3100 Chem. Mater., Vol. 22, No. 10, 2010
Zhang et al.
Table 1. Syntheses of the Aluminosilicate ZSM-34 Products under Various Conditions
SiO2/Na2O SiO2/Al2O3 L seeds solution (mL) cryst. temp. (°C) cryst. time (days)
runa
products
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
2.76
2.76
2.76
2.76
2.76
2.76
2.76
5.52
3.68
2.94
2.47
2.21
1.84
2.76
2.76
2.76
2.76
2.76
2.76
2.76
2.76
2.76
2.76
47
47
47
47
47
47
47
47
47
47
47
47
47
47
47
47
47
47
47
94
31
47
47
0
120
120
120
120
120
120
120
120
120
120
120
120
120
80
100
110
130
140
160
120
120
120
120
7
7
7
7
7
7
7
14
14
9
7
7
7
14
14
7
5
5
Amorb
0.88
1.31
1.75
2.19
2.63
3.0
Amor þ ZSM-34
ZSM-34 þ Amor
ZSM-34 (SiO2/Al2O3 = 8.0) (I2/I1 = 0.028)c
ZSM-34 þ L
ZSM-34þL
ZSM-34 þ L
1.75
1.75
1.75
1.75
1.75
1.75
1.75
1.75
1.75
1.75
1.75
1.75
1.75
1.75
Amor
Amor
1.9
1.10
1.11
1.12
1.13
1.14
1.15
1.16
1.17
1.18
1.19
1.20
1.21
1.22
1.23
ZSM-34 þ MOR
ZSM-34 þ PHI
ZSM-34 þ PHI
PHI
Amor
ZSM-34 þAmor
ZSM-34 (I2/I1 = 0.063)
ZSM-34 þ PHI
ZSM-34 þ PHI
Orthoclase
ZSM-34 (SiO2/Al2O3 = 9.2) (I2/I1 = 0.032)
ZSM-34 (SiO2/Al2O3 = 6.6) (I2/I1 = 0.036)
Amor þ ZSM-34
ZSM-34 þ CHA þ PHI
5
5
9
7
1.75d
e
7
a Synthetic conditions for Run 1.1-1.7 (47SiO2:1Al2O3:17Na2O:1457H2O, 120 °C, 0-3.0 mL of zeolite L seeds solution), Run 1.8-1.13
(47SiO2:1Al2O3:8.5-25.5Na2O:1457H2O, 120 °C, 1.75 mL of zeolite L seeds solution), Run 1.14-1.19 (47SiO2:1Al2O3:17Na2O:1457H2O, 80-
160 °C, 1.75 mL of zeolite L seeds solution), Run 1.20-1.21 (47SiO2:0.5-1.5Al2O3:17Na2O:1457H2O, 120 °C, 1.75 mL of zeolite L seeds solution), Run
1.22 (47SiO2:1Al2O3:17Na2O:1457H2O, 120 °C, 1.75 mL of unaged “zeolite L seeds solution”), and Run 1.23 (47SiO2:1Al2O3:17Na2O:1457H2O, 120 °C
in the presence of KOH). b Amor: amorphous product, the phase appearing first is the major phase. c The ratio (I2/I1) of XRD peak intensity at 7.7° (I1)
and 9.6° (I2). d Unaged zeolite L seeds solution. e The use of KOH solution.
and the first example was the successful synthesis of
ZSM-5 zeolite a long time ago.20-22 Recently, several
aluminosilicate zeolites such as ECR-1, Beta, and RTH
have been successfully synthesized in the absence of
organic templates.23-25
Additionally, it has been reported that heteroatom-
substituted zeolites strongly influence their catalytic
properties.26-28 For example, the presence of frame-
work Ga in ZSM-5 zeolite is favorable for catalytic
aromatization of propane;26 ZSM-5 zeolite containing
framework Fe is catalytically active for benzene hydroxy-
lation with nitrous oxide;27 ZSM-5 containing frame-
work B is a very active and selective catalyst for the vapor-
phase Beckmann rearrangement of cyclohexanone oxime
to ε-caprolactam;28 the isomorphous substitution of
heteroatoms including Ga, Fe, and B in the framework
of CHA zeolite can effectively improve the selectivities for
olefins and catalyst life in methanol-to-olefin (MTO).29,30
Notably, the synthesis of heteroatom-substituted zeolites
usually requires the use of organic templates in the
starting gels.31-33
Aluminosilicate zeolite ZSM-34 is an intergrowth of
offretite (OFF) and erionite (ERI) zeolites containing
zeolitic building units of cancrinite (CAN) cages,34,35
and its pore size (5.2 A) is smaller than that of ZSM-5
(5.6 A). This feature has attracted much attention in the
expectation of selective catalysis for conversion from
methanol to ethylene and propylene, which are important
chemicals for the polymer industry.36-38 ZSM-34 zeolite
is originally synthesized in the presence of organic templates
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