Materials Letters 217 (2018) 259–262

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Materials Letters
journal homepage: www.elsevier.com/locate/mlblue

Preparation of zeolite P by desilication and recrystallization of zeolites

ZSM-22 and ZSM-35
Lenivaldo V. Sousa a, Antonio O.S. Silva b, Bruno J.B. Silva b, Paulo H.L. Quintela c, Celmy B.M. Barbosa a,
Roger Fréty a, Jose G.A. Pacheco a,⇑
a
Federal University of Pernambuco, Department of Chemical Engineering, CEP: 50740-521 Recife, PE, Brazil
b
Federal University of Alagoas, Department of Chemical Engineering, CEP: 57072-900 Maceio, AL, Brazil
c
Federal University of Sergipe, Department of Chemical Engineering, CEP: 49100-000 São Cristóvão, SE, Brazil

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

Article history: This work describes an original way to obtain zeolite P through dissolution and recrystallization of zeo-
Received 5 October 2017 lites ZSM-22 and ZSM-35. The starting zeolites, in their H-form, were subjected to desilication and recrys-
Received in revised form 4 December 2017 tallization in a single step in the presence of a NaOH solution at 100 °C for 20 h. The X-ray diffraction
Accepted 14 January 2018
(XRD) results confirmed the formation of crystalline zeolite P. Specific surface areas from 20 to 70 m2/
Available online 17 January 2018
g were obtained with mesoporous volumes between 0.03 and 0.22 cm3/g. Scanning Electron
Microscopy (SEM) micrographs showed that the obtained materials had been formed by agglomerates
Keywords:
of nanosized crystallites.
Zeolite P
Desilication
Ó 2018 Elsevier B.V. All rights reserved.
Recrystallization
ZSM-22
ZSM-35
Nanosized

1. Introduction Zeolite P is used in the separation of small molecules of gases

Zeolite desilication is a well-known post-synthesis procedure
for obtaining mesoporous or hierarchical materials. It consists of
subjecting the material to alkaline treatments usually with NaOH
solutions, generating partial dissolution of the zeolite structure
due to silicon extraction, and consequently leading to the forma-
tion of mesopores [1–4]. These materials make it possible to obtain
catalysts with high acidity and greater accessibility of large mole-
cules to active centres [5]. Another approach in the formation of
hierarchical materials is the desilication and subsequent recrystal-
lization of the zeolite in the presence of structural directing agents
(SDA), leading to the production of composite materials (for exam-
ple ZSM-5/MCM-41), formed by mesoporous materials with walls
composed of fragments of zeolites [3,6,7]. Therefore, synthesis
methodologies that allow the formation of catalysts that combine
some of the mentioned characteristics may be used in a number
of chemical processes.
Zeolite P, with GIS topological structure, has pore openings
formed by eight-membered rings with dimensions of 0.31  0.45
nm in the crystallographic [1 0 0] direction and 0.28  0.48 nm in
the [0 1 0] direction. These pore openings are smaller than those
found in structures of the zeolites LTA, TON, MFI and FAU [8,9].
and liquids, in the removal of toxic and/or radioactive species
(Cs+, Sr2+, Ba2+, Pb2+ and cations of U), from water effluents, and
in the production of ecological detergents [10–13].
Recent studies on the preparation of zeolite P have focused on
synthesis using alternative sources of silicon and/or aluminium,
such as kaolin [14], fly ash [13,15,16], and hazardous aluminium
solid wastes [17]. Tang et al. [18] have obtained porous zeolite P
beads from a geopolymer composed of metakaolin, sodium silicate,
sodium dodecyl sulfate and polyethylene glycol. Zubowa et al. [19]
have synthesized NaP zeolite starting from a typical synthesis com-
position for MCM-22 formation, applying microwave heating.
Behin et al. [20] have prepared zeolite P starting from the natural
zeolite Clinoptilolite, by using ultrasonic energy and hydrothermal
treatment.
The present work reports a new single step synthesis method
for zeolite P through a desilication and recrystallization of the
ZSM-22 (TON) and ZSM-35 (FER) zeolite structures.
2. Experimental section
2.1. Materials

⇑ Corresponding author. The following materials were employed in the desilication and
E-mail address: jose.pacheco@ufpe.br (J.G.A. Pacheco). recrystallization experiments: ZSM-22 (TON), ZSM-35 (FER),

https://doi.org/10.1016/j.matlet.2018.01.069
0167-577X/Ó 2018 Elsevier B.V. All rights reserved.
260 L.V. Sousa et al. / Materials Letters 217 (2018) 259–262

ZSM-5 (MFI) and MCM-22 (MWW). ZSM-35, from Zeolyst
(CP914C), has a SiO2:Al2O3 ratio of 20:1 and a specific surface area
of 400 m2/g. ZSM-22 was synthesized using the following reagents:
1,6-diaminohexane (Sigma-Aldrich, 98%), potassium hydroxide
(Sigma-Aldrich, 85%), colloidal silica (Ludox AS-40, Sigma-
Aldrich), hydrated aluminum sulfate (Merck), sulfuric acid (98%,
JT Baker) and distilled water, according to the methodology
described in [21]. The reaction mixture, with a molar composition
of 27NH2(CH2)6NH2:13.5K2O:Al2O3:90SiO2:3600H2O, was trans-
ferred to a Teflon vessel (700 mL) and placed in a 1 L Parr reactor.
Crystallization was carried out at 160 °C under stirring of 400 rpm,
for 20 h. After crystallization, the recovered solid was washed with

Fig. 1. Diffractograms of the zeolites. A) ZSM-22; B) ZSM-35; C) Zeolite P obtained from desilication of ZSM-22; D) Zeolite P obtained from desilication of ZSM-35.

Fig. 2. Nitrogen adsorption and desorption isotherms of NaP zeolites.

 L.V. Sousa et al. / Materials Letters 217 (2018) 259–262 261

water and dried at 120 °C for 12 h. Calcination occurred at 550 °C
(5 °C/min heating rate) for 6 h under air.
A commercial ZSM-5 was obtained from Zeolyst (CBV2314).
MCM-22 was synthesized in the laboratory according to reference
[24].
2.2. Desilication and recrystallization
The desilication and recrystallization experiments were carried
out in a glass flask placed on a magnetic stirrer with a hot plate. A
suspension of 3 g of the starting zeolite in 240 mL of a 0.3 M NaOH
solution was heated to 100 °C and kept under stirring for 20 h. The
recovered solids were washed with water and dried at 120 °C for
12 h.
2.3. Characterization
The X-ray diffractograms were obtained on a Shimadzu XRD-
6000 diffractometer in the 2h range between 3 and 40°, using CuKa
radiation, 30 kV, 30 mA, with a Ni filter, a goniometer speed of 2°/
min, and a step of 0.02°. The relative crystallinity of the zeolite P
samples was determined by comparing the areas under the peaks
between 15 and 35°, considering the material with the highest
sum of the areas as 100% crystalline. Using a Micromeritics ASAP
2020 analyzer, the textural properties were determined by nitro-
gen adsorption at 196 °C, after sample outgassing under vacuum
for 12 h at 350 °C. The micrographs were obtained on a TESCAN
MIRA3 scanning electron microscope.

Table 1
Textural parameters of the zeolites ZSM-22, ZSM-35, NaP/ZSM-22, and NaP/ZSM-35.

Sample Micropore area (m2/g) a

Mesopore area (m2/g)c Total surface area (m2/g)b VMICRO (cm3/g)a VMESO (cm3/g)e VTOTAL (cm3/g)d
ZSM-22 221 37 258 0.09 0.12 0.21
ZSM-35 271 40 311 0.13 0.09 0.22
NaP/ZSM-22 4 66 70 0.002 0.22 0.22
NaP/ZSM-35 3 7 20 0.005 0.03 0.04
a
t-plot method.
b
BET method.
c
(Total Area Micropore Area).
d
Nitrogen adsorbed at P/P0 = 0.98.
e
VMESO = VTOTAL VMICRO.

Fig. 3. Micrographs of zeolite P obtained from the desilication of ZSM-22 (A and B) and ZSM-35 (C and D).
262 L.V. Sousa et al. / Materials Letters 217 (2018) 259–262
3. Results and discussion
NaOH treatment causes the dissolution and/or depolymeriza-
tion of the zeolites, destroying the existing structure and forming
zeolitic basic construction units. By maintaining the energy supply
to the system, these basic units may recrystallize and form a new
structure, depending on the reaction conditions [7]. After NaOH
treatment, the ZSM-22 and ZSM-35 samples were recrystallized
in the form of the GIS structure (Zeolite P) as shown in Fig. 1.
Fig. 1A and 1B show, respectively, the diffractograms of ZSM-22
(JCPDS card N° 38-197) and ZSM-35 (JCPDS card N° 79-1799) zeo-
lites before desilication. Fig. 1C and D demonstrate that after the
alkaline treatment the ZSM-22 and ZSM-35 samples were fully
converted to zeolite P (JCPDS card N° 40-1464). Comparing the rel-
ative crystallinities of the zeolite P samples obtained from ZSM-22
(NaP/ZSM-22) and ZSM-35 (NaP/ZSM-35), the former is less crys-
talline (88% relative crystallinity) than the latter. Debye-Scherrer
equation [22] indicated the average crystallite size of the initial
zeolites, ZSM-22 and ZSM-35, to be 24 nm and 42 nm, respectively.
After recrystallization as zeolite P, the crystallite sizes decreased to
20 nm and 34 nm respectively for the NaP/ZSM-22 and NaP/ZSM-
35 samples.
Fig. 2 shows the N2 adsorption/desorption isotherms of zeolite P
powders. Table 1 summarizes the results of specific surface area
and pore volume of the samples. The total specific surface area
for the NaP/ZSM-22 and NaP/ZSM-35 samples, calculated by the
BET method, were 70 and 20 m2/g, respectively. This significant
difference is due mainly to the mesopore area of the NaP/ZSM-22
which was much higher than that of the NaP/ZSM-35.
These values are significantly lower than the specific surface
areas of the precursor zeolites, but are equal or higher than the val-
ues reported in the literature for zeolite P [11–13,16–18]. The
mesoporous characteristics of the samples are probably due to sec-
ondary porous arrangement resulting from particle-particle aggre-
gation [23].
The SEM images in Fig. 3 illustrate details of the particles mor-
phology. For the two cases shown particle aggregates were formed
with sizes greater than the crystallite sizes estimated by the
Debye-Scherrer equation obtained from Fig. 1 (see above). The
NaP/ZSM-22 sample is formed by particles with a pseudo-
spherical shape [13], while the NaP/ZSM-35 sample presents a
morphology similar to that described in reference [12], with a
cactus-like shape with strong aggregation.
The SEM images and the Scherrer equation data make it possi-
ble to confirm the results presented previously, in which the NaP/
ZSM-22 sample with smaller particles (Fig. 3A and B) has a higher
specific surface area than NaP/ZSM-35. On the other hand, the NaP/
ZSM-35 sample is formed from larger particles (Fig. 3C and D),
resulting in a smaller specific surface area.
The same alkaline treatment carried out on commercial ZSM-5
and MCM-22 samples did not promote the formation of zeolite P
under the experimental conditions employed, causing only a par-
tial dissolution of the materials and consequent loss of
crystallinity.
4. Conclusions
In this work, zeolite P was obtained after desilication and
recrystallization of zeolites ZSM-22 and ZSM-35. Zeolite P samples
were obtained with high crystallinity (80–100%) and specific sur-
face area between 20 and 70 m2/g. The materials obtained pre-
sented a morphology formed by agglomerates of nanocrystallites
with mesoporous characteristics, mainly in the zeolite P produced
from the desilication of ZSM-22.
Acknowledgements
We acknowledge the financial support of CAPES/PROCAD, FINEP,
RECAT, CETENE, Prof. Celso Melo (UFPE/DF), National Council for
Scientific and Technological Development, CNPq/INCT-EMA, and
Laboratory LSCat, Federal University of Alagoas. English revision
by Sidney Pratt.
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