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Red de Revistas Científicas de América Latina y el Caribe, España y Portugal
SYNTHESIS OF ZEOLITIC MATERIALS FROM VOLCANIC ASH IN PRESENCE AND
ABSENCE OF CETYLTRIMETHYLAMMONIUM BROMIDE
Vilma Mayerling SANHUEZA NÚÑEZ* and Leonardo Daniel BENNUN TORRES
Universidad de Concepción. Edmundo Larenas s/n, Concepción 3, Chile
*Autor de correspondencia: vsanhuez@udec.cl
(Recibido marzo 2014; aceptado enero 2015)
Key words:
zeolites, phillipsite, chabazite, analcime, ash, synthesis
ABSTRACT
Zeolitic materials as Na-phillipsite, Na-K-phillipsite-like zeolites and the mixtures of
zeolites (phillipsite+analcime and phillipsite+chabazite+analcime) were synthesized
from volcanic ash, either in presence and absence of cetiltrimetilamonium bromide
(CTAB). The ash sample used in the laboratory experiments contains 75.36 % SiO
2
and 14.11 % Al
2
O
3
, abundances. The reaction time as well as the infuence oF CTAB
were studied in the zeolitic materials crystallization. The experiments were carried out
under hydrothermal conditions, autogenic pressure and temperature of 150 ºC, as well
as reaction time from 8 to 116 h. Products from this hydrotermal treatment were identi-
±ed by X-ray diFFraction (XRD) and characterized by scanning electron microscopy-
energy dispersive X-ray spectroscopy (SEM-EDS). OF the zeolitic materials obtained
the Na-K-phillipsite-like zeolite was found to be the most effective for the retention
of cations Pb
2+
, Zn
2+
, and Ba
2+
.
Palabras clave: zeolitas, phillipsita, chabazita, analcima, ceniza, síntesis
RESUMEN
Materiales zeolíticos tipos Na-phillipsita, Na-K-phillipsita y mezclas de zeolitas
(phillipsita+analcima y phillipsita+chabazita+analcima) fueron sintetizados a partir de
ceniza volcánica, en presencia y ausencia de bromuro de cetiltrimetilamonio (BCTA).
La muestra de ceniza usada en los experimentos de laboratorio posee un 75.36 % de
SiO
2
y 14.11 % de Al
2
O
3
. El tiempo de reacción y la infuencia del BCTA Fueron los
parámetros estudiados en la cristalización de los materiales zeolíticos. Los experi-
mentos se llevaron a cabo bajo condiciones hidrotermales, a presión autógena y una
temperatura de 150 ºC, así como tiempos de reacción de 8 a 116 h. Los productos de
este tratamiento hidrotermal Fueron identi±cados por diFracción de rayos-X (DRX) y
caracterizados por microscopía electrónica de barrido con espectrometría dispersiva
de rayos-X (MEB-EDRX). La zeolita Na-K-phillipsita resultó ser la más eFectiva para
la retención de los cationes Pb
2+
, Zn
2+
y Ba
2+
.
Rev. Int. Contam. Ambie. 31 (2) 185-193, 2015
V.M. Sanhueza Núñez and L.D. Bennun Torres
186
INTRODUCTION
Zeolites are microporous aluminosilicate crystal-
line materials with well-defned pore structures and
compositions. Because of their properties such as
thermal stability, adsorption, catalytic activity, acid-
ity, cation exchange and molecular sieves, zeolites
have important applications in refning processes at
the petrochemical industry, as well as gas separation,
water purifcation at mining industry and environ
-
mental catalysis (Zhang
et al.
2011, Izidoro
et al.
2012).
Most zeolites are synthesized from commercial
materials (Martucci
et al.
2009, Tanaka
et al.
2009,
Trejda
et al.
2010, Morales-Pacheco 2011, Xue
et
al.
2012). Many of them have been synthesized, at a
given temperature and crystallization time, from gels
containing Na
2
O-Al
2
O
3
-SiO
2
-H
2
O. Some sources
of silicon are: Na-silicate HS-40 (Sig and Seung
2004, Chen
et al.
2009), Na-silicate, Cab-O-Sil M-5
fused silica (Rivallan
et al.
2010), Fumed silica (Xu
et al.
2010), UltraSil silica TMA-SiO
2
and Cab-O-
Sil TMA-SiO
2
(Shvets
et al.
2008). On the other
hand, some of the sources of aluminum that have
been employed are: Na-aluminate (Anuwattana and
Khummongkol 2009, Gupta
et al.
2009) and Al-
isopropylate (Tosheva
et al.
2005). Surfactants of
different chain lengths have been used as templates.
Among them, the following can be mentioned:
C
16
H
33
(CH
3
)
3
N-OH/Cl, C
12
H
25
(CH
3
)
3
N-OH/Cl,
C
14
H
29
(CH
3
)
3
N-Br, C
16
TMA-OH and C
8
TMA-Br
(Han
et al.
2009, Sakthivel
et al.
2009).
Ashes generated by thermoelectric plants are an-
other starting material that has been widely used to
synthesize zeolites. In fact different zeolites such as
NaA, NaP1, analcime, gmelite and phillipsite, have
been synthesized From ±y ash (Moriyama
et al.
2005,
Terzano
et al.
2005, Tanaka
et al.
2008, Walek
et al.
2008, Font
et al.
2009, Kumar
et al.
2009, Ríos
et
al.
2009, Goni
et al.
2010), lignite and rice husk ash
(Ahmaruzzaman 2010).
On the contrary experiments oriented to synthe-
size zeolites by means of natural products as starting
materials are relatively scarce. The chemical synthe-
sis of zeolites is subject to disturbance caused by the
impurities present in these materials. Some natural
raw materials that have been used are kaolin (San-
hueza
et al.
1999, Mignoni
et al.
2008, Miao
et al.
2009), bentonite (Boukadir
et al.
2002, Hongchao
et
al.
2010), pumice (Sanhueza
et al.
2006), diatomite
(Sanhueza
et al.
2003, 2004, 2006, 2011 and Chilean
patents 2004, 2006, 2009, 2010), and perlite glass
(Christidis and Papantoni 2008).
Other raw materials for obtaining zeolites are
natural zeolitic rocks hydrotermally treated (Wata-
nabe
et al.
2005). Phillipsite and chabazite were
obtained from trachytic glass by hydrothermal
conversion at 200 ºC (De Gennaro
et al.
1999).
Wilkin and Barnes (2000) used Na-clinoptilolite
zeolite as a starting material to synthesize anal-
cime zeolite. Phillipsite and merlinoite zeolites
have been synthesized by chemical reaction be-
tween an obsidian and NaOH or KOH solutions
at hydrothermal conditions, autogenic pressure
and temperatures between 150 ºC and 200 ºC
(Kawano and Tomita 1997).
The products from Chaitén volcano (eruption
occurred on May 2, 2008) including its ash are vitro-
phyric and mostly rhyolitic in composition, constitut-
ing a natural low cost source of silicon and aluminium
(Lara 2009). The Chaitén volcano is located in the
southern area of the Southern Volcanic Zone of the
Andes-Chile at 42º50’S.
Fortunately in this kind of events, not all is
disaster and always there is something positive
that can be rescued from. This fact motivated us to
evaluate the possibility of investigating the reactiv-
ity of ash as a raw material thrown by the Chaitén
volcano eruption in the formation of zeolites and/
or zeolitic materials.
MATERIALS
The volcanic ash comes from the Chaitén (2008)
volcanic eruption. The chemical composition of the
ash was determined by X-ray ±uorescence (XR²;
Table I
), and it was used to carry out the experiments.
The volcanic ash (molar ratio SiO
2
/Al
2
O
3
= 9.1)
TABLE I
. MAJOR ELEMENTS COMPOSITION (NORMA-
LIZED TO 100 %, VOLATILE FREE) OF THE
VOLCANIC ASH
Oxide
Volcanic ash (wt %)
SiO
2
75.36
TiO
2
0.17
Al
2
O
3
14.11
Fe
2
O
3
1.73
MnO
0.06
MgO
0.28
CaO
1.63
Na
2
O
3.95
K
2
O
3.07
P
2
O
5
0.01
Total
100.37
SYNTHESIS OF ZEOLITIC MATERIALS FROM VOLCANIC ASH
187
was collected at the bottom of the Chaitén volcano.
Minerals found correspond mainly to anorthite and
quartz, followed by minor amounts of rutile, anatase,
amphibole, chlorite and ilmenite, which probably
come from the volcanic ash. With the aim of convert-
ing the volcanic ash into zeolite or zeolitic materials,
several experiments were done.
Zeolites preparation
The volcanic ash sample was dried at room
temperature, ground and the grain size employed in
the synthesis was less than 200 mesh. The experi-
ments (
Tables II
and
III
) were carried out in Parr
steel autoclave reactor (150 cc of capacity) in static
conditions under hydrothermal conditions, autogene
pressure, temperature of 150 ºC, with high and low
concentrations of cetiltrimetilamonium bromide
(
Table II
). The runs 1, 2, 3, 4 and 5 were prepared
with high CTAB concentration. The aim of runs 6,
7, 8, 9 and 10 was to investigate whether phillipsite-
like zeolite and zeolitic materials would be formed
by introducing half CTAB (low concentration of
cetiltrimetilamonium bromide). The runs in
Table III
were prepared without CTAB.
Once the run was completed and the system
cooled down, the products were washed off with
abundant distilled water (Milli-Q water 18.2 MΩ/
cm resistivity), fltered using Advantec 5C flter pa
-
per and dried at 120 ºC for 15 h. The calcination of
samples prepared with template agent were carried
out in air at 600 ºC for 6 h. The heating rate of the
furnace was 1.5º/min.
The retention capacity of the zeolitic materials
was determined through aqueous solutions of Pb
(NO
3
)
2
, ZnCl
2
and BaCl
2
. 100 mL were taken of
each solution containing 400 ppm of the cation to
be analyzed. 0.1 g of zeolitic material was added
in polyvinylchloride bottles at room temperature
under continuous stirring until equilibrium. Then the
samples were fltered and the solutions were stored at
4 ºC for later analysis.
Characterization
The major elemental components of volcanic ash
were determined using a Rigaku X-ray Fuorescence
spectrometer. Mineralogy was determined by a Qem-
scan with Tescan System Vega LSH. The zeolites
were identifed through a D4 Endeavor X-ray Di±
-
±raction equipment, Cu-α1 radiation (λ = 1.5406 Å)
at 30 kV and 15 mA was employed. The morphol-
ogy of the zeolites was determined by means of a
JEOL JMS 6380 LV with EDS. Before mounting,
the samples were ultrasonically dispersed in a 40 %
solution of water/ethanol. Metal concentrations were
analyzed using a Hitachi Z-8100 Polarized Zeeman
Atomic Absorption Spectrophotometer.
RESULTS AND DISCUSSION
Fifteen experiments were carried out (
Tables
II
and
III
). In both cases products are the result of a
chemical reaction between the volcanic ash and a
NaOH 0.3M solution at 150 ºC temperature reaction
whether in presence or in absence of CTAB, respec-
tively. Phillipsite-like zeolite crystallized at 25 h of
reaction time (
Fig.
1
).
If the concentration of CTAB
halved the crystallization time for phillipsite-like
zeolite decreases to 20 h of reaction (
Fig. 2
).
TABLE II.
EXPERIMENTAL CONDITIONS AND REAC
-
TION PRODUCTS RELATED TO THE CHEMI-
CAL REACTION BETWEEN THE VOLCANIC
ASH WITH LOW AND HIGH CTAB CONCEN-
TRATIONS AND A 0.3 M NaOH SOLUTION
RUN
Volcanic
ash (g)
CTAB
(g)
Time
(h)
Reaction products
1
1.00
0.44 (high)
15
(An + Qz)
2
1.00
0.44
20
(An + Qz)
3
1.00
0.44
25
PHI + (An + Qz)
4
1.00
0.44
96
PHI, ANA + (An + Qz)
5
1.00
0.44
116
ANA, PHI + ( An + Qz)
6
1.00
0.22 (low)
15
(An + Qz)
7
1.00
0.22
20
PHI, Ha
8
1.00
0.22
25
PHI, ANA + (An + Qz)
9
1.00
0.22
96
ANA, PHI + (Qz)
10
1.00
0.22
116
ANA, scarce PHI + (Qz)
PHI = phillipsite, ANA = analcime, Ha: Halloysite, An =
anorthite, Qz = quartz. (An+Qz) = comming from the ashes,
CTAB =
cetiltrimetilamonium bromide
TABLE III
. EXPERIMENTAL CONDITIONS AND REAC
-
TION PRODUCTS RELATED TO THE CHEMI-
CAL REACTION BETWEEN THE VOLCANIC
ASH AND A 0.3 M NaOH SOLUTION
RUN
Volcanic ash (g)
Time(h)
Reaction products
1
1.00
8
(An + Qz)
2
1.00
15
PHI + (An + Qz)
3
1.00
21
PHI, CHA, ANA
4
1.00
33
PHI, CHA, ANA
5
1.00
48
PHI, ANA
PHI = phillipsite, ANA = analcime, CHA = chabazite, An =
anhortite, Qz = quartz. (An+Qz) = comming from the ashes.
V.M. Sanhueza Núñez and L.D. Bennun Torres
188
Within a 25 h time of reaction (
Fig. 2
) and a low
concentration of CTAB, two phases crystallize (PHI,
ANA), whereas if the CTAB concentration increases,
then a 96 h time of reaction would be needed to reach
the same phases (PHI, ANA;
Fig. 1
)
The XRD pattern of the sample synthesized with
-
out CTAB shows high intensity peaks that correspond
to the phillipsite-like zeolite
(
Fig.
3
, 15 h). On the
other hand, the patterns of the samples obtained at the
same reaction time (15 h) with low and high CTAB
concentrations (
Figs. 1
and
2
) show only quartz and
anorthite coming from the volcanic ash. An extra
peak at 20 h appeared in the pattern (
Fig. 2
) indicat-
ing that another phase, most probably halloysite, was
forming together the phillipsite-like zeolite.
In
fgure 3
no crystallization is observed during
the Frst 8 h of reaction. Two new zeolite-like are
added to the reaction (21 and 33 h) chabazite and
analcime-like phases. Similar mixtures of natural
zeolites phillipsite + chabazite and phillipsite + cha-
bazite + analcime have been reported by Dwairi
et
al.
(2009) in Tall Amir and Tall Juhira, two important
volcanoes located in southern Jordan.
The study ended after 48 h of reaction where the
mixtures of zeolites phillipsite + analcime prevail.
The results of the kinetics experiments to measure
the retention of metal ions from aqueous solutions
as a function of time are shown in
fgure 4a
,
b
,
c
and
d
. Differences in the sequences of selectivity of
cations by the zeolitic materials are expected due to
differences in composition. In
fgure 4a
selectivity
sequence is Ba
2+
> Zn
2+
> Pb
2+
, in about an hour and
then reaches equilibrium. In
fgure
4b
the sequence
selectivity is Pb
2+
> Zn
2+
> Ba
2+
, it takes about 2 h to
reach equilibrium. Sequence selectivity in
fgure 4c
is Zn
2+
> Pb
2+
> Ba
2+
, with a period of approximately
2 h to reach equilibrium. And Fnally
fgure
4d
shows
the preference of cations in descending order: Pb,
Ba and Zn. The Na-K-phillipsite-like zeolite was
the most effective with a 60 % retention for Pb
2+
,
56 % for Zn
2+
and 43 % for Ba
2+
. The retention of
cations by the ash is very low. 3.6 % for Zn
2+
, 3.9 %
for Ba
2+
and 4.6 % for Pb
+2
.
10
20
30
40
50
60
70
80
–500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
A
A
A
116h
96h
25h
15h
A:analcime
P: phillipsite
An:anhortite
Q:quartz
Intensity (cps)
An
Q
P
A
Q
An
Q
An
Q
Volcanic ash
Q
P
An
An
An
An
P
P
Q
A
A
A
A
A
P
P
P
P
2Theta
Fig. 1.
XRD patterns of the phillipsite-type zeolite and zeolitic
mixture (analcime + phillipsite) at reaction time of 25
and 96 h, respectively. Synthesized by the chemical re-
action between the volcanic ash and a solution of 0.3M
NaOH. The samples were synthesized with high CTAB
concentration
10
20
30
40
50
60
70
80
0
2000
4000
6000
8000
10000
12000
14000
16000
116h
96h
25h
20h
15h
A:analcime
P: phillipsite
An:anhortite
Q:quartz
Intensity (cps)
Q
Q
Q
Q
Q
Q
Q
Volcanic ash
A
A
A
A
A
A
A
An
An
An
Ha
A
A A
A
A
A
A
A
A
A
A
A
A
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
2Theta
Fig. 2.
XRD patterns of phillipsite zeolite and the zeolitic
mixture (phillipsite + analcime) synthesized by the
chemical reaction between the volcanic ash and a so-
lution of 0.3 M NaOH. The
samples synthesized with
low CTAB concentration. Anorthite and quartz come
from the volcanic ash
10
20
30
40
50
60
70
80
0
2000
4000
6000
8000
10000
Intensity (cps)
C
P
A
C
P
P
P
A,P
A
A
P
Q
Q
An
An
An
Q
volcanic ash
15 h
8 h
48 h
33 h
21 h
A
P
C
A
A
A
P
A
A
A
P
P
P
P
P
P
P
P
P
P
P
An
P
P
P
A:analcime
C:chabazite
P:phillipsite
An:anhortite
Q:quartz
2Theta
Fig. 3.
XRD patterns of the zeolite and zeolitic material (analci
-
me + chabazite + phillipsite) synthesized by the chemical
reaction between the volcanic ash and a solution of 0.3 M
NaOH, in absence of CTAB at different reaction times.
Anorthite and quartz come from the volcanic ashes
SYNTHESIS OF ZEOLITIC MATERIALS FROM VOLCANIC ASH
189
Under SEM examination, the volcanic ash shows
evidence of angular glassy shards (
Fig. 5
). In
fgure
6a
, it is possible to observe Na-phillipsite-like zeolite
(Si/Al = 1.6). In
fgure
6b
, trapezohedron crystals of
analcime and groups of prismatic crystals of phillip-
site are observed. In
fgure
6c
, analcime appears as
the most abundant zeolite. All the above experiments
were performed with high concentrations of cetyl-
trimethylammonium bromide. When the previous
experiments were carried out with low cetyltrimethyl-
ammonium bromide, concentration clearly decreases
the crystallization time of analcime. The transfor-
mation of a zeolite phase into another by dissolu-
tion–recrystallization is frequently observed during
hydrothermal syntheses, this transformation is known
as metastability. In this case it shows the formation of
analcime at expense of phillipsite-like zeolite (
Fig.
6d
) at a reaction time of 25 h. Photographic evidence
not previously reported. Presumably temperature of
150 ºC is lost structural water phillipsite-like zeolite
lattice destabilizing its evolving into the more stable
cubic phase thermodynamically. In presence or in
absence of CTAB the morphology of the phillipsite
is the same. Phillipsite exhibits a well defned mor
-
phology called sword blade (
Figs. 6a
and
7a
). In
fgure
6f
analcime crystals fnalizing the process oF
crystallization can be observed.
Highly crystalline Na-K-PHI-like zeolite with a Si/
Al = 3.1 ratio crystallizes at 15 h of reaction (
Fig.
7a
).
After 21 h a mixture of phillipsite and chabazite is
05
0
100
0
10
20
30
40
50
60
Pb
Ba
Zn
Cation retention (%)
Time (min)
05
0
100
15
02
00
25
03
00
0
10
20
30
40
50
60
70
Ba
Zn
Pb
Cation retention (%)
Time (min)
05
0
100
150
20
02
50
300
0
10
20
30
40
50
Ba
Pb
Zn
Cation retention (%)
Time (min)
05
0
100
150
200
250
300
0
5
10
15
20
25
30
35
40
Zn
Ba
Pb
Cation retention (%)
Time (min)
(a
)(
b)
(c)
(d)
Fig. 4.
Retention (%) of Pb, Zn and Ba cations by: (a) Na-phillipsite, (b) Na-K-phillipsite-like zeolite, (c) phil-
lipsite + chabazite + analcime and (d) phillipsite + analcime
10μm
Fig. 5.
SEM image of volcanic ash from the eruption of Chaitén
Volcano
V.M. Sanhueza Núñez and L.D. Bennun Torres
190
obtained (
Fig.
7b
). Increasing the reaction time to 33 h,
analcime is added to the phillipsite and chabazite
(
Fig.
7c
). This suggests that the crystallization se-
quence is phillipsite → chabazite → analcime. De
Gennaro
et al.
(1999) obtained similar results from
synthetic monocationic glasses. However, they
obtained the chabazite → phillipsite → analcime
sequence at 200 ºC and not at 150 ºC, like in our
experiments. Probably, the difference in the reaction
temperature caused the change of the crystallization se-
quence. Following the methodology of De Gennaro
et
al.
(1999) a temperature of 200 ºC and 48 h of reaction
time are required to crystallize the phillipsite. In our
case, the phillipsite crystallization took place at 150 ºC
and in just 15 h of reaction time.
Höller and Wirsching (1988) reported the syn-
thesis of chabazite with different morphologies
using volcanic glasses as starting materials. Among
2 μm
PHI
2 μm
PHI
ANA
2 μm
ANA
ANA
ANA
ANA
PHI
PHI
PHI
2 μm
10 μm
2 μm
0246 81
01
21
41
61
820
keV
Ful scale 2516 cts
Cursor: 0.000 keV
Si
Spectrum 1
O
Al
Na
ab
cd
ef
Fig. 6.
SEM images of the products corresponding to the chemical reaction between volcanic ash and a NaOH
0.3M solution, at 150 ºC and reaction times of: 25 h (
a
and
d
), 96 h (
b
and
e
) and 116 h (
c
and
f
). Images
a
,
b
and
c
show the materials prepared with a high CTAB concentration. Images
d
,
e
and f show the materials
prepared with a low CTAB concentration. ANA: analcime, PHI: phillipsite
SYNTHESIS OF ZEOLITIC MATERIALS FROM VOLCANIC ASH
191
Fig. 7.
SEM images of the products corresponding to the chemical reaction between volcanic ash and a NaOH
0.3M solution, in absence of CTAB. ANA: analcime, CHA: chabazite and PHI: phillipsite
5 μm
PHI
ab
2 μm
PHI
CHA
ANA
5 μm
PHI
CHA
ANA
ANA
PHI
5 μm
0246 81
01
21
41
61
820
keV
Ful scale 2516 cts
Cursor: 0.000 keV
Si
Spectrum 1
O
Al
Na
K
K
cd
the products they obtained at 200 ºC and 20 days of
reaction time, there was a mixture of chabazite +
phillipsite + analcime. However they did not specify
the crystallization sequence of the members of this
mixture.
On the other hand, Ibrahim (2004) reports the
following paragenetic sequence: smectite®phillipsi
te®chabazite®natrolite®analcime®calcite. The zeo-
lites were synthesized using volcanic glass granules
transformed into palagonite as starting material by
the action of percolating waters in a closed hydro-
thermal system. The paragenetic sequence is similar
to the one we obtained in the sense that the chabazite
crystallization took place after the crystallization of
phillipsite.
CONCLUSIONS
It is possible to synthesize a single phillipsite-like
zeolite and zeolitic mixtures (phillipsite + analcime
and phillipsite + chabazite + analcime) by chemical
reactions between the Chaitén volcanic ash and a
NaOH 0.3 M solution at 150 ºC, under hydrothermal
conditions, autogenic pressure and either in presence
or absence of the template agent CTAB. The Na-K-
phillipsite-like zeolite was the most effective to retain
cations with about a 60 % retention for Pb
2+
, 56 %
for Zn
2+
and 43 % for Ba
2+
.
Obtaining phillipsite-like zeolite at 150 ºC and
15 h of reaction time would represent an economi-
cal advantage if the process could be carried out at
industrial level. This would contribute to mitigate
the socioeconomic damages produced by the Chai-
tén (2008) volcanic ash. In the light of the results
obtained it is possibly to postulate that zeolites could
be also synthesized from others SiO
2
, Al
2
O
3
and K
2
O
rich volcanic products like rhyolitic domes and silicic
pyroclastic deposits.
ACKNOWLEDGMENTS
This paper was possible thanks to the collabora-
tion of the Instituto GEA. We also give our thanks
to the Vicerrectoría de Investigación y Desarrollo
of the Universidad de Concepción (Chile). The
authors are grateful to Dr. Andrés Tassara and
V.M. Sanhueza Núñez and L.D. Bennun Torres
192
Priscilla Riveros who donated the Chaitén volcano
ash samples analyzed, also to Mónica Uribe for her
help in the identifcation oF the synthesized minerals
by XRD and to Julio Pugin and Hugo Pacheco For
their assistance in the SEM characterization of the
synthesized zeolites.
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