Microporous and Mesoporous Materials 280 (2019) 306–314

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Microporous and Mesoporous Materials

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Fast and efficient synthesis of SSZ-13 by interzeolite conversion of Zeolite T

Beta and Zeolite L
Lingxue Tanga, Kok-Giap Hawa, Yiying Zhanga, Qianrong Fanga, Shilun Qiua,
Valentin Valtcheva,b,∗
a
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun, 130012, China
b
Normandie Univ, ENSICAEN, UNICAEN, CNRS, Laboratoire Catalyse et Spectrochimie, 6 Marechal Juin, 14050, Caen, France

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

Keywords: Highly crystalline and pure SSZ-13 zeolite is obtained by interzeolite conversion of zeolite Beta and zeolite L.
Zeolite synthesis Zeolite Beta is used without preliminary treatment, while zeolite L is subjected to dealumination in order to
Interzeolite conversion reach the Si/Al ratio appropriate for the synthesis of SSZ-13. The formation of SSZ-13 from conventional che-
SSZ-13 micals is also studied. The crystallization from zeolite precursors is much faster and provides pure and highly
Crystal growth kinetics
crystalline SSZ-13. The improved crystal growth kinetics is attributed to the directing effect of the dissolved Si-O-
Al fragments from zeolite Beta and zeolite L frameworks. CHA-type zeolites obtained from dealuminated zeolite
L crystallized faster, showed higher crystallinity and more defined crystals morphology in respect to those ob-
tained from zeolite Beta. The dealuminated zeolite L was found to be an outstanding starting material for the
crystallization of SSZ-13.

1. Introduction (MTO) reaction [15–21].

The zeolite formation is a complex process which includes several
Zeolites are important industrial catalysts and separation materials stages, it starts with the gel formation, followed by the induction
thanks to their define micropore structure, high specific surface area, period, viable nuclei formation and their growth into crystals [22]. The
the presence of active sites of different nature and strength and their zeolite nucleation is a spontaneous reaction which takes place after
molecular sieve and ion exchange properties [1–6]. In general, the reaching a specific stage of evolution of the amorphous phase [23].
synthetic zeolites are prepared under hydrothermal conditions from Using alternative initial sources such as crystalline zeolite type mate-
amorphous silica and alumina sources, alkali metal cations and/or or- rials introduce specific differences in the zeolite formation mechanism
ganic structure directing agent (SDA). However, alternative methods of [24].
synthesis which could improve the zeolite properties or the synthesis During the last decade the potential of hydrothermal conversion of
process are the focus of continuous research. one zeolite into another, i.e., interzeolite transformation from the
The structure commission of International Zeolite Association (IZA) standpoint of an alternative strategy for zeolite synthesis, was in-
approved 241 zeolite framework types up to now [7], as the number of tensively investigated [25–28]. These studies are based on the under-
the new zeolite structures is growing steadily through the years. The standing that locally ordered aluminosilicate species may exist in the
CHA-type material, first discovered in nature as mineral Chabazite, is conversion process and their assembly under a specific structure-di-
one of the most largely used zeolites. The framework contains ellip- recting agent gives rise to a fast crystallization rate and a high se-
soidal-shaped cages (6.7 × 10 Å) connected through a three-dimen- lectivity to a particular zeolite [29–31]. Another advantage of this
sional pore system with 8-membered ring windows (3.8 × 3.8 Å). synthesis route is that the nucleation/crystallization processes can be
Chabazite can be synthesized as low silica (Si/Al ∼ 2) material when modified compared to conventional amorphous aluminosilicate gels
solely alkali metals are employed as structure directing agent [8,9], or [32].
as high silica (SSZ-13) material when a specific organic SDA is involved The extensive interest to small pore cage-type zeolites and in par-
in the synthesis [10]. High silica zeolite is widely used in NOx abate- ticular to SSZ-13 motivated us to study the conversion of appropriate
ment [11–13], in CO2/CH4 separation [14] and in Methanol-to-Olefins zeolites with the goal to optimize the synthesis of this material. This

∗
Corresponding author.State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun, 130012, China.
E-mail address: valentin.valtchev@ensicaen.fr (V. Valtchev).

https://doi.org/10.1016/j.micromeso.2019.02.021
Received 24 October 2018; Received in revised form 31 January 2019; Accepted 12 February 2019
Available online 13 February 2019
1387-1811/ © 2019 Elsevier Inc. All rights reserved.
L. Tang, et al. Microporous and Mesoporous Materials 280 (2019) 306–314

approach has already been used to synthesize aluminosilicates with Reagent). The starting zeolite Beta with Si/Al = 11 was purchased from
CHA-type structure. Zones converted GIS-type zeolite to CHA-type SANBANG Chemicals, China.
material in NaOH [33]; and Faujasites to high-silica chabazite SSZ-13 in
the presence of N, N, N-Trimethyl-l-adamantammonium iodide [34]. 2.2. Synthesis of Zeolite L
Itakura et al. obtained high-silica CHA-type zeolite from FAU-type
zeolite in the presence of benzyltrimethylammonium hydroxide [35]. A Nanosized zeolite L was synthesized using the following molar
classic example is the transformation of zeolite Y (FAU-type) into composition 1SiO2:0.05Al2O3:0.5K2O:20H2O. The potassium solution
chabazite using a K+ - Na+ synthesis solution [36]. Sano and co- was prepared by dissolving 6.580 g of KOH in 20.216 g deionized water
workers also used organic template-free system to synthesize chabazite in an ice bath, then 0.273 g of aluminum powder was added. The
from H-FAU material [37]. The same group discovered a way to syn- mixture was stirred for 15 min to obtain a clear solution. 20.09 g of
thesize CHA-type from a denser LEV-type structure without using or- Ludox HS-30 was then added and the mixture was stirred for 10 min.
ganic SDA [38]. Goel and Ji converted FAU-type to CHA-type without The resulting solution was then transferred into a 30 mL teflon-lined
organic SDA [32,39]. Takata et al. utilizes FAU-type zeolite for hy- autoclave. The hydrothermal treatment was performed at 170 °C for
drothermal conversion in the presence of seed crystals and templating 16 h in an oven under static condition. The sample was collected by
agents to obtain nanosized CHA-type zeolite with high thermal and centrifugation and washed with deionized water until a near neutral pH
hydrothermal stability [40]. Xiong et al. converted FAU-type zeolite to was achieved, and then dried overnight at 60 °C.
high silica CHA-type zeolite in the absence of water [41]. Takata et al.
successfully transformed heterometal-incorporated FAU-type alumino- 2.3. Dealumination of Zeolite L
silicates (M-FAU) to heterometal-incorporated CHA-type aluminosili-
cate zeolites (M-CHA, M = Fe, Ga, Sn) [42]. Martín et al. synthesized Zeolite L with Si/Al ratio equal to 11, 22, 26 and 77 was prepared
chabazite with high solid yields by the rational combination of di- by dealumination of the nanosized zeolite L (Si/Al = 3). Hydrochloric
recting effects of Si- and Al- extracts of USY zeolites and the tetra- (HCl) acid with concentration of 0.48 M, 0.49 M, 0.50 M, 1.00 M was
ethylammonium cations [43]. Bhadra et al. converted zeolite FAU-Y to used. The dealumination was performed at 25 °C for 4 h under stirring.
chabazite SSZ-13 in the presence of tetraethylammonium hydroxide The liquid:solid weight ratio was 30. The solid was collected by cen-
[44]. Finally, Geng et al. used zeolite LTA as the aluminum source to trifugation, thoroughly washed with deionized water to pH ∼7 and
rapidly synthesize zeolite SSZ-13 in the presence of colloidal silica, dried overnight at 60 °C.
NaOH and N, N, N-trimethyladamantammonium hydroxide [45].
We selected zeolite Beta and zeolite L as starting materials in order 2.4. Synthesis of SSZ-13
to obtain high silica SSZ-13. The choice of zeolite Beta is based to the
appropriate Si/Al ratio, while the structural proximity between CHA- The two materials (zeolite Beta and zeolite L) were hydrothermally
and LTL-type zeolites is the reason for the selection of the later as converted to SSZ-13 using N,N,N-trimethyl-1-adamantammonium
starting material. (TMAD) as a structure directing agent. Gel molar composition was
Zeolite beta has been extensively used as a substrate for inter- xMOH:yTMAD:zH2O, where M is Na, K, Li, Cs, x = 0.3–0.5, y = 0.2–0.3
mediate zeolite conversion. Zones et al. reported the conversion of and z = 20 and 30 for zeolite L and zeolite Beta conversion, respec-
various zeolites such as B-Beta to B-SSZ-24, B-SSZ-31 and B-SSZ-33, and tively. Zeolite Beta and zeolite L were used as silicon and aluminum
Al-Beta to Al-SSZ-24 and Al-SSZ-31 in the presence of amantadine ca- sources and no additional SiO2 or Al2O3 was added to the gel. In a
tions and its derivatives [46,47]. Kubota et al. [48] and Ahedi et al. typical experiment, 1.7 g zeolite beta and the TMAD solution were
[49] also successfully converted Al-Beta and Ti-Beta to Al-SSZ-31 and mixed (solid/liquid weight ratio = 0.14) under stirring for 2 h at room
Ti-SSZ-24, respectively. OU-1 and MTW were synthesized from high temperature. 1.3 g zeolite L and the TMAD solution were mixed (solid/
silica Beta using tetraethylammonium hydroxide as a structure-di- liquid weight ratio = 0.16) under stirring for 2 h at room temperature.
recting agent [50]. The use of FAU-type and Beta zeolites as initial si- The optimized compositions of the systems used for transformation of
lica-alumina source resulted in highly crystalline and pure RUT-type zeolite L (CL) and zeolite Beta (CB) was as follows:
zeolites [51]. Goel et al. converted BEA-type into MFI-type without
addition of seed and template [52]. Khan et al. synthesized zeolite SSZ- CL: 1SiO2:0.0455Al2O3:0.19K2O:0.26TMAD:20H2O;
13 by adding Na2SiO3 to zeolite Beta [53]. CB: 1SiO2:0.0455Al2O3:0.18K2O:0.31TMAD:30H2O.
The objective of the present study is optimizing the synthesis of SSZ-
13 by using interzeolite conversion synthetic approach. By employing The SiO2/Al2O3 ratio (zeolite L and zeolite Beta) of two systems is
two different zeolites, which differ in composition and structure type, similar, but they differ in water, K+ and TMAD content, which was
we also aim to shed more light on the key factors controlling the in- necessary in order to get pure SSZ-13. After homogenization, the mix-
terzeolite conversion. Finally, the conversion of zeolite L to SSZ-13 ture was transferred in a 30 mL Teflon-lined stainless-steel autoclave.
(CHA-type) was not reported to date to the best of our knowledge. The hydrothermal conversion was carried out at 150 °C and 180 °C in an
electric oven. After crystallization step, the solid product was collected
2. Experimental by vacuum filtration and washed thoroughly with deionized water until
a near neutral pH and then dried overnight at 60 °C.
2.1. Materials Reference SSZ-13 samples were synthesized using conventional
chemicals and preparing gels with chemical compositions similar to CB
All chemicals and materials used were collected from commercially and CL systems. The two systems corresponding to the zeolite L (CC-1)
available sources and used without further purification. The chemicals and zeolite Beta (CC-2) conversion exhibit the following molar com-
used in this work are Potassium hydroxide (KOH 98%, Aladdin position:
Chemistry), Lithium hydroxide (LiOH 98%, Sigma-Aldrich), Sodium
hydroxide (NaOH 98%, Aladdin Chemistry), Cesium hydroxide (CsOH CC-1: 1SiO2:0.05Al2O3: 0.19K2O:0.26TMAD:20H2O;
50 wt% in water, Adamas-beta), N,N,N-trimethyl-1-adamantammo- CC-2: 1SiO2:0.05Al2O3: 0.18K2O:0.31TMAD:30H2O.
nium (TMAD 98%, Aladdin Chemistry), deionized water, aluminum
powder (99.5%, Aladdin Chemistry), Sodium nitrate (99.5%, Aladdin Ludox HS-40 and alunimum powder were employed as silicon and
Chemistry), Ludox HS-40 (40 wt% SiO2, Sigma-Aldrich), and Ludox HS- aluminum source, respectively. CC-1 was prepared by dissolution of
30 (30 wt% SiO2, Sigma-Aldrich). HCl (12%, Sinopharm Chemical 0.62 g of KOH in 7.6 g deionized water, then 0.072 g of aluminum

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powder was added. The mixture was stirred for 15 min to obtain a clear Fig. 1a. Only a halo revealing the amorphization of the zeolite and the
solution. 1.62 g of TMAD was added and the mixture was stirred for peak at 5.5° Two Theta can be observed. It is worth noting that the
10 min. 4.43 g of Ludox HS-40 was then added and the mixture was dealumination with HCl is quite efficient, even a small change in the
stirred for 24 h at ambient temperature. CC-2 was prepared by dis- HCl concentration (0.48–0.50 M) changed the Si/Al ratio substantially.
solution of 0.6 g of KOH in 10.55 g deionized water, then 0.072 g of The chemical analysis of treated sample showed that the Si/Al ratio
aluminum powder was added. The mixture was stirred for 15 min to increases from 3 in the parent zeolite to 11, 21, 26 and 77 after deal-
obtain a clear solution. 1.95 g of TMAD was added to the mixture and uminated in 0.48, 0.49, 0.50 and 1.0 M HCl, respectively (Fig. 1b).
stirred for 10 min. 4.43 g of Ludox HS-40 was then added and the The initial zeolite L (Si/Al = 3, run CL-7) was subjected to hydro-
mixture was stirred for 24 h at ambient temperature. The mixture was thermal treatment at 150 °C for 24 h (Table 1). The zeolite remained
then transferred into a 30 mL Teflon-lined autoclave and hydro- intact after the hydrothermal treatment (Fig. 2a). In contrast, all deal-
thermally treated at 150 °C for 24 h and 72 h in an oven under static uminated samples were hydrothermally transformed and no trace of
condition. Then, the sample was collected by vacuum filtration and zeolite L was observed in the products. The level of zeolite L deal-
washed with deionized water until a near neutral pH and dried over- umination strongly influenced the formation of SSZ-13. Thus, the
night at 60 °C. highly dealuminated material (Si/Al = 77) does not yield CHA-type
zeolite. Instead, a layer type material was synthesized, which reveals
2.5. Characterization the importance of the initial Si/Al ratio for the successful synthesis of
SSZ-13. The other three sources were successfully converted in SSZ-13
All materials were characterized by Powder X-ray diffraction as X-ray crystallinity of the products was similar (Fig. 2a). The silica-
(PXRD) analysis using a PANalytical B.V. Empyrean powder dif- alumina conversion for all SSZ-13 was about 40%. On the other hand,
fractometer with Cu Kα radiation (λ = 1.5418 Å) operating at 40 kV the framework composition of SSZ-13 was influenced by the initial
and 40 mA. XRD diffraction analysis was used to study the crystals zeolite L. Thus, the dealuminated samples with Si/Al ratio 11 and 21
growth kinetics of SSZ-13 zeolite. The kinetics of conversion was de- yielded zeolites with Si/Al ratio of 6.7 and 7.5 respectively. From the
termined by the surface of the peak at 9.3° Two Theta. SSZ-13 prepared sample with Si/Al = 26, SSZ-13 with Si/Al = 16 was formed. In gen-
according to ref. 8 was used as a reference sample. Thermogravimetric eral, the crystalline product exhibits a Si/Al ratio lower than the deal-
analysis (TGA) was performed on a SHIMADZU DTG-60 thermal ana- uminated zeolite L.
lyzer system. Approximately 10 mg of each sample was introduced in an The nitrogen adsorption isotherm of CHA-type zeolites obtained
alumina crucible and loaded in the analyzer chamber. The samples from dealuminated zeolite L is type I. The differences between the three
were heated from 30 to 700 °C with a heating ramp of 10 °C·min−1 samples are negligible (Table 1). The micropore volume of the samples
under air (flow rate: 40 mL min−1). Scanning electron microscopy corresponds to highly crystalline CHA-type zeolite confirming the high
(SEM) micrographs were taken on a JEOL JSM7400F microscope op- quality of the materials obtained from zeolite L. Fairly similar in size
erated at 3–10 keV and 10 μA. Transmission electron microscopy (TEM) and crystal morphology SSZ-13 was obtained from the dealuminated
analysis was performed on a JEM-2100F. Prior to the measurement, a zeolite L sources (Fig. S4). Individual well-shaped crystals with the
diluted colloidal suspension of sample was sonicated for 5 min and then typical rectangular morphology were yielded, no matter of the Si/Al
dropped on a carbon-film-covered 300-mesh copper electron micro- ratio of the dealuminated zeolite L.
scope grids and dried. Elemental analysis of the sample was measured In summary, the dealuminated zeolite L is an appropriate source for
by Energy Dispersive X-Ray Fluorescence Spectrometer (EDX) operated the synthesis of SSZ-13. Further, we selected the source with Si/Al = 11
under TEM (JEM-2100F). Nitrogen adsorption measurements were for a more detail investigation of the crystallization process. This se-
performed on a Micromeritics ASAP 2040 surface area analyzer. The lection is justified by the high crystallinity of the obtained SSZ-13 and
calcined samples were analyzed after degassing at 300 °C. The iso- the similar Si/Al ratio with the zeolite Beta source, which allowed
therms were recorded using ASAP 2040 analysis program. The micro- comparing the efficiency of two zeolites in the production of SSZ-13.
porous volume (Vmic, cm3 g−1) was obtained from t-plot based on the
Harkins-Jura equation. 3.3. Comparative study of zeolite Beta and zeolite L conversion to SSZ-13

3. Results and discussion The reaction conditions and the results of zeolite Beta and zeolite L
hydrothermal conversion at 150 °C and 180 °C are summarized in
3.1. Physicochemical characterization of initial zeolites Table 2. The preliminary experiments allowed to optimize the synthesis
conditions so as to use a close ratio between the reactants used to
Zeolite Beta and zeolite L used as initial silica-alumina sources do convert zeolite Beta and Zeolite L to SSZ-13. CHA-type zeolites were
not contain impurities (Fig. S1). The TEM inspection showed that both successfully obtained from both zeolite Beta and zeolite L with Si/Al
samples contain nanosized crystals building complex aggregates (Fig. ratios of 11. However, the ratio between components of the starting
S2). Nitrogen adsorption isotherms are characteristic of nanosized mixture plays an important role. For instance, the KOH/SiO2 ratio is
zeolite materials. The fast uptake at low relative pressure is followed by crucial for the conversion of zeolite Beta into SSZ-13 and for the purity
moderate inclination of isotherm in the 0.2–0.8 P/Po range and second of the final product. Thus at KOH/SiO2 = 0.2 no formation of SSZ-13
uptake at high relative pressure (Fig. S3). These features are due to the after 24 h crystallization at 150 °C was observed. Highly crystalline SSZ-
textural porosity generated by the aggregation of nanosized zeolite Beta 13 was obtained at both temperature 150 °C and 180 °C when a gel with
and zeolite L crystals. The micropore volume and SBET of zeolite Beta KOH/SiO2 = 0.36 was used. The crystallization was much faster at
was 0.18 cm3 g−1 and 520 m2 g−1, respectively. Zeolite L showed mi- 180 °C, where a substantial conversion of zeolite Beta into SSZ-13 was
cropore volume and SBET of 0.13 cm3 g−1 and 438 m2 g−1, respectively. observed after 4 h crystallization (CB-5). After 8 h the same system gave
The Si/Al ratio of zeolite Beta was 11, which is appropriate for the high crystalline SSZ-13 (CB-6). The extension of synthesis time to 10 h
synthesis of SSZ-13. The Si/Al ratio zeolite L was 3, which required a did not improve the crystallinity of the product, showing that the
dealumination step in order to reach the range appropriate for the conversion is almost completed after 8 h. The increase of the KOH/SiO2
synthesis of SSZ-13. to 0.5 and 0.6 resulted in a mixture of SSZ-13 and Mordenite.
In the case of zeolite L conversion the KOH/SiO2 ratio of 0.38 was
3.2. Dealumination of zeolite L and its conversion to SSZ-13 found to be the most appropriate for the formation of SSZ-13. A ratio of
TMAD/SiO2 = 0.26 was used in most of the synthesis with deal-
The XRD patterns of dealuminated zeolite L samples are shown in uminated zeolite L. Highly crystalline SSZ-13 was obtained at both

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Fig. 1. XRD patterns (a) and Si/Al ratio of dealuminated zeolite L samples (b).

Table 1
Synthesis conditions and physicochemical properties of the products obtained from zeolite L subjected to different levels of dealumination.
a
Run Synthesis conditions Product

Si/Al KOH/SiO2 TMAD/SiO2 Crystalline phase Yield/% Si/Al SBET/m2g−1 Vmic/cm3g−1

CL-7 3 0.38 0.26 Zeolite L 90 3 – –

CL-3 11 0.38 0.26 SSZ-13 38.5 6.7 526 0.26
CL-8 21 0.38 0.26 SSZ-13 42 7.5 552 0.27
CL-9 26 0.38 0.26 SSZ-13 40 16 550 0.26
CL-10 77 0.38 0.26 Layered silicate 43 – – –

a
The synthesis is performed at 150 °C for 24 h.

Fig. 2. XRD patterns (a) and N2 adsorption isotherms (b) of SSZ-13 samples obtained from dealuminated zeolite L at 150 °C for 24 h.

temperatures, 150 °C and 180 °C. The crystallization at 180 °C was zeolite Beta and zeolite L are presented in Fig. 3a and b, respectively. A
much faster, after only 4 h the product contained some amount of SSZ- decrease of crystallinity of zeolite Beta and first traces of SSZ-13 are
13 plus amorphous material. After 8 and 10 h synthesis the system observed after 4 h hydrothermal treatment. The crystallinity increased
yielded pure and highly crystalline CHA-type zeolite. It took 24 h in with time and reached the maximum after 24 h. It is worth noting that
order to obtain highly crystalline product from the same initial system no amorphous intermediate, i.e. a halo, was detected by XRD. Deal-
at 150 °C, which is still substantially faster than the conventional uminated zeolite L precursors reacted faster with the synthesis solution.
synthesis of SSZ-13. A similar initial system prepared from conventional After 1 h treatment traces of zeolite L were observed and first CHA-type
reactants took 72 h to obtained highly crystalline SSZ-13. The crystal- material was recorded after 3 h hydrothermal conversion (Fig. 3b).
line yield was calculated by SiO2 + Al2O3 in the initial system. The With the extension of the synthesis time, the crystallinity increased and
highest conversions (CC-1 = 66% and CC-2 = 77%) was recorded for fully crystalline solid was obtained after 24 h. The transformation of
the systems prepare from conventional reactants. The conversion of zeolite L to CHA-type material was different from zeolite Beta. It in-
zeolite Beta to SSZ-13 varied from 45 to 59% in different syntheses, cludes two steps process, first an intermediate amorphous phase was
while the one from zeolite L was between 50 and 53%. formed which was converted to CHA-type zeolite.
Fig. 3 provides a more detail picture of the transformation of two The physical transformation of two zeolites to SSZ-13 was followed
zeolites in SSZ-13. XRD patterns of the products obtained at 150 °C from by SEM. Both products contain rectangular well shaped crystals typical

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Table 2
Experimental conditions, crystalline products and yields of SSZ-13 obtained from zeolite Beta, zeolite L, and conventional reactants.
Sample Si/Al KOH/SiO2 TMAD/SiO2 Temperature/°C Time/h Crystalline Product(s) Yield/%

CB-1 11 0.60 0.31 150 24 SSZ-13 + MOR –

CB-2 11 0.50 0.31 150 24 SSZ-13 + MOR –
CB-3 11 0.36 0.31 150 24 SSZ-13 59
CB-4 11 0.20 0.31 150 24 Beta –
CB-5 11 0.36 0.31 180 4 Beta + SSZ-13 –
CB-6 11 0.36 0.31 180 8 SSZ-13 45
CB-7 11 0.36 0.31 180 10 SSZ-13 48
CL-1 11 0.20 0.31 150 24 Layered silicate –
CL-2 11 0.30 0.26 150 24 SSZ-13 + L –
CL-3 11 0.38 0.26 150 24 SSZ-13 53
CL-4 11 0.38 0.26 180 4 Amorp.+ SSZ-13 –
CL-5 11 0.38 0.26 180 8 SSZ-13 50
CL-6 11 0.38 0.26 180 10 SSZ-13 51
CC-1 11 0.36 0.26 150 72 SSZ-13 + MOR 70
CC-2 11 0.38 0.31 150 72 SSZ-13 + MOR 66

of CHA-type material. Up to 10 h hydrothermal treatment, the products amount of mordenite was at detection limit in the system corresponding
contain aggregates of small particles, which are non reacted zeolite Beta to zeolite L conversion, while larger amount (ca. 10%) was found in the
(Fig. 4) and amorphous zeolite L precursor (Fig. 5). After this stage, system corresponding to zeolite Beta conversion. Three days were ne-
only the rectangular crystals of SSZ-13 can be seen. The product ob- cessary to reach a full conversion of amorphous silica-alumina sources.
tained by conversion of zeolite L is more uniform with 2–3 μm crystals The SEM inspection of the CC-1 crystalline product showed the typical
(Fig. 4), while the one synthesized by conversion of zeolite Beta con- rectangular morphology of the product (Fig. 6 right). Product with si-
tains two populations of crystals with size 1–2 and 4–5 μm (Fig. 5). milar size and crystal size distribution was obtained in the CC-2 system.
Conventional reactants were used to prepare initial systems similar As can be seen the uniformity of the products is lower than those
to those used for zeolite Beta and zeolite L conversion to SSZ-13. The synthesized via interzeolite conversion. All these features show that the
syntheses were performed at 150 °C and resulted in highly crystalline zeolite precursors are more efficient source for the synthesis of SSZ-13.
SSZ-13 (Fig. 6 left). However, both products contained mordenite. The The highly crystalline sample obtained from zeolite L (CL-3) and

Fig. 3. XRD patterns of CB-3 (a) and CL-3 (b) synthesized at 150 °C, and CB-6 (c) and CL-5 (d) synthesized at 180 °C.

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Fig. 4. SEM images of the products of zeolite Beta conversion to SSZ-13 (CB-3) at 150 °C for 2, 4, 10, 16, 20, and 24 h.

Fig. 5. SEM images of the products of zeolite L conversion to SSZ-13 (CL-3) at 150 °C for 1, 3, 4, 10, 16, and 24 h.

Fig. 6. Left: XRD patterns of two SSZ-13 samples synthesized from conventional reactants. Right: SEM image of the CC-1 product.

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were used in this series of experiments. TMAD was employed as organic

structure directing agent. Alkali metal and TMAD/SiO2 contents differ
slightly in the systems used for the conversion of zeolite Beta and
zeolite L, which was necessary in order to adapt the synthesis solution
to the particularities of the zeolite precursor. The results are summar-
ized in Table 3.
XRD patterns of the obtained products are presented in Fig. S6.
Zeolite Beta and zeolite L were successfully converted to SSZ-13 in the
presence of sodium and potassium. These two cations are equally effi-
cient in the formation of CHA-type material. The products showed si-
milar crystallinity and particle size. The crystalline products synthe-
sized from zeolite Beta and zeolite L employing Na as alkali cation
showed similarities in terms of crystallinity and particle size (2–3 μm).
The only difference is that the crystals obtained from zeolite Beta are
well shaped, whereas more spherical crystals are obtained from zeolite
L (Fig. S7). The use of Li resulted in the formation of unknown crys-
Fig. 7. Thermal analysis of SSZ-13 obtained from zeolite Beta (CB-3), zeolite L
talline phase, no matter zeolite Beta or zeolite L is used in the synthesis.
(CL-3) and conventional chemicals (CC-1) at 150 °C.
The difference between the products synthesized with Li is that zeolite
Beta is largely present in the solid product, while no trace of zeolite L
zeolite Beta (CB-3) were subjected to physicochemical analysis to study was found. This result is expectable having in mind lower stability of
their properties. The two samples showed similar thermogravimetrical dealuminated zeolite L. The use of Cs resulted in the formation of
profiles with a total weight loss of 22 wt% and 21 wt% for CB-3 and CL- Pollucite with both, zeolite Beta and zeolite L sources. These set of
3, respectively (Fig. 7). CB-3 exhibited higher weight lost (5.5 wt%) in experimental results points out the importance of the alkali metal ca-
the low temperature range (25–200 °C) revealing higher water content, tion in the formation of CHA-type aluminosilicates. Although an effi-
while the amount of the structure directing agent decomposed at high cient structure directing agent was employed, the presence of Li and Cs
temperature (400–650 °C) was lower. SSZ-13 synthesized from con- changed the crystallization pathway and resulted in the formation of
ventional chemicals showed similar weight loss in the low temperature undesired products. On the other hand, no significant difference in the
range, but lower weight loss in the range where the organic structure impact of Na and K on the formation of SSZ-13 was found.
directing agent is released (Fig. 7). CL-3 released about 2 wt% water
below 200 °C, while the content of the template was about 18 wt%. The 3.5. Kinetics and mechanism of zeolite transformation
huge weight loss between 400 °C and 650 °C corresponded to the de-
composition of TMAD. The two zeolites showed similar Si/Al ratio, 7.2 Previous studies showed that the interzeolite conversion is strongly
and 6.7 for CB-3 and CL-3, respectively. Therefore, the difference in influenced by the structural similarities of zeolite used as a source of
water content cannot be attributed to the differences in the chemical nutrients and the synthesized zeolite [50]. CHA- and LTL-type struc-
composition and hydrophilic-hydrophobic properties. Hence, the most tures have obvious similarities, both are built exclusively of 4- and 6-
plausible explanation is differences in the crystallinity, which is diffi- member rings and the double 6-member rings (D6R) are mostly present.
cult to be detected by the XRD analysis. Physisorption measurements Zeolite beta contains 4- and 6-member rings, but the 5-member ring is
confirmed this hypothesis. The micropore volume (0.26 cm3 g−1) and the main structural unit, which place the zeolite in the family of pen-
SBET area (526.0 m2g-1) of CL-3 are substantially higher in respect to tasils. Nevertheless, zeolite Beta was successfully converted in SSZ-13.
CB-3 (0.23 cm3g-1; 489 m2g-1) revealing higher crystallinity of SSZ-13 In order to gain more insight in the transformation process we have
obtained from zeolite L. As can be seen in Fig. S5, the low pressure studied the crystal growth kinetics of SSZ-13 at 150 °C and 180 °C using
uptake of CL-3 is higher than that of CB-3. The two isotherms are type I zeolite Beta (Si/Al = 11) and dealuminated zeolite L (Si/Al = 11) as
with negligible hysteresis loop. As shown in Figs. 4 and 5, the SSZ-13 initial silica-alumina source. A substantial difference in the transfor-
crystals are well shaped with limited intergrowth between the particles. mation of zeolite L and zeolite Beta to SSZ-13 was observed at 150 °C
Consequently, the amount of mesopores is very limited in the material. (Fig. 8a). The zeolite L source was completely converted in CHA-type
zeolite within 8 h, while 18 h were necessary to re-crystallized zeolite
3.4. Effect of alkali metal cation on the SSZ-13 formation Beta. Since the Si/Al ratio of the two sources is similar we attribute the
observed difference to the structural similarity between LTL- and CHA-
Since the alkali metal cation plays an essential role in the zeolite type zeolites. It should be added that the structure of zeolite L was
synthesis, the effect of Li+, Na+, K+, Cs+ on the formation of SSZ-13 partially destroyed by the dealumination, which certainly increases its
was studied. Zeolite Beta and zeolite L precursors with Si/Al ratio 11 reactivity. In contrast, no difference between the transformation of

Table 3
The impact of different alkaline metal cations on the formation of SSZ-13 from zeolite Beta and zeolite L at 150 °C for 24 h.
Alkaline cation (M) Synthesis conditions Product

a
Si/Al MOH/SiO2 TMAD/SiO2 Crystalline phase Yield/% Si/Al

CB-Li 11 0.36 0.31 Beta + Unknown – –

CB-Na 11 0.36 0.31 SSZ-13 50 5.7
CB-K 11 0.36 0.31 SSZ-13 43.5 7.2
CB-Cs 11 0.36 0.31 Pollucite – –
CL-Li 11 0.38 0.26 Unknown – –
CL-Na 11 0.38 0.26 SSZ-13 50 7
CL-K 11 0.38 0.26 SSZ-13 43.5 6.7
CL-Cs 11 0.38 0.26 Pollucite – –

a
M − Li, Na, K, Cs.

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L. Tang, et al. Microporous and Mesoporous Materials 280 (2019) 306–314

Fig. 8. SSZ-13 conversion rates at 150 °C (a) and 180 °C (b) using zeolite L (CL-3, CL-5) and zeolite Beta (CB-3, CB-6) as starting materials.

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