A R T I C L E S
Lee et al.
1
6
including ITQ-13 or IM-7 (ITH), ITQ-22 (IWW), ITQ-24
coal. Their catalytic results are compared to those obtained
from H-SAPO-34 (CHA), H-SAPO-17 (ERI), and H-SSZ-13
(CHA) which are the best and the most widely studied catalysts
for this reaction, the silicoaluminophosphate counterpart of
H-UZM-12, and the aluminosilicate one of H-SAPO-34,
(
IWR), IM-10 (UOZ), and ITQ-33 when combined with the
-
8
structure-directing effects of F and/or Ge. Among those
organic SDAs studied thus far, however, of the greatest success
story may be the (C
+
+
5 2 n 5
H11)N (CH ) N (C H11) ions with n )
4
,16
4
-6, composed of two 1-methylpyrrolidinium groups connected
respectively.
We also use gas chromatography-mass spec-
by tetra-, penta-, and hexamethylene chains, which yield novel
medium-pore materials TNU-9 (TUN), IM-5 (IMF), and SSZ-
7
zeolite syntheses using such flexible, linear diquaternary alky-
lammonium ions as organic SDAs has shown that the phase
selectivity of the crystallization can be altered according not
only to the oxide composition of synthesis mixtures, but also
to the length of the central polymethylene chain of the
diquaternary ammonium ion employed and the size of its
troscopy (GC-MS) to identify the hydrocarbon species formed
on these zeolitic materials during MTO.
9
-11
4 (-SVR), respectively.
In fact, a series of our studies on
Experimental Section
Organic SDA Synthesis. Six series of diquaternary alkylam-
monium ions characterized by different types of the end groups
containing the charged nitrogen, i.e., N,N,N,N′,N′,N′-hexamethy-
+
+
3 3 2 n 3 3 6
lalkanediammonium ((CH ) N (CH ) N CH ) , Me -diquat-n with
n ) 3-8), N,N,N′,N′-tetramethyl-N,N′-diethylalkanediammonium
+
+
6
,9,12-15
((CH
-8),
(C
3
)
2
(C
2
H
5
)N (CH
2 n 2 5 3 2 4 2
) N (C H )(CH ) , Me Et -diquat-n with n )
aliphatic or cyclic moieties.
3
(
N,N,N′,N′-tetraethyl-N,N′-dimethylalkanediammonium
+
+
The purpose of the present study is to investigate the effects
of both inorganic and organic synthetic parameters on the
crystallization of UZM-12 using a CDM approach. Here we
have tested the ability of a large number of diquaternary
alkylammonium ions with different central chain lengths and
end group sizes as organic crystallization SDAs in UZM-12
synthesis, with TEA and K ions present as a CDM SDA and
an inorganic crystallization SDA, respectively. We have also
attempted to crystallize this small-pore zeolite in the presence
of various alkali metal cations other than K in combination
with TEA and one of diquaternary ammonium ions prepared
here. The UZM-12 zeolites crystallized are characterized by
using powder X-ray diffraction, computer modeling studies,
elemental and thermal analyses, scanning electron microscopy,
2
5
H )
2
(CH
3 2 n 3 2 5 2 4 2
)N (CH ) N (CH )(C H ) , Et Me -diquat-n with n )
3-6), N,N,N,N′,N′,N′-hexaethylalkanediammonium (C H ) -
2
5 3
+
+
N (CH
methylpyrrolidinium)alkane ((C
diquat-n with n ) 3-8), and 1,n-bis(N-methylpiperidinium)alkane
2 n 2 5 3 6
) N (C H ) , Et -diquat-n with n ) 3-6), 1,n-bis(N-
+ +
5 2 n 5 2
H11)N (CH ) N (C H11), MPr -
+
+
(
(C
6 2 n 6 2
H13)N (CH ) N (C H13), MPp -diquat-n with n ) 3-8) ions
were prepared and recrystallized according to the procedures
described in our previous studies.
+
+
9,12-15
After purification, the
formation and purity of the dibromide salt of 32 different organic
1
13
species described above were confirmed by H and C NMR and
stored in a desiccator prior to their use as crystallization SDAs.
Zeolite Synthesis. The reagents used for UZM-12 synthesis
included diquaternary cations prepared here, tetraethylammonium
hydroxide (TEAOH, 35% aqueous solution, Aldrich), aluminum
+
+
trisec-butoxide (Al[OCH(CH
3 2 5 3
)C H ] , 97%, Aldrich), colloidal silica
+
+
+
+
(
Ludox AS-40, DuPont) and the chlorides of Li , Na , K , Rb
2
7
2
multinuclear MAS NMR, Al MQ MAS NMR, N sorption,
+
and Cs ions. The final composition of the synthesis mixture was
3.0TEAOH ·2.0RBr ·1.5MCl·0.5Al ·16SiO ·400H O, where
R is diquaternary alkylammonium ion and M is Li , Na , K , Rb
and temperature-programmed desorption of ammonia. In par-
ticular, the materials with similar Si/Al ratios but different
crystallite sizes (0.1-2.5 µm in length) are tested as catalysts
for the methanol-to-olefin (MTO) reaction that has been steadily
regarded as an alternative technology to produce ethene and
propene from nonpetroleum sources such as natural gas and
1
2
2
O
3
2
2
+
+
+
+
+
or Cs , respectively. After being stirred at room temperature for 1
day, the synthesis mixture was charged into Teflon-lined 45-mL
autoclaves and heated at 100 °C, with rotating (60 rpm), for 7-35
days. For comparison, some syntheses were carried out after the
diquaternary cation in synthesis mixtures was replaced by their
specific precursors: for example, 1,6-dibromohexane (1,6-DBH,
96%, Aldrich) and trimethylamine (TMA, 33% solution in ethanol,
(
8) (a) Corma, A. In Proceedings of the 14th International Zeolite
Conference; van Steen, E., Callanan, L. H., Claeys, M., Eds.;
Document Transformation Technologies: Cape Town, 2004; p 25. (b)
Mathieu, Y.; Pailaud, J. L.; Caullet, P.; Bats, N. Microporous
Mesoporous Mater. 2004, 75, 13. (c) Corma, A.; Diaz-Cabanas, M.;
Jorda, J.; Martinez, C.; Moliner, M. Nature 2006, 443, 842.
Aldrich) instead of Me
ments, the gel composition was fixed to 13.0TEAOH ·
.0P ·6.0P ·1.5KCl·0.5Al ·16SiO ·400H O, where P and P
6
-diquat-6. In this set of synthesis experi-
2
1
2
2
O
3
2
2
1
2
are R,ω-dibromoalkane and aliphatic or cyclic triamine, respectively.
The solid products were recovered by filtration or centrifugation,
washed repeatedly with water, and then dried overnight at room
temperature.
(
9) (a) Hong, S. B.; Lear, E. G.; Wright, P. A.; Zhou, W.; Cox, P. A.;
Shin, C.-H.; Park, J.-H.; Nam, I.-S. J. Am. Chem. Soc. 2004, 126,
5
817. (b) Gramm, F.; Baerlocher, Ch.; McCusker, L. B.; Warrender,
S. J.; Wright, P. A.; Han, B.; Hong, S. B.; Liu, Z.; Ohsuna, T.;
Terasaki, O. Nature 2006, 44, 79. (c) Hong, S. B.; Min, H.-K.; Shin,
C.-H.; Cox, P. A.; Warrender, S. J.; Wright, P. A. J. Am. Chem. Soc.
As-made UZM-12 was calcined in air at 550 °C for 8 h and
refluxed twice in 1.0 M NH NO solutions (1.0 g solid per 100
4 3
2
007, 129, 10870.
mL solution) for 6 h followed by calcinations at 550 °C for 4 h in
order to obtain its proton form (i.e., H-UZM-12). For catalytic
comparison, two SAPO-34 materials with similar Si contents but
different crystallite sizes (1 and 2-4 µm, respectively) were
(
(
(
10) Baerlocher, Ch.; Gramm, F.; Mass u¨ ger, L.; McCusker, L. B.; He, Z.;
Hovm o¨ ller, S.; Zou, X Science 2007, 315, 1113.
11) Baerlocher, Ch.; Xie, D.; McCusker, L. B.; Hwang, S.-J.; Wong, K.;
Burton, A. W.; Zones, S. I. Nat. Mater. 2008, 7, 631.
17
synthesized via a double organic SDA strategy. Here we refer to
12) (a) Lee, S.-H.; Shin, C.-H.; Hong, S. B. Chem. Lett. 2003, 32, 542.
the materials with small and large crystallite sizes as SAPO-34(I)
and SAPO-34(II), respectively. In addition, SAPO-17 and SSZ-13
were prepared and converted into their proton form following the
(b) Lee, S.-H.; Shin, C.-H.; Yang, D.-K.; Ahn, S.-D.; Nam, I.-S.; Hong,
S. B. Microporous Mesoporous Mater. 2004, 68, 97. (c) Shin, J.; Hong,
S. B. Microporous Mesoporous Mater. 2009, 124, 227.
(
13) (a) Paik, W. C.; Shin, C.-H.; Hong, S. B. Chem. Commun. 2000, 1609.
18,19
procedures previously reported.
(
b) Lee, S.-H.; Lee, D.-K.; Shin, C.-H.; Paik, W. C.; Lee, W. M.;
Hong, S. B. J. Catal. 2000, 196, 158. (c) Lee, S.-H.; Shin, C.-H.;
Choi, G. J.; Park, T.-J.; Nam, I.-S.; Han, B.; Hong, S. B. Microporous
Mesoporous Mater. 2003, 60, 237.
(16) (a) St o¨ cker, M. Microporous Mesoporous Mater. 1999, 29, 3. (b) Haw,
J. F.; Song, W.; Marcus, D. M.; Micholas, J. B. Acc. Chem. Res. 2003,
36, 317.
(
(
14) Lee, S.-H.; Lee, D.-K.; Shin, C.-H.; Park, Y. K.; Wright, P. A.; Lee,
W. M.; Hong, S. B. J. Catal. 2003, 215, 151.
(17) (a) Lee, K. Y.; Chae, H.-J.; Jeong, S.-Y.; Seo, G. Appl. Catal., A 2009,
369, 60. (b) Mertens, M.; Stromaier, K. G. U.S. Patent 6,773,688,
2004.
15) (a) Han, B.; Lee, S.-H.; Shin, C.-H.; Cox, P. A.; Hong, S. B. Chem.
Mater. 2005, 17, 477. (b) Han, B.; Shin, C.-H.; Nam, I.-S.; Hong,
S. B. Stud. Surf. Sci. Catal. 2005, 158, 183.
(18) Prakash, A. M.; Kevan, L. Langmuir 1997, 13, 5341.
1
2972 J. AM. CHEM. SOC. 9 VOL. 132, NO. 37, 2010