Published on Web 05/19/2010

Confinement Effect and Synergistic Function of H-ZSM-5/

Cu-ZnO-Al2O3 Capsule Catalyst for One-Step Controlled
Synthesis
Guohui Yang,† Noritatsu Tsubaki,*,†,‡ Jun Shamoto,† Yoshiharu Yoneyama,† and
Yi Zhang†
Department of Applied Chemistry, School of Engineering, UniVersity of Toyama, Gofuku 3190,
Toyama 930-8555, Japan, and JST, CREST, Sanbancho 5, Chiyoda-ku, Tokyo 102-0075, Japan
Received March 5, 2010; E-mail: tsubaki@eng.u-toyama.ac.jp

Abstract: Dimethyl ether (DME) is an industrially important intermediate, as well as a promising clean fuel, but
the effective production through traditionally consecutive steps from syngas to methanol and then to DME has
been hindered by the poorly organized structure of the conventional physical mixture catalyst. Here, a novel
zeolite capsule catalyst possessing a core-shell structure (millimeter-sized core catalyst and micrometer-sized
acidic zeolite shell) was proposed initially through a well-designed aluminum migration method using the core
catalyst as the aluminum resource and for the first time was applied to accomplish the DME direct synthesis
from syngas. The selectivity of the expected DME on this zeolite capsule catalyst strikingly exceeded that of
the hybrid catalyst prepared by the traditional mixing method, while maintaining the near-zero formation of the
unexpected alkanes byproduct. The preliminary methanol synthesis reaction on the core catalyst and the following
DME formation from methanol inside the zeolite shell cooperated concertedly and promoted mutually. This
zeolite capsule catalyst with a synergetic confinement core-shell structure can be used to efficiently realize the
combination of two and more sequential reactions with many synergistic effects.

Introduction However, previous studies paid more attention to the simply

Alternative energy sources have moved into the spotlight in mechanical mixing of the two types of catalysts, improving
recent years with soaring oil prices and dwindling resources.1 catalyst lifetime, performance, or activity.8-10 The effective
In addition to utilization as an important chemical intermediate, structure combination of two active catalysts was not deeply
DME is also very promising as a new energy source, being studied until now.
available for various purposes such as an LPG alternative, a In heterogeneous catalysis, the active chemical composition
fuel for power generation, synthetic diesel, and hydrogen of a catalyst can work more efficiently only in combination with
resource for fuel cells.2-4 Traditionally, DME can be produced a well-organized structure.11-13 A catalyst having a finely
through two methods. One is methanol dehydration on a single designed structure usually exhibits better catalytic perfor-
dehydration catalyst, where the methanol is separately made mance.14 Recently, a material study on nano- or micro-sized
from syngas,5 and another is a couple of consecutive reactions particles with a special core-shell structure has attracted
for DME direct synthesis from syngas on a hybrid catalyst, tremendous interest.15 The core-shell particles have broad
where the hybrid catalyst is a simple mixture of methanol promising application in many fields, such as drug delivery,16
synthesis catalyst and methanol dehydration catalyst.6 The latter photonic devices,17 and catalytic and separation processes.18
method is more thermodynamically favorable than the former
because methanol synthesis is generally severely limited by (7) Mao, D.; Yang, W.; Xia, J.; Zhang, B.; Song, Q.; Chen, Q. J. Catal.
thermodynamics and in situ conversion of the formed methanol 2005, 230, 140–149.
(8) Lewnard, J. J.; Hsiung, T. H.; White, J. F.; Brown, D. M. Chem. Eng.
to DME can enhance the maximum syngas conversion.6,7 Sci. 1990, 45, 2735–2741.
(9) Sofianos, A. C.; Scurrell, M. S. Ind. Eng. Chem. Res. 1991, 30, 2372–
†
University of Toyama. 2378.
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JST, CREST. (10) Xia, J. C.; Mao, D. S.; Zhang, B.; Chen, Q. L.; Tang, Y. Catal. Lett.
(1) Farrell, A. E.; Plevin, R. J.; Turner, B. T.; Jones, A. D.; O’Hare, M.; 2004, 98, 235–240.
Kammen, D. M. Science 2006, 311, 506–508. (11) Ueda, W.; Oshihara, K.; Vitry, D.; Hisano, T.; Kayashima, Y. Catal.
(2) San, X.; Zhang, Y.; Shen, W.; Tsubaki, N. Energy Fuels 2009, 23, SurV. Jpn. 2002, 6, 33–44.
2843–2844. (12) Takehira, K.; Shishido, T.; Shoro, D.; Murakami, K.; Honda, M.;
(3) Cheung, P.; Bhan, A.; Sunley, G. J.; Iglesia, E. Angew. Chem., Int. Kawabata, T.; Takaki, K. Catal. Commun. 2004, 5, 209–213.
Ed. 2006, 45, 1617–1620. (13) Zhang, Y.; Liu, Y.; Yang, G. H.; Sun, S. L.; Tsubaki, N. Appl. Catal.,
(4) Faungnawakij, K.; Tanaka, Y.; Shimoda, N.; Fukunaga, T.; Ka- A 2007, 321, 79–85.
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10.1021/ja101882a  2010 American Chemical Society J. AM. CHEM. SOC. 2010, 132, 8129–8136 9 8129
ARTICLES Yang et al.

Usually, the core-shell structure is made up of two or more coprecipitation method.24 An ethanol solution of oxalic acid was
varied materials, in which the different materials (organic and/ added rapidly to a mixed ethanol solution of copper, zinc, and
or inorganic) are spatially separated in different locations, aluminum nitrates (Cu/Zn/Al in molar ratio 45/20/10) at room
promoting mutually at the same time. In our previous reports, temperature under vigorous stirring. The gel-like precipitate was
the zeolite capsule catalysts with a supported metallic core aged at room temperature for 24 h and then separated by centrifuge.
The drying process was conducted at 393 K for 6 h followed by
catalyst and a zeolite shell exhibited excellent properties for calcination in air at 643 K for 1 h. Before the following utilization,
isoparaffin direct synthesis that are significantly different from the raw CZA catalyst was granulated into a new grain with the
their physical mixture analogy, which makes them better than size of 0.85-1.70 mm.
the conventional hybrid catalyst usually used for the consecutive Zeolite Capsule Catalysts Preparation. In this report, two
reactions.19,20 However, it is difficult to prepare the defect-free different zeolite membrane hydrothermal synthesis methods were
H-type zeolite shell on the pure metallic catalyst, coprecipitated adopted to directly construct two types of H-type ZSM-5 zeolite
catalyst, or alloy catalyst without sodium hydroxide in the shell onto the CZA catalysts. One was the traditional acidic
precursor synthesis solution, protecting the core catalyst from H-ZSM-5 zeolite membrane synthesis method with the aluminum
damage by hydrothermal treatment at the same time. Especially, resource in the precursor solution. Another was the close-to-neutral
the coprecipitated catalyst used here as the core generally has Silicalite-1 zeolite membrane preparation method without an
aluminum resource in the synthesis solution; here, the core CZA
mechanical and chemical strength much weaker than that of a catalyst acted as the support and Al resource for H-ZSM-5 zeolite
supported catalyst and can very easily be decomposed or membrane growth simultaneously.
dissolved in the hydrothermal synthesis process of zeolite In preparation, the structure directed reagent TPAOH (tetrapro-
membrane. pylammonium hydroxide, 10% in water), silica resource TEOS
Herein, we report a millimeter-sized zeolite capsule catalyst (teraethyl orthosilicate, 95%), and aluminum resource (aluminum
possessing a special core-shell structure (a tricomponent core nitrate, 99.9%) were the Wako Co. products. Dehydrated ethanol
catalyst enwrapped by one layer of H-ZSM-5 zeolite shell) with (99.5%) and nitric acid (69%) were both purchased from Kanto
a coprecipitated catalyst as core. Different from the traditional Chemical Co. The first H-ZSM-5 zeolite shell was prepared on the
zeolite membrane preparation methods, such as in situ or seeding CZA core catalyst using a traditional acidic H-ZSM-5 zeolite
method using the aluminum-containing precursor solution for synthesis recipe of 0.48 TPAOH:2 TEOS:8 EtOH:120 H2O:
zeolite layer growth on various supports,21-23 here an acidic 0.025Al2O3. The second H-ZSM-5 zeolite shell was prepared by
H-ZSM-5 zeolite shell was directly prepared successfully the close-to-neutral Silicalite-1 zeolite synthesis recipe of 0.48
TPAOH:2 TEOS:8 EtOH:120 H2O:0.24 HNO3. All reagents were
through an unreported way of aluminum migration from the mixed in a Teflon container with vigorous stirring at room
core catalyst body. The aluminum-containing core catalyst acted temperature for 6 h. Then the CZA pellets (0.85-1.70 mm) were
as the substrate for zeolite membrane growth and at the same added into the precursor solutions, and the Teflon container was
time as the sole aluminum resource to construct the zeolite placed into the stainless steel autoclave for hydrothermal synthesis.
framework in the total synthesis process, resulting in the defect- Zeolite shell synthesis was performed in a rotation oven with the
free covering and tightly enwrapping of the zeolite shell on its rotation rate of 2 rpm at 453 K for 72 h. Here, the rotation synthesis
surface. For the first time, this zeolite capsule catalyst was effectively prevented the cementation of catalyst pellets during the
applied to accomplish a successive reaction, DME direct hydrothermal synthesis process, improving the integrity of the
synthesis from syngas. The selectivity of the expected DME zeolite shell simultaneously. Without the rotation, for example, using
on this zeolite capsule catalyst strikingly exceeded that of the a static autoclave instead, it was difficult to enwrap all core catalyst
surfaces completely. The final samples were separated from the
traditional hybrid catalyst (the simple blending of core catalyst mother liquid and then were calcined at 773 K in air for 5 h,
and zeolite powder), while maintaining zero formation of the removing the organic template stored in the zeolite pores. The
unexpected alkane byproducts. The encouraging results proved zeolite capsule catalyst obtained by this process using different
that this novel method for the preparation of H-type zeolite shell synthesis methods were named as CZA-Z and CZA-S respectively,
on aluminum-containing metallic catalyst was feasible and very where the “Z” stands for the preparation using the H-ZSM-5 zeolite
reliable, effectively protecting the vulnerable metallic core synthesis recipe and “S” means the synthesis utilizing the Silicalite-1
catalyst from damage by the hydrothermal synthesis process zeolite synthesis recipe. It is noted that no aluminum resource was
and realizing the controlled synthesis of the target product on adopted for CZA-S preparation. Moreover, it is very important that
a single catalyst. The zeolite capsule catalyst preparation method commonly used reagent containing NaOH, KOH, Cl-, or Br- cannot
reported here together with its application in DME controlled be used here for zeolite shell synthesis, as they will deactivate the
Cu/ZnO/Al2O3 core catalyst severely. For the same reason, Na-
synthesis from syngas have the potential to inspire not only the type or NH3-type zeolite membrane is not permitted for our zeolite
zeolite membrane synthesis but also heterogeneous catalysis. capsule catalyst as ion-exchange to H-type zeolite will deactivate
Experimental Section core catalyst. We must synthesize H-type capsule catalyst in one
step.
Core Catalyst Preparation. The core catalyst, tricomponent Cu/ Hybrid Catalyst Preparation. Self-made H-ZSM-5 (Si/Al )
ZnO/Al2O3 (CZA), was prepared by the conventional oxalate 163, atomic ratio) zeolite powder was used for the preparation of
the physically mixed catalyst. This zeolite powder was physically
(18) Ren, N.; Yang, Y. H.; Shen, J.; Zhang, Y. H.; Xu, H. L.; Gao, Z.; well mixed with the CZA catalyst with a weight ratio of 1:10 and
Tang, Y. J. Catal. 2007, 251, 182–188. then granulated to 0.85-1.70 mm at 60 MPa pressure. This catalyst
(19) Yang, G. H.; He, J. J.; Yoneyama, Y.; Tan, Y. S.; Han, Y. Z.; Tsubaki, was named as CZA-M, where the “Z” means H-ZSM-5 zeolite and
N. Appl. Catal., A 2007, 329, 99–105. “M” means the mechanical mixture of H-ZSM-5 with CZA.
(20) Bao, J.; He, J.; Zhang, Y.; Yoneyama, Y.; Tsubaki, N. Angew. Chem.,
Int. Ed. 2008, 47, 353–356.
Catalysts Characterization. X-ray diffraction (XRD) patterns
(21) Lai, R.; Yan, Y.; Gavalas, G. R. Microporous Mesoporous Mater. were collected using a Rigaku RINT 2400 X-ray powder diffrac-
2000, 37, 9–19. tometer equipped with a Cu KR radiation source at 40 KV and 40
(22) Yan, Y.; Davis, M. E.; Gavalas, G. R. Ind. Eng. Chem. Res. 1995,
34, 1652–1661.
(23) Yang, G.; Zhang, X.; Liu, S.; Yeung, K. L.; Wang, J. J. Phys. Chem. (24) Sun, Q.; Zhang, Y.-L.; Chen, H.-Y.; Deng, J.-F.; Wu, D.; Chen, S.-
Solids 2007, 68, 26–31. Y. J. Catal. 1997, 167, 92–105.
8130 J. AM. CHEM. SOC. 9 VOL. 132, NO. 23, 2010
H-ZSM-5/Cu-ZnO-Al2O3 Capsule Catalyst ARTICLES

was adopted to directly coat a H-ZSM-5, not Na-ZSM-5, shell

onto the CZA core catalyst surface. The obtained catalyst,
denoted as CZA-Z, was separated from the mother liquid,
washed, and calcined, removing the template settled in the
zeolite pores. The XRD pattern of this CZA-Z zeolite capsule
catalyst in Figure 1 identified the classic X-ray diffraction peaks
of H-ZSM-5 zeolite in the ranges of 2θ ) 5-10 and 21-25,
indicating that H-ZSM-5 zeolite had crystallized on the CZA
core catalyst successfully.25
The surface SEM image and EDS analysis of CZA-Z in
Figure 3a and b gives the surface morphology and elemental
composition of zeolite shell. After this zeolite shell preparation,
the surface of CZA core catalyst had been homogeneously
covered by one layer of randomly oriented H-ZSM-5 zeolite
crystals. The average size of zeolite crystals of the zeolite shell
was about 1 µm. The surface EDS analysis result in Figure 3b
presented that the Si/Al ratio of zeolite shell was about 32. The
signals of Cu and Zn on the zeolite shell surface were zero,
Figure 1. XRD patterns of CZA, CZA-Z, CZA-S, CZA-M, and pure which proved that this H-ZSM-5 zeolite shell was compact and
H-ZSM-5 zeolite. integrated, indicating that this zeolite shell preparation method
was successful. Figure 3c and d shows the cross-section SEM
mA. A JEOL JSM-6360LV scanning electron microscope (SEM) image and EDS line analysis results of CZA-Z zeolite capsule
and JED-2300 energy dispersive spectroscopy (EDS) were used catalyst, respectively. A well-intergrown zeolite shell had
for SEM imaging and EDS analyzing on the catalyst surface and enwrapped the CZA core catalyst perfectly. The related EDS
cross-section.
line analysis along the white line in the SEM image exhibited
Reaction and Analysis of Products. Before the reaction, the
catalyst was first reduced in situ at 493 K by a 5% H2 in nitrogen the change of element signals from the zeolite shell to the
flow (60 mL/min) for 10 h. Reactions were carried out in a down catalyst core part. The Si KR signal increased in the zeolite
flow fixed-bed stainless steel reactor. The reaction conditions were shell and then deceased sharply at the interface between zeolite
523 K, 5.0 MPa, WCZA catalyst/Fsyngas ) 10 g · h/mol, and syngas (H2 shell and core catalyst, indicating the change from zeolite shell
59.22%, CO 32.60%, CO2 5.16%, Ar 3.02%). The effluent products to core catalyst, as well as identifying that the thickness of
from the heated line were first analyzed by an online gas zeolite shell was about 3.9 µm. The Al KR signal kept a stable
chromatograph (Shimadzu, TCD, GC-8A) for CO and CO2, and level in both the zeolite shell and the core catalyst. For Cu KR
then the tail gases were analyzed online using another gas and Zn KR, they were close to zero in the zeolite shell, which
chromatograph (Shimadzu, FID, GC-8A) for other products. All suggested that there was no obvious weight loss for the active
analysis lines and valves were heated to prevent possible condensa-
species of core catalyst during this hydrothermal synthesis
tion of the products before entering the gas chromatograph, ensuring
reliable materials balance. process.
For the second type of zeolite shell preparation, the traditional
Results and Discussion Silicalite-1 zeolite synthesis method was utilized to construct
Capsule Catalysts Preparation and Characterization. The zeolite shell on CZA core catalyst. No aluminum in the precursor
tricomponent catalyst Cu/Zn/Al2O3 (CZA) made by the copre- synthesis solution was the specific feature of this preparation
cipitation method is a conventional catalyst usually used for process. The Al used to construct the framework of H-ZSM-5
methanol synthesis. In this report, it was selected as the core zeolite shell here would be extracted from the CZA core catalyst
catalyst for preparation of the zeolite capsule catalysts. The bare during the hydrothermal synthesis process, as designed. The
CZA catalyst without hydrothermal treatment had a pellet size obtained zeolite capsule catalyst by this preparation method was
of 0.85-1.70 mm. For its X-ray diffraction (XRD) analysis, named as CZA-S, where the “S” means this Silicalite-1 zeolite
no crystalline peaks of H-ZSM-5 zeolite were observed, as synthesis method. The XRD pattern of CZA-S zeolite capsule
shown in Figure 1. The surface scanning electron microscope catalyst is presented in Figure 1. This sample exhibited the MFI
(SEM) and energy dispersive spectroscopy (EDS) analysis structure with major peaks located at 2θ ) 7.9, 8.9 and the
results in Figure 2 indicated that this CZA catalyst had the molar characteristic triplet at 2θ ) 23.5, confirming the formation of
composition of Cu/Zn/Al ) 61.90:24.50:13.60. It was very zeolite with MFI structure on the CZA core catalyst. In addition,
similar to its original bulk ratio in this catalyst preparation recipe. some comparable peaks of CZA-S catalyst to that of the bare
The hybrid catalyst named as CZA-M was prepared by mixing CZA catalyst were observed in the range of 2θ ) 30-40,
CZA catalyst with pure H-ZSM-5 (Si/Al ) 163) zeolite powder. indicating that the CZA core catalyst was still stable after this
The XRD peaks assigned to CZA or H-ZSM-5 zeolite can be hydrothermal synthesis treatment.
distinguished by comparing the XRD patterns of CZA-M with Zeolite shell surface morphology and elemental composition
pure H-ZSM-5 zeolite or bare CZA core catalyst independently of CZA-S zeolite capsule catalyst are shown in Figure 4a and
in Figure 1. 4b, respectively. The average size of zeolite crystal constructed
In this report, two different methods for zeolite membrane this zeolite shell was much larger than that of CZA-Z zeolite
preparation were adopted to construct two types of H-ZSM-5 capsule catalyst as above, probably because of the special zeolite
zeolite shell directly on the millimeter-sized CZA core catalyst. synthesis solution for CZA-S preparation without aluminum
For the first type of zeolite shell preparation, the traditional
acidic H-ZSM-5 zeolite synthesis method using the aluminum- (25) Olson, D. H.; Kokotailo, G. T.; Lawton, S. L.; Meier, W. M. J. Phys.
containing precursor solution, but without sodium hydroxide, Chem. 1981, 85, 2238–2243.
J. AM. CHEM. SOC. 9 VOL. 132, NO. 23, 2010 8131
ARTICLES Yang et al.

Figure 2. (a) Surface SEM image and (b) EDS analysis of the bare CZA core catalyst.

Figure 3. (a) Surface SEM image and (b) surface EDS analysis; (c) cross-section SEM image and (d) EDS line analysis of the zeolite capsule catalyst
CZA-Z.

resource, in conjunction with the lower pH value.26,27 In the XRD pattern of CZA-S in Figure 1, confirmed that the
addition, there were no pinholes and cracks on the zeolite shell, zeolite shell of the CZA-S catalyst had the MFI zeolite structure
which indicated that this hydrothermal synthesis process was and belonged to a H-ZSM-5 zeolite membrane. The surface Si/
successful. Surface EDS analysis on the zeolite shell gave zero Al ratio of this zeolite shell was 221, as listed in Table 1, much
signals of Zn and Cu, suggesting that this zeolite shell was higher than that of the conventional H-ZSM-5 zeolite powder
compact and well integrated as well. The most interesting finding usually used for DME direct synthesis from syngas. However,
was the Al content in the zeolite shell. Actually, it was not zero the total acid amount of this zeolite capsule catalyst was similar
despite the close-to-neutral Silicate-1 zeolite synthesis method to that of hybrid catalyst CZA-M (see Figure S1, Table S1 in
for zeolite shell preparation. Nonzero Al signal, together with Supporting Information). These should be attributed to the
aluminum-containing CZA core catalyst used here. It acted
(26) Persson, A. E.; Schoeman, B. J.; Sterte, J.; Otterstedt, J. E. Zeolites as the substrate and aluminum resource simultaneously for
1994, 14, 557–567.
(27) Persson, A. E.; Schoeman, B. J.; Sterte, J.; Otterstedt, J. E. Zeolites zeolite shell growth, which could lead to a concentration
1995, 15, 611–619. gradient of Al in the zeolite shell.22 The cross-section SEM
8132 J. AM. CHEM. SOC. 9 VOL. 132, NO. 23, 2010
H-ZSM-5/Cu-ZnO-Al2O3 Capsule Catalyst ARTICLES

Figure 4. (a) Surface SEM image and (b) surface EDS analysis; (c) cross-section SEM image and (d) EDS line analysis of the zeolite capsule catalyst
CZA-S.

Table 1. Catalyst Properties and Catalytic Performance in STD also form H-ZSM-5 zeolite shell with lower aluminum
Reactiona content on aluminum-containing supports.
selectivity (%) Both of the zeolite shell preparation methods, acidic zeolite
zeolite CO conversion synthesis and close-to-neutral zeolite synthesis, can realize the
b
catalyst Si/Al (%) (%) MeOH DME others
formation of a complete, well-intergrown acidic zeolite shell
CZA 44.02 98.38 0.50 1.12
CZA-Zc 32 7.60 5.59 3.41 96.59 0.00
on the CZA core catalyst. Here, the realization of core catalyst
CZA-Sd 221 9.63 30.40 21.43 78.57 0.00 enwrapped tightly by one layer of zeolite shell should be
CZA-Me 163 10.0 58.07 57.29 40.51 2.20 attributed to the aluminum-containing CZA core catalyst. The
aluminum migrated from the aluminum supports and was
a
Reaction conditions: 523 K, 5.0 MPa, WCZA/Fsyngas ) 10 g · h · mol-1. incorporated into the MFI zeolite framework.22,28 At the same
Syngas: H2/CO/CO2/Ar ) 59.22/32.60/5.16/3.02. b Si/Al ratio of zeolite
shell or zeolite powder. c “Z” means the H-ZSM-5 synthesis method.
time, a transition layer of zeolite crystals with aluminum-
d
“S” stands for the Silicalite-1 synthesis method. e “M” means the containing supports could be formed at the interface area
physical mixing of CZA with H-ZSM-5 zeolite powder. between the zeolite shell and CZA core catalyst. These factors
ensured the integrity of zeolite capsule catalyst even if undergo-
image and EDS line analysis of CZA-S zeolite capsule ing calcination and the following catalysis reaction. In addition,
catalyst are shown in Figure 4c and 4d, respectively. In the the zeolite shells prepared by two different methods had different
SEM image, the zeolite shell could be distinguished easily structural properties, not only in regard to the element composi-
and was also in a good state, enwrapping the CZA core tion but also the shell thickness, as well as zeolite loading
catalyst. The signal intensity of Si KR, Cu KR, and Zn KR amount and acidic sites distribution shown in NH3-TPD curves
in the EDS line analysis result gave a change similar to that (Supporting Information). Therefore, only by an ordinary
of CZA-Z zeolite capsule catalyst along the direction from method, with/without the initial aluminum resource in precursor
the zeolite shell to the core catalyst, but the thickness of the solution, the physical and chemical properties of zeolite capsule
zeolite shell was 5 µm here. It is noteworthy that the Al KR catalyst could be dominated well.
signal in the zeolite shell also was not zero, even if the Capsule Catalysts Activity. The direct conversion from syngas
synthesis solution for the CZA-S preparation did not contain to dimethyl ether (STD reaction) was the application of zeolite
any aluminum resource. For the aluminum constructing the capsule catalysts CZA-Z and CZA-S. The bare CZA catalyst
final H-ZSM-5 zeolite shell, it must come from the core and hybrid catalyst CZA-M were also performed under the same
catalyst, the sole aluminum resource in this total hydrothermal
synthesis process. Accordingly, it can be concluded that the (28) Beving, D. E.; McDonnell, A. M. P.; Yang, W.; Yan, Y. J.
hydrothermal synthesis solution without Al resources could Electrochem. Soc. 2006, 153, B325–B329.
J. AM. CHEM. SOC. 9 VOL. 132, NO. 23, 2010 8133
ARTICLES Yang et al.

Figure 5. Products distribution of the CZA catalyst, zeolite capsule catalyst CZA-Z and CZA-S, and the hybrid catalyst CZA-M.

reaction conditions as references. The catalyst activity is considered. In the hydrothermal process, part of the synthesis
summarized in Table 1. The hybrid catalyst CZA-M consisted solution entered the core catalyst pores and then crystallized
of two types of catalysts, CZA and zeolite catalyst, for different into zeolite over some active sites of core catalyst, and the ease
reactions, respectively. In the STD reaction on this hybrid of Cu species reduction can essentially control the catalyst
catalyst, the formed methanol on the CZA catalyst was randomly activity.29 However, increasing metal content of the core catalyst
converted to DME on the zeolite catalyst via its dehydration or extending contact time of the reactant with zeolite capsule
reaction, which broke the thermodynamic equilibrium of the catalyst can enhance CO conversion very easily.
reaction from syngas to methanol on CZA catalyst, enhancing Reaction Products Distribution. Table 1 also gives the product
the CO conversion from 44.02% (on single CZA catalyst) to selectivity on the bare CZA catalyst, hybrid catalyst CZA-M,
58.07%. It is well-known that the reaction combination of and zeolite capsule catalysts CZA-Z and CZA-S. The corre-
methanol synthesis with its in situ dehydration to DME is sponding products distribution patterns are compared in Figure
thermodynamically more favorable than either occurring solely.6 5. For CZA catalyst, the highest methanol selectivity of 98.38%
The results obtained on this hybrid catalyst CZA-M also proved was obtained, and DME was only a tiny product with a
it. selectivity of 0.50%. Light hydrocarbons, such as methane and
For the CZA-Z zeolite capsule catalyst, its CO conversion C2+, could be found in the final products. In the case of CZA-
was 5.59%, much lower than that of the bare CZA catalyst. M, the selectivity of DME reached 40.51% along with a sharp
The CZA-Z zeolite capsule catalyst was prepared by the acidic decrease of methanol selectivity compared with the single CZA
zeolite synthesis solution with aluminum resource. Possibly, the catalyst. However, there was only random contact between
lower catalytic activity should be attributed to some damage methanol and the active sites of zeolite catalyst in the hybrid
on the core CZA catalyst during the hydrothermal synthesis catalyst CZA-M during STD reaction, which was decided by
process, such as dissolution of Cu or Zn, by the formation of a hybrid catalyst structure (simply mechanical blend of CZA with
coordinated compound between TPAOH and Cu or Zn, or zeolite catalyst). As a result, only a fairly ordinary selectivity
weakening interaction between Cu and Zn by TPAOH when for DME was obtained, accompanyied by the existence of
the aluminum resource existed in the precursor solution, which unexpected alkanes in the final products.
led to the change of composition and structure of the core CZA Different from the physically mixed catalyst, zeolite capsule
catalyst. However, as a new method to overcome the problem catalysts had a special core-shell structure in which the zeolite
of CZA-Z synthesis, the CZA-S zeolite capsule catalyst prepared shell enwrapped the core catalyst perfectly, which offered an
by a close-to-neutral Silicalite-1 zeolite synthesis method, where inevitable way, passing through the zeolite shell, for methanol
HNO3 was added to lower the pH value of TPAOH-containing to escape from the zeolite capsule catalyst. Here, all of the
synthesis solution, without aluminum resource, stopping forma- methanol must contact the H-ZSM-5 zeolite shell. Capsule
tion of coordinated compounds, exhibited remarkably enhanced catalyst CZA-Z was prepared by the acidic H-ZSM-5 zeolite
catalytic activity compared with the CZA-Z zeolite capsule synthesis method. Its zeolite shell had higher acidic intensity
catalyst, as shown in Table 1. The CO conversion of CZA-S but slightly lower zeolite loading amount compared with another
reached 30.40%, which indicated that the close-to-neutral zeolite capsule catalyst CZA-S. In the STD reaction on CZA-Z
Silicalite-1 zeolite synthesis method could effectively reduce catalyst, the DME selectivity reached 96.59% together with zero
the damage from synthesis solution to core catalyst. alkanes byproduct, probably benefiting from the high acidic
In addition, for the lower catalytic activity of zeolite capsule intensity and thinner zeolite shell thickness of capsule catalyst.
catalysts compared with bare CZA catalyst and hybrid catalyst
CZA-M, another factor that some active sites of the core catalyst (29) Prasad, P. S. S.; Bae, J. W.; Kang, S. H.; Lee, Y. J.; Jun, K. W. Fuel
were partially covered by zeolite crystals should also be Process. Technol. 2008, 89, 1281–1286.
8134 J. AM. CHEM. SOC. 9 VOL. 132, NO. 23, 2010
H-ZSM-5/Cu-ZnO-Al2O3 Capsule Catalyst ARTICLES

The strongly acidic sites ensured that almost all methanol formed Scheme 1. (a) Schematic Diagram Showing DME Direct Synthesis
on the core catalyst could be converted into DME, while the from Syngas on a Single Zeolite Capsule Catalyst, (b) Schematic
Diagram of the Bare Catalyst with Zeolite Layer Loading in
thinner zeolite shell thickness offered a short residence time Reactor in the Form of a Dual Layer, and (c) Zeolite Capsule
for DME within the zeolite shell, inhibiting the formation of Catalysts in Reactor
alkanes by DME further dehydration. Another zeolite capsule
catalyst CZA-S was prepared using a close-to-neutral zeolite
synthesis method that exerted less damage to core catalyst, and
the CZA core catalyst acted in situ as the aluminum resource
during hydrothermal synthesis process. The zeolite shell of
CZA-S had a lower zeolite loading amount and similar acid
amount compared with the physically mixed catalyst CZA-M
(Supporting Information) but higher weight increment and
greater thickness (5 µm) than zeolite capsule catalyst CZA-Z.
In the STD reaction on the CZA-S zeolite capsule catalyst, there
was still zero selectivity for the alkane byproducts as shown in
Table 1, but the DME selectivity reached 78.57%, nearly twice
that of the hybrid catalyst CZA-M even if the latter was prepared
using the H-ZSM-5 zeolite with similar acid amount and larger
weight proportion. Also, it was only slightly lower than that of
the CZA-Z zeolite capsule catalyst, possibly due to the low
acidic intensity and smaller acid amount together with the
insufficient distance offered by the zeolite shell for methanol
dehydration, leading to the partial conversion of the methanol
to DME. It is referred that increasing the acidic sites intensity,
density, and thickness of the zeolite shell of CZA-S, which will
be easily realized only by controlling the hydrothermal synthesis
conditions or recipe, can further reduce the selectivity of
methanol, thereby enhancing the selectivity of DME.

Discussion
The STD reactions on the zeolite capsule catalyst CZA-Z
and CZA-S exhibited a completely different product distribution viewpoint of energy efficiency, it should be mentioned that the
compared with that on the bare CZA and hybrid CZA-M reaction heat from the exothermic methanol synthesis on the
catalyst, realizing an exclusive DME selectivity, very low core catalyst could be in situ recycled inside the zeolite capsule
methanol selectivity, and zero byproduct formation simulta- by the DME synthesis from methanol on the zeolite shell to
neously, as shown in Figure 5. The outstanding capability of protect the catalyst lifetime from overheating.
the capsule catalyst should be attributed to its specific core-shell It should also be noted that this capsule method, with a zeolite
structure. For hybrid catalyst CZA-M, there was no spatially shell enwrapping the millimeter-sized core catalyst, provided a
confined effect between the methanol synthesis reaction and new method to avoid the difficulty of large-area membrane
methanol dehydration reaction, demonstrating that these two preparation due to the easy formation of pinholes or cracks.
consecutive reactions occurred independently and randomly. As Especially, the ratio of membrane surface area to catalyst bed
a result, a part of the methanol formed on the methanol synthesis volume of the zeolite capsule catalyst was extremely high
catalyst could escape from the catalyst bed directly without compared to that of a dual-layer method or other membrane
undergoing dehydration on zeolite catalyst. In addition, the reactor configurations, providing excellent catalysis and separa-
random nature of the process also demonstrated that some DME tion since each core catalyst is enwrapped by the zeolite shell,
may get more opportunities to be further dehydrated on the as illustrated in Scheme 1b and c.
zeolite catalyst or transformed to alkanes or alkenes. However,
Conclusions
the zeolite capsule catalysts with the core-shell structure might
control the occurrence of the two reactions in a consecutive Two direct preparation methods were demonstrated to
order. As illustrated in Scheme 1a, the feed gas first passed fabricate two types of H-ZSM-5 zeolite capsule catalyst with a
through the zeolite shell to enter the core catalyst, where the tailor-made millimeter-sized catalyst core and microsized zeolite
methanol was produced on the core catalyst. Then the methanol shell. One method was the traditional acidic H-ZSM-5 zeolite
formed in the core catalyst must go through the zeolite shell to synthesis, and another was a close-to-neutral Silicate-1 zeolite
escape, which ensured that all of the methanol had enough synthesis using the core catalyst as the aluminum provider. The
opportunities to contact the active sites of the H-type zeolite latter method explored a facile, reliable synthetic method for
shell, to be converted into the expected products. As a result, acidic zeolite membrane growth on an aluminum-containing
the selectivity for DME was increased sharply. Moreover, the support and effectively reduced the damage from zeolite
zeolite shell had a fixed position, uniform thickness, and precursor solution to substrates during the hydrothermal syn-
homogeneous property, which made it an equal opportunity thesis process. In the consecutive reactions of DME direct
provider to each methanol molecular that diffused from the core synthesis from syngas, zeolite capsule catalysts exhibited an
catalyst, improving the conversion from methanol to DME extreme selectivity for DME compared with the conventional
concertedly, while suppressing its further dehydration to generate hybrid catalyst, suppressing the further dehydration of DME to
the alkane or alkene byproducts simultaneously. From the form alkane/alkene byproducts. This concept of a zeolite capsule
J. AM. CHEM. SOC. 9 VOL. 132, NO. 23, 2010 8135
ARTICLES Yang et al.

catalyst with the effect of an equilibrium shift, shape selectivity, on Priority Areas “Chemistry of Concerto Catalysis” from Ministry
and synergetic confinement is therefore promising to be widely of Education, Culture, Sports, Science and Technology, Japan.
used for many consecutive reactions such as multiple-step
organic synthesis. In addition, it is clear that the original Supporting Information Available: Further characterization
preparation method of the acidic H-ZSM-5 zeolite shell using and detailed discussion on the concentration and strength of
a close-to-neutral Silicalite-1 zeolite synthesis method on an acid sites of bare CZA catalysts, zeolite capsule catalyst CZA-
aluminum-containing substrate can give a novel inspiration to S, CZA-Z, and hybrid catalyst CZA-M by the temperature
the science of zeolite membranes. programmed desorption of ammonia (NH3-TPD). This material
is available free of charge via the Internet at http://pubs.acs.org.
Acknowledgment. This work was supported by Nippon Oil
Corporation and in part by a Grant-in-Aid for Scientific Research JA101882A

8136 J. AM. CHEM. SOC. 9 VOL. 132, NO. 23, 2010