Microporous and Mesoporous Materials 278 (2019) 322–326

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Microporous and Mesoporous Materials

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

Synthesis of high silica SSZ-13 in fluoride-free media by dry gel conversion T

method
Hasna Al Jabria, Koji Miyakea,∗, Kaito Onoa, Masahiro Nakaia, Yuichiro Hirotaa, Yoshiaki Uchidaa,
Manabu Miyamotob, Norikazu Nishiyamaa
a
Division of Chemical Engineering, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka, 560-8531, Japan
b
Department of Chemistry and Biomolecular Science, Gifu University, 1-1 Yanagido, Gifu, 501-1193, Japan

A R T I C LE I N FO A B S T R A C T

Keywords: Chabazite SSZ-13 has attracted wide attention due to its physiochemical properties and excellent potential as a
SSZ-13 catalyst for various application. In this study, pure phase SSZ-13 CHA zeolite with wide range of Si/Al ratio has
High silica zeolite been synthesized in a fluoride-free media by dry gel conversion method where the conversion of SSZ-13 from
Fluoride-free aluminosilicates precursor gel occurs under water vapor. The difference between products produced by con-
Dry gel conversion
ventional hydrothermal synthesis method and the new method has been investigated and characterized with
XRD, SEM, XRF, and N2 adsorption. Pure SSZ-13 with wide range of Si/Al up to 182 was obtained by dry gel
conversion method while pure SSZ-13 with higher Si/Al ratio than 20 with similar starting gel composition could
not synthesized by hydrothermal synthesis method. Our work has demonstrated that dry gel conversion method
was an effective method to synthesize pure SSZ-13 with a wide range of Si/Al ratio under fluoride media-free
condition.

1. Introduction particular, it has been difficult to synthesize high-silica SSZ-13. It was

Zeolites are known for their excellent properties due to their out-
standing solid acidity, adsorption properties, and shape selectivity,
which make them usable for various applications including: catalysis,
adsorption, separation, and ion-exchange [1,2]. This has attracted
many researches to improve the zeolites available and synthesize new
types of zeolites that can be used in fields of nanotechnology, green
chemistry, reactions, medicine, cosmetics, and so on [3–7].
SSZ-13 is aluminosilicates zeolite with well-defined channel system
and cavities. SSZ-13 belongs to Chabazite (CHA) type zeolite family,
where its structure consists of 3-Dimesional network of 8-members ring
with pore opening of 3.8 Å × 3.8 Å and large ellipsoidal cavities of
8.35 Å [8–10]. SSZ-13 zeolite has attracted wide attention because of its
important physiochemical properties and excellent potential as a cata-
lyst for various applications due to its small pore and relatively large
cavities in its structure. In particular, SSZ-13 is considered to have great
potential for various application such as catalysis for methanol-to-ole-
fins (MTO), ethanol-to-olefins (ETO) reaction, NOx reduction reaction,
separation and absorbers [11–19].
CHA type was found in its natural composition of Ca2Al12Si24O72,
but the application of SSZ-13 requires a wide range of Si/Al ratio, in
first discovered and synthesized by Zones at Chevron by hydrothermal
treatment method [20,21]. SSZ-13 is typically synthesized using col-
loidal silica as silica source, aluminum oxide Al(OH)3 as alumina source
with N,N,N-trimethyl-1-adamantanammonium hydroxide (TMAdOH)
as organic structure directing agent under alkaline condition. Different
Si/Al ratios ranging from 10 to 54 have been synthesized con-
ventionally by hydrothermal method [22–26].
Effect of using seed crystals in the synthesis of high silica SSZ-13
was reported to strongly effect the nucleation and crystallization pro-
cess. The crystallization time was shortening by one day and higher
seed loading resulted in higher crystallinity. Seed assisted synthesis of
high silica SSZ-13 combined with OSDA resulted in Si/Al ratio up to
100 [27,28].
Pure silica CHA type zeolite has been synthesized in fluoride and
TMAdOH media. The high concentration of fluoride and TMAdOH en-
courage the formation of single phase CHA zeolite and the use of col-
loidal silica as a silica source improves the hydrophobicity of Si-CHA
[29,30]. Many factors affect the synthesis of SSZ-13 which includes the
effect of amount of water and NaOH, and crystallization time on the
preparation of SSZ-13. An optimum alkalinity, amount of water, and
crystallization period of time is required to produce a pure SSZ-13

∗
Corresponding author.
E-mail address: kojimiyake@cheng.es.osaka-u.ac.jp (K. Miyake).

https://doi.org/10.1016/j.micromeso.2019.01.006
Received 12 November 2018; Received in revised form 18 December 2018; Accepted 4 January 2019
Available online 08 January 2019
1387-1811/ © 2019 Elsevier Inc. All rights reserved.
H. Al Jabri et al. Microporous and Mesoporous Materials 278 (2019) 322–326

Table 1
Synthetic conditions and molar ratio of precursor.
Sample No. Si/Al Method Time (h) SiO2 Al Na TMAdOH H2O

(a) 10 DGC 96 100 10 20 150 5810

(b) 26 DGC 96 100 3.8 20 150 5810
(c) 25 DGC 96 100 4 20 100 3500
(d) 50 DGC 96 100 2 20 100 3500
(e) 136 DGC 96 100 0.7 20 255 9500
(f) 102 DGC 96 100 0.98 20 100 3900
(g) 104 DGC 96 100 0.96 20 150 5900
(h) 188 DGC 72 100 0.53 26 255 9500
(i) 200 DGC 72 100 0.5 26 250 9350
(j) 222 DGC 72 100 0.45 26 250 9350
(k) 250 DGC 72 100 0.4 26 150 5810
(l) 363 DGC 72 100 0.27 26 150 5810
(m) 11 Hydrothermal 96 100 9.1 20 150 5810
(n) 50 Hydrothermal 96 100 2 20 100 3500
(o) 90 Hydrothermal 96 100 1.1 20 150 5900
(p) 102 Hydrothermal 96 100 1 20 100 3900
(q) 146 Hydrothermal 96 100 0.68 20 100 3900

Fig. 3. XRD patterns of product synthesized by conventional hydrothermal

method.

Fig. 1. XRD patterns of Pure SSZ-13 synthesized by dry gel conversion method Table 2
with different Si/Al ratios. Physicochemical properties of synthesized SSZ-13.
Sample No. Si/Al of precursor Si/Al of product (XRF) Particle size

(a) 10 10.5 250 nm

(b) 26 24.8 250 nm
(c) 25 25 200–400 nm
(d) 50 48 500 nm −1 μm
(e) 136 63 1 μm −2 μm
(f) 102 76 700 nm −1 μm
(g) 104 88 500 nm
(h) 188 102 1 μm −2 μm
(i) 200 182 1 μm −2 μm
(m) 11 9.3 5 μm
(n) 50 19.8 1 μm −2 μm

vapor-phase transport or steam assisted conversion has an advantages

Fig. 2. XRD patterns of SSZ-13 with SSZ-23 peaks as impurities at high Si/Al
ratios synthesized by dry gel conversion method.
zeolite [31]. However, the toxic fluoride media was necessary to syn-
thesize high silica SSZ-13, which is not favorable in terms of the com-
mercialization.
Previously, we have developed various zeolites with unique prop-
erty by dry gel conversion (DGC) [32–37]. DGC synthesis is relatively a
new method for the synthesis of zeolites. DGC method or also called
of producing zeolite with higher yield and it also reported to produce
less waste in addition it needs less reactor volume and reduction in
crystallization time. Direct conversion by crystallization of dry alumi-
nosilicates gels to zeolite by treatment with steam or amine vapor was
first demonstrated by Xu et al. [38] In this case, a pre-prepared sodium
aluminosilicates dried gel was suspended above liquid in an autoclave
at temperature range between 180 °C and 200 °C. While heating, only
the mixed vapor of water, ethylenediamine, and triethylamine came in
direct contact with the gel to finally forming ZSM-5 zeolite. The com-
position of Si/Al ratio for the amorphous gel prepared and the final
crystal product remained the same, suggesting the occurrence of solid-
phase transformation. Later on, synthesizing different types of zeolites

323
H. Al Jabri et al.
Fig. 4. Fe-SEM and SEM images of SSZ-13 synthesized with various Si/Al ratios.
such as; ANA, FER, ZSM, MOR, etc. was accomplished. Much higher Si/
Al ratio of beta zeolite was synthesized by the use of DGC method with
Si/Al ratio in the range of 15–365 while it was reported to synthesize
beta zeolite with Si/Al ratio of 125 by hydrothermal method [39–47].
Herein, we have synthesized high silica SSZ-13 (Si/Al up to 182) by
method without any fluoride medias or seed crystals.
2. Experimental (methods, techniques and materials studied)
2.1. Materials
The following chemicals were used for the synthesis of SSZ-13:
N,N,N-trimethyl-1-adamantanammonium hydroxide (25 wt%
TMAdaOH in H2O, SACHEM, Inc), colloidal silica (Ludox HS-40 Sigma-
Aldrich), aluminum hydroxide Al(OH)3 (Wako Pure Chemical
Industries, Ltd), and NaOH (Wako Pure Chemical Industries, Ltd).
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Microporous and Mesoporous Materials 278 (2019) 322–326
2.2. Synthesis of high silica SSZ-13
Modified synthesis was performed by following the producers from
literature [27] N,N,N-trimethyl-1-adamantanammonium hydroxide is
first mixed with NaOH. Then colloidal silica was added in and finally
aluminum hydroxide was added to the solution. Then the resulting
mixture was stirred at room temperature for 6 h to obtain a homo-
geneous gel. In the DGC method, the homogeneous gel was dried at
90 °C overnight then the dry gel is transferred to a closed Teflon-lined
stainless steel autoclave with water separately where the reaction take
place with the steam produced. 3 g of dried gel with 22 g of water se-
parately was added in a 200 cm3 reaction vessel. The treatment was
carried out at 160 °C for 3–4 days. The product was then centrifuged,
washed, and calcined at 600 °C for 10 h. The molar ratio of the pre-
cursor solution is summarized in Table 1.
H. Al Jabri et al.
Fig. 5. Nitrogen adsorption of SSZ-13. Samples (a), (b), (c), (g), (i) synthesized
by DGC and sample (m) synthesized by conventional method.
2.3. Characterizations
The crystal structure of the products was identified by X-ray dif-
fraction (XRD) measurement recorded on a PANalytical X'Pert-MPD
diffractometer using Cu-Kα radiation. The presence of Si and Al species
in the samples was confirmed by X-ray fluorescence (XRF) using an S8
TIGER (BRUKER). To observe the crystal size of the samples, scanning
electron microscope (SEM) and field emission scanning electron mi-
croscopy (FE-SEM) images of the samples were recorded on a Hitachi S-
5000 microscope. The porosity of the products was characterized by N2
adsorption measurements at 77 K using a BELSORPmax (MicrotracBEL).
3. Results and discussion
Fig. 1 shows XRD patterns of pure SSZ-13 synthesized with different
Si/Al ratios. SSZ-13 with high Si/Al ratio up to 182 has been synthe-
sized in a fluoride-free media by DGC method. The XRD patterns of SSZ-
13 correspond to CHA structure, indicating that the synthesized zeolites
are pure CHA phase. Higher TMAdaOH content was required for the
synthesis of high silica SSZ-13 and shorter crystallization time.
The diffraction peaks of SSZ-23 (SST-type zeolite) were observed as
impurity when further increasing Si/Al ratio in Fig. 2. The number of
impurity peaks increased with the reduction of aluminum concentration
in the precursor.
Fig. 3 shows the XRD patterns of SSZ-13 synthesized with similar
precursor but crystallization took place by conventional hydrothermal
treatment method. Pure SSZ-13 was synthesized for samples with Si/Al
ratios of 10 and 50 but the attempt to synthesize higher silica SSZ-13
with Si/Al ratios of 90, 102, and 146 resulted in a formation of SSZ-23
impurity. The synthesis results show that high silica SSZ-13 is not a
stable phase which makes it difficult to be synthesized by con-
ventionally hydrothermal treatment method in a seed-free or fluoride-
free. The hydrothermal treatment method is having a faster crystal-
lization which is easier for impurities to occur. The crystallization rate
is assumed to be slower in the DGC method which facilitate the for-
mation of pure high silica SSZ-13.
XRF was measured for the samples synthesized by both the methods
as shown in Table 2. Sample (d) and (n) was synthesized with the same
precursor of Si/Al ratio of 50 but resulted in different final ratios. DGC
method produces samples with similar Si/Al ratio to the precursor
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Microporous and Mesoporous Materials 278 (2019) 322–326
where the conventional method produces much lower values of Si/Al.
The difference between Si/Al ratios of processor and final product for
SSZ-13 synthesized by hydrothermal method is similar to results shown
in literature [13–15].
The crystal size and morphology of SSZ-13 was observed by FE-SEM
and SEM. The images are shown in Fig. 4. Synthesized SSZ-13 zeolites
show cubic crystals with sizes varying according to the synthesis
method. The images also show that samples are well crystallized and
without any amorphous phase for samples synthesized by DGC method.
Crystal size of samples synthesized by DGC method was much
smaller compared with SSZ-13 synthesized by conventionally hydro-
thermal method. Samples synthesized by DGC has smaller particle size
ranging from 100 to 300 nm and 5 μm for the sample synthesized by
conventionally hydrothermal method. Especially, the effect can be
clearly seen in samples (a) and (m) synthesized with the similar pre-
cursor. In the hydrothermal synthesis method, the nucleation and
crystal growth occurs in the solution which causes low nucleation
density that results in rapid crystal growth forming larger crystal size.
Where the high nucleation density and slow crystal growth in the DGC
method produces smaller crystal size. Controlling the particle size and
its uniformity plays an important role in its catalytic applications.
It was also observed that controlling the uniformity of crystals size
became more challenging with the increase in Si/Al ratio of SSZ-13
produced by DGC method.
N2-adsorption measurements were performed to study the micro-
porosity of SSZ-13 produced by DGC method. The adsorption isotherms
are shown in Fig. 5. All synthesized samples isotherm is type I which is
the characteristic of microporous zeolite materials. SSZ-13 by DGC has
a large BET surface area (over 750 m2/g) and micropore volume (over
0.29 cm3/g) compared with samples synthesized by hydrothermal
method. As for the micropore volume, the result in Fig. 5 shows samples
with high micropore volume for DGC method compared with samples
synthesized by HT method. The increase at P/P° = 0.9–1.0 can be ex-
plained as intercrystal voids among nanocrystals of SSZ-13 in sample
(a) and (b), which is in good agreement with the results of SEM ob-
servation.
4. Conclusions
In this study, pure SSZ-13 with different Si/Al ratio up to 182 has
been successfully synthesized by DGC method in a fluoride-free media.
SSZ-13 synthesized by DGC method resulted in smaller particle size
with higher crystallinity compared with SSZ-13 synthesized by con-
ventional method.
Acknowledgements
This work was supported by CREST, JST. We would like to thank
GHAS laboratory at Osaka University for the XRD measurements and
FE-SEM observations. We also would to like to thank Sachem, Inc. for
their kind donation of the organic structure-directing agent (N,N,N-
trimethyl-1-adamantanammonium hydroxide) used in the synthesis of
SSZ-13.
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