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order of seconds
Zhendong Liua, Kotatsu Okabea, Chokkalingam Ananda, Yasuo Yonezawaa, Jie Zhua, Hiroki Yamadaa, Akira Endob,
Yutaka Yanabac, Takeshi Yoshikawac, Koji Oharad, Tatsuya Okuboa, and Toru Wakiharaa,1
a
Department of Chemical System Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan; bNational Institute of Advanced
Industrial Science and Technology, Ibaraki 305-8565, Japan; cInstitute of Industrial Science, The University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo,
153-8505, Japan; and dJapan Synchrotron Radiation Research Institute/SPring-8, Kouto 1-1-1, Sayo-gun, Hyogo 679-5198, Japan
Edited by Mark E. Davis, California Institute of Technology, Pasadena, CA, and approved November 8, 2016 (received for review September 23, 2016)
The hydrothermal synthesis of zeolites carried out in batch reactors established (1113). The ultrafast route on the order of minutes
takes a time so long (typically, on the order of days) that the not only enabled the continuous flow synthesis but also demon-
crystallization of zeolites has long been believed to be very slow strated that the crystallization of zeolites can proceed much faster
in nature. We herein present a synthetic process for ZSM-5, an than generally observed.
industrially important zeolite, on the order of seconds in a contin- Owing to specific physical and chemical properties, supercritical
uous flow reactor using pressurized hot water as a heating medium. water or pressurized water with extremely high temperatures
Direct mixing of a well-tuned precursor (90 C) with the pressurized (usually near or above 300 C) offers several potential advantages
water preheated to extremely high temperature (370 C) in the mil- for hydrothermal processing (14). Continuous flow hydrothermal
limeter-sized continuous flow reactor resulted in immediate heating synthesis of functional nanostructured materials in those mediums
to high temperatures (240300 C); consequently, the crystallization has been extensively exploited in recent years, and the associated
of ZSM-5 in a seed-free system proceeded to completion within tens merits, such as rapid formation of crystalline materials and facile
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of or even several seconds. These results indicate that the crystalli- tuning of the properties, have been demonstrated (15, 16). The
zation of zeolites can complete in a period on the order of seconds. hydrothermal synthesis of zeolites using supercritical water or
The subtle design combining a continuous flow reactor with pres- pressurized water with extremely high temperatures, however,
surized hot water can greatly facilitate the mass production of zeo- has rarely been reported. The challenge arises from the intrinsic
lites in the future.
complexity of zeolite formation. Zeolites are formed as a metastable
phase compared with their dense-phase counterparts, which implies
crystal growth | continuous flow synthesis | zeolites | ultrafast synthesis | that overly high temperatures may only lead to the formation of
ZSM-5
nonporous materials (17, 18). Meanwhile, the complicated assembly
of inorganicorganic species leading to the formation of zeolites
Z eolites have typically been synthesized via hydrothermal
treatment, a process designed to artificially mimic the geo-
logical formation conditions of natural zeolites (1, 2). Depending
may not be favored under the less hydrophilic conditions of water
with too high temperatures (19). Finally, the organic structure-
directing agent (OSDA) tends to decompose at high temperatures,
on the targeted framework and composition, several hours to days which imposes further restrictions (20). To realize a synthesis in
(or even several weeks) are required to complete the synthesis of a such environments, it is of paramount importance that the crystal-
crystalline product (3). As a great improvement over the hundreds lization of the target phase should be completed before the for-
or thousands of years required for the formation of natural zeolites, mation of a dense phase as well as the complete decomposition
artificial synthesis on the order of days allows us more opportu- of OSDA.
nities to obtain zeolites with tunable properties (4, 5). Nevertheless,
the hydrothermal synthesis of zeolites has remained a time-con-
Significance
suming process. Long periods of hydrothermal treatment, for one
thing, cause a burden on both energy efficiency and operational
costs. Furthermore, pressure-tight vessels used for the hydrother- Zeolites have greatly contributed to modern industries. Con-
sumption of zeolites is expected to increase with the emergence
mal treatment as well as harsh conditions therein make mechanistic
of newly commercialized applications. Typical synthesis of zeo-
studies using in situ techniques difficult to perform (6, 7). The
lites relies on batchwise hydrothermal synthesis, which usually
complexity of crystallization, in turn, hinders the attempts at short-
takes tens of hours or even several days to complete. People have
ening the synthesis period. This dilemma explains to some extent the
thus long believed that the crystallization of zeolites is very slow
reason behind the long-held belief that crystallization of zeolites is
in nature. We herein demonstrate the continuous flow synthesis
extremely slow in nature.
of ZSM-5, an industrially important zeolite, on the order of sec-
The other major hurdle for the widespread application of zeolites
onds. Crystallization from amorphous state to full crystallinity
is the difficulty in mass production. Batchwise synthesis using au-
could be completed in tens of or even several seconds. The syn-
toclaves is convenient for basic laboratory investigations but poses thesis on the order of seconds provides a great potential to fa-
several challengesin terms of economic efficiency, quality control, cilitate the mass production as well as to deepen the fundamental
and operation flexibilitywhen large-scale manufacturing is con- understanding of zeolite crystallization.
sidered (8). In contrast, continuous flow process has proved to be
beneficial in the production of various chemicals (9, 10). Due to the Author contributions: T.W. designed research; Z.L., K. Okabe, C.A., Y. Yonezawa, and J.Z.
time-consuming hydrothermal treatment used for the synthesis of performed research; A.E., Y. Yanaba, T.Y., and K. Ohara contributed new reagents/analytic
zeolites, however, making a direct switch from batchwise synthesis tools; Z.L., H.Y., T.O., and T.W. analyzed data; and Z.L., T.O., and T.W. wrote the paper.
to continuous flow manufacturing is not easy. To realize continuous The authors declare no conflict of interest.
flow production, shortening the synthesis period is therefore an This article is a PNAS Direct Submission.
issue of the highest priority. Recently, we have developed an Freely available online through the PNAS open access option.
ultrafast route to synthesize industrially important zeolitic materials 1
To whom correspondence should be addressed. Email: wakihara@chemsys.t.u-tokyo.ac.jp.
on the order of minutes (e.g., 10 min for aluminosilicate SSZ-13), This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.
based on which the continuous flow synthesis was successfully 1073/pnas.1615872113/-/DCSupplemental.
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aluminum block and operated in batch, was also attempted. The temperature was not sustained, as seen from the NMR spectra for
results show that it took around 5 min to obtain a fully crystalline the longer synthesis periods. One possible reason for this obser-
ZSM-5 product as opposed to 6 s in the continuous flow synthesis vation is the low stability of OSDA at high temperatures, that
(Fig. S5). Measurement of the decomposition of TPAOH, the is, higher temperatures cause faster decomposition of OSDA,
OSDA used in this study, was also carried out using the aluminum resulting in a slower crystal growth rate during the later stages of
block as a heating medium (Fig. S6). The result clearly shows that crystallization. Overly high temperatures are not good for zeolite
considerable amount of oil phase (mainly comprising tripropyl- crystallization as a dense phase might be formed due to the de-
amine, one of the products of the TPAOH decomposition) was composition of OSDA. Although the formation of a dense phase
generated after a heating period of 3 min at 260 C, indicating that was not observed in this study, the results obtained from the batch
apparent decomposition took place even within a short period experiments clearly prove that adverse effects, including slower
of heating. crystallization rates, were observed at 300 C (Fig. S5) primarily
The duration of aging played an important role in determining because of the enhanced decomposition of OSDA.
the crystallization rate. Fig. 4A shows the crystallinity curves (on the Although it is considered that zeolites are susceptible to hot water
basis of XRD peaks, shown in Fig. S7) for the syntheses using the owing to the accelerated hydrolysis of silanol groups at high tem-
aluminosilicate gels with different aging periods at 90 C. Clearly, peratures (27, 28), they can withstand the hot water environment
extremely fast synthesis within 16 s could also be achieved even
when gels with an aging period as short as 2 h were used. Syn-
thesis of zeolites starts from the mixing of raw materials, which is
usually followed by an aging period, performed either at room
temperature or at an elevated temperature. During the aging
process, not only physical mixing occurs but also several impor-
tant chemical reactions toward the formation of precursors are
also triggered, leading to the formation of species that can ini-
tiate the nucleation and significantly influence the crystallization
rate as well as the properties of the resultant crystals (24). The
XRD patterns in Fig. 4B show that peaks due to aluminum
source [gibbsite Al(OH)3] rather than MFI structure are ob-
served, indicating that samples collected after aging were largely
amorphous. The 29Si MAS NMR spectra in Fig. 4C demonstrate
the formation of aluminosilicates and silicates [Q4(2Al) and Q3 spe-
cies, as represented by the broad peak centered around 101 ppm].
No long-range order could be detected, which is further con-
firmed by the results obtained from HEXTS (shown in Fig. S8).
The high-resolution transmission electron microscopy (HRTEM)
images shown in Fig. 4 DF demonstrate that long-range order
has not yet formed, as no lattice can be found. However, thermal
gravimetric analysis (TGA) results show that the weight loss for
the samples collected after certain aging periods became higher
Fig. 4. Effect of aging. (A) Crystallinity curves for the syntheses using the
compared with the one separated from the initial gel, implying a
synthesis mixture aged for different periods at 90 C (synthesis temperature,
stronger interaction between inorganic and organic species along 260 C). (B) XRD patterns of the solids collected after different aging periods
with the aging period (Fig. S9). Because the gibbsite Al(OH)3 [the circles denote the peaks due to gibbsite Al(OH)3]. (C) The 29Si MAS NMR
remained partially undissolved (Fig. 4B and Fig. S9) after aging, spectra of the solids collected after different aging periods. (DF) HRTEM
the inorganicorganic species may mainly come from the images for the samples aged for 2, 6, and 16 h, respectively.
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