ELSEVIER

Hydrothermal synthesis of alkali cation

heulandite aluminosilicate molecular
sieves
Dongyuan Zhao and Larry Kevan
Department of Chemisty, University of Houston, Houston, Texas, USA

Rosemarie Szostak
Department of Chemistry, Clark Atlanta University;, Atlanta, Georgia, USA

Heulandite molecular sieves with a SVAI ratio of 3.2 - 3.8 have been synthesized hydrothermally
in the presence of the alkali cations Li+; Li, K; and Nat, K at 190C at autogenous pressure.
They have been characterized by X-ray powder diffraction and scanning electron micrographs.
Heulandites can be formed in the Li+ and Na, K cation systems only with -10 wt% seed
crystals. But heulandite can be synthesized in the presence of Li., K cations without seed
crystals. The formation of heulandite-type zeolites occurs over a narrow crystallization field and
depends on the SVAI ratio, the OH-/Si ratio, and on the presence of seed crystals. Scanning
electron micrographs show a thin-plate topology for the crystals. Heulandite is thermally unsta-
ble for calcination beyond 350 - 450C. 0 Elsevier Science Inc. 1997

Keywords: Heulandite; molecular sieves; synthesis

INTRODUCTION reported the synthesis of heulandite in NaK and Ca

systems under quite high pressure (1000 atm) and
Heulandite and clinoptilolite are classified as heu-
quite high temperature (235 - 275C) for a lengthy
landite-type zeolites and are the most abundant natural
zeolites. However, convenient laboratory synthesis of period (50 days) using amorphous solid materials such
heulandite and clinoptilolite has been difficult. 1-sa-3c as Na,K-clinoptilolite and Ca-epistilbite as the silica and
Heulandite has Si/Al ratios between 2.8 and 4 with alumina sources.
predominantly calcium cations in the natural material More recently, Khodabandeh et a1.9+3c synthesized
and is thermally unstable above 400C. Clinoptilolite is heulandite by first synthesizing zeolite Pl and then
a member of the heulandite family and has the same hydrothermally converting that for 8 - 16 days at
structure, with a Si/Al ratio > 4, with predominantly 240C and autogenous pressure with 3-20 wt% seed
sodium and potassium cations in the natural material. crystals to finally obtain heulandite. They did not ob-
Silica-rich clinoptilolite is thermally stable in contrast to tain heulandite without seed crystals. Also, several syn-
heulandite. theses of clinoptilolite have been reported, mostly us-
Natural heulandite and clinoptilolite have found use ing seed crystals,-4 except for two recent successes
in ion-exchange, adsorption, and radioactive waste-re- without seed crystal~.~~
moval applications. 4-h However, impurities such as Here we report one-step direct hydrothermal synthe-
iron, commonly found in natural samples, limit their ses of heulandites in the presence of Lit; Lif, Kf; or
applications as catalysts. Thus, a reliable, convenient Na+, K+ alkali cations at 190C for 7 to 8 days. In
synthesis is desirable. Koizumi and Roy synthesized addition in the Li+, K+ system it is possible to obtain
Ca-heulandite under rather extreme high pressure and heulandite without seed crystals.
temperature (P > 1000 atm; T > 250C) without seeds.
Wirsching8 synthesized Ca-heulandite from rhyolitic
glass as seed crystals at 250C with quite long synthesis
times of 32 to 56 days. Nakajima and MatsusueHa-gc also EXPERIMENTAL
Syntheses were carried out in stainless steel autoclaves
with Teflon liners at 190C and autogenous pressure.
Address reprint requests to Dr. Kevan at the Dept. of Chemistry, Natural clinoptilolite from Ash Meadows deposit in
University of Houston, Houston, TX 77204.
Received 9 April 1997; revised 19 August 1997; accepted 21 California was purified by settling and used as seed
August 1997 crystals.

Zeolites 19:366-369, 1997

0 Elsevier Science Inc. 1997 0144-2449/97/$17.00
655 Avenue of the Americas, New York, NY 10010 PII SO144-2449(97)00134-S
 Hydrothermal synthesis: D. Zhao et al.

Synthesis with Li+ cation

In a typical synthesis, 1.75 g dried aluminum hydrox-
ide (10.1 mmol Al,O,) (USP, Pfaltz & Bauer) was
added to a solution containing 3.36 g LiOH * H,O (80
mmol) and 36 g deionized water with stirring. After
stirring for 2 h, 20.0 g of aqueous colloidal silica (100
mmol SiO,) (Ludox LS, Aldrich) solution was added
and stirred for an additional 2 h. Then 2.0 g (10 wt%)
natural clinoptilolite was added as seed crystals. This gel
was heated at 190C for 194 h. The final pH was 10.3.

Synthesis with Li+ and K+ cations

In a typical synthesis, 0.44 g dried aluminum hydrox-
ide (25 mmol AlTO,) was added to a solution of 0.64 g
of LiOH * H,O (15.1 mmol), 7.0 g water, and 0.79 g
(3.78 mmol KOH) of 6 M KOH solution with stirring.
After stirring for 2 h, 3.88 g of aqueous colloidal silica
(19.4 mmol SiO,) was added and stirring continued for
2 h. This gel was heated at 190C for 168 h. The final
pH was 10.1.
1000

Synthesis with Na+ and K+ cations

In a typical synthesis, 1.56 g dried aluminum hydrox-
ide (8.97 mmol Al,O,) was added to 0.88 g (4.32 mmol 05
NaOH) of 6 M NaOH solution and 4.10 g (19.7 mmol 10 15 20 25 30 35 40
KOH) of 6 M KOH solution with stirring. After stirring
2 e degree
for 0.5 h, 10 g of aqueous colloidal silica (50 mmol
SiO,) was added and stirring continued for 1 h. Then Figure 1 X-ray powder diffraction patterns of as-synthesized
heulandite: (a) Li-heulandite synthesized with 10 wt% seed crys-
1.0 g (10 wt%) natural clinoptilolite was added as seed tals; (b) Li, K-heulandite synthesized without seed crystals; and
crystals and stirred for 1 h. This gel was heated at 190C (c) Na, K-heulandite synthesized with 10 wt% seed crystals.
for 168 h. The final pH was 10.0.
The products were recovered by filtration, washed to
neutral pH 7.0 by deionized water, and dried in air at seed crystals. The X-ray diffraction pattern is similar to
that of Li-heulandite (F@re Ib). Synthetic Li, K-heu-
70C. The products were analyzed on a Siemens D5000
X-ray diffractometer and a Phllhps 1840 powder diffrac- landite has a formula Li,.,,K,.,,[Al,.,+8 Si,,,,O,,]) with
Si/Al = 3.8 and is indFxed to a mOonoclinic unit cell
tometer with Cu KCY radiation (40 kV, 30 mA) with a
0.02 step size and 1-set step time. The Si/Al ratio was (C2/m) with a = 17.7 A, b = 18.0 A, c = 7.4 A, and p
= 116.5, which is similar to that of Li-heulandite. The
analyzed by a JEOL JXA 8600 electron microprobe.
estiqated standard deviations of the cell parameters are
Scanning electron microscopy (SEM) was performed
on a Cambridge 2500 MK3 microscope. 0.2 A.
Heulandite synthesis is dependent on the Li/K + Li
cation ratio. Analcime is formed at Li/K + Li ratios
RESULTS AND DISCUSSION between 0 - 0.4 and heulandite is formed coexisting
with analcime at ratios of 0.5 - 0.7. When the ratio is
Synthesis between 0.9 - 1, heulandite is formed coexisting with
The X-ray powder diffraction patterns (XRD) of the an unidentified phase. However, with seed crystals (10
products are shown in Figure 1; all can be identified as wt%) or without them, pure heulandite is formed with
heulandite.,-:~,I~ With 2 g of added seeds, the crys- Li/K+Li ratios of 0.8 - 1 for a similar OH-/Si ratio,
tallized heulandite product was 16 to 18 g. Thus, the which is calculated based on the amount of the LiOH,
XRD patterns demonstrate heulandite formation. KOH, etc., bases.
Heulandite formed with Li+ cation is designated Li- Keeping the Li/K+Li ratio at 0.8 and the OH-/Al
heulandite. As-synthesized Li-heulandite has a for- ratio at 3.8, a series of zeolites with the heulandite
mula (Li7.h,,[A17,ti, SiL8,h072]) as determined by elec- structure were synthesized with a Si/Al ratio of 3.5 -
tron microprobe analysis with Si/Al = 3.7 and is 7.0 in the gel. Elemental analysis shows that clinoptilo-
indexed to a monoclinic unit cell (C2/m) with a = lite zeolites (Si/Al ratio = 4.0 - 7.5 in the product) are
17.8 A, b = 18.0 A, c = 7.4 A, and p = 116.4. formed with a Si/Al ratio of 4.0 - 7.0 in the gel. When
Although pure Li-heulandite is synthesized with 10 the Si/Al ratio goes lower than 3.5 in the gel, we have
wt% seed crystals, only 50 wt% Li-heulandite is not been able to synthesize heulandite-type zeolite.
formed without seed crystals. Another unidentified Na, K-heulandite with a Si/Al ratio of 3.2 in the
phase coexists with the heulandite. product is also hydrothermally synthesized in seeded
Li, K-heulandite is synthesized with Li+, Kf cations systems (10 wt%) in the presence of Nat and Kt cat-
with a Li/K+Li ratio of 0.8 at 190C for 194 h without ions at 190C (see F&re Ic). Na, K-heulandite has a

Zeolites 19:366-369, 1997 367

Hydrothermal synthesis: D. Zhao et al.

of 5.0 to 6.0 in the gel, mordenite and phillipsite coex-

ist with clinoptilolite. Only mordenite is crystallized
with a Si/Al ratio > 6 in the gel.
We also note that the final pH is about 10. Synthesis
of heulandite is very dependent on the OH-/Si ratio.
At higher OH-/Si ratios, analcime is formed: at lower
OH-/Si ratios, only amorphous material is obtained.

Thermal stability
The X-ray diffraction intensity of all synthetic heu-
landites decreases after calcination at 300C in air over-
night. Li-heulandite and Na, K-heulandite lose all crys-
tallinity after calcination at 35OC, indicating that
synthetic heulandite is quite thermally unstable.. The
framework of Li, K-heulandite collapses only after cal-
cination at 450C. Its higher thermal stability might be
due to its higher Si/Al ratio of 3.8.

Scanning electron microscopy

Scanning electron micrographs (SEM) of synthetic
heulandites show a thin-plate morphology of the crys-
tals, as shown in Figure 2. which is similar to the mor-
phology of natural heu1andite.l All synthetic heu-
landites show similar morphology. The crystal sizes are
typically 1 - 4 pm.

CONCLUSIONS
Heulandite zeolites with Si/Al ratios of 3.2 - 3.8 have
been synthesized hydrothermally in the presence of
Li+; Li+, K+; or Na+, K+ alkali cations at 190C at
autogenous pressure. Heulandite is formed only for a
narrow crystallization field of conditions and depends
critically on the Si/Al and OH-/Si ratios in the gel as
well as on the presence of seed crystals. Heulandite is
thermally unstable after calcination at 350 - 450C.

ACKNOWLEDGMENT
This research was supported by the National Science
Figure 2 Scanning electron micrograph of (top) Li-heulandite Foundation, the Robert A. Welch Foundation, and the
synthesized with 10 vvt% seed crystals and (bottom) Li,K-heu-
University of Houston Energy Laboratory. R.S. thanks
landite synthesized without seed crystals.
the Environmental Protection Agency assistance ID CR-
818689 for partial support.
formula Na,.,&,,[Al,.,, Si27..1072] and is indexed to a
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