Artigo Da Aula Tatiana
Artigo Da Aula Tatiana
Artigo Da Aula Tatiana
a r t i c l e i n f o a b s t r a c t
Article history: In this work, and for the first time, fly ash (FA)-based geopolymer (d ¼ 2.6 mm) spheres were used to
Received 10 April 2018 extract methylene blue from synthetic wastewaters. The influence of sorption time, dye initial concen-
Received in revised form tration and adsorbent amount on the dye removal efficiency and uptake by the porous spheres was
12 September 2018
evaluated. The adsorbents' recyclability and their dye fixation efficiency were also considered. The initial
Accepted 30 September 2018
Available online 3 October 2018
dye concentration strongly affected the uptake and removal efficiency by the porous bodies, the former
rising from 1.1 to 30.1 mg/g when the dye initial concentration jumped from 10 to 250 ppm, and the
latter increasing from 82.3% to 94.3% when the dye initial concentration varied from 10 to 125 ppm.
Keywords:
Adsorption
Results showed a much faster (24 h) and higher (30.1 mg/g) methylene blue uptake in comparison with
Inorganic polymer the other bulk-type geopolymers reported to date (30 h; 15.4 mg/g). The cumulative methylene blue
Geopolymer uptake shown by these innovative spheres (79.7 mg/g) surpasses all other powdered geopolymer ad-
Porosity sorbents, being among the highest values ever reported for geopolymers. The adsorbent was successfully
Dye regenerated and reused eight times. Regeneration was found to negatively affect the MB uptake, but
Waste nevertheless, even after eight regeneration cycles a very high MB removal efficiency (83%) was main-
tained. The use of these bulk-type waste-based geopolymer adsorbents is a low-cost, more eco-friendly,
safer and easier alternative to the use of powdered adsorbents in wastewater treatment systems, since
these ~3 mm spheres may be used directly in packed beds, and were produced using significant amounts
of waste material.
© 2018 Elsevier Ltd. All rights reserved.
1. Introduction its high production cost (Rafatullah et al., 2010) has led to extensive
research for lower cost alternatives. One exciting approach could be
The removal of dyes from industrial wastewaters is of the the use of low cost and eco-friendly inorganic polymers (also
utmost importance, not only because most of them are toxic and known as geopolymers). Inorganic polymers are synthesised at
show carcinogenic properties, but also because treated industrial near-ambient temperatures (Novais et al., 2016b) by chemical
wastewaters may provide a vital source of clean water to mitigate activation of aluminosilicate sources, such as metakaolin (Zhu et al.,
the most pressing concern of our society e water scarcity. In the 2018), fly ash (Novais et al., 2016c) and waste glass (Novais et al.,
next 30 years, around 40% of the world's population will live in 2016a). They have a negatively charged aluminosilicate network,
areas with extreme water scarcity (OECD, 2012). Effective and low balanced by cations such as sodium or potassium, which may in
cost technologies for wastewater treatment are being eagerly pur- turn be exchanged with cations is solution. This feature suggests
sued. Adsorption is considered the most effective, simple and the feasibility of using inorganic polymers as dye or heavy metal
universal technique for water decontamination (Gupta et al., 2012), adsorbent materials. Despite this, the study of the use of geo-
activated carbon being the benchmark adsorbent material (Mestre polymers as adsorbents is fairly recent (Minelli et al., 2018; Novais
et al., 2014). Despite the unique adsorption capacity of this material, et al., 2016d). Moreover, the vast majority of the investigations are
focussed on the use of powdered adsorbents (Falah et al., 2016; Liu
et al., 2016), which cannot be easily recovered, and so cannot be
* Corresponding author. used in field applications or directly in packed beds. Powdered
E-mail address: [email protected] (R.M. Novais).
https://doi.org/10.1016/j.jclepro.2018.09.265
0959-6526/© 2018 Elsevier Ltd. All rights reserved.
R.M. Novais et al. / Journal of Cleaner Production 207 (2019) 350e362 351
adsorbents may require the use of support materials (e.g. porous Table 1
ceramics, polymer foams) (Zhang et al., 2016) to allow their in- Chemical composition from XRF of metakaolin (MK) and fly ash (FA).
The feasibility of reusing the GS as adsorbents after initial MB 3.1. Geopolymer spheres characterisation
adsorption was evaluated only for the specimens showing the
highest MB removal capacity. Samples were heated at 400 C for 2 h Fig. 1a shows a representative optical micrograph of the FA-
to induce MB decomposition. Then the specimens were reused, and based GS, while Fig. 1b presents their size distribution measured
their adsorption ability evaluated using a 50 ppm MB solution. by image analysis. The geopolymers have an elongated spheroidal
shape, with average diameter and length being 2.6 ± 0.2 mm and
2.9 ± 0.3 mm, respectively. These results demonstrate that the
Table 2
production method described here is effective and reproducible,
Linearised forms of the Langmuir equation.
leading to a narrow size distribution. The mm size spheres can be
Linear regression Plot directly used in packed beds and easily retrieved after exhaustion,
Type I Ce/qe versus Ce this being a crucial advantage over powdered adsorbents.
Type II 1/qe versus 1/Ce Fig. S1 (Supplementary Material) shows a high magnification
Type III qe versus qe/Ce SEM micrograph and the corresponding EDS map of the GS surface.
Type IV qe/Ce versus qe
As observed, a geopolymeric gel composed of silica and alumina
R.M. Novais et al. / Journal of Cleaner Production 207 (2019) 350e362 353
Fig. 1. a) Optical characterisation of the FA-based geopolymer spheres and their b) cumulative size distribution (measured using image analysis). Horizontal lines corresponding to
cumulative values of 10, 50 and 90% were included.
was formed, which demonstrates that the alkali activation of the FA and interior pore microstructure. The spheres present a smooth and
and the metakaolin has occurred. This observation is in line with homogeneous surface with several small pores being visible, which
other literature studies which have shown that these two alumi- could allow the MB diffusion into the specimens, thus enhancing
nosilicate sources (FA and metakaolin) can be used as precursors in the adsorption ability of the geopolymers. Fig. 2bec show an
the production of geopolymers (Novais et al., 2016b, 2016c). extremely porous microstructure, in which most of the pores are
Fig. 2 presents SEM micrographs of the spheres' exterior surface closed. The micrographs clearly show the presence of small-sized
Fig. 2. SEM micrographs of the FA-based geopolymer spheres: a) surface and (b, c) interior. Fig. 2d presents the EDS spectra of the geopolymer spheres surface and interior (at two
different positions).
354 R.M. Novais et al. / Journal of Cleaner Production 207 (2019) 350e362
Table 3
Refinement parameters and phase composition of the specimens.
R(2F ) (%) Rwp (%) c2 aequartz calcite mica microcline anatase amorphous
Fig. 5. Equilibrium time of various methylene blue adsorbents reported in literature. When available the size of the adsorbents was included above the columns (in blue colour) for
comparison (Nasrullah et al., 2018). (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)
Fig. 7. Optical micrographs of the inner part of the geopolymer spheres after MB adsorption illustrating the influence of the MB initial concentration on the MB diffusion throughout
the spheres (real colours are shown). MB initial concentration being: a) 10, b) 25, c) 75, d) 100, e) 175 and f) 200 ppm. (For interpretation of the references to colour in this figure
legend, the reader is referred to the Web version of this article.)
~10. Interestingly, this pH value is extremely close to that found to absent from MK composition. This explains the heterogeneous
induce the highest charge density (10.5) for this innovative adsor- distribution of sulphur (identified in purple in the EDS map) on the
bent (section 3.1), which explains the strong attraction between the spheres' surface before adsorption. The EDS elemental mapping
cationic dye molecules and the negatively charged geopolymer before adsorption also shows sodium agglomerates (identified in
framework. blue), suggesting the presence of unreacted alkalis. After adsorp-
To further understand the MB adsorption by the porous GS, EDS tion, the sodium distribution on the spheres' surface is remarkably
maps from the spheres' surface before and after MB adsorption similar to that of the aluminium and silicon distribution (Fig. 8b).
tests were collected, and are shown in Fig. 8. According to the XRF This observation suggests that the free sodium observed in the GS
data, the FA contains around 3 wt.% of SO3, while this element is before adsorption has leached to the solution, while the remaining
Fig. 8. EDS elemental mapping of FA-based geopolymer spheres' surface a) before and b) after methylene blue adsorption tests. (For interpretation of the references to colour in this
figure legend, the reader is referred to the Web version of this article.)
R.M. Novais et al. / Journal of Cleaner Production 207 (2019) 350e362 357
sodium in acting as a charge-balancing cation for the negatively (1355 and 1335 cm1, and ~1410 cm1, respectively) (Coates, 2006)
charged aluminosilicate network, which explains the above- occurred, providing clear evidence of MB adsorption.
mentioned pH increase. After MB adsorption, the sulphur distri-
bution also changes, with two clear features being distinguished: i) 3.2.3. Influence of adsorbent concentration
a homogeneous distribution associated with the geopolymer The effect of the adsorbent amount on the MB uptake and
structure (derived from the FA composition); and ii) the presence of removal efficiently by the GS was evaluated to determine the op-
small sulphur concentrations (not observed before) which were timum adsorbent dosage, and results are shown in Fig. 10. The MB
associated with the MB adsorption by the porous GS (MB molecular uptake and the removal efficiency were affected differently by the
formula: C16H18ClN3S). increase in the adsorbents amount, the uptake drops and the
FT-IR spectra are depicted in Fig. 9. They all show similar char- removal efficiency increases (exceptions to this general trend will
acteristics: the strong asymmetric band, having its maximum at be discussed below) when rising the GS amount. Increasing the
around 3350 cm1, is due to adsorbed molecular H2O, which also adsorbents amount increases the number of available adsorption
generates the feature at around 1630 cm1, assigned to HeOeH sites, therefore increasing the amount of adsorbed MB (i.e. removal
bending (Tobaldi et al., 2010). The band located at ~980 cm1 be- efficiency). However, the amount adsorbed per unit of mass (i.e.
longs to the asymmetric AleOeAl/SieOeSi stretching (Kumar et al., uptake) decreases which is explained by the presence of unsatu-
2015). The band at ~1440 cm1 can be assigned to sodium car- rated adsorption sites (Aljeboree et al., 2017). The decrease in the
bonate, due to the reaction of residual sodium with atmospheric MB uptake when rising the adsorbents amount has been previously
CO2 (Cheng-Yong et al., 2017). reported (Liu et al., 2016).
After being in contact with MB (24 h), additional features Results also showed that the MB removal efficiency was affected
appeared (cf the blue continuous line in Fig. 9). The band centred at by the dye initial concentration: i) C0 ¼ 10 ppm e the removal ef-
~1610 cm1, belonging to the stretching vibration of aromatic rings, ficiency significantly dropped from 82 to 75% when the spheres
and features due to methyl and methylene bending vibrations content was above 1.5 g; ii) C0 ¼ 50 ppm e the removal efficiency
increased up to 2.0 g, and then slightly decreased (~1%) afterwards;
iii) C0 ¼ 100 ppm e the removal efficiency increased steadily with
the rise of the adsorbent amount, from ~88 up to ~96%, until a
plateau was reached. These different trends are better illustrated in
Fig. 11 where the removal efficiency versus contact time is shown.
As depicted, the sorption kinetics are MB concentration-dependent,
with higher C0 inducing a faster MB uptake, this being independent
from the amount of adsorbents used. These differences were
associated with the above-mentioned mass transfer resistance. In
any case, for the higher C0 values, an increase in the amount of
spheres from 1.0 to 1.5 g enhanced the removal efficiency by around
5%. Increasing the quantity of spheres used to 2.0 and 2.5 g of
spheres promoted even higher removal efficiencies, an increase of
~2% and ~3%, respectively, in comparison with the use of 1.5 g.
Despite the slight gain in performance when using greater quan-
tities of spheres, the use of 1.5 g of spheres seems to be the most
cost-effective solution (E ¼ 93%). This is the reason why 1.5 g of
spheres was used as a proxy for the isotherm model studies, see
below.
Fig. 9. FTIR spectra of the geopolymer spheres before, after MB adsorption, (contact
3.3. Isotherm model studies
time ¼ 24 h; adsorbent dose: 1.5 g; C0 ¼ 200 ppm), as well as being regenerated. Note:
the noise in the 2450e2000 cm1 region is due to atmospheric CO2. Linear regression results, for both the Freundlich and Langmuir
Fig. 10. Influence of the adsorbent amount on a) the MB uptake and b) removal efficiency by the FA-based geopolymer spheres for various concentrations of MB (contact time: 24 h).
358 R.M. Novais et al. / Journal of Cleaner Production 207 (2019) 350e362
Fig. 11. Influence of the adsorbent amount and MB initial concentration on the removal efficiency kinetics.
isotherm equations, are reported in Fig. S3. As seen in Fig. S3, the Table 4
linearisation resulted in a two-step trend, with the turning point Isotherm constants for MB adsorption onto GS (1.5 g of adsorbent in 0.2 L MB
solution).
(for the system considered here, i.e., 1.5 g of GS as the adsorbent
medium, MB as the solute, in 0.2 L of solution) being located at Type I Type II Type III Type IV
~100 ppm of MB (Freundlich model) and 125 ppm of MB (Langmuir Langmuir constants, MB concentration range: 10e125 ppm
model).
qm (mg/g) 4.028 3.619 4.070 4.131
This is better visualised in Table 4, where the Langmuir (Type I to KL (L/mg) 0.110 0.116 0.110 0.109
IV) and Freundlich constants are listed, considering MB concen- R2 0.954 0.991 0.994 0.994
tration intervals of 10e100 and 125e250 ppm for the Freundlich Freundlich constants, MB concentration range: 10e100 ppm
isotherm model, and 10e125 and 125e250 ppm for the Langmuir
KF (mg/g)(L/g)n 0.276
model. As derived from Table 4, at relatively low MB concentrations 1/n 1.895
(10e125 ppm), the data follows the Freundlich isotherm equation. R2 0.993
The determination coefficient of the Freundlich model, at this
Langmuir constants, MB concentration range:125e250 ppm
concentration range, is 0.993; although the R2 of the Langmuir
qm (mg/g) 45.434 45.809 43.562 46.960
models (Types III and IV) are slightly better than that (i.e. 0.994), the
KL (L/mg) 0.076 0.074 0.084 0.072
Langmuir isotherm constants are all negative (for all of the four R2 0.959 0.996 0.822 0.822
type of linear methods) e this being physically meaningless. On the
Freundlich constants, MB concentration range: 125e250 ppm
contrary, when dealing with higher MB concentrations
(i.e. 100 ppm), the Langmuir isotherm model became more KF (mg/g)(L/g)n 6.227
1/n 0.495
applicable; in particular the Type II has a very good R2 (0.996), with
R2 0.946
an adsorption capacity qm equal to 45.809 mg/g, this suggesting the
prevalence of monolayer adsorption as the dominant sorption The bold identifies the isotherm model that better fits the experimental results.
Fig. 14. SEM micrographs of the spheres' surface (a) and inner part (b) after eight regeneration cycles illustrating the microstructural changes induced in the geopolymer spheres by
the multiple adsorption and thermal regeneration cycles. Fig. 14c presents the EDS spectrum of the geopolymer sphere surface.
reusing this innovative adsorbent in multiple MB adsorption cycles, that after 9 cycles (1 adsorption þ 8 adsorptions after regeneration)
this being a crucial advantage over benchmark activated carbons, the sample losses ~61% of its initial mass (49% þ 12%). Nevertheless,
whose recovery after use is extremely challenging. After the 1st these results suggest that additional regeneration cycles could be
regeneration cycle, seven other cycles (adsorption and thermal performed. This will be considered in future work.
regeneration) were performed without any further performance The cumulative MB uptake of the GS (79.7 mg/g), shown in
compromise. At the end of the eight regeneration cycles, the GS Fig. 12, demonstrates the interesting potential of this bulk adsor-
maintained their integrity, as demonstrated by the SEM micro- bent for wastewater treatment systems. The removal efficiency
graphs shown in Fig. 14, although an increase in porosity was throughout the nine cycles was always above 83% (results not
observed. A continuous and gradual mass reduction (reaching 12% shown by the sake of brevity), much higher than the other study
after the 8th cycle) was observed throughout the tests. This means addressing the use of bulk-type geopolymer adsorbent whose
Table 5
Maximum methylene blue adsorption capacity of various adsorbents reported in literature.
removal efficiency after the 1st adsorption test was only 55%, The MB uptake by the porous geopolymer spheres is affected by the
dropping to values below 50% when using the regenerated samples dye initial concentration, adsorbent amount and contact time. Re-
(up to 5 cycles) (Novais et al., 2018a). sults showed a faster (20% smaller equilibrium time) and higher MB
The maximum (experimental) adsorption capacity observed for uptake (twofold increase) in comparison with the other bulk-type
the GS (79.7 mg/g) was compared with that reported for other MB geopolymer reported to date, demonstrating the performance
adsorbents, and results are shown in Table 5. The GS show very high advantage of using spheres (d ¼ 2.6 mm) instead of cylindrical discs
MB removal capacity, surpassing all reported values for powdered (thickness ¼ 3 mm; d ¼ 22 mm) for wastewater decontamination.
geopolymers, such as those prepared from coal FA (Li et al., 2006; After adsorption tests, the geopolymer spheres could be re-
Liu et al., 2016), MK (Khan et al., 2015), Cu2O-modified geopolymers generated and reused (up to 8 cycles) resulting in a very high cu-
(Falah et al., 2016; Falah and Mackenzie, 2015), kaolin-based mulative MB uptake (79.7 mg/g) which surpasses all other
(Yousef et al., 2009), and acid treated zeolites (Hor et al., 2016), powdered geopolymer adsorbents. These remarkable materials
among others (Rida et al., 2013; Wang et al., 2015). The GS may be used directly in wastewater systems (e.g. packed beds), and
adsorption capacity is inferior to that previously reported by the are easily retrieved after exhaustion, these being crucial advantages
authors when using geopolymer monoliths (Novais et al., 2018a). over conventional powdered adsorbents. The proposed solution
However, in this previous investigation the removal efficiency was (use of mm size geopolymer spheres instead of powdered adsor-
48.4% and the sorption time was 30 h (Novais et al., 2018a), while bents) increases the simplicity of wastewater treatment systems,
here a significantly higher efficiency (84.9%) with lower sorption being a safer alternative to conventional powdered adsorbents,
time (24 h) was achieved. Moreover, the GS are synthesised whose recovery after use is extremely challenging.
through one-step, while two steps are required for the monoliths Moreover, this innovative adsorbent also promotes waste min-
production (i) synthesis of the porous bodies; and ii) cutting of imisation, since biomass FA wastes were used to partially replace
cylindrical discs; thus, a simplified strategy is used here. (50 wt.%) commercial metakaolin in the geopolymer spheres' syn-
Table 5 also shows that the GS adsorption capacity is superior to thesis, which is aligned with the need to reduce the consumption of
that reported for Ficus carica bast (Pathania et al., 2017) and acrylic virgin raw materials and prevent landfill disposal of wastes.
fibrous waste (Naeem et al., 2017) activated carbons, whilst being
inferior to that of Fe3O4 nanoparticles (Ghaedi et al., 2015), and to Acknowledgements
palm shell (Wong et al., 2016) and waste rice straw (Sangon et al.,
2018) activated carbons. Nevertheless, the proposed strategy (use This work was developed within the scope of the project
of mm size spheres instead of powders) may allow the adsorbent's CICECO-Aveiro Institute of Materials, POCI-01-0145-FEDER-007679
direct use in wastewater treatment facilities, and its easy recovery (FCT Ref. UID/CTM/50011/2013), financed by national funds
after exhaustion, while the recovery of nanoparticles or activated through the FCT/MEC and when appropriate co-financed by FEDER
carbons after adsorption is a complex and expensive procedure. under the PT2020 Partnership Agreement. R.C. Pullar thanks the
Furthermore, the GS were synthesised are near room temperature FCT for funding under grant IF/00681/2015.
(24 h at 40 C), preventing the need for very high processing tem-
peratures (700 C) typically employed in the production of acti-
Appendix A. Supplementary data
vated carbons (Sangon et al., 2018), and thus being an
environmental friendlier approach.
Supplementary data to this article can be found online at
The outstanding recyclability of the GS, assuring very high cu-
https://doi.org/10.1016/j.jclepro.2018.09.265.
mulative MB adsorption capacity, associated with the possibility of
being directly used in wastewater systems without the need for
support materials, makes this bulk-adsorbent an excellent and safer References
alternative to conventional powdered adsorbents for wastewater
Albadarin, A.B., Collins, M.N., Naushad, M., Shirazian, S., Walker, G., Mangwandi, C.,
decontamination. Future work will evaluate the possibility of 2017. Activated lignin-chitosan extruded blends for efficient adsorption of
reusing the GS as aggregates in the production of eco-friendly methylene blue. Chem. Eng. J. 307, 264e272.
Al Duri, B., Mckay, G., 1988. Basic dye adsorption on carbon using a solid-phase
mortars, after their exhaustion as adsorbent material, which
diffusion model. Chem. Eng. J. 38, 23e31.
would contribute towards the circular economy, besides decreasing Aljeboree, A.M., Alshirifi, A.N., Alkaim, A.F., 2017. Kinetic and equilibrium study for
the carbon footprint of the spheres. the adsorption of textile dyes on coconut shell activated carbon. Arab. J. Chem.
10, S3381eS3393.
Allen, S.J., Gan, Q., Matthews, R., Johnson, P.A., 2003. Comparison of optimized
3.5. Methylene blue desorption tests isotherm models for basic dye adsorption by kudzu. Bioresour. Technol. 88,
143e152.
To evaluate the MB fixation onto the GS desorption tests were Cheng-Yong, H., Yun-Ming, L., Al Abdullah, M.M., Hussin, K., 2017. Thermal resis-
tance variations of fly ash geopolymers: foaming responses. Sci. Rep. 7, 45355.
performed in distilled water. All specimens showed low leaching Coates, J., 2006. Interpretation of infrared spectra, a practical approach. In:
values, ranging from 0.21 to 0.57%, suggesting a strong fixation of Meyers, R.A. (Ed.), Encyclopedia of Analytical Chemistry. John Wiley & Sons Ltd,
the dye onto the spheres. The quantity of spheres used did not Chichester, pp. 10815e10837.
El Qada, E.N., Allen, S.J., Walker, G.M., 2006. Adsorption of methylene blue onto
significantly affect the MB desorption level, although a slight activated carbon produced from steam activated bituminous coal: a study of
decrease was observed when increasing the amount of spheres: equilibrium adsorption isotherm. Chem. Eng. J. 124, 103e110.
0.57% (1.0 g), 0.37% (1.5 g), 0.22% (2.0 g) and 0.21% (2.5 g). These Falah, M., Mackenzie, K.J.D., Hanna, J.V., Page, S.J., 2015. Novel photoactive inorganic
polymer composites of inorganic polymers with copper (I) oxide nanoparticles.
results indicate that leaching in water medium is ineffective, J. Mater. Sci. 50, 7374e7383.
meaning that the adsorbent can be used for longer equilibrium Falah, M., Mackenzie, K.J.D., Knibbe, R., Page, S.J., Hanna, J.V., 2016. New composites
times than those employed here (Section 3.2.1) to ensure the of nanoparticle Cu (I) oxide and titania in a novel inorganic polymer (geo-
polymer) matrix for destruction of dyes and hazardous organic pollutants.
maximum MB removal (saturation of the spheres).
J. Hazard Mater. 318, 772e782.
Falah, M., Mackenzie, K.J.D., 2015. Synthesis and properties of novel photoactive
4. Conclusions composites of P25 titanium dioxide and copper (I) oxide inorganic polymers.
Ceram. Int. 41, 13702e13708.
Febrianto, J., Kosasih, A.N., Sunarso, J., Ju, Y.-H., Indraswati, N., Ismadji, S., 2009.
In this investigation, and for the first time, FA-based geopolymer Equilibrium and kinetic studies in adsorption of heavy metals using biosorbent:
spheres were evaluated as a methylene blue adsorbent material. a summary of recent studies. J. Hazard Mater. 162, 616e645.
362 R.M. Novais et al. / Journal of Cleaner Production 207 (2019) 350e362
Foo, K.Y., Hameed, B.H., 2012. Dynamic adsorption behaviour of methylene blue Porous biomass fly ash-based geopolymers with tailored thermal conductivity.
onto oil palm shell granular activated carbon prepared by microwave heating. J. Clean. Prod. 119, 99e107.
Chem. Eng. J. 203, 81e87. Novais, R.M., Buruberri, L.H., Seabra, M.P., Bajare, D., Labrincha, J.A., 2016c. Novel
Ge, Y., Cui, X., Liao, C., Li, Z., 2017. Facile fabrication of green geopolymer/alginate porous fly ash-containing geopolymers for pH buffering applications. J. Clean.
hybrid spheres for efficient removal of Cu (II) in water: batch and column Prod. 124, 345e404.
studies. Chem. Eng. J. 311, 126e134. Novais, R.M., Buruberri, L.H., Seabra, M.P., Labrincha, J.A., 2016d. Novel porous fly
Ghaedi, M., Hajjati, S., Mahmudi, Z., Tyagi, I., Agarwal, S., Maity, A., Gupta, V.K., 2015. ash-containing geopolymer monoliths for lead adsorption from wastewaters.
Modeling of competitive ultrasonic assisted removal of the dyes e methylene J. Hazard Mater. 318, 631e640.
blue and safranin-O using Fe3O4 nanoparticles. Chem. Eng. J. 268, 28e37. Novais, R.M., Carvalheiras, J., Seabra, M.P., Pullar, R.C., 2018b. J.A. Labrincha Inno-
Gualtieri, A.F., 2000. Accuracy of XRPD using combined Rietveld-RIR method. vative application for bauxite residue: red mud-based inorganic polymer
J. Appl. Crystallogr. 33, 267e278. spheres as pH regulators. J. Hazard Mater. 358C, 69e81.
Gualtieri, A.F., Brignoli, G., 2004. Rapid and accurate quantitative phase analyses Novais, R.M., Gameiro, T., Carvalheiras, J., Seabra, M.P., Tarelho, L.A.C., Labrincha, J.A.,
using a fast detector. J. Appl. Crystallogr. 37, 8e13. Capela, I., 2018c. High pH buffer capacity biomass fly ash-based geopolymer
Gupta, V.K., Ali, I., Saleh, T.A., Nayak, A., Agarwal, S., 2012. Chemical treatment spheres to boost methane yield in anaerobic digestion. J. Clean. Prod. 178,
technologies for waste-water recycling e an overview. RSC Adv. 2, 6380e6388. 258e267.
Hajjaji, W., Ganiyu, S.O., Tobaldi, D.M., Andrejkovi cova, S., Pullar, R.C., Rocha, F., Novais, R.M., Seabra, M.P., Labrincha, J.A., 2017. Geopolymer spheres as novel pH
Labrincha, J.A., 2013. Natural Portuguese clayey materials and derived TiO2- buffering materials. J. Clean. Prod. 143, 1114e1122.
containing composites used for decolouring methylene blue (MB) and orange II OECD (Organisation for Economic Co-operation and Development), 2012. 2012
(OII) solutions. Appl. Clay Sci. 83e84, 91e98. OECD (Organisation for Economic Co-operation and Development) OECD
Hor, K.Y., Chee, J.M.C., Chong, M.N., Jin, B., Saint, C., Poh, P.E., Aryal, R., 2016. Eval- Environmental Outlook to 2050: the Consequences of Inaction. OECD Publish-
uation of physicochemical methods in enhancing the adsorption performance ing, Paris. https://doi.org/10.1787/9789264122246-en.
of natural zeolite as low-cost adsorbent of methylene blue from wastewater. Pathania, D., Sharma, S., Singh, P., 2017. Removal of methylene blue by adsorption
J. Clean. Prod. 118, 197e209. onto activated carbon developed from Ficus carica bast. Arab. J. Chem. 10,
Khan, M.I., Min, T.K., Azizli, K., Sufian, S., Man, Z., Ullah, H., 2015. Effective removal of S1445eS1451. https://doi.org/10.1016/j.arabjc.2013.04.021.
methylene blue from water using phosphoric acid based geopolymers. RSC Adv. Rafatullah, M., Sulaiman, O., Hashim, R., Ahmad, A., 2010. Adsorption of methylene
5, 61410e61420. blue on low-cost adsorbents: a review. J. Hazard Mater. 177, 70e80.
Kumar, K.V., Sivanesan, S., 2007. Isotherms for malachite green onto rubber wood Richter, E., Schütz, W., Myers, A.L., 1989. Effect of adsorption equation on prediction
(hevea brasiliensis) sawdust: comparison of linear and non-linear methods. of multicomponent adsorption equilibria by the ideal adsorbed solution theory.
Dyes Pigments 72, 124e129. Chem. Eng. Sci. 44, 1609e1616.
Kumar, S., Krista ly, F., Mucsi, G., 2015. Geopolymerisation behaviour of size frac- Rida, K., Bouraoui, S., Hadnine, S., 2013. Adsorption of methylene blue from aqueous
tioned fly ash. Adv. Powder Technol. 26, 24e30. solution by kaolin and zeolite. Appl. Clay Sci. 83e84, 99e105.
Larson, A.C., Von Dreele, R.B., 2004. General Structure Analysis System (GSAS). Rouquerol, F., Rouquerol, J., Sing, K.S.W., 1998. Adsorption by Powders and Porous
National Laboratory Report LAUR, Los Alamos, pp. 86e748. Solids, Principles, Methodology and Applications, first ed. Academic Press, New
Li, C.-m., He, Y., Tang, Q., Wang, K.-t., Cui, X.-m., 2016. Study of the preparation of York. 978-0-08-052601-0.
CdS on the surface of geopolymer spheres and photocatalyst performance Sangon, S., Hunt, A.J., Attard, T.M., Mengchang, P., Ngernyen, Y., Supanchaiyamat, N.,
Materials. Chem. Phys. 178, 204e2010. 2018. Valorisation of waste rice straw for the production of highly effective
Li, L., Wang, S., Zhu, Z., 2006. Geopolymeric adsorbents from fly ash for dye removal carbon based adsorbents for dyes removal. J. Clean. Prod. 172, 1128e1139.
from aqueous solutions. J. Colloid Interface Sci. 300, 52e59.
Tobaldi, D.M., Tucci, A., Skapin, A.S., Esposito, L., 2010. Effects of SiO2 addition on
Liu, Y., Yan, C., Zhang, Z., Gong, Y., Wang, H., Qiu, X., 2016. A facile method for TiO2 crystal structure and photocatalytic activity. J. Eur. Ceram. Soc. 30,
preparation of floatable and permeable fly ash-based geopolymer block. Mater. 2481e2490.
Lett. 185, 370e373. Toby, B.H., 2001. EXPGUI, a graphical user interface for. GSAS J. Appl. Crystallogr. 34,
Li, Z., Wang, G., Zhai, K., He, C., Li, Q., Guo, P., 2018. Methylene blue adsorption from 210e213.
aqueous solution by loofah sponge-based porous carbons. Colloids Surf., A 538, Wang, S., Boyjoo, Y., Choueib, A.A., 2015. A comparative study of dye removal using
28e35. fly ash treated by different methods. Chemosphere 60, 1401e1407.
Mestre, A.S., Pires, R.A., Aroso, I., Fernandes, E.M., Pinto, M.L., Reis, R.L., Wong, K.T., Eu, N.C., Ibrahim, S., Kim, H., Yoon, Y., Jang, M., 2016. Recyclable
Andrade, M.A., Pires, J., Silva, S.P., Carvalho, A.P., 2014. Activated carbons pre- magnetite-loaded palm shell-waste based activated carbon for the effective
pared from industrial pre-treated cork: sustainable adsorbents for pharma- removal of methylene blue from aqueous solution. J. Clean. Prod. 115, 337e342.
ceutical compounds removal. Chem. Eng. J. 253, 408e417. https://doi.org/10.1016/j.jclepro.2015.12.063.
Minelli, M., Papa, E., Medri, V., Miccio, F., Benito, P., Doghieri, F., Landi, E., 2018. Yousef, R.I., El-Eswed, B., Alshaaer, M., Khalili, F., Khoury, H., 2009. The influence of
Characterization of novel geopolymer - zeolite composites as solid adsorbents using Jordanian natural zeolite on the adsorption, physical, and mechanical
for CO2 capture. Chem. Eng. J. 341, 505e515. properties of geopolymers products. J. Hazard Mater. 165, 379e387.
Naeem, S., Baheti, V., Wiener, J., Marek, J., 2017. Removal of methylene blue from Zhang, W., Dong, L., Yan, H., Li, H., Jiang, Z., Kan, X., Yang, H., Li, A., Cheng, R., 2011.
aqueous media using activated carbon web. J. Textil. Inst. 108, 803e811. Removal of methylene blue from aqueous solutions by straw based adsorbent in
Nasrullah, A., Bhat, A.H., Naeem, A., Isa, M.H., Danish, M., 2018. High surface area a fixed-bed column. Chem. Eng. J. 173, 429e436.
mesoporous activated carbon-alginate beds for efficient removal of methylene Zhang, Y., Liu, L., 2013. Fly ash-based geopolymer as a novel photocatalyst for
blue. Int. J. Biol. Macromol. 107, 1792e1799. degradation of dye from wastewater. Particuology 11, 353e358.
Novais, R.M., Ascens~ ao, G., Seabra, M.P., Labrincha, J.A., 2016a. Waste glass from end- Zhang, Z., Li, L., He, D., Ma, X., Yan, C., Wang, H., 2016. Novel self-supporting zeolitic
of-life fluorescent lamps as raw materials in geopolymers. Waste Manag. 52, block with tunable porosity and crystallinity for water treatment. Mater. Lett.
245e255. 178, 151e154.
Novais, R.M., Ascensa ~o, G., Tobaldi, D.M., Seabra, M.P., Labrincha, J.A., 2018a. Zhu, W., Rao, X.H., Liu, Y., Yang, E.-H., 2018. Lightweight aerated metakaolin-based
Biomass fly ash geopolymer monoliths for effective methylene blue removal geopolymer incorporating municipal solid waste incineration bottom ash as
from wastewaters. J. Clean. Prod. 171, 783e794. gas-forming agent. J. Clean. Prod. 177, 775e781.
Novais, R.M., Buruberri, L.H., Ascensa ~o, G., Seabra, M.P., Labrincha, J.A., 2016b.