regarding the uses of eggshell as 2015) found no differences between the properties and catalytic
catalyst have been developed on hen eggshell, some authors have performance of the CaO catalysts prepared from hen or quail egg-
employed other bird eggs. As it has been commented above, Cho shells. A 98% oil conversion in 120 min of reaction (60 C, methanol/
and Seo (2010) reported a greater catalytic activity of CaO oil molar ratio 12:1 and catalyst 2 wt%) was achieved with the
A. Laca et al. / Journal of Environmental Management 197 (2017) 351e359 355
catalyst calcined at 850 C for 3 h. These authors reported very shapes become more regular (Correia et al., 2014; Tan et al., 2015;
similar catalytic activities despite of the type of eggs, the procedure Zeng et al., 2015; Yin et al., 2016). Khemthong et al. (2012)
of milling and the size fraction of the calcined eggshells. described the shape of CaO particles as rod, dumbbell, and rod-
Chen et al. (2014) obtained a CaO catalyst from ostrich eggshell dumbbell connected shapes constructing a termite nest-like mac-
and reported a biodiesel yield of 93% using an ultrasonic method roporous structure. Reyero et al. (2015) and Tan et al. (2015) also
(catalyst 8 wt%, methanol/oil molar ratio 9:1 and ultrasonic power indicated that calcination contribute to homogenize the catalyst
60% amplitude). This catalyst was reused without loss of activity for textural properties, particularly at temperatures above 850 C. An
more than 8 times. Tan et al. (2015), also investigated the perfor- example of the commented structures can be observed in Figs. 2
mance of ostrich- and chicken-eggshells as catalyst for biodiesel and 4. The surface area of a solid catalyst has direct impact on its
production from used cooking oil. In both cases yields above 90% catalytic activity. Specifically, and, as it is well known, a higher
were obtained (1.5 wt% catalyst, methanol/oil molar ratio 12:1 and surface area is expected to show higher catalytic activity. BET
65 C). Calcined duck eggshell has also been employed as catalyst in analysis demonstrated that the surface area of eggshells after cal-
biodiesel production employing as substrate soybean oil (Yin et al., cinations was higher than before the thermal treatment (Viriya-
2016). Different temperatures of calcination were assayed and the empikul et al., 2010; Tan et al., 2015; Zeng et al., 2015).
best results were achieved at 900 C, in accordance with Reyero Concretely, Reyero et al. (2015) pointed out that BET surface of
et al. (2015). The biodiesel yield at optimal conditions (catalyst eggshell catalyst exhibited an optimum around 600 C and 12 h of
10 wt%, methanol/oil molar ratio 10:1 and 60 C) was 94.6%. The calcination (17 m2/g) since higher temperatures and/or longer
reusability of the catalyst was evaluated and after 5 cycles biodiesel times led to sintering of the CaO particles formed with the conse-
yield was still above 80%. Additionally, Zeng et al. (2015) prepared quent loss in surface area.
an eggshell catalyst by KF modification and thermal treatment. This If attention is paid to catalyst reuse, the deactivation of eggshell
catalyst could be reusable at least 10 times with a yield higher than derived catalyst may be attributed to its structure change. In fact,
80% (catalyst 2 wt%, methanol/oil molar ratio 12:1 and 65 C). XRD analyses indicated that after several cycles the major phase of
According to all the studies reported above, it is evident that catalyst has changed from CaO to Ca(OH)2 since the reactants
different factors are involved in the performance of eggshell as
heterogeneous catalyst in biodiesel production: methanol/oil ratio,
reaction time, raw material, catalyst load, etc. However, catalyst
surface area and calcium oxide content have been identified as the
key parameters which specifically affect the catalytic activity
(Viriya-empikul et al., 2010). Furthermore, these two parameters
are determined by the calcination step. In fact, and as it is sum-
marized in Table 1, the calcination, with slightly modifications, is a
common procedure in eggshell catalyst preparation in all works
related to biodiesel production. Several characterization techniques
have been employed in order to obtain information that can be
correlated with catalyst activity, i.e., X-ray diffraction (XRD), Fourier
transform infrared (FTIR) spectroscopy, differential thermal anal-
ysis/thermogravimetric analysis (DTA/TGA), BET adsorption
isotherm and scanning electron microscopy (SEM).
Regarding composition, XRD an FTIR analysis verified the pres-
ence of calcium carbonate in the uncalcined eggshell catalyst,
whereas calcium oxide was identified in the calcined catalyst (Wei
et al., 2009; Sharma et al., 2010; Khemthong et al., 2012; Navajas
et al., 2013; Correia et al., 2014; Yin et al., 2016). Additionally, Tan
et al., 2015 found that the eggshell based catalyst contained a
mixture of CaO and Ca(OH)2. The existence of hydroxyl species was
attributed to the adsorption of atmospheric moisture onto the
surface of calcined eggshells. As above commented, when the un-
calcined eggshell was used as catalyst no conversion was observed
(Navajas et al., 2013). However, during calcination, the CaCO3 is
decomposed to CaO, which did show catalytic activity. In this
context, TGA analyses indicated that, although decomposition of
calcium carbonate started at 700e800 C, complete decomposition
occurred at 800e900 C. Calcination of chicken eggshells above
800 C could completely convert CaCO3 to CaO and CO2 (Wei et al.,
2009; Viriya-empikul et al., 2010; Navajas et al., 2013; Yin et al.,
2016). Hence, the need for calcination of the eggshell at
800e900 C is justified in order to appropriately activate the cat-
alysts by completely removing of the CaCO3 from the surface
(Reyero et al., 2015).
According with Tan et al. (2015), the change of eggshell struc-
ture is mainly originated from the change of composition. It can be
found in literature that the morphology of natural eggshell Fig. 4. SEM microstructures of calcined hen egSgshells. Eggshells were washed and
membranes were manually removed, then they were dried (100 C, 2 h), crushed by
exhibited a typical layered architecture with macropores and mortar and calcined (900 C at a heating rate 2 C/min for 3 h), finally calcined power
irregular particles of different sizes. On the contrary, when the was sieved by 250 mm opening). Magnification and bars: 500, 50 mm (A) and 5000,
eggshell is calcined the morphology of calcium oxide particle 5 mm (B).
356 A. Laca et al. / Journal of Environmental Management 197 (2017) 351e359
contained a little amount of water (Wei et al., 2009). Yin et al. absorbed by CaO, promoting H2 generation by water gas shift re-
(2016) noted that the XRD pattern of the recycled catalyst action (Taufiq-Yap et al., 2013). These authors also reported that the
showed notable displacement of the peaks and the peaks of CaO addition of eggshell catalyst favoured tar and char gasification,
and CaCO3 disappeared. These authors justified this result as the increasing the amount of gaseous products. The effect of catalyst
used catalysts were covered by intermediates or products such as loading was investigated and hydrogen production was increased
glycerol or biodiesel. In addition, it was observed that after 5 times with the catalyst loading to a maximum of 73% compared to gasi-
usage, the cluster of CaO cubic crystal wass disappeared, and the fication without catalyst. Moreover, it was observed that CH4 pro-
pores in the used catalyst were almost destroyed reducing the duction temperature was lower when catalyst load was higher. This
surface area of the catalyst. Tan et al. (2015) also reported the was explained by the fact that CH4 is mainly produced from
agglomeration of the catalyst particles by the glycerol coverage on cracking reactions of liquid hydrocarbons that are catalyzed by the
the catalyst surface as responsible of the gradual drop in activity presence of CaO. More recently, the effect of composite catalyst
during repeated cycles. In this context, Reyero et al. (2015) identi- (K2CO3 and CaO derived from eggshell) on gasification of coal has
fied by XRD the formation of calcium glyceroxide in the regener- been studied (Fan et al., 2016). After completion of the pyrolysis
ated samples. process, chars produced were gasified with a flow of H2O and N2.
Zeng et al. (2015) characterized by means XRD, FTIR and SEM a Higher amounts of H2 and CO, compared with the non-catalytic
catalyst prepared from waste eggshell by KF modification and gasification, were obtained in the presence of the composite cata-
thermal treatment. In this case, the characterization show that KOH lyst. Specially, this composite catalyst increased the yields of H2 by
generated in the modification process enhances the basicity and 6% and 123%, in comparison with the utilization of pure K2CO3 and
catalytic ability of the catalyst. absence of catalyst, respectively. Additionally, the carbon conver-
A new trend is to combine eggshell with other compounds to sion rate was increased by more than three times by the composite
improve catalyst activity. Indeed, Chen et al. (2015a) synthetized catalyst. Various kinetic models have been studied in order to
CaOeSiO2 catalysts from eggshell and Na2SiO3. When they were explain the char gasification mechanism, the random pore model
used for transesterification of palm oil, these catalysts showed a (RPM) is widely used and it is applied in terms of a pore size dis-
decrease in catalytic activity and an increase in reusability as the tribution in the reacting solid. In this work the RPM was success-
amount of Si compounds increased. Small differences were found fully employed to describe the conversion rates.
by SEM between catalyst with and without Si, i.e. the Si catalyst Another possible source to produce syngas is methane, an
showed larger and more regular pieces, which could be due to the abundant resource that can be found in natural gas reserves and
coverage of CaO surface with Si compounds. FTIR spectra suggested can be produced by anaerobic digestion from organic wastes
that, with the lowest Na2SiO3 concentration, all the SiO2 generated (Osman et al., 2016). Catalytic partial oxidation of methane into
from the silicification process reacted with CaO to form a new syngas suitable for synfuels generation is considered as an advan-
CaSiO3 or Ca2SiO4 compound. XRD patterns proved that the peaks tageous route from both economic and technical points of view
of SiO2, CaSiO3 and Ca2SiO4 appeared when the Na2SiO3 concen- (Shelepova et al., 2016). In this context, Karoshi et al. (2015) tested
tration increased, while CaO and Ca(OH)2 phases completely dis- the use of calcined eggshell as catalyst for selective oxidation of
appeared. In other work, these same authors (Chen et al., 2015b) methane using a packed bed reactor. The partial oxidation of
employed rice husk ash and calcined eggshell to prepare catalysts. methane on calcined eggshell yielded higher hydrocarbons
The catalysts developed with 30% and 70% of calcined eggshell and (C2eC7). Nevertheless, the achieved average fractional methane
calcined rice husk, respectively, presented the highest activity. conversion was quite low, approximately 30%. Several factors, like
More specifically, the biodiesel yield was 91.5% when the reaction flow rate, temperature and oxygen concentration, influence
was carried out with methanol/oil molar ratio of 9:1, a reaction methane conversion and product selectivity. In literature it is pro-
time of 4 h and catalyst loading of 7 wt%. Besides, the yield achieved posed that oxidation of methane over pure CaO catalyst proceeded
was above 80% after being reused 8 cycles. via formation and homogeneous coupling of methyl radicals
assisted by active O2 and Ca2þ Karoshi et al. (2015). In this work,
2.2. Synthesis of hydrogen/syngas the authors suggested that methane was converted into ethylene
and ethane via oxidative coupling of methane and was further
CO2 is considered the major greenhouse gas emitted through transformed to C3eC7 hydrocarbons via coupling or aromatization.
anthropogenic activities, for this reason, hydrogen has recently Additionally, it was suggested that the CaO active sites in the
been receiving a lot of attention as a clean alternative fuel. In calcined eggshell could retain certain degree of orientation which
particular, hydrogen production from gasification has become an facilitates surface bound coupling or aromatization reaction.
interesting research topic in the last decades. A variety of carbo- However, the reaction mechanism that occurs on eggshell catalyst
naceous material, such as wood and coals, can be gasified for the is not clear and further studies on kinetics of methane oxidation
production of hydrogen through advanced gasification processes. should be carried out.
These processes can be improved by the use of catalyst (Mostafavi The syngas so synthetized could be used to produce synthetic
et al., 2016). petroleum via the Fischer-Tropsch process. Precisely, Han et al.
Taufiq-Yap et al. (2013) evaluated the hydrogen production from (2016) have recently reported a multiscale analysis of an
wood gasification favoured by waste eggshell catalyst. Specifically, eggshell-Co-based catalyst prepared by wetness impregnation for
biomass gasification of Azadirachta excelsa wood was carried out this synthesis.
with addition of CaO catalyst derived from eggshells. As indicated
in Table 1, the eggshell was calcined at 900 C for 2 h and the 2.3. Synthesis of dimethyl carbonate (DMC)
catalyst so obtained showed a cubic structure, similar to pure CaO,
observed by SEM. A temperature-programmed gasification tech- DMC is an important methylating and carbonylating agent
nique was employed (50e1000 C in 5% O2/He with flow rate 10 ml/ because of its biodegradability, low bioaccumulation and persis-
min). During gasification process, biomass is decomposed into tence, as well as its low toxicity. So the production and chemical
various gases (H2, CH4, CO and CO2) and some unwanted products application of this compound have attracted much attention in the
such as tar and char. Compared to the reaction without catalyst, the so-called “green chemistry”. DMC can be used for replacing dime-
addition of eggshell suppressed CO2 production, which was thylsulfate and methylhalides in methylation reactions and harmful
A. Laca et al. / Journal of Environmental Management 197 (2017) 351e359 357
phosgene in polycarbonate and isocyanate synthesis (Gao and Xu, The activity of calcined eggshell was compared with the activity of
2012; Wang et al., 2015). As it is reported in Table 1, the only pure CaO and a similar catalytic performance was obtained with the
research work focused on the use of eggshell-derived catalyst for advantage of being derived from a renewable resource.
DMC synthesis was developed by Gao and Xu (2012). In their work, More recently, Morbale et al. (2015) used modified eggshells as
they studied this chemical synthesis by the transesterification of catalyst for the synthesis of 1,4-dihydropyridine and poly-
propylene carbonate and methanol employing eggshell as catalyst. hydroquinolines. These compounds show different biological ac-
The conversion of propylene carbonate and the yield of DMC tivities (antitumor, anti-inflammatory, antianginal, antitubercular
reached maximum values after 1 h (80 and 75%, respectively) under and analgesic). These authors reported as advantages for the
the optimum conditions (methanol/propylene carbonate molar developed process the removal of corrosive catalysts, organic sol-
ratio 10:1, 0.8 wt% eggshell catalyst, room temperature and 1 atm vents and toxic reagents. Additionally, the in vitro assays have
pressure). In addition, the eggshell catalyst can be reused in four shown interesting antibacterial and antifungal effects of these
cycles with slightly deactivation. The eggshell showed a catalytic synthesized molecules. The reaction was also evaluated employing
behaviour similar to pure CaO. The catalyst was characterized by pure CaO as catalyst. A very low amount of the desirable molecules
XRD, TGA and nitrogen adsorption (BET) and similar results to was obtained, in addition, a reaction time of five times higher was
those described in section 2.1 were reported. In short, calcium needed than using eggshell.
carbonate from eggshell is decomposed to calcium oxide during Benzothiazoles exhibit antitumor, antimicrobial, anticancer and
calcination and this change regarding composition originates a antidiabetic activities (Stone et al., 2015; Bhoi et al., 2016; Borhade
homogenization of structure increasing the BET area. In this work it et al., 2016; Harrouche et al., 2016). In this context, Borhade et al.
was concluded that the eggshell-derived material is a renewable (2016) reported a one-pot synthesis of 2-arylbenzothiazoles by a
effective solid base catalyst. reaction of o-aminothiophenol with differently substituted aro-
matic aldehydes. The reaction was carried out at room temperature
2.4. Synthesis of bioactive compounds and a mixture of a suitable aldehyde, o-aminothiophenol and, as
catalyst, calcinized eggshell were grinded under solvent free
Catalysts based on eggshell wastes have been also used to conditions.
synthetize different bioactive compounds summarized in Table 1. These authors compared their work with other procedures re-
Chromenones are bioactive compounds extensively employed ported in the literature for the synthesis of 2-arylbenzothiazole
as pigments, cosmetics and potential biodegradable agrochemicals. derivatives and concluded that calcined eggshell was an effective
They also possess diuretic, anticarcinogenic, antioxidative, antide- catalyst with regards to yields and reaction times. In addition, the
pressant, antihypertensive, anticoagulant, antibacterial, antifungal method was also developed with Ca(OH)2, CaCO3 and pure CaO, as
and antiviral activities (Kachkovski et al., 2004). The use of eggshell catalysts. It was observed that the reaction did not take place by
in the synthesis of chromenones was investigated by Mosaddegh using pure Ca(OH)2 and CaCO3 even after a long time (5 h). On the
(2013), specifically 2-aminochromenes, under thermal solvent- contrary, pure CaO catalyzed the reaction, but with a very low yield
free conditions. This heterogeneous nanocatalyst was sonochem- (30%), and it takes a longer time (5 h) than using the eggshell
ical prepared in a CH2Cl2 solution. Furthermore, a trial to develop catalyst, which obtained a 92% yield in 16 min.
nano eggshell powder using microwave irradiation was also carried Special attention should be pay to lactulose as bioactive com-
out without success. This author found that sonicated eggshell pound. In recent year, this chemical has obtained increasing in-
catalyzed the reaction with more effectiveness than CaCO3 and terest because of its commercial applicability in food and
eggshell powder obtained by ball milling. Moreover, the nano pharmaceutical fields. Lactulose is considered a prebiotic as it
eggshell catalyst could be repeatedly used six times without any stimulates the growth of bifidobacteria and lactobacilli in the
loss of activity. In addition, this same author (Mosaddegh and gastrointestinal tract and at the same time inhibits pathogenic
Hassankhani, 2013) employed eggshells washed with distilled bacteria such as Salmonella (Seo et al., 2016; Panesar and Kumari,
water, dried at room temperature and crushed by mortar, as cata- 2011). Other functionalities of lactulose include reduction of
lyst to synthesis of 7,8-dihydro-4H-chromen-5(6H)-ones at blood ammonia and serum lipids, anti-gallstone formation, anti-
ambient temperature. The eggshell catalyst could be reused in five endotoxic effects, control of blood glucose and insulin, relieve
cycles keeping its catalytic activity. Furthermore, these authors constipation, mineral absorption stimulation and anti-carcinoma
proved that without the addition of the catalyst, only alkene 5 and effects (Panesar and Kumari, 2011; Seo et al., 2016; Nooshkam
neither 2-amino-chromenes 4 nor 7,8-dihydro-4H-chromen- and Madadlou, 2016). Lactulose can be obtained from lactose by
5(6H)-one 4 were produced. So, it was concluded that the eggshell isomerization. Montilla et al. (2005) employed raw eggshell as
has an essential effect on the reaction selectivity. catalyst for this process, and investigated the effect of catalyst
Many pyran derivatives have been described as compounds loadings, lactose concentration and pH. The maximum production
with important bioactive properties (antimicrobial, antifungal, of lactulose achieved from milk permeate was around 25%, with
antiviral, anticancer and anti-inflammatory activities). Nano-bio respect to the initial lactose concentration, after 90 min at 98 C and
calcite (CaCO3) and nano-CaO prepared from hen eggshell were using 4 mg/mL of catalyst. Recently, Nooshkam and Madadlou
used as catalyst in the production of pyrano[4,3-b]pyrans. Both (2016) employed milk ultrafiltration permeate in a similar pro-
catalysts exhibited a high catalytic activity (yields ~ 90%) and also cedure to obtain lactulose. The isomerization was carried out by
high reusability in the synthesis of these compounds (Mosaddegh heating the permeate at 97 C in the presence of eggshell power for
et al., 2013; Mosaddegh and Hassankhani, 2014). 60 min. Approximately 17% of lactose were converted into lactu-
Calcined eggshell has been evaluated too for Knoevenagel lose. The isomerized permeate was afterwards purified to a
condensation of aromatic aldehydes (Patil et al., 2013). This is a lactulose-rich product through crystallizing lactose out by meth-
procedure employed for the synthesis of organic compounds with anol. Hence, eggshell was employed with success as catalyst for
interesting properties from a pharmaceutical point of view. Knoe- lactose isomerization to lactulose. Furthermore, isomerization
venagel condensation using calcined eggshell were compared with yields were similar to those reported for other calcium carbonate-
other reported catalysts for the synthesis of benzylidenepropane- based catalysts (18e21%) (Panesar and Kumari, 2011); however,
dinitrile. Results showed that this eggshell catalyst gave better they were lower than those obtained using ammonium carbonate
yields and at the same time allowed to reduce the reaction time. catalyst (28%) (Seo et al., 2016).
358 A. Laca et al. / Journal of Environmental Management 197 (2017) 351e359
A characterization of the described eggshell catalysts was car- due to structure modifications and/or deposits of intermediates on
ried out in some of these works and they agree again that surface catalysts surface that leads to a decrease of catalytic activity.
area and composition were the determinant factors on catalyst Eggshell-derived catalysts have been also tested in the synthesis
performance. Additionally, possible mechanisms for the formation of H2/syngas, DMC and different bioactive compounds such as
of the described products were proposed in several cases. However, chromenones, pyrans, benzothiazoles or lactulose. Moreover, it is
in general, further studies are necessary to contribute to clarify the noticeable that in most cases eggshell catalysts achieved yield
role played by eggshell catalysts in the synthesis of these different values similar or even better than those obtained with catalysts
bioactive compounds. developed from other sources. Although there is less information
published about the relationship between catalyst characteristics
2.5. Wastewater treatment and properties in these applications, the calcination step, which is
determining for catalysts structure and composition, is in most
Nasrollahzadeh et al. (2016) proposed a one-step green route for cases again reported as the main responsible of the catalyst
the synthesis from waste hen eggshell of Cu/eggshell, Fe3O4/ behaviour. Additionally, eggshell has also been employed as sup-
eggshell and Cu/Fe3O4/eggshell nanocomposites. Aqueous extract port for the development of nanocomposites to treat wastewaters.
of the leaves of Orchis mascula L. was used as a stabilizing and Further investigations about catalysts properties and catalytic
reducing agent for the synthesis of the nanoparticles. The process of mechanisms focused on these processes should be developed.
synthesis is recorded in Table 1, dried powered of eggshell was To sum up, the successful application of eggshell waste-derived
mixed with CuCl2 and/or FeCl3 and the aqueous plant extract in catalysts, with so many different purposes, highlights the interest
alkaline medium. The mixture was shaken, while heating at 70 C, of testing the use of these renewable catalysts in multiple other
in order to form the nanocomposite, and finally filtered. These processes, which, as exposed in this review, can include from
materials were characterized by field emission scanning electron synthesis of value-added products to wastewater treatment.
microscope (FESEM), energy-dispersive X-ray spectroscopy (EDS)
and FTIR. Results showed that, as was already commented, the Acknowledgements
eggshell is a macroporous network composed of C, Ca and O, on
whose surface the copper and iron nanoparticles were immobi- This study was developed thanks to funding from the Economy
lized. The highly porous structure increased the contact area and and Employment Office of Principality of Asturias (Spain) through
allowed high loads of nanoparticles. In fact, eggshell porous were project GRUPIN14-140.
almost covered with Cu and Fe3O4 particles uniformly distributed
on the superficies, which modified the roughness of the eggshell
surface. These metallic nanocomposites showed high catalytic ac- References
tivity in the reduction of a variety of dyes in water at room tem-
Balaz, M., 2014. Eggshell membrane biomaterial as a platform for applications in
perature. Moreover, these catalysts could be easily removed from materials science. Acta Biomater. 10, 3827e3843.
the media and reused in several cycles without any loss on the Bhoi, M.N., Borad, M.A., Pithawala, E.A., Patel, H.D., 2016. Novel benzothiazole
efficiency, which remained almost constant up to seven reuses. containing 4H-pyrimido[2,1-b]benzothiazoles derivatives: one pot, solvent-free
microwave assisted synthesis and their biological evaluation. Arab. J. Chem. (in
Additionally, eggshells can be employed to develop different press).
materials that can be potentially used in sorption processes for Borhade, A.V., Uphade, B.K., Gadhave, A.G., 2016. Calcinized eggshell: an environ-
environmental protection and waste treatment (soil, water, and mentally benign green catalyst for synthesis of 2-arylbenzothiazole derivatives.
Res. Chem. Intermediat 42, 6301e6311.
air). For example, CaO prepared from the pyrolysis of chicken Chavan, S.B., Kumbhar, R.R., Madhu, D., Singh, B., Sharma, Y.C., 2015. Synthesis of
eggshells was employed as starting material for the synthesis of biodiesel from Jatropha curcas oil using waste eggshell and study of its fuel
calcium zeolite type A (CaNaAlSi2O7) (Tangboribooron et al., 2011). properties. RSC Adv. 5, 63596e63604.
Chen, G., Shan, R., Shi, J., Yan, B., 2014. Ultrasonic-assisted production of biodiesel
The specific surface area was 55.15 m2/g, a value quite moderate in
from transesterification of palm oil over ostrich eggshell-derived CaO catalysts.
comparison with commercial zeolites, and the average pore Bioresour. Technol. 171, 428e432.
diameter was 37.19 nm. These authors suggested the possible Chen, G., Shan, R., Shi, J., Yan, B., 2015a. A biomimetic silicification approach to
synthesize CaO-SiO2 catalyst for the transesterification of palm oil into bio-
employment of this material as adsorbent in wastewater treatment.
diesel. Fuel 153, 48e55.
Other properties that could make this zeolite interesting for in- Chen, G.Y., Shan, R., Shi, J.F., Yan, B.B., 2015b. Transesterification of palm oil to
dustrial uses would be its ability as catalyst, ion exchanger or mo- biodiesel using rice husk ash-based catalysts. Fuel Process. Technol. 133, 8e13.
lecular sieve. However, further work would be necessary in this Cho, Y.B., Seo, G., 2010. High activity of acid-treated quail eggshell catalysts in the
transesterification of palm oil with methanol. Bioresour. Technol. 101,
area. 8515e8519.
Correia, L.M., Saboya, R.M.A., de Sousa Campelo, N., Cecilia, J.A., Rodríguez-
3. Conclusions Castellon, E., Cavalcante, C.L., Vieira, R.S., 2014. Characterization of calcium
oxide catalysts from natural sources and their application in the trans-
esterification of sunflower oil. Bioresour. Technol. 151, 207e213.
Green eggshell-derived catalysts were successfully used for El-Gendy, N.Sh., Deriase, S.F., 2015. Waste eggshells for production of biodiesel from
biodiesel production with numerous works published about this different types of waste cooking oil as waste recycling and a renewable energy
process. Energy. Sources Part A 37, 1114e1124.
topic. When eggshell is calcined different changes in composition Eletta, O.A.A., Ajayi, O.A., Ogunleye, O.O., Akpan, I.C., 2016. Adsorption of cyanide
and structure can be observed. During calcination, the CaCO3 is from aqueous solution using calcinated eggshells: equilibrium and optimisation
decomposed to CaO. Simultaneously, this thermal treatment con- studies. JECE 4, 1367e1375.
Fan, S.M., Yuan, X.Z., Zhao, L., Xu, L.H., Kang, T.J., Kim, H.T., 2016. Experimental and
tributes to homogenize the catalyst textural properties, originating kinetic study of catalytic steam gasification of low rank coal with an environ-
a homogeneous macroporous structure and increasing its surface mentally friendly, inexpensive composite K2CO3-eggshell derived CaO catalyst.
area. The effect of these factors on catalyst activity for biodiesel Fuel 165, 397e404.
Gao, Y., Xu, C., 2012. Synthesis of dimethyl carbonate over waste eggshell catalyst.
production has been widely studied and it is clear that in the
Catal. Today 190, 107e111.
development of eggshell catalyst to obtain biodiesel the calcination Han, T., Li, X., Lin, C., Zhang, H., Gao, P., Zhao, Y., Du, F., Chen, Y., Sun, Y., 2016. 3D
conditions are determinant on catalyst performance. Temperatures Imaging and structural analysis of a mesoporous-silica-body-supported
given as optimal for calcinations vary between 600 and 1000 C, eggshell cobalt catalyst for Fischer-Tropsch synthesis. ChemCatChem 8,
2920e2929.
depending on the authors. In addition, catalyst deactivation after Harrouche, K., Renard, J.F., Bouider, N., de Tullio, P., Goffin, E., Lebrun, P., Faury, G.,
several cycles of use was related to a reduction of the surface area Pirotte, B., Khelili, S., 2016. Synthesis, characterization and biological evaluation
A. Laca et al. / Journal of Environmental Management 197 (2017) 351e359 359
of benzothiazoles and tetrahydrobenzothiazoles bearing urea or thiourea natural catalyst for Knoevenagel condensation under aqueous condition. Jour-
moieties as vasorelaxants and inhibitors of the insulin releasing process. Eur. J. nal of Chemical Sciences 125, 851e857.
Med. Chem. 115, 352e360. Quina, M.J., Soares, M.A.R., Quinta-Ferreira, R., 2016. Applications of industrial
Kachkovski, O.D., Tolmachev, O.I., Kobryn, L.O., Bila, E.E., Ganushchak, M.I., 2004. eggshell as a valuable anthropogenic resource. Resour. Conserv. Recycl. (in
Absorption spectra and nature of electron transitions in azomethine dyes as 6- press).
derivatives of 2H-2-chromenone. Dyes Pigments 63, 203e211. Ramkumar, S., Kirubakaran, V., 2016. Biodiesel from vegetable oil as alternate fuel
Karoshi, G., Kolar, P., Shah, S.B., Gilleskie, G., Das, L., 2015. Calcined eggshell as an for C.I engine and feasibility study of thermal cracking: a critical review. Energy
inexpensive catalyst for partial oxidation of methane. J. Taiwan Inst. Chem. E 57, Convers. Manag. 118, 155e169.
123e128. Ramesh, S., Natasha, A.N., Tan, C.Y., Bang, L.T., Ramesh, S., Ching, C.Y., Chandran, H.,
Khemthong, P., Luadthong, C., Nualpaeng, W., Changsuwan, P., Tongprem, P., Viriya- 2016. Direct conversion of eggshell to hydroxyapatite ceramic by a sintering
empikul, N., Faungnawakij, K., 2012. Industrial eggshell wastes as the hetero- method. Ceram. Int. 42, 7824e7829.
geneous catalysts for microwave-assisted biodiesel production. Catal. Today Reyero, I., Bimbela, F., Navajas, A., Arzamendi, G., Gandía, L.M., 2015. Issues con-
190, 112e116. cerning the use of renewable Ca-based solids as transesterification catalysts.
Laca, A., Paredes, B., Rendueles, M., Díaz, M., 2014. Egg yolk granules: separation, Fuel 158, 558e564.
characteristics and applications in food industry. Food Sci. Technol.-LEB 1, 1e5. Roschat, W., Siritanon, T., Yoosuk, B., Sudyoadsuk, T., Promarak, V., 2017. Rubber
Laca, A., Paredes, B., Rendueles, M., Díaz, M., 2015. Egg yolk plasma: separation, seed oil as potential non-edible feedstock for biodiesel production using het-
characteristics and future prospects. Food Sci. Technol.-LEB 62, 7e10. erogeneous catalyst in Thailand. Renew. Energy. 101, 937e944.
Li-Chang, E.C.Y., Kim, H.O., 2008. Structure and chemical composition of eggs. In: Seo, Y.H., Sung, M., Han, J.I., 2016. Lactulose production from cheese whey using
Mine, Y. (Ed.), Egg Bioscience and Biotechnology. John Wiley & Sons Inc., USA, recyclable catalyst ammonium carbonate. Food Chem. 197, 664e669.
pp. 1e96. Semwal, S., Arora, A.K., Prakash, S., Puri, S.K., Tuli, D.K., 2011. Preparation of novel
Majhi, S., Ray, S., 2016. A study on production of biodiesel using a novel solid oxide catalyst composition from natural waste for biodiesel production. JSIR 70,
catalyst derived from waste. Environ. Sci. Pollut. Res. Int. 23, 9251e9259. 1054e1060.
Montilla, A., Castillo, M.D., Sanz, M.L., Olano, A., 2005. Egg shell as catalyst of lactose Shan, R., Zhao, C., Lv, P., Yuan, H., Yao, J., 2016. Catalytic applications of calcium rich
isomerisation to lactulose. Food Chem. 90, 883e890. waste materials for biodiesel: current state and perspectives. Energy. Convers.
Morbale, S.T., Shinde, S.S., Jadhav, S.D., Deshmukh, M.B., Patil, S.S., 2015. Modified Manag. 127, 273e283.
eggshell catalyzed, one-pot synthesis and antimicrobial evaluation of 1,4- Sharma, Y.C., Singh, B., Korstad, J., 2010. Application of an efficient nonconventional
dihydropyridines and polyhydroquinolines. Der Pharm. Lett. 7, 169e182. heterogeneous catalyst for biodiesel synthesis from Pongamia pinnata oil. En-
Mosaddegh, E., 2013. Ultrasonic-assisted preparation of nano eggshell powder: a ergy fuels. 24, 3223e3231.
novel catalyst in green and high efficient synthesis of 2-aminochromenes. Shelepova, E., Vedyagin, A., Sadykov, V., Mezentseva, N., Fedorova, Y., Smorygo, O.,
Ultrason. Sonochem 20, 1436e1441. Klenov, O., Mishakov, I., 2016. Theoretical and experimental study of methane
Mosaddegh, E., Hassankhani, A., 2013. Application and characterization of eggshell partial oxidation to syngas in catalytic membrane reactor with asymmetric
as a new biodegradable and heterogeneous catalyst in green synthesis of 7,8- oxygen-permeable membrane. Catal. Today 268, 103e110.
dihydro-4H-chromen-5(6H)-ones. Catal. Commun. 33, 70e75. Sinha, D., Murugavelh, S., 2016. Comparative studies on biodiesel production from
Mosaddegh, E., Hassankhani, A., Pourahmadi, S., Ghazanfari, D., 2013. Ball mill- waste cotton cooking oil using alkaline, calcined eggshell and pistachio shell
assisted preparation of nano-CaCO3 as a novel and green catalyst-based catalyst (Conference Paper). In: International Conference on Energy Efficient
eggshell waste: a green approach in the synthesis of pyrano[4,3-b]pyrans. Int. Technologies for Sustainability, ICEETS 2016, Nagercoil (India), 7 April 2016
J. Green Nanotechnol. 5, 1e5. through 8 April 2016, pp. 130e133. Category number CFP1675U-PRT, Code
Mosaddegh, E., Hassankhani, A., 2014. Preparation and characterization of nano- 1241644. Article number 7582912.
CaO based on eggshell waste: novel and green catalytic approach to highly Stone, E.L., Citossi, F., Singh, R., Kaur, B., Gaskell, M., Farmer, P.B., Monks, A., Hose, C.,
efficient synthesis of pyrano[4,3-b]pyrans. Chin. J. Catal. 35, 351e356. Stevens, M.F.G., Leong, C.O., Stocks, M., Kellam, B., Marlow, M., Bradshaw, T.D.,
Mostafavi, E., Mahinpey, N., Rahman, M., Sedghkerdar, M.H., Gupta, R., 2016. High- 2015. Antitumour benzothiazoles. Part 32: DNA adducts and double strand
purity hydrogen production from ash-free coal by catalytic steam gasification breaks correlate with activity; synthesis of 5F203 hydrogels for local delivery.
integrated with dry-sorption CO2 capture. Fuel 178, 272e282. Bioorg. Med. Chem. 23, 6891e6899.
Nasrollahzadeh, M., Sajadi, S.M., Hatamifard, A., 2016. Waste chicken eggshell as a Tan, Y.H., Abdullah, M.O., Nolasco-Hipolito, C., 2015. The potential of waste cooking
natural valuable resource and environmentally benign support for biosynthesis oil-based biodiesel using heterogeneous catalyst derived from various calcined
of catalytically active Cu/eggshell, Fe3O4/eggshell and Cu/Fe3O4/eggshell eggshells coupled with an emulsification technique: a review on the emission
nanocomposites. Appl. Catal. B Environ. 191, 209e227. reduction and engine performance. Renew. Sust. Energy Rev. 47, 589e603.
Navajas, A., Issariyakul, T., Arzamendi, G., Gandía, L.M., Dalai, A.K., 2013. Develop- Tangboriboon, N., Wongkasemjit, S., Kunanuruksapong, R., Sirivat, A., 2011. An
ment of eggshell derived catalyst for transesterification of used cooking oil for innovative synthesis of calcium zeolite type A catalysts from eggshells via the
biodiesel production. Asia Pac. J. Chem. Eng. 8, 742e748. sol-gel process. JIOPM 21, 50e60.
Nooshkam, M., Madadlou, A., 2016. Maillard conjugation of lactulose with poten- Taufiq-Yap, Y.H., Wong, P., Marliza, T.S., Nurul Suziana, N.M., Tang, L.H.,
tially bioactive peptides. Food Chem. 192, 831e836. Sivasangar, S., 2013. Hydrogen production from wood gasification promoted by
Nys, Y., Gautron, J., 2007. Structure and formation of the eggshell. In: Huopalati, R., waste eggshell catalyst. Int. J. Energy Res. 37, 1866e1871.
Lopez-Fandin ~ o, R., Anton, M., Schade, R. (Eds.), Bioactive Egg Compounds. Viriya-empikul, N., Krasae, P., Puttasawat, B., Yoosuk, B., Chollacoop, N.,
Springer-Verlag, Berlin Heidelberg (Germany), pp. 99e102. Faungnawakij, K., 2010. Waste shells of mollusk and egg as biodiesel production
Oliveira, D.A., Benelli, P., Amante, E.R., 2013. A literature review on adding value to catalysts. Bioresour. Technol. 101, 3765e3767.
solid residues: egg shells. J. Clean. Prod. 46, 42e47. Wang, S., Wei, L., Yuanyuan, D., Zhao, Y., Ma, X., 2015. Dimethyl carbonate synthesis
Olutoye, M.A., Lee, S.C., Hameed, B.H., 2011. Synthesis of fatty acid methyl ester from from methyl nitrite and CO over activated carbon supported Wacker-
palm oil (Elaeis guineensis) with K y(MgCa) 2xO 3 as heterogeneous catalyst. typecatalysts: the surface chemistry of activated carbon. Catal. Commun. 72,
Bioresour. Technol. 102, 10777e10783. 43e48.
Osman, A.I., Abu-Dahrieh, J.K., Laffir, F., Curtin, T., Thompson, J.M., Rooney, D.W., Wei, Z., Xu, C., Li, B., 2009. Application of waste eggshell as low-cost solid catalyst
2016. A bimetallic catalyst on a dual component support for low temperature for biodiesel production. Bioresour. Technol. 100, 2883e2885.
total methane oxidation. Appl. Catal. B: Environ 187, 408e418. Yin, X., Duan, X., You, Q., Dai, C., Tan, Z., Zhu, X., 2016. Biodiesel production from
Panesar, P.S., Kumari, S., 2011. Lactulose: production, purification and potential soybean oil deodorizer distillate using calcined duck eggshell as catalyst. En-
applications. Biotechnol. Adv. 29, 940e948. ergy Convers. Manag. 112, 199e207.
Park, S., Choi, K.S., Lee, D., Kim, D., Lim, K.T., Lee, K.-H., Seonwoo, H., Kim, J., 2016. Zeng, D., Zhang, Q., Chen, S., Liu, S., Chen, Y., Tian, Y., Wang, G., 2015. Preparation
Eggshell membrane: review and impact on engineering. Biosyst. Eng. 151, and characterization of a strong solid base from waste eggshell for biodiesel
446e463. production. JECE 3, 560e564.
Patil, S., Jadhav, S.D., Deshmukh, M.B., 2013. Calcined eggshell (CES): An efficient