The Preparation of Pure Zeolite Nay and Its Conversion
to High-Silica Faujasite
An Experiment for Laboratory Courses in Inorganic Chemistry
Fritz Blalier and Emst Schumacher
Institute for lnorganic. Analytical and Physical Chemistry, University of Bern, Freiestrasse 3, CH-3012 Bern. Switzerland
Every student of chemistry meets the fascinating proper-
ties of molecular sieve zeolites during his or her career. We
encounter them as drying agents, selective gas adsorbents,
ion exchangers, chromatographic media, catalysts, or cata-
lyst supports (I).A large number of interesting experiments
can be performed with the many varieties of commercial
zeolites, e.g., Linde A, X, and Y (2).However, the prepara-
tion of these highly organized porous crystalline systems
remains a mystery tomost users. This does not change dras-
tically when the synthetic and patent literature is examined
(3).
There are many motives for synthesizing zeolites in the
laboratory: Commercial zeolites have unknown chemical pu-
rity and are often crystallographically not well character-
ized. All commercial zeolites are contaminated by heavy
metals, mostly iron, which produce all sorts of artifacts if one
studies EPR spectra of sorbed free radicals (4). Last but not
least: One takes great satisfaction from successfully synthe-
sizing one of these enigmatic substances and from proving
that i t is monophasic, conforms to a specific type of crystal-
lographically well-defined zeolite species, and s h o w all the
expected properties even better than the commercial prod-
uct. Since the architectural variations for assembly of zeolite
structures from the prototype "bricks" ( 5 ) are not yet ex-
hausted by far, it iseven possibleto discover systematically a
new phase with unusual adsorptive properties, e.g., built-in
chiral discrimination.
The published synthesis procedures are mostly uncom-
meuted recipes. Only meager information is given regarding
reaction steps, reaction paths or mechanisms. The impor-
tant reaction parameters are not clearly described, which
creates the reader's impression that the process can hardly
be reproducible. However, recent investigations with novel
tools have led to a better understanding of the reaction
conditions, e.g., MAS (magic angle spinning) NMR of 27Al
and 29Si, light scattering and photon correlation spectrosco-
py of the phase nucleation steps, and computer simulations.
The results allow one to infer what happens and how t o
control the conditions for a specific synthesis. But predic-
tions of how t o proceed for creating new zeolites are still
unreliable (3).
Plannlng a Synthesis
Systematic studies of zeolite preparation involve careful
consideration of the following important areas:
the nature and composition of the reactants and the formation of
precursor species,
nucleation kinetics and crydtal growth,
phase transformations,temperature, and pressure factors.
At least six different zeolites (NaA, NaX, Nay, PI,P2,
CHA) and "mixtures" are obtained in hydrothermal pro-
cesses using the same set of reactants (SiOa, Al, Al2(SO4)8,
NaOH, and HzO) under different reaction conditions (3,6);
on the other hand pure N a y can be obtained by several
procedures. Because subsequent crystal separation is impos-
sible, 100% yield of amonophasicproduct has to be achieved.
Zeolite N a y is a synthetic faujasite with an SilAl ratio of
2.4 f 0.8.We eive a simole. reoroducible method. adanted
(n,
f r o m ~ a s a h a r a eal.
t for its preparation from analytically
Dure chemicals. The ~rocedureis based on the senaration of
nucleation and growth processes. Nucleation of ;he desired
seed ia induced in a clear solution with hieh NaOH concen-
tration. The dissolution of aluminum and silica in concen-
trated solutions of NaOH begins with the following reac-
tions:
+
-
or 2 I A l l t 20H- + 6H,O 2[AI(OH)J + 3H,
SiO, NaOH -Na[SiO,OH] dissolved (2)
Condensation leads to the formation of dimeric, trimeric,
and finally oligomeric anions, which are already the struc-
tural subunits of the zeolite. Equation 3 suggests a first
--
condensation step:
Al(OH),- + Na[SiO,OH] Na[(OH),A1+SiOOH] + OH-
+
or Al(OH),- [BO,OHl- [(HO),Al-O-SiOOHI- + OH-
(3)
The surrounding cations compensate the charge of the an-
ionic network and serve as template agents for the three-
dimensional arrangement. All the secondary building units
(SBU) of zeolites have been probed by high resolution FT-
NMR of 27Aland 29Siin the liquid phase, a method that is
powerful enough to discriminate aluminosilicate species
havinguo to 10 Sior A1 atoms (8).The formation of colloidal
particies-is indicated by the decrease of visible light trans-
mittance of the nucleation solution during the aging process.
.. ..
A simple spectrophotometer is adequatefor these measure.
ments. Both methuds combined give strong evidence for the
formation of aggregates with about one unit cell dimension
from the smaller structwal subunits in the clear nucleation
solution.
The clear nucleation solution is mixed with a precipitated
eranular sodium-alumina-silica eel in the ratio 15. Mixine
Gf the two systems (probably) lea& t o a steady state equilib':
rium between dissolution of the a m o r ~ h o u eel
s and further
*
crystal growth. Crystallization a t 92 2 OC needs 24-72 h.
The nucleation solution is decisive for the zeolite obtained,
and small changes of the composition, aging time, or tem-
perature cause remarkable effects on the zeolite crystalliza-
tion process.
Zeollte Nay: Experlmenial Procedure
For all theswpa w be described below laboratory glassware has to
be avoided. Polyethylene or polypropylene flasks with tight screw
caps have to b~ applied. Why?!
Nucleation
Solution A (eq 1) is prepared by dissolution of 1.35 g (0.05 mol)
metallic A1 (99.999%obtained from Alusuisse) in a solution of 15.0g
(0.375 mol) best purity NaOH in 35 mL distilled water. Solution B
(eq 2) is produced by dissolving 15.0 g (0.25 mol) dry SiOn(Fluka No.
Volume 67 Number 6 June 1990 519
60780) in 15.6 g NaOH in 35 mL distilled water. Both solutions are
*
mixed in polyethylene flasks in an oil thermostat at 42 3 'C and
aged for 90 10 min at the same temperature. This is the "nucle-
ation solution" wherein the formation of seed structures takes place
as has been proved withlight-scatteringexperiments (7).The nucle-
ation solution should he clear after the given time of aging. If some
turbidity is left, the concentration of sodium hydroxide has heen too
low or sodium carbonate is a contaminant,
The Aiuminosilicete Gel
Solution C is 31.5 g (0.05 mol) Alz(S0A (Merck p.a.1 dissolved in
125 mL water, and solution D consists of 30.0 g SiOz and 16.0 g
NaOH dissolved in 75 mL HzO. Then D is slowly poured into C
under vigorous stirring while the granular sodium-alumina-silicate
gel precipitates,which is subsequently washed with cold water. The
washed gel is transferred to a polypropylene flask and water is
admitted to 180 g total weight.
Wex apparaNs tor Hw Mment of zeolltes wlth SlC14vapor: (I) and (4) cold
The Ctystai Growth Process traps, (2)ooldtrap with breakseal ampule, (3)reactlonvessel, (5)RoNlex 1919
The formation of zeolite crystals from the small snbunita formed ccnnenlons, (6)breakseal ampule with SiC14,(7) iron bar.
in the nucleation solution occurs in a gel with defined molar compo-
+
sition: 30 g of the nucleation solution (A + B) are added to (C D),
and, after mixing well, the gel is distributed in two flasks,which are
kept in a drying oven at (92 r 2 "C). The composition in mole % of (I =
+ + 1')'"
An(hZ kZ
the reactant eel is now: HgO: 88.45%.NaOH: 5.70%.SiO?: 5.26%.Al: 2 sin 8
~ ~~
~.~~ is controlledh;~-ravdiffraction after 24 h bv
0.59%.~rvst&ization
~ ~,
where n = 1, 2, 3,. . . , a = unit cell length, X = X-ray
taking the samples directly from ;he Re:; as urually20-30 h is
sufficient for complete reaction, the gel is filtered and washed with waveleneth. and B = Braze anele. Both elementarv cell oa-
boiling water as soon as the X-ray analysis shows a crystalline rametersare ohtained wiihhigh precisionso that t<eshrink-
product. The result is zeolite Nay of high purity with an average ape of the unit cell of the Si-exchanged zeolite can be used to
crystal diameter of approximately 0.9 pm. estimate the SiIAI ratio with help of literature data (9). The
difference of 2% between the two unit cell constants is
Hlgh-Slllca Zeollte caused by the different bond lengths dsi.0 = 1.61Aand d~1.0
In a second exoeriment the svnthesized zeolite Y (SilAl- = 1.69 A. MID-IR spectroscopy from 300-1400 em-' is also
2.5) is converted to high-silica'faujasite with ~ i l ~ l ' r a t of
io well suited to the orobine of structural alterations in zeolite
-100 or even more. if it is treated with silicon tetrachloride frameworks. T h e bands i f both zeolites show a 1:l correla-
vapor (9) a t 450 OC: T h e reaction
xSiC1, + Na5,(Al0,),,(SiOz),,, - Na,,(AlO,),,-,(Si0~),36tl
+ rNaCI+ zAlC13 (4)
tion with each other and band assignments should be made
(9). T h e higher ordering of the lattice atoms and the unit cell
contraction lead to sharper absorption bands and shifts of
approx. 8%to higher frequencies in the modified form. For
is a substitution of the lattice Alnl of the zeolite by SiN with reproducible X-ray diffraction and (optional) thermogravi-
a n almost c o m ~ l e t emaintenance of the crvstal structure. metric analysis standardized humidity conditions are neces-
.&l3 volatilizes from the zeolite phase and condenses on the sary, e.g., by keeping the zeolites in a desiccator over a
elass surface: NaCl or nonvolatile NaA1C14 is leached with saturated MgClz solution. X-ray diffraction and IR analysis
water. show that the crystal structure is well preserved and that
only a small part of the degree of crystallinity is lost during
Experlrnental the exchange reaction.
SiClr is previously distilled into breakseal tubes; each tube should
contain approx. 5 mL of liquid SEl+ On the basis of the tube
content one estimates the stoichiometric quantity of Nay to weigh Conclusions
into the reaction vessel 3 (figure) from eq 4. For complete AlISi
exchange a 10-20% excess of SiCln is recommended. Pedagogically valuable characterizations and interpreta-
The Pyrex apparatus is connected as indicated in the figure, and tions are possible with the zeolite conversion experiment:
the breakseal tube is attached to the cold trap 2. The zeolite is
sufficientlydried in a flow of pure Nz(g)(2 bat 450 O C after predry- Determination of the cubic unit cell constant by powder X-ray
ing in an oven). Cold trap 1is cooled with liquid Nz. The breakseal diffractometry;a reference substance, e.g., sodium chloride, is to
ampule is opened with the iron bar 7 and a magnet. Cold trap 4
might be cooled with liquid nitrogen, or, if not, the gas flow (approx.
1mL1s) is led into a NaOH solution to remove the unreacted SiCL.
. he used for precise determination.
The size of the unit cell is connected with the bond lengths.
IR spectroscopy is sensitive for hond lengths in macromolecular
The SiCL input is regulated by the gas flow or the ampule aperture. systems, and highly symmetric structural subunits are proved.
The complek reaction takes appron. 4 h, and then the oven tem. The zeolites prepared are adequately identified by X-ray
prrature is slowly diminished from 450 'C to 200 ' C in 1 h; the
oroduct is washed with0.01 M HCIor NH.CIsolutronand hot water, diffractometry and solid state IR. Scanning electron micros-
hried at 110 "C, and investigated with IR spectroscopy (1-3% in copy, determination of adsorption isotherms for different
KBr) and Debye-Schemer powder X-ray diffraction. substances, and thermogravimetric analysis are additional
tools to reveal the large physicochemical differences be-
Results and lnterpretatlon tween the two zeolites. Most important are the hydrophobic
The DebyeScherrer diffraction pattern allows one to de- nature. Brdnsted aciditv of the H+ form. adsorotion heats.
termine the unit cell parameters of both zeolites N a y and and therefore catalytic-properties. ore over,
t h e synthe:
the modified high-silica form. T o every diffraction line sized zeolite N a y is free from paramagnetic impurities and
Miller indices (h. . . k.. 1). can be assiened. Thev are found to be therefore adequate for research purposes. EPR measure-
either odd or even and not of &xed parity, e.g., (331) or ments of small metal clusters in zeolites are possible even if
. .. but not (321). This moves the presence of a face-
(242). very weak signals result from the metallic particles (4).
centered cubic lktice (spacegroup ~ 3 d k )From . the diffrac- All experiments have been checked by the students of the
tion anele B we extract the elementary cell length according second-year course in inorganic chemistry a t the University
to ~ r a g g ' law
s (9--11): of Bern.

520 Journal of Chemical Educatlon

Acknowledgment
.
.... - . . --
H.stud. surf. SC;. c n i . 1~81,24,107-128.~ar~are~ar,
3. ~echart, R.M. s l u d surf. sei. cot

We thank the SNF grant no. 2.273.86 and the Kommission

zur F6rderung der Wissenschaftlichen Forschung, grant No.
146111211,for financial support, W. M. Meier, Giline Har-
vey, B. Lathy for introduction in the art of zeolite synthesis;
R. Giovanoli, M. Faller, R. Steiner, and Beatrice Frey for X-
ray service and scanning electron microscopy.
Literature CRed
10. Berry, R.8.; dice. S. A,:
Ross,J. ~hya&iChernistry; Wiley: N m Yark. 1980.
11. Buerger. M. J.; Azaroff. L. V . The Pouder Method in X - m y C r y a f d o ~ r a p h y :
1. Bmck, D. W . Zeolitr Molecular Siouas: W h y :NelvYork, 1974. McGrsw-Hill: New York, 1958.
2. ~ ~ w..
~Y.;r j ~i r n a .k~ ward,&
.: ~ i E~S.
. N*W Deu.ropmantainzootite seiowe
Technology; Elsener: Amtfcrdam. 19%.

Volume 67 Number 6 June 1990 521