Applied Clay Science xxx (xxxx) xxx–xxx

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Applied Clay Science

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

Research paper

Hydrothermal synthesis of zeolites using sanitary ware waste as a raw

material
⁎
Fátima García-Villéna,b, Eduardo Flores-Ruíza, Cristóbal Verdugo-Escamillaa, F. Javier Huertasa,
a
Instituto Andaluz de Ciencias de la Tierra, CSIC-University of Granada, 18100 Armilla, Granada, Spain
b
Department of Pharmacy and Pharmaceutical Technology, University of Granada, 18071 Granada, Spain

A R T I C L E I N F O A B S T R A C T

Keywords: Zeolites are extensively produced by hydrothermal treatment of different raw materials, such as kaolin. Sanitary
Synthetic zeolites ware (SW) is a kaolin-based ceramic ware usually found in sinks, urinals and bathtubs whose production is led by
Sanitary ware Spanish domestic clay product industry. SW production generates approximately 8% of solid waste in Spain,
Hydrothermal treatment which increases landfills sizes and pose economic, social and technical problems.
Cancrinite
This study aims to evaluate the feasibility of solid waste of SW industry to produce zeolites once subjected to a
Analcime
conventional hydrothermal treatment during different times and temperatures. Ground SW was subjected to
dissolution in a highly basic medium (NaOH 5 M) inside a Teflon-lined stainless steel reactors, at temperatures of
100, 150 and 200 °C for 1 to 30 days. X-ray powder diffraction (XRD), Fourier-transform infrared spectroscopy
(FTIR) and scanning electron microscopy (SEM) were used to characterize both the raw material and resultant
mineral phases. Quartz and mullite present in SW transform into zeolites, as temperature and time increase.
Mineral assemblage at 100 °C includes zeolite P, Na-faujasite and sodalite as major component and analcime,
natrolite, and zeolite A as minor, which behave as metastable phases and their relative abundance depends on
aging time. Analcime and cancrinite crystallization is favored by high temperature (150 °C to 200 °C) and in-
creasing aging time produces analcime disappearance. Cancrinite is the dominant mineral after 30 days.
Conventional SW waste is an optimal raw material for zeolites synthesis under high alkaline hydrothermal
conditions. Combining time and temperature it is possible to drive crystallization towards a target phase.

1. Introduction
Zeolites are crystalline, microporous, hydrated aluminosilicate mi-
nerals widely used in numerous technical applications mainly as cata-
lysts, adsorbents and ion exchangers that can be classified into natural
or synthetic materials and have demonstrated to be useful in industry,
agriculture, veterinary, human health as well as for environmental re-
mediation and protection.
Synthetic zeolites can be obtained using several source materials,
both natural and synthetic, as well as from pure chemical reagents. In
any case, the starting material(s) or chemical(s) must be a rich source of
Si and Al. A wide variety of different materials have been studied for
the synthesis of zeolites, most of them considered as waste materials
produced by different industries. Particularly, the use of waste mate-
rials as starting sources of alumina and silica contributes to the re-
duction of environmental problems and minimizes zeolites production
costs, which are considered high valuable minerals. Among the sub-
strates studied in recent years it is possible to mention fly ash (Belviso
et al., 2012, 2015a, 2015b; Cardoso et al., 2015a, 2015b; Aldahri et al.,
2016; Ojumu et al., 2016), other zeolites (Covarrubias et al., 2006;
Honda et al., 2014; Behin et al., 2016), asbestos (Saada et al., 2009),
perlite (Wang et al., 2007) and less commonly diatomite (Chaisena and
Rangsriwatananon, 2005; Garcia et al., 2016), red mud (Belviso et al.,
2015a), rice husk (Petkowicz et al., 2008; Atta et al., 2012), oil shale
ash (Fernandes-Machado and Malachini-Miotto, 2005) and aluminum
foil (Bayati et al., 2008). Apart from fly ashes, clay minerals highlight as
proper zeolites raw materials (Yue et al., 2014; Liu et al., 2015), more
particularly kaolinite (Covarrubias et al., 2006; Mignoni et al., 2008;
Ríos et al., 2009; Atta et al., 2012; Mackinnon et al., 2012; Belviso et al.,
2013; Yue et al., 2014; Belviso et al., 2015b; Shams and Ahi, 2013;
Wang et al., 2013, 2014; Prokof'ev and Gordina, 2014; Zhou et al.,
2014; Ayele et al., 2016; Maia et al., 2015; Tang et al., 2016;
Villaquirán-Caicedo et al., 2016). Johnson and Arshad (2014) recently
reviewed the hydrothermal synthesis of zeolites based on kaolinite as
raw material and analyzed the main factors governing the process.
Hydrothermal treatments are the bases of zeolites synthesis proce-
dures. In order to improve the efficiency of the processes, new techni-
ques have been recently applied, such as ultrasonic techniques (Shams

⁎
Corresponding author.
E-mail address: javierhuertas@ugr.es (F.J. Huertas).

https://doi.org/10.1016/j.clay.2018.02.004
Received 16 October 2017; Received in revised form 2 February 2018; Accepted 5 February 2018
0169-1317/ © 2018 Elsevier B.V. All rights reserved.

Please cite this article as: García-Villén, F., Applied Clay Science (2018), https://doi.org/10.1016/j.clay.2018.02.004
F. García-Villén et al. Applied Clay Science xxx (xxxx) xxx–xxx

and Ahi, 2013; Behin et al., 2016; Bukhari et al., 2015, 2016; ray fluorescence (XRF), Fourier-transform infrared spectroscopy (FTIR)
Vaičiukynienė et al., 2015; Aldahri et al., 2016; Ojumu et al., 2016; and scanning electron microscopy (SEM).
Jusoh et al., 2017) and microwave-assisted procedures (Chandrasekhar X-ray diffraction (XRD) was carried out using a PANalytical X'Pert
and Pramada, 2008; Youssef et al., 2008). Two main hydrothermal Pro diffractometer equipped with an X'Celerator solid-state detector
treatments can be distinguished: (i) the conventional hydrothermal and a sample holder spinning. X-ray powder diffraction patterns were
procedure (Petkowicz et al., 2008; Saada et al., 2009; Chandrasekhar recorded using random oriented mounts with CuKα radiation, operated
and Pramada, 2001; Heller-Kallai and Lapides, 2007; Lapides and at 45 kV and 40 mA, in the range 3–70°2θ. Semi-quantitative estimation
Heller-Kallai, 2007; Alkan et al., 2005; Bayati et al., 2008; Mackinnon of the solid composition in crystalline phases was obtained by X'Pert
et al., 2012; Jha and Singh, 2014; Cardoso et al., 2015a, 2015b; Maia HighScore Plus (PANalytical, 2005), on basis of the Reference Intensity
et al., 2015; Prokof'ev and Gordina, 2014; Wang et al., 2010, 2013; Ratio (RIR) values (Chung, 1974a, 1974b; Chung, 1975). TOPAS
Covarrubias et al., 2006; Wang et al., 2014; Tang et al., 2016; Garcia (Bruker, 2014) software was used to estimate the degree of crystallinity
et al., 2016) and (ii) the alkaline fusion followed by hydrothermal re- (DOC), also reported in literature as crystalline index. The DOC method
action (Wang et al., 2016; Ríos et al., 2009; Ayele et al., 2016; Belviso is based on the estimation of the total intensity or area contributing to
et al., 2012, 2013, 2015a, 2015b; Liu et al., 2015; Molina and Poole, the overall diffraction pattern by each component in the analysis. We
2004). In both cases the reactions occur in a highly basic medium used the following formulae:
(pH > 10) but the main difference lies in the state of the alkaline
substance: in the first (i) the aluminosilicate solid raw materials are Cristalline Area
DOC =
mixed with an alkaline solution, while in the second (ii) the raw ma- Crystalline Area + Amorphous Area
terials are mixed with a solid basic compound and thermally activated
by fusion. Integrated areas under the Bragg peaks and amorphous band were
Sanitary ware is a ceramic ware usually found in sinks, urinals and measured by a profile fitting procedure using TOPAS, taking into ac-
bathtubs. SW production is led by Spanish domestic clay product in- count the background. The weight fraction of the amorphous material,
dustry (Medina et al., 2012). The traditional sanitary ware vitreous Wamorphous, can be calculated from:
body composition is made up of 50 wt% clay minerals (mainly kaoli-
Wamorphous = 1 − DOC
nite), 25 wt% quartz and 25 wt% feldspar, known as the “tri-axial white
ware”. After the firing process (1250 to 1290 °C) water is released and
Chemical analysis by X-Ray fluorescence (XRF) was performed
crystalline networks of the raw materials are destroyed to give rise to
using a Bruker® S4 Pioneer equipment, with LIF200, PET, OVO55 lens,
metastable and new crystalline components (Medina et al., 2012).
a Rh anode X-ray tube and operated at 60 kV and 150 mA. Elements (Si,
During the sintering of a porcelain body, clay minerals (such as kaoli-
Al, Ti, K, Mg, Fe, Na, Ca, Mn, P, Zr, Sr) were measured as fused beads
nite) transform themselves into mullite, thus giving plasticity and me-
using glass discs by fusing 0.9 g of SW in lithium tetraborate. The
chanical strength to the product. On the other hand, feldspars are
quality of the analysis was monitored by measuring 25 different re-
fluxing agents and quartz acts as a filler, maintaining the structure
ference materials whose standard deviation are < 0.3% for Si, < 0.05%
during sintering. This final composition makes SW apparently ideal for
for Na, Mg, Al and Fe and a < 0.010% for K, Ca, Ti and 10 μg/g for
zeolites synthesis due to the high quantity of Si and Al. ZrSiO4 is added
trace elements. Reproducibility was higher than ± 0.05% for both
in order to enhance the opacity of SW, especially in the presence of
major and trace elements.
ZnO, although ZrO2, ZnO, TiO2, and SnO2 are also used as opacifying
Fourier-transform Infrared Spectroscopy (FTIR) was performed
agents. They also provide an increase in whiteness and shine, which are
using a PerkinElmer Spectrum One spectrometer equipped with a li-
valuable commercial properties (Boudeghdegh et al., 2015). Industrial
thium tantalate (LiTaO3) detector. Each sample was diluted in KBr to
production of sanitary ware generates approximately 8% of solid wastes
obtain 1% (w/w) pellets and were recorded in absorbance mode in the
in Spain, which increase landfills sizes and pose economic, social and
4000–400 cm−1 range with a wavenumber resolution of 4.0 cm−1. A
technical problems (Medina et al., 2012). Therefore, any usage that
total of 100 scans were collected for each spectrum at a scan speed of
could be given to these materials will help minimize these problems.
0.2 cm/s.
Chamotte obtained by grinding solid waste derived from the sani-
SEM observation were performed with a Zeiss Supra 40VP micro-
tary ware production could be used as an appropriate raw material for
scope operated under high-vacuum conditions, equipped with an en-
hydrothermal zeolite synthesis due to its chemical and mineralogical
ergy dispersive X-ray detector (EDS). Before examination, sample was
composition. That could contribute to minimize environmental pro-
suspended in water and filtered through a polycarbonate filter (pore
blems associated to industrial ceramic wastes. Zeolites synthesis lit-
diameter of 0.2 μm); a piece of the filtered sample was mounted on a
erature, however, does not report the use of SW solid waste as a raw
stub with a graphite ribbon and then carbon-coated. Samples were in-
material. The aim of the present study is to evaluate the feasibility of
vestigated using secondary (SE) and backscattered electron (BSD) de-
SW to produce zeolites once subjected to a conventional hydrothermal
tectors.
treatment at several aging times (1–30 days) and temperatures
Hydrothermal synthesis process was performed in 50 mL Teflon-
(100–200 °C) and to identify and characterize the resulting mineral
lined stainless steel reactors (Parr 4744). The reactors were heated in an
phases.
oven and the pressures inside reactors corresponded to vapor water
pressure at all working temperature. Powdered SW (2 g) was hydro-
2. Materials and methods
thermally activated in NaOH 5 M solution (10 mL), by heating at pre-
fixed temperatures (100, 150 and 200 °C). Aging times varied from
Commonly used sanitary ware was obtained in large pieces, as a
1 day to 30 days. At the end of each experiment, the reactors were
construction waste material. SW pieces were washed with distilled
cooled quickly with water to quench the reaction, and solid and solu-
water and ethanol and then pulverized in order to obtain small and
tion were immediately separated by centrifugation (15 min.,
homogeneous particle sizes (smooth powder). Firstly, SW was crash
5000 rpm). Solids were repeatedly washed with pure water (MilliQ
into irregular and large pieces with an iron mortar and then with a jaw
grade) by 10 cycles of centrifugation (also 5000 rpm, 15 min.) and dried
crusher (Retsch®, BB200). After this, SW was grinded during 20 min in a
in an oven at 50 °C. Finally, each sample was manually grounded and
mechanic mortar grinder and finally the resulting powder was sub-
stored in plastic vials at room temperature. No specific precautions
jected to grinding in a vibratory disc mill (Retsch®, RS 200) equipped
were taken to control the influence of environmental CO2 during the
with agate rings.
hydrothermal synthesis.
SW sample was characterized by X-ray powder diffraction (XRD), X-

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F. García-Villén et al. Applied Clay Science xxx (xxxx) xxx–xxx

Fig. 1. XRD pattern of SW raw material. Legend: Qz for quartz; Mul for mullite; Zrn for zircon.

3. Results 1050 cm−1 correspond to stretching frequencies of SieO, SieOeSi and

SieOeAl bonds and asymmetric vibrations of tetrahedra (Boudeghdegh
3.1. Raw material characterization et al., 2015; Lavat et al., 2007). The shoulder at 1160 cm−1 can be
attributed to mullite SieO asymmetrical vibrations (Medina et al.,
According to XRD results, the mineral fraction of SW raw material 2016). The bands at 797 cm−1 and 774 cm−1 can be ascribed to sym-
(Fig. 1) is composed approximately of a 55% of quartz, 42% of mullite metrical stretching vibrations of quartz (Medina et al., 2016) and be-
and minor amounts of zircon. A small fraction of amorphous material tween them there is an overlapping band with a frequency of 787 cm−1
should be present. The presence of an amorphous phase can be con- which belongs to symmetrical stretching vibrations of Si-O-Si and Si-O-
firmed by the existence of an increase of the background signal from 17 Al bonds (Boudeghdegh et al., 2015). According to Lavat et al. (2007),
to 30°2θ. The DOC of the raw material was estimated on 92.5%, and overlapping bands in the region 560–530 cm−1 belong to AleO
confirmed a small fraction of vitreous material (Wamorphous = 7.5%). stretching vibration of AlO6 in mullite and the band at 460 cm−1 is
SW's XRF results are summarized in Table 1. Results are in agree- characteristic of Si-O-Si and Si-O-Al bending vibrations linkages in
ment with those recently performed by Medina et al. (2016) for Spanish mullite, quartz and amorphous aluminosilicates (Medina et al., 2016
sanitary ware samples. According to these results, SW is an alumino- and Boudeghdegh et al., 2015). Characteristics bands of ZrSiO4 are not
silicate with small quantities of alkaline and alkaline earth elements, clearly visible due to the low quantity of this compound in SW.
together with Fe and Ti (Table 1). Among trace elements zirconium General aspect of the SW (Fig. 3) is characterized by angular par-
highlights, which was probably added during the SW elaboration pro- ticles of very different sizes due to the pulverization of the raw material.
cess in order to enhance opacity, whiteness, shine and softness Pores of polycarbonate filters are observable in the background of all
(Boudeghdegh et al., 2015). Moreover, bearing in mind the errors as- SEM images. Zircon crystals are clearly distinguishable in the corre-
sociated with semi-quantification of both techniques, the estimations sponding BSD images as bright particles, showing homogeneous sizes
based on XRD and XRF are consistent each other. around 1 μm (Fig. 3B).
The FTIR spectra (Fig. 2) of SW raw material show the absence of
3700–3600 cm−1 bands related to OH stretching vibrations in phyllo-
silicates what confirms the transformation of kaolinite into mullite 3.2. Hydrothermal products characterization
during SW firing process. Intense overlapping bands from 1080 to
3.2.1. X-ray powder diffraction
Identification of mineral phases in the samples was performed using
Table 1 PDF2 database (Table 2). No phase remains unidentified. However,
Chemical composition of SW raw material ob-
experimental pattern of some phases shows changes in relative in-
tained by XRF. Major elements in wt% and ele-
ments in trace in ppm. tensities and slight shift in position of reflections compared with re-
cords in database. The neo-formed crystals may have some deviation in
Oxide wt% crystal size, chemical composition and habit compared with mineral
used to obtain the records. This is common in crystals produced in
SiO2 69.0
TiO2 0.36 synthesis processes at relatively low temperature and short time, as the
Al2O3 22.59 present experiments. This fact should affect the accuracy of the semi-
Fe2O3 0.76 quantitative estimation of crystalline phases, that could have errors in
Na2O 2.17 the order of 10–15%. Phases identified in trace amounts were indicated
K2O 2.63
MgO 0.28
in Table 2 as Trace, and should correspond to < 5% amount.
CaO 1.37 XRD patterns of samples treated at 100 °C shown that the starting
MnO 0.01 mineral phases, mullite and quartz, progressively disappeared as time
P2O5 0.18 passed (Fig. 4). Amorphous material present in SW completely dis-
LOI 0.40
appeared after 1 day of reaction, its DOC being 99.6%. After 30 days,
Zr (ppm) 4752
Sr (ppm) 314 quartz was totally absent while mullite reflections were still detectable.
Sodium faujasite, zeolite P, analcime, natrolite and sodalite were the

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F. García-Villén et al.
Fig. 2. FTIR spectrum of SW raw material.
Fig. 3. SEM photograph of SW raw material. A) Secondary electron and B) BSD images.
The arrows mark the presence of zircon crystals.
mineral phases newly formed at 100 °C.
Particularly, Na-faujasite and sodalite crystallized from day 1 to day
7, but they disappeared after 30 days of hydrothermal treatment.
Zeolite P reflections were also present from day 1, until day 30, their
intensity increasing during the whole period. At 100 °C after 30 days of
treatment analcime and natrolite were detected as minor amounts.
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Applied Clay Science xxx (xxxx) xxx–xxx
Amorphous and vitreous phases are much more reactive than
crystals, dissolving quickly during the hydrothermal alkaline treatment
and contributing to the formation of zeolite seeds. Mullite dissolution
was the main source of Al for zeolites, being likely the limiting process
for zeolites crystallization at this temperature. After 1 day, sodalite, Na-
faujasite, zeolite A and zeolite P formed in a very small amount. Zeolite
A and Na-faujasite behave as metastable phases, remaining as accom-
panying minerals. As time passed, sodalite and zeolite P became the
dominant phases. Sodalite (Si/Al~1/1) crystallized faster than zeolite P
(Si/Al~9/7). Moreover, analcime (Si/Al~2/1) formed only after
30 days in trace amount. The early crystallization of sodalite depleted
solution in Al and likely favor the crystallization of zeolites with Si/Al
higher than 1 as increasing aging time.
According to the literature, previously to the crystallization of so-
dalite and zeolite P, zeolite A appears as metastable phases (e.g., Alkan
et al., 2005; Lapides and Heller-Kallai, 2007; Bayati et al., 2008; Ríos-
Reyes et al., 2013). This could justify the detection of trace amounts of
zeolite A during the first moments of reaction (1 and 2 days, Table 2). In
fact, the formation of zeolite A, zeolite P and sodalite at reaction times
lower than 5 days coincided with data obtained from previous hydro-
thermal synthesis performed using kaolin as raw material. Ayele et al.
(2016) reported that only 3 h are needed to crystalize zeolite A, which
then progressively dissolves and gives rise to sodalite. Prokof'ev and
Gordina (2014) affirmed that high NaOH concentration (4 M) induces
the crystallization of SOD zeolite-types while low NaOH concentration
(2 M) favor the crystallization of LTA zeolites, and the excess of alu-
minum oxide favors crystallization of zeolite A.
The mineral assemblage at 150 °C is simpler than at 100 °C (Fig. 5).
The increase in temperature produced the faster dissolution of quartz
and mullite, which were not detected for aging time longer than 1 and
4 days, respectively. The mineral assemblage is analcime and cancri-
nite. In comparison with 100 °C series, where analcime crystallized
after 30 days as a minor phase, at 150 °C analcime formed at 1 day
presumably due to the rapid dissolution of glass, quartz and mullite.
The faster dissolution of quartz than mullite produced crystallization of
analcime, with Si/Al ratio of 2. Conditions of analcime crystallization
are consistent with those previously reported in the literature (Cundy
and Cox, 2005; Cardoso et al., 2015a, 2015b). Nevertheless, as the
experiment progressed analcime became unstable and partially dis-
solved. Cancrinite (Si/Al~1/1) reflections were present in all samples
treated at 150 °C.
The slightly faster dissolution of quartz in relation to mullite leads
F. García-Villén et al. Applied Clay Science xxx (xxxx) xxx–xxx

Table 2
Semi-quantitative abundance of mineral phases according to XRD results. Legend: Qz for quartz; Mul for mullite; Sdl for sodalite; Zeo A for zeolite A; Zeo P for zeolite P; Anl for analcime;
Fau for faujasite-Na; Zrn for zircon; Ccn for cancrinite and Ntr for natrolite; Tr for traces (below 5%).

SW 100 °C 150 °C 200 °C

Time (days) 0 1 2 4 7 30 1 2 4 7 30 1 2 4 7 30

Mineral (%) Qz 55 45 30 30 19 – 5 – – – – – – – – –
Mul 42 40 37 34 35 20 14 15 Tr – – – – – – –
Sdl – Tr 21 22 30 35 – – – – – – – – – –
Zeo A – Tr Tr – – – – – – – – – – – – –
Zeo P – Tr Tr 8 10 30 – – – – – – – – – –
Anl – – – – – Tr 45 44 37 31 18 51 30 Tr Tr Tr
Fau – Tr Tr Tr Tr Tr – – – – – – – – – –
Zrn Tr Tr Tr Tr Tr Tr Tr Tr Tr Tr Tr Tr Tr Tr Tr Tr
Ccn – – – – – – 33 38 57 63 76 46 67 92 92 92
Ntr – – – – – Tr – – – – – – – – – –

to the crystallization of analcime with higher amounts of Si than Al (see
Table 2). As time passed, analcime dissolution provided the system with
Al and Si, favoring the crystallization of cancrinite (Si/Al = 1). Can-
crinite became the major phase under these conditions.
Mineral phases of samples after hydrothermal treatment at 200 °C
are shown in Fig. 6. At 200 °C, the effect of temperature enhanced the
dissolution of reactive minerals in the raw material (quartz and mul-
lite), which were undetectable after 1 day of aging. The mineral as-
semblage and time evolution at 200 °C were similar to those at 150 °C.
Analcime crystals presented high intensity reflections from day 1 to day
2, but were detected as traces from 4 to 30 days. Cancrinite was present
in all samples and it reached a maximum of 92% (Table 2). The ap-
parent stabilization of cancrinite from 4 days onwards coincided with
the destruction of analcime, which confirmed that analcime dissolution
provided the substrate for cancrinite crystallization once quartz and
mullite destroyed.
At 150 °C and 200 °C the dissolution of mullite occurred faster than
at 100 °C, making aluminum earlier available and consequently, the
differences in Si/Al molar ratio of crystalline phases during the first
moments were less remarkable. The crystallization and dissolution of
analcime indicated that it behaves as a metastable phase, whose
crystallization/dissolution kinetics was enhanced by temperature. The
formation of metastable phases and the evolution of the abundance of
major zeolites suggested a kinetic control of the hydrothermal crystal-
lization of zeolites under the conditions studied.
3.2.2. Fourier-transform infrared spectroscopy
FTIR absorption spectra of SW raw material (A) and samples syn-
thesized during 7 and 30 days (B through G) at the three temperatures
tested are plotted in Fig. 7. Broad bands between 3600 and 3400 cm−1
corresponded to OeH groups, typically related to zeolitic structures. In
samples C, D, E, F and G it was possible to distinguish more easily a
band around 3600 cm−1, which belong to bridging OH groups with
Brönsted acidic character (Karge, 2001). In sample B this band was not
well defined, probably because of low crystallinity of newly formed
zeolites. Interstitial bonded water gave rise to a typical deformation
band around 1640 cm−1 due to the stretching vibration of OH groups
(Karge, 2001). The presence of these bands in all samples, except in raw
material, confirmed the presence of zeolites. Broad, low intensity band
at 1450 cm−1 was also present in all samples and is typical of C-O-H
deformation, corresponding to the presence of carbonate anion (Karge,
2001) absorbed onto mineral. Stretching frequencies between 1170 and

Fig. 4. XRD patterns of 100 °C series, organized by time (0–30 days) from top to bottom. Legend: Qz for quartz; Mul for mullite; Zrn for zircon; Fau for sodium faujasite; Zeo A for zeolite
A; Zeo P for zeolite P; Ntr for natrolite; Sdl for sodalite; Anl for analcime.

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F. García-Villén et al. Applied Clay Science xxx (xxxx) xxx–xxx

Fig. 5. XRD patterns 150 °C series, organized by time (0–30 days) from top to bottom. Qz for quartz; Mul for mullite; Zrn for zircon; Ccn for cancrinite; Anl for analcime.

1000 cm−1 corresponded to SieO and SieOeAl bonds and asymme-
trical vibrations of SieOeSi in tetrahedra. Formation of new bonds
produced a displacement of bands towards greater wavelengths (Lavat
et al., 2007; Boudeghdegh et al., 2015), which confirmed the synthesis
of new compounds in all samples in comparison to SW raw material
spectrum. Three bands (1105, 1006 and 970 cm−1) were clearly dis-
tinguishable in D, F and G spectra, due to the increased purity of the
systems, whose major phase is cancrinite. Region 800–400 cm−1 is
considered as the fingerprint region of zeolites. Bands at 785, 626 and
570 cm−1 are characteristic of cancrinite (Linares and Brikgi, 2006) and
are related to symmetric stretching vibrations. The absence of these
bands in B and E confirmed the absence of cancrinite on these samples.
Symmetrical stretching of external linkages in zeolites tetrahedra ap-
peared at 760 cm−1 (Karge, 2001), which was also typical of cancrinite
since it only appears in samples where this mineral account as a major
phase (C, D, F and G). Low-intensity bands at 730–660 cm−1 in E are

Fig. 6. XRD patterns of 200 °C series, organized by time (0–30 days) from top to bottom. Qz for quartz; Mul for mullite; Zrn for zircon; Ccn for cancrinite; Anl for analcime.

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F. García-Villén et al.
Fig. 7. FTIR spectra of samples A) SW; B) sample 100 °C, 7 days; C) sample 150 °C, 7 days; D) sample 200 °C, 7 days; E) sample 100 °C, 30 days; F) sample 150 °C, 30 days; G) sample
200 °C, 30 days.
associated to symmetrical stretching of internal tetrahedra in sodalite,
being the major mineral phase in this sample. Natrolite bands are
slightly distinguishable in this sample at around 610–570 cm−1. Bands
in the region 420–500 cm−1 were related to internal bending vibrations
of SieO and AleO in tetrahedra. These bands have the same intensity
and shape in sodalite and cancrinite (Karge, 2001; Ríos et al., 2009),
which explain their presence in spectra C-D and F-G.
3.2.3. Scanning electron microscopy
A selected group of samples was investigated by SEM-EDS to iden-
tify neo-formed zeolites and their composition. Samples obtained at
100 °C showed relicts of starting mineral phases (Fig. 8A and B) that
exhibited intense dissolution, as well as crystallized new phases as
particle of small size. After 2 days of reaction (Fig. 8C) spheres with
sodalite composition (1.5–2 μm in diameter) and octahedral crystals of
Na-faujasite (~1 μm) could be seen next to acicular crystals (1–3 μm in
length) whose composition (Si/Al~9/7) resembles zeolite P. After
7 days, the sample contained aggregates of small crystals, some of them
are fibers similar to the zeolite P-like particles detected at 2 days
(Fig. 8D). The sample aged for 30 days showed orthorhombic natrolite
crystals (~12 μm thick, Fig. 8E) as well as trapezohedral analcime
(~28 μm in diameter, Fig. 8F). Samples produced at 100 °C and short
time were characterized by submicrometer particles as average.
Sample synthesized at 150 °C were characterized by the total dis-
appearance of SW raw material morphologies and a mineral association
dominated by analcime and cancrinite crystals (Fig. 9). Analcime
crystalized as trapezohedral crystals (~30 μm in diameter) (Fig. 9AB),
but was not observed in 30 days experiment. Cancrinite crystallized as
hexagonal prismatic crystals with variable length and thickness
(Fig. 9CD).
Samples treated at 200 °C were characterized by the presence of
numerous crystals and no relict of starting material (Fig. 10). After 7
and 30 days of hydrothermal treatment, cancrinite was the dominant
mineral, as elongated hexagonal prisms of variable length and thick-
ness. No other zeolites were identified, which was in agreement with
XRD results.
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Applied Clay Science xxx (xxxx) xxx–xxx
4. Discussion
The synthesis of zeolites from sanitary ware waste as a low-cost
silica and alumina source has been the aim of a number of hydro-
thermal experiments combining aging time and temperature. In view of
the obtained results, conventional SW waste seems an optimal raw
material for zeolite synthesis under high alkaline hydrothermal condi-
tions, since all newly mineral phases formed during the process corre-
spond to this group of minerals. The zircon coming from the glazing
process during the industrial fabrication of SW remains as an inert
phase under synthesis conditions.
The transformation of SW into zeolites under highly alkaline hy-
drothermal conditions occurs under kinetic control. The initial solution
(5 M NaOH) contains sodium in excess. The complete conversion of raw
material in zeolites would reduce NaOH concentration to 4 M. Solution
pH would remain above 13 over the experiment span. Differential
dissolution rates of quartz and mullite and the relative release rate of Si
and Al, affect the availability of these elements in solution and con-
straint the mineral assemblage, its temporal evolution and the domi-
nant zeolites. Aluminum is likely the limiting cation. A summary of the
experimental results is depicted in Fig. 11, where each field corresponds
to predominant phase(s) (> 25%) as a function of temperature and
aging time.
According to literature, the Si/Al molar ratio of the starting material
plays an important role in controlling the zeolitic phases synthesized
(Gualtieri et al., 1997; Park et al., 2001; Lapides and Heller-Kallai,
2007; Belviso et al., 2015a, 2015b). Johnson and Arshad (2014) sug-
gested that zeolites with Si/Al ≤ 5 ratio should be considered low Si/Al
zeolites and their synthesis is favored by low Si/Al reaction mixtures
and strong alkalinity. The present experiments agree with Johnson and
Arshad conclusions, since all the zeolites identified in the present study
can be classified as low Si/Al zeolites.
The resultant zeolite type and relative abundance depend on the
hydrothermal conditions. The increase of temperature produces faster
dissolution of starting phases together with the nucleation and crystal
growth rates of new minerals. Moreover, longer reaction time improves
F. García-Villén et al. Applied Clay Science xxx (xxxx) xxx–xxx

Fig. 8. SEM photographs of samples treated at 100 °C. A) sample 100 °C, 2 days; B) image of BSE corresponding to A; C) detailed image of sample 100 °C, 2 days; D) sample 100 °C, 7 days;
E) and F) sample 100 °C, 30 days. Legend: Z-P, for zeolite P-like (see text for discussion); Sdl for sodalite and Fau for Na-faujasite.

Fig. 9. SEM photographs of samples treated at 150 °C. A) and B) sample 150°, 7 days; C) and D) sample 150 °C, 30 days. The arrow marks the presence of zircon crystals.

8
F. García-Villén et al. Applied Clay Science xxx (xxxx) xxx–xxx

Fig. 10. SEM photographs of samples treated at 200 °C. A) sample 200 °C, 7 days; B) detailed view of a cancrinite crystal; C) and D) sample 200 °C, 30 days.

crystallinity. Quartz dissolves faster than mullite, affecting the Si/Al dissolution rate of mullite compared with quartz (Table 2) results in low
ratio in solution during the experiment span. At constant temperature, Al concentration conditions that likely favored analcime. The complete
the zeolite association evolves with time, Na concentration and Si/Al dissolution of mullite increases Al concentration and cancrinite forms as
ratio. Johnson and Arshad (2014) affirmed that concentrations of so- the most stable phase. Rising temperature enhances the analcime dis-
dium hydroxide higher than 3.99 M lead to the appearance of zeolites appearance and cancrinite crystallization, as also reported in literature
mixtures which include zeolite A, sodalite, analcime and cancrinite. (Chaisena and Rangsriwatananon, 2005; Cundy and Cox, 2005; Ríos
Depending on temperature some phases may behave as metastable, et al., 2009).
as sodalite, Na-faujasite, zeolite A, zeolite P, natrolite and analcime.
The mineral assemblage at 100 °C contains relicts of quartz and mullite
5. Conclusions
as well as a complex mixture of several zeolites though any of them
surpassed 40% of abundance (Table 2). It is widely accepted that zeolite
Solid waste derived from conventional sanitary ware industry could
A gives rise to sodalite (Cundy and Cox, 2005), thus explaining the
be used as an optimal raw material for zeolites synthesis under high
crystallization-dissolution of zeolite A and the formation of sodalite in
alkaline hydrothermal conditions, since zeolites were detected after all
the experiment performed at 100 °C. Ríos-Reyes et al. (2013) also ob-
experimental procedures performed. Zeolite nucleation and growth
served that metastable zeolite A transforms into sodalite at 100 °C.
appear to be a kinetically controlled complex process. A detailed study
The final mineral assemblage is simpler at temperatures above
of the evolution of zeolitic phases and the combination of reaction time
100 °C (Fig. 11). At 150 and 200 °C, analcime and cancrinite crystallize,
and temperature would permit to drive the crystallization reaction to-
although for longer experiments analcime dissolved. The slower
wards a dominant zeolitic phase under alkaline hydrothermal

Fig. 11. Tentative representation of the relative abundance of mineral phases (> 25% by XRD semi-quantitative estimation) as a function of temperature and aging time.

9
F. García-Villén et al.
conditions using sanitary ware as a starting material. Thus, the main
advantage of the present results lies on the fact that environmental
problems posed by solid waste of SW production could be solved by
transforming these wastes into zeolites, which are considered as useful
materials in a wide variety of fields.
Acknowledgments
This research was supported by funding from MINECO (CGL2014-
55108P). FGV benefit from JAE-intro (CSIC) and FPU (MECD) grants.
We thank I. Guerra (CIC, University of Granada) and A. Salido (IACT)
for expertise with SEM and FRX, respectively. CVE acknowledges to
Excellence Network of Crystallography and Crystallization “Factoría de
Cristalización” FIS2015-71928-REDC supported by Spanish MINECO
and RMN143 of Junta de Andalucía. FJH, amdg.
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