Organotemplate-Free Synthesis of a High-Silica Zeolite with a TON Structure in the Absence of Zeolite Seeds

Article abstract of DOI:10.1002/ejic.201501223

A high-silica zeolite with a TON structure designated as ZJM-4 was successfully synthesized in the absence of any organic templates and zeolite seeds. Many factors such as the SiO₂/K₂O ratio, Si/Al ratio, SiO₂/H₂O in the starting aluminosilicate gels, crystallization temperature, and crystallization time strongly influence the formation of the ZJM-4 zeolite. Interestingly, this synthesis shows very efficient silica utilization in the starting gels (>80 %). Catalytic tests on the isomerization of m-xylene to p-xylene show that the ZJM-4 catalyst has high selectivity to p-xylene (ca. 80 %), which could be potentially important for industrial applications for the ZJM-4 zeolite as a candidate catalyst in the future.

Full text of DOI:10.1002/ejic.201501223

DOI: 10.1002/ejic.201501223
Full Paper
Zeolites
Organotemplate-Free Synthesis of a High-Silica Zeolite with a
TON Structure in the Absence of Zeolite Seeds
Yeqing Wang,[a] Chenqi Zhu,[a] Jing Qiu,[a] Fan Jiang,[a] Xiangju Meng,*[a] Xiong Wang,[a]
Chi Lei,[a] Yinying Jin,[a] Shuxiang Pan,[a] and Feng-Shou Xiao*[a]
Abstract: A high-silica zeolite with a TON structure designated ingly, this synthesis shows very efficient silica utilization in the
as ZJM-4 was successfully synthesized in the absence of any starting gels (>80 %). Catalytic tests on the isomerization of m-
organic templates and zeolite seeds. Many factors such as the xylene to p-xylene show that the ZJM-4 catalyst has high select-
SiO2/K2O ratio, Si/Al ratio, SiO2/H2O in the starting aluminosil- ivity to p-xylene (ca. 80 %), which could be potentially impor-
icate gels, crystallization temperature, and crystallization time tant for industrial applications for the ZJM-4 zeolite as a candi-
strongly influence the formation of the ZJM-4 zeolite. Interest- date catalyst in the future.
Introduction
On the other hand, it is interesting to note that many indus-
trially used zeolites are completely synthesized in the absence
of organic templates such as ZSM-5, Y, and A. Besides their
unique structural features, low-cost and organotemplate-free
syntheses are also important factors for the wide applications in
the industrial processes. Currently, it is a challenge to produce
a complete organotemplate-free synthesis of ZJM-4 zeolite in
the absence of ZSM-22 zeolite seeds.
Structural analyses of ZSM-22 and ZSM-5 zeolites show that
both zeolites have similar zeolite building units, and a key factor
for the synthesis of the ZSM-5 zeolite in the absence of organic
templates is to induce the formation of zeolite building units.[18]
Inspired by the organotemplate-free synthesis of ZSM-5 zeolite,
we have carefully adjusted the composition of the starting gels
to be favorable for the formation of the zeolite building units
of the TON structure in the absence of any organic templates.
When the crystallization time is long enough, high silica zeolite
with a TON structure could be successfully synthesized in the
absence of any organic templates.
Zeolites have unique porosity and high surface area, playing
important roles in ion exchange, catalysis, adsorption, and sepa-
ration. The high-silica zeolite with a TON structure, with a one-
dimensional 10-membered ring pore system with medium-
sized pores of ca. 0.47 × 0.55 nm,[1,2] has been widely applied
in catalytic conversions such as isomerization,[3–7] paraffin
hydroconversion,[8] and propene trimerization.[9] Notably, the
high-silica zeolite with a TON structure such as ZSM-22 is syn-
thesized in the presence of organic templates.[10] The use of
organic templates not only increases the synthesis cost but also
produces polluted wastes, which strongly limit its practical
applications in the industrial processes. Therefore, low-cost and
environmentally friendly synthesis of ZSM-22 is highly desira-
ble.[11,12]
Recently, it has been reported that seed-directed synthesis
is a generalized route for the synthesis of zeolites in the ab-
sence of organic templates. The first example is the synthesis
of Beta zeolite,[13] followed by syntheses such as FER,[14] RTH,[15]
and MTT.[16] More recently, Wang et al. reported a successful
seed-directed synthesis of high-silica ZSM-22 zeolite in the ab-
sence of organic templates, which was designated as ZJM-4.[17]
This route significantly reduces the ZSM-22 zeolite cost and pol-
luted wastes in the synthesis, but it is worth noting that the
synthesis of ZSM-22 zeolite seeds still requires organic tem-
plates. In other words, the organic templates cannot be entirely
avoided in the synthesis of the ZJM-4 zeolite.
Herein, we have demonstrated an organotemplate-free syn-
thesis of ZJM-4 zeolite in the absence of ZSM-22 zeolite seeds
by adjusting the composition of the starting gels. The ZJM-4
zeolite has high crystallinity and similar textural parameters to
those of ZSM-22 synthesized in the presence of organic tem-
plates. More importantly, the synthesis of the ZJM-4 zeolite has
very high silica utilization.
Results and Discussion
[a] Department of Chemistry, Zhejiang University
Hangzhou 310028, P. R. China
Organotemplate-Free Synthesis of the ZJM-4 Zeolite in the
Absence of the Zeolite Seeds
E-mail: mengxj@zju.edu.cn
fsxiao@zju.edu.cn
Figure 1 shows the XRD pattern and SEM image of the as-syn-
thesized ZJM-4 zeolite as well as the Ar sorption isotherms of
H-ZJM-4. The sample XRD pattern (Figure 1, a) shows a series
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of characteristic peaks associated with the TON structure.[19,20] for industrial applications. As shown in Figure 2 (B), the three
The sample SEM image (Figure 1, b) exhibits pure and very major peaks at about –111, –113, and –115 ppm are assigned
uniform rod-like crystals with a length of 2–3 μm, in good to the Si(4Si) species. The peak at –104.5 ppm is assigned to
agreement with the typical morphology of aluminosilicate zeo- Si(3Si,1Al) and/or Si(3Si,1OH). These results indicate that most
lites with a TON structure, reported previously.[10] The sample of the silicon atoms in the ZJM-4 zeolite are Si (4Si) species.
Ar sorption isotherms (Figure 1, c) exhibit a steep increase in
the curve at a relative pressure of 10–6 < P/P0 < 0.01, which
is characteristic of Langmuir adsorption from the filling of the
micropores. The HK pore size distribution is estimated at
0.55 nm. The BET surface area and micropore volume are
171 m2/g and 0.066 cm3/g, respectively. These values are con-
sistent with those of the ZSM-22 zeolite synthesized in the pres-
ence of diaminooctane.[21]
Figure 2. (A) 27Al MAS NMR spectra of the (a) as-synthesized and (b) calcined
ZJM-4 sample and the (B) 29Si MAS NMR spectrum of the as-synthesized ZJM-
4 zeolite.
The Si/Al ratio of the ZJM-4 was analyzed by inductively cou-
pled plasma (ICP) as 41 (Table S3). It is worth mentioning that
the silica utilization in the organotemplate-free synthesis of the
ZJM-4 zeolite is over 80 %. Normally, the organotemplate-free
and seed-directed synthesis of zeolites such as Beta (30–40 %)
have relatively low silica utilization.[23] Obviously, the high silica
utilization in the organotemplate-free synthesis in the absence
of zeolite seeds should be potentially important for industrial
applications of this ZJM-4 zeolite.
The Factors for Organotemplate-Free Synthesis of the
ZJM-4 Zeolite in the Absence of Zeolite Seeds.
Figures 3 and 4 show XRD patterns and SEM images of the
samples synthesized under various conditions, respectively, as
presented in Tables S1 and S2. Clearly, the amount of KOH
added to the starting gels significantly influences the formation
Figure 1. (a) XRD pattern and (b) SEM image of the as-synthesized ZJM-4
sample as well as (c) Argon sorption isotherms of the H-ZJM-4 sample.
of the ZJM-4 zeolite. When the ratio of SiO2/K2O is 14.29, amor-
Figure 2 shows the 27Al NMR spectra of the as-synthesized phous product is obtained (parts a in Figures 3 and 4, and Run
and calcined ZJM-4 zeolite and the 29Si MAS NMR spectrum of 1 in Table S1); When the SiO2/K2O ratio is decreased to 12.84,
the as-synthesized ZJM-4 zeolite. In Figure 2 (A), the samples the product contains a little of the amorphous phase (parts b
exhibit one strong peak at δ = 57.5 ppm, which corresponds in Figures 3 and 4 and Run 2 in Table S1); When the SiO2/K2O
with the tetrahedral coordination aluminum in the framework ratio is reduced to 11.88, a pure phase of ZJM-4 zeolite is ob-
of the ZJM-4 zeolite.[22] The absence of the signal at ca. 0 ppm tained (Figure 1, a and b, and Run 3 in Table S1); When the
confirms that all aluminum atoms in the samples are tetra- SiO2/K2O ratios are below 10, the product consists of cristobal-
hedrally located in the zeolite framework. After calcination at ite (Figure 3, d, Figure 4, c and d, and Runs 4 and 5 in Table S1).
550 °C for 5 h, we still do not observe the signal at ca. 0 ppm Hence, the ratios of K2O/SiO2 play an important role in obtain-
in the ZJM-4 sample, indicating that these aluminum species in ing the pure phase of the ZJM-4 zeolite, which should be care-
the framework are quite thermally stable, which is important fully adjusted.
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The crystallization temperature in the synthesis is also an
important factor for obtaining the pure phase of the ZJM-4
zeolite. The products only consist of the amorphous phase
when the temperature is 135 °C (parts i in Figures 3 and 4, and
Run 14 in Table S1); when the temperature is increased to
150 °C, a pure phase of the ZJM-4 zeolite is obtained (Run 3 in
Table S1); when the temperature is 165 °C, an impurity of cristo-
balite is formed in the final product (parts j in Figures 3 and 4,
and Run 15 in Table S1).
The rotation crystallization is also necessary for the organo-
template-free synthesis of the ZJM-4 zeolite. When the sample
is crystallized under static conditions all of the products are
amorphous (Run 16 in Table S1). These results suggest that the
rotation conditions are favorable for the nucleation and crystal-
lization of the ZJM-4 zeolite.
Besides, the crystallization time influence the synthesis of the
ZJM-4 zeolite. When the crystallization time is less than 26 h,
the major product is amorphous SiO2 (Run 1 in Table S2). When
the crystallization time reaches 60 h, a small amount of cristo-
balite occurs in the products (Run 3 in Table S2).
As presented in Tables S1 and S2, it is apparent that many
factors such as the SiO2/K2O ratio, Si/Al ratio, SiO2/H2O in the
starting aluminosilicate gels, crystallization temperature, and
crystallization time influence the synthesis of the ZJM-4 zeolite.
The pure ZJM-4 zeolite could only be obtained in a narrow
phase diagram of K2O–Al2O3–SiO2–H2O by a comprehensive
consideration of these factors.
Figure 3. XRD patterns of the ZJM-4 samples synthesized under various condi-
tions. The SiO2/K2O ratios of (a) 14.29, (b) 12.84, (c) 11.88, and (d) 8.33 under
a temperature of 150 °C, a Si/Al ratio of 50, and SiO2/H2O ratio of 0.0225; the
Si/Al ratios of (e) 40 and (f) 75 under a temperature of 150 °C, a SiO2/K2O
ratio of 11.88, and SiO2/H2O ratio of 0.0225; SiO2/H2O ratio of (g) 0.0667 and
(h) 0.0200 under a temperature of 150 °C, a Si/Al ratio of 50, and SiO2/K2O
ratio of 11.88; a temperature of (i) 135 °C and (j) 165 °C, a SiO2/K2O ratio of
11.88, Si/Al ratio of 50, and SiO2/H2O ratio of 0.0225.
Importance of Starting Composition Adjustment for the
Synthesis of the ZJM-4 Zeolite
It has been reported that the zeolite building units play an
important role in the formation of the zeolite structure.[24,25]
Therefore, in this work, it is proposed to form the zeolite build-
ing units to induce the crystallization of the ZJM-4 zeolite. Fig-
ure 5 (a) shows the IR spectrum obtained from the suitable
molar ratio of the starting gels for the synthesis of the ZJM-
4, giving a weak band at about 554 cm–1 associated with the
asymmetric mode of five rings in the zeolite building units,
which is consistent with that (551 cm–1) of the ZJM-4 zeolite
(Figure 5, b).[26,27] This result suggests that the starting alumino-
Figure 4. SEM images of the ZJM-4 samples synthesized under various condi-
tions. The SiO2/K2O ratio of (a) 14.29, (b) 12.84, (c) 10.00, and (d) 8.33 under
a temperature of 150 °C, a Si/Al ratio of 50, and SiO2/H2O ratio of 0.0225; the
Si/Al ratios of (e) 40 and (f) 75 under a temperature of 150 °C, a SiO2/K2O
ratio of 11.88, and SiO2/H2O ratio of 0.0225; the SiO2/H2O of (g) 0.0667 and
(h) 0.0200 under a temperature of 150 °C, a Si/Al ratio of 50, and SiO2/K2O
of 11.88; a temperature of (i) 135 °C and (j) 165 °C, a SiO2/K2O ratio of 11.88,
Si/Al ratio of 50, and SiO2/H2O ratio of 0.0225 (scale bar: 2 μm).
In addition, the ratios of Si/Al in the starting aluminosilicate
gels also influence the purity of the ZJM-4 zeolite. For example,
when the Si/Al ratio in the starting gel is 25, it is always an
amorphous phase (Run 6 in Table S1); when the Si/Al ratios in
the starting gel reaches 40, the major product is the ZJM-4
zeolite together with a small amount of the amorphous phase
(parts e in Figures 3 and 4, and Run 7 in Table S1); when the
Si/Al ratio in the starting gel reaches 50, pure ZJM-4 zeolite can
be obtained; when the Si/Al ratios are over 60 (parts f in Fig-
ures 3 and 4, and Runs 8 and 9 in Table S1) an impurity of
cristobalite can be obtained.
Furthermore, it is observed that the ratios of SiO2/H2O
should be carefully adjusted. The suitable ratio is 0.0225. Too
few or too much water in the starting gels always results in the
impurity of cristobalite (parts g in Figures 3 and 4, and Runs 10
and 11 in Table S1) or the amorphous phase (parts h in Fig-
ures 3 and 4, and Runs 12 and 13 in Table S1).
Figure 5. FTIR spectra of (a) the starting gel for the synthesis of the ZJM-4
zeolite with a molar ratio of 0.01 Al2O3/1.0 SiO2/0.084 K2O/45 H2O and the
(b) as-synthesized ZJM-4 zeolite.
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silicate gel already contained the TON building units. These the synthesis, the excellent selectivity is potentially important
building units are possibly favorable for the crystallization of for catalytic applications of low-cost ZJM-4 zeolite in the future.
the ZJM-4 zeolite. In contrast, when these building units are
absent in the starting gels, it is difficult to obtain the ZJM-4
Conclusions
crystals. After crystallization of the ZJM-4 zeolite, along with
new bands at 808 and 640 cm–1 the band at 551 cm–1 becomes
In summary, ZJM-4 zeolite with a TON structure has been suc-
very strong (Figure 5, b). These bands are typically characteristic
cessfully synthesized under organotemplate-free and seed-free
of zeolite ZJM-4 with a TON zeolite structure. These results con-
conditions. This route has efficient silica utilization, which is of
firm the importance of the zeolite building units in the starting
great significance for reduction of polluted wastes and zeolite
cost. The ZJM-4 zeolite has a stable tetrahedral aluminum spe-
gels for the formation of the ZJM-4 zeolite.
cies and strong acidic sites, which is important for catalytic ap-
plications in the future.
Catalytic Tests of ZJM-4
The acid strength of the H-ZJM-4 zeolite has been characterized
by NH3–TPD (Figure 6), giving two peaks centered at 221 and
450 °C, which are assigned to relatively weak and strong acidic
sites in the sample. The quantitative estimation of this curve
Experimental Section
Materials: Potassium hydroxide (KOH) was purchased from Sino-
pharm Chemical Reagent Co. Ltd. Tetraethyl orthosilicate (TEOS)
shows that the concentration of the weak and strong acidic
sites is 0.33 and 0.38 mmol/g, respectively. These results indi-
cate that the H-form of the ZJM-4 zeolite has both strong and
weak acidic sites, which are very similar to those of conven-
tional zeolites with a TON structure.
and aluminum sulfate [Al2(SO4)3·18H2O] were purchased from Chi-
nasun Specialty Products Co. Ltd. Ammonium nitrate was purchased
from the Chengdu Kelong Chemical Reagent Factory. m-Xylene was
obtained from the Aladdin Chemical Reagent Company.
Materials Synthesis: ZJM-4 zeolite was hydrothermally synthesized
from the starting gels with molar ratios of 0.0067–0.02 Al2O3/1.0
SiO2/0.07–0.12 K2O/15–55 H2O in a poly-(tetrafluoroethylene)-lined
stainless steel autoclave dynamically (50 rpm) at a temperature of
135–165 °C for 0–60 h. As a typical run for the synthesis of ZJM-4
in the absence of organic templates and the zeolite seeds, KOH
(0.16 g) and Al2(SO4)3·18H2O (0.096 g) were dissolved in deionized
water (11.5 g), followed by the addition of TEOS (3.0 g). After stirring
for 4 h, the mixture was transferred into a Teflon®-lined autoclave
oven and crystallized at 150 °C for 48 h under rotation conditions
(50 rpm). Finally, the product was collected by filtration, washed
with deionized water, and dried at 100 °C for 6 h.
The H-form of the ZJM-4 zeolite was obtained by ion-exchange with
a NH4NO3 solution (1
M) at 80 °C for 1 h (1 g of ZJM-4 zeolite
in 50 mL of solution), which was performed three times. The ion-
exchanged ZJM-4 zeolite was heated to 550 °C at a heating rate of
1 °C/min–1 and kept at 550 °C for 5 h in flowing O2. The sample
was designated as H-ZJM-4.
Figure 6. NH3–TPD curve of the H-ZJM-4 zeolite.
Figure 7 presents catalytic data from the m-xylene isomeriza-
tion over the H-ZJM-4 zeolite. The H-ZJM-4 exhibits excellent
selectivity to p-xylene (ca. 80 %). This value is comparable with
that of the H-ZJM-4 zeolite synthesized from seed-directed and
organotemplate-free conditions.[17] Considering the complete
avoidance of organic templates and efficient silica utilization in
Characterization: The crystallinity and phase purity of the samples
were determined by X-ray powder diffraction (XRD) with a Rigaku
Ultimate VI X-ray diffractometer (40 kV, 40 mA) using Cu-Kα (λ =
1.5406 Å) radiation from 4° to 40° with 2θ. Scanning electron mi-
croscopy (SEM) experiments were performed with Hitachi SU1510
electron microscopes. The Argon sorption isotherms were carried
out with a Micromeritics ASAP 2020M and Tristar system. Solid-state
27Al and 29Si NMR spectra were recorded with a Varian Infinity plus
400 spectrometer. The sample compositions were determined by
inductively coupled plasma (ICP) with a Perkin–Elmer 3300DV emis-
sion spectrometer after dissolving the solid products in a hydroflu-
oric acid solution in a volumetric flask (50 mL). FTIR spectra were
recorded with a Thermo Scientific Nicolet iS5 FTIR spectrometer.
Temperature-programmed desorption of the NH3 (TPD-NH3) curve
was carried out with a TCD detector. As a typical run, H-ZJM-4
(200 mg) was placed in a quartz tubular reactor and pretreated at
500 °C in a nitrogen stream. After cooling to 100 °C, gaseous NH3
was passed through the sample for 30 min. After removal of physi-
cally adsorbed NH3 by flowing nitrogen for 2 h at 100 °C, the NH3–
TPD curve of the sample was recorded by programmed heating
from 100 to 600 °C with a heating rate of 10 °C/min.
Figure 7. Catalytic (■) conversion of m-xylene and (▲) selectivity for p-xylene
in m-xylene isomerization over the H-ZJM-4 zeolite catalyst.
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Acknowledgments
This work is supported by the National Natural Science Founda-
tion of China (NSFC) (grant numbers 21333009, 21422306 and
91545111), the Fundamental Research Funds for the Central
Universities (2015XZZX004-04), and Zhejiang Provincial Natural
Science Foundation of China under grant LR15B030001.
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Received: October 24, 2015
Published Online: March 2, 2016
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