Phys Chem Minerals (1997) 24: 191199 C Springer-Verlag 1997

OR IG I NA L P A P E R

A. Gualtieri ? P. Norby ? G. Artioli ? J. Hanson

Kinetics of formation of zeolite Na-A [LTA] from natural kaolinites

Received April 18, 1996 y Revised, accepted September 27, 1996

Abstract The kinetics and mechanism of hydrothermal

formation of zeolite A from natural kaolinites have been Introduction
studied using as starting materials two international
The understanding on the nucleation processes of alumi-
kaolinite standards (KGa-1 and KGa-2 from Georgia,
nosilicate zeolites (Barrer 1982; Rollman 1984) is of pri-
USA) exhibiting a different degree of stacking disorder.
mary importance for the engineering and production of
Precursors utilized for the synthesis were prepared by
valuable industrial materials, but it also has implication
heating the kaolinites at 800 8C. Metakaolinite was also
for the interpretation of poorly understood formation
prepared from KGa-1 by thermal activation at 600 8C.
processes of naturally occurring zeolites in hydrother-
The hydrothermal syntheses were accomplished by heat-
mally altered or sedimentary rocks. This study focuses
ing the samples in NaOH solutions at temperatures be-
on the formation of zeolite Na-A [LTA] from natural
tween 70 and 110 8C. The kinetic experiments were per-
kaolinites exhibiting a different density of stacking fault
formed by time-resolved synchrotron powder diffraction
defects. The aim is to interpret the influence of the
in isothermal mode using a transmission geometry and
structural state of the precursor materials (pseudo-amor-
an Image Plate detector. The results of the kinetic analy-
phous gel or metakaolinite) on the kinetics of formation
sis are interpreted in the light of the structural state of the
of zeolite A. Zeolite A is one of the few synthetic zeolites
starting kaolinite, and of the temperature of activation of
to have a stable large scale market and there is of course
the precursor material. For kaolinite activated at high
a continuing search for raw materials to be used in its
temperature the nucleation and crystallization of zeolite
synthesis, and for the optimization of synthesis para-
A is essentially independent of the defect density of the
meters (Kerr 1966; Roozeboom et al. 1984; Rocha
original kaolinite, and the thermal history of the precur-
et al. 1991). Zeolite Na-A of average composition
sor seems to be the main controlling parameter. The for-
Na96Al96Si96O3843216 H2O (Gramlich and Meier 1971)
mation process of zeolite A from metakaolinite materials
has been produced using clay minerals (Drag et al.
obtained at lower activation temperatures shows signifi-
1985). The process of synthesis from kaolinite has been
cantly faster reaction rates and lower apparent activation
the subject of many investigations (Barrer et al. 1968;
energies. This is again interpreted in the light of the short
Barrer and Mainwaring 1972; Barrer 1982; Madani et al.
range inhomogeneities present in metakaolinite. As the
1990; Rocha et al. 1991; Murat et al. 1992). It is well
reaction proceeds metastable zeolite A transforms into
consolidated that in order to produce a reactive precur-
hydroxy-sodalite.
sor, it is necessary to activate kaolinite at 600 8C or
higher temperature. The interaction of the activated pre-
cursor with sodium hydroxide at about 100 8C leads to
the formation of zeolite Na-A according to the following
A. Gualtieri ()1 ? P. Norby ? J. Hanson scheme:
Chemistry Department, Brookhaven National laboratory,
Upton 11973, NY, USA 6Al2Si2O7112NaOH121H2O
G. Artioli 12 (NaAlSiO432.25H2O)
Dipartimento di Scienza della Terra, Universita di Milano,
20133 Milano, Italy Breck (1974) observed that a well-crystallized variety of
kaolinite converted directly to hydroxy-sodalite whereas
Present address:
1
Dipartimento di Scienze della Terra, Universita di Modena, a halloysite of low crystallinity formed zeolite Na-A.
Via S. Eufemia 19, I-41100 Modena, Italy Murat et al. (1992) found that a larger quantity of zeolite
Fax: 39-59-417399; e-mail: alessandro@imomn2.unimo.it A is formed from the ordered kaolinite activated at ca.
192

900 8C with respect to the disordered sample activated at

the same temperature. The history of the reactants plays Experimental
a major role in determining the products and kinetics of
crystallization. For example, when kaolinite or meta- Selection and preparation of the samples
kaolinite are used for the synthesis in aqueous solutions The kaolinite samples used in this work were analysed in Artioli
of Ba(OH)21LiOH the resulting products are complete- et al. (1995) and Bellotto et al. (1995) by X-Ray diffraction analy-
ly different: zeolite (Li,Ba)-ABW [ABW] is obtained ses, chemical and thermal analyses, laser diffraction for determin-
from metakaolinite, and zeolite (Ba,Li)-Q[YUG] from ing the grain size distribution, and nitrogen absorption measure-
ments for the calculation of the surface area. They are the ordered
kaolinite (Barrer et al. 1974; Barrer 1985). kaolinite international standard KGa-1 from a Cretaceous sedi-
Regarding the kinetics, earlier studies on the forma- mentary deposit (Georgia, USA) and the disordered kaolinite in-
tion of zeolite A from oxide mixtures were described ternational standard KGa-2 from Warren County (Georgia, USA).
using the Avrami equation (Bamford and Tipper 1980) Both specimens were thermally activated at 800 8C for 1 hour
to obtain quasi-amorphous precursors (KGa1-800 and KGa2-800
yielding a kinetic order n55 (Barrer 1982). The calculat- hereafter). These precursors are amorphous to X-ray diffraction
ed value of the apparent activation energy is around but retain a short range order as shown in Gualtieri (1995).
15 kcalymole. This value is in agreement with the ex- Kaolinite KGa-1 was also heated at 600 8C for 1 hour, in order to
pected activation energy of a growth process controlled obtain a more structured metakaolinite-like precursor (KGa1-
by a chemical step, possibly involving aluminosilicate 600).
The activated powders were ground in agate mortar, sieved and
units added to the growing surfaces by condensation mixed with a 4M NaOH solution (solidus:liquidus51: 2). The so-
polymerization, and elimination of water molecules be- lutions were syringed into 0.7 mm diameter quartz capillaries.
tween appropriate pairs of terminal OH groups (Barrer
1982).
The synthesis of zeolite A has been as well studied Time-resolved diffraction experiments
using different theoretical approaches such as the reac-
tion engineering theory (Thompson and Dyer 1985a), The capillaries were mounted using a conic ferrule in a T-piece
(Fig. 1, after Norby 1996) which is set on a standard goniometer
the population balance model (Subotic and Graovac head for the data collection (Artioli and Norby 1995). The go-
1985; Katovic et al. 1989, 1990; Warziwoda and Thomp- niometer heads were mounted on a Huber 4-circle diffractometer
son 1989; Warziwoda et al. 1989), and the combined at the X7B beamline at the National Synchrotron Light Source,
population balance model (Thompson and Dyer 1985b). Brookhaven National Laboratory. The X7B beamline optics is
described in detail by Hastings et al. (1983). The }-circle of the
In spite of the large amount of studies in the literature, goniometer was used to keep the sample capillary oscillating dur-
a number of aspects of the zeolite A synthesis process ing the data collection. The pressure inside the capillary was
from clays should be elucidated. The kinetic order and kept at 10 atm. using a nitrogen pressure applied from a cylinder
the apparent activation energy are still unknown and the
following issues are still open to debate: a) the rate-limit-
ing step is undefined; b) there is to date no systematic
study aimed to establish the dependence of the process
on the nature of the starting kaolinite material and the
activation temperature of the precursor; c) the process
has to be described in the light of the Ostwalds rule of
successive transformations, that is the first polymorph to
be formed tends to be the least stable thermodynamically
which is then in succession replaced by more and more
stable polymorphs. The replacement takes place by sec-
ondary nucleation or ripening (direct transformation
usually defined as Ostwalds ripening) of the more stable
phase upon the less stable one. In this particular case, at
higher temperature andyor with prolonged heating, zeo-
lite A should be replaced by hydroxy-sodalite as ob-
served by Kostinko (1982).
The present study attempts to face the above prob-
lems, by studing in situ the crystallization process of
zeolite Na-A under well defined conditions and using
two perfectly characterized kaolinites as starting materi-
als. The experimental setting is the same employed by
Norby et al. (1994) which used in situ synchrotron pow-
der diffraction to follow crystallization of zeolite LTA
and its subsequent transformation into hydroxy-sodalite.
Fig. 1 The HT setting for the real time isothermal experiments
(from Artioli and Norby 1995): A5T-piece; B5capillary (blown-
up view to the left); C5tubing for applied pressure or gas-flow;
D5goniometer head

through the T-piece. The high temperature was obtained by a flow
of hot air produced by a tube equipped with a resistance coil, and
positioned below the central part of the capillary. The temperature
was maintained within 28 of the set temperature by a feedback
control of the electrical power in the heating gun and it was moni-
tored through a thermocouple inserted at the center of the tube
opening, about 1 mm below the capillary.
All data collections were performed using a wavelength of
1.2109(3) A, calibrated against the lattice parameters of standard
LaB6 (NIST standard no. 660). X-ray powder patterns were accu-
mulated on a flat Image Plate (IP) detector (Amemiya 1990) using
a Translating Image Plate System (TIPS) (Norby 1996). The IP is
mounted on a computer controlled translating slide and is moving
behind a vertical steel slit with a horizontal opening of 3 mm. A
continuous series of powder patterns can be obtained where the
time resolution is defined by the translation speed of the IP detec-
tor combined with the width of the vertical slit.
Since the horizontal length of the IP plate is limited to about
20 cm, it is important to estimate the time of the reaction process
at each temperature, so as to optimize the exposure time for each
powder pattern (i.e. the translation speed of the IP detector). In our
experiments the exposure time of the diffraction pattern were in
the range 4 to 32 systep, using translation steps of 0.2 mm. The
image collected on the IP were retrieved using the Fuji BAS2000
scanner by He-Ne laser stimulation.
The isothermal experiments on the three precursor materials
(KGa1-800, KGa2-800, and KGa1-600) were performed at 70, 80,
90, 100, and 110 8C. The heating rate used to reach the set temper-
ature was 100 8Cymin. The reaction at each temperature was fol-
lowed by observing the changes in the integrated intensity of sev-
eral diffraction peaks as a function of time. Figures 2(a) and 2(b)
are examples of the raw powder patterns showing the crystalliza-
tion of zeolite A at 70 and 90 8C from KGa-1 activated at 800 8C.
The phase identification was performed by comparison of the ob-
served powder pattern with a model pattern calculated using the
structural parameters of the cubic structure of Hydrated Linde A
with a524.61 A (Gramlich and Meier 1971). A multiple line inte-
gration procedure allows to measure the crystallization % in time.
The (200), (220), (222), (420), (600), (442), (622), (642), (820),
(644), (840), and (664) peak integrated intensities were normal-
ized and transformed into phase fractions and conversion values
(a) to be used in a vs. time curves. The effect of time dependent
decay of the synchrotron primary beam, which was monitored by
an ion chamber placed along the beam path between the slits and
the sample, and the effect of time dependent decay of the IP stored
image, checked for by collecting the powder pattern of the stan-
dard LaB6 as a function of time, were taken into account. Since we
Fig. 2a, b 3-dimensional plots 2theta-intensity-time of the syn-
thesis of zeolite A at 70 8C (a) and 90 8C (b) from KGa-1 activated
at 800 8C. The non-reactive peak at ca. 16 82u is attributed to
quartz impurities
193
do not observe any significant changes in the LaB6 intensities, this
effect can be considered negligible for data collecting times com-
parable to those employed in our experiments. It is likely that the
opposing action of the effects of decay of the ring current and
decay of the image cancel each other.
As a further check on the reproducibility of the data, we re-
peated the isothermal experiment at 100 8C on KGa1-800, and
found no deviations from purely statistical fluctuations of the scat-
tered signal. Plots of the kinetic curves relative to the KGa1-800
and KGa2-800 experiments are shown in Fig. 3(a) and 3(b). The
plot for the isothermal experiments on KGa1-600 is shown in
Fig. 3(c).
SEM observations
The products of the synthesis experiments were analyzed by Scan-
ning Electron Microscopy (SEM) observations to evaluate size and
morphology of the newly formed zeolite A crystals, and possible
relationship with other phases. The observations were performed
using a Philips XL-40y604 electron microscope.
Results
Figure 4 shows a plot of the time at which the conversion
factor is 50% (t(a550)) during the formation of zeolite A
from the three precursor materials (KGa1-800, KGa2-
800, and KGa1-600). This plot shows that the rate of the
reaction and the crystallization % of zeolite A formed are
roughly equal for both KGa-1 and KGa-2 precursors ac-
tivated at 800 8C. The KGa1-600 precursor exhibits low-
er t(a550) at all temperatures, i.e. the reaction of forma-
tion of zeolite A is faster.
The kinetic analysis of zeolite formation was per-
formed using both the Avrami and the population balance
methods. The Avrami equation can provide a good em-
pirical fit of the kinetic curves and it can be used for the
calculation of the apparent activation energies. However,
since the Avrami equation essentially describes solid-
state reactions and not solution-mediated processes it
does not refer to any particular mechanism. To obtain a
better description of the kinetic mechanism, the popula-
tion balance model is also applied.
The earlier studies of Subotic and Graovac (1985) on
the formation of zeolite A in hydrothermal environment
showed that the reaction is governed by autocatalytic nu-
cleation. This means that the nucleation rate increases
194
Fig. 3ac Plot of conversion factors vs. time for the isothermal
experiments: a KGa-1 activated at 800 8C; b KGa-2 activated at
800 8C; c KGa-1 activated at 600 8C
Fig. 4 Plot of the time for the 50% conversion factor vs. T of the
isothermal experiment
during the crystallization process because not only the
aluminosilicate units formed in the liquid phase are po-
tential nuclei, but also the gel regions with ordered struc-
ture (mainly at the outer surface following Gonthier et al.
1993) become potential nucleation sites. Due to the rela-
tively low supersaturation of the limpid phase with active
aluminosilicate species, the rate of homogeneous nucle-
ation is negligible and only heterogeneous and autocata-
lytic nucleation processes are promoted.
If we make some assumption on the crystallization
conditions, it is possible to utilize a reduced form of the
general equation of zeolite formation described by the
population method. We assume that the volume and tem-
perature are constant, that the components in the vessel
are uniformly mixed, that the crystal growth is largely
size-independent (which assumption is tested during the
last part of the process by plotting the experimental line
breadth of the (200), (220) and (222) peaks of the form-
ing zeolite A vs. time), and finally that the solution con-
centration is constant at least during the early stages of
the reaction.
The mass fraction of zeolite crystallized up to the time
tc5t2t0 where t0 is the time where crystallization starts,
can then be expressed as (Warzywoda and Thompson
1989):
tc
mz(tc)5G?q? N0 ? K3g ? t3c1G?q? Na ? K3g & (tc2t)(dmzydt) dt
0
the first term on the right represents growth of the het-
ero-nuclei and the second term accounts for the growth of
the gel-hidden nuclei upen their release into the solution.
G is a geometrical shape factor of growing particles; q is
the specific density of the zeolite crystallized; N0 is a
constant and represents the number of hetero-nuclei;
Kg5dLydt is the rate of linear crystal growth; Na is the
number of particles of the zeolite nuclei released from
the mass of gel needed for the crystallization; t is the
time at which nuclei-II (particles of quasi-crystalline
phase) start to grow. Warzywoda and Thompson (1989)
analytically solved the general equation in the form:
mz5(sy3)[exp (atc)12exp (2atcy2)cos(%2atcy2)23]
where s5N0yNa (ratio of hetero- to autocatalytic nuclei)
and a5(6 ? G ? q ? Na ? K3g)1y3. If the reaction is autocatalyt-
ic, it is possible to use the simple kinetic equation (Ka-
tovic et al. 1989a, b):
mz(tc)5K ? tqc
where K and q are constants. The numerical values of K
and q can be calculated by the plots log (mz) vs. log (tc) in
the time interval from t50 to t5t(a550%), when the
 195

1985). The calculated q values are greater than 4 sup-

porting the evidence that the reaction is autocatalytic
(Subotic and Graovac 1985; Thompson and Dyer 1985a,
1985b). Up to T5100 8C, q is constantly greater than 4,
that is the reaction displays a random autocatalytic nucle-
ation (increasing rate) and 3D growth (constant rate) of
the crystals of the cubic phase. For all the samples, q has
a tendency to decrease at higher temperature (100
110 8C) because of the decrease of the nucleation rate. In
fact at higher temperature hydroxy-sodalite is more sta-
ble than zeolite A (Ostwalds law) and the decrease of the
nucleation rate for both samples is due to a competition
Fig. 5ac Plot of ln(2ln(1-a)) vs. ln(t) for the isothermal experi- of forming nuclei of the two phases. Hydroxy-sodalite
ments. The slope of the regression lines (n) is related to the order formation is clearly observed in the runs at 110 8C de-
of the reaction. a KGa-1 activated at 800 8C; b KGa-2 activated at
800 8C; c KGa-1 activated at 600 8C spite the nature of the precursors.
If we consider the Avrami equation 2ln (12a)5ktn,
where a is the conversion factor, k5daydt is the rate
Table 1 Results of the kinetic analysis using the balance popula- constant and n is the parameter which describes reaction
tion and the Avrami models: q the kinetic order from the balance mechanism (Bamford and Tipper 1980), in the logarith-
population method; n, the kinetic order from the Avrami method
mic form, the slope of the graph of ln (2ln (1-a)) vs. ln (t)
run q n is characteristic of the kinetic expression since it yields
to the calculation of n (Hancock and Sharp 1972). The fit
ord 800 iso 70 8C 5.5(1) 6.4(1) coefficients of the linear regression for the calculation of
ord 800 iso 80 8C 4.6(1) 5.8(2)
ord 800 iso 90 8C 4.2(1) 5.3(1) n are within the range 0.9850.997. These graphs are
ord 800 iso 100 8C 3.9(1) 5.1(2) reported in Fig. 5(a) and 5(b) for KGa1-800 and KGa2-
dis 800 iso 70 8C 5.7(1) 6.8(2) 800 respectively, and in Fig. 5(c) for KGa1-600: The
dis 800 iso 80 8C 4.0(2) 5.3(1) values of n calculated using the Avrami equation are re-
dis 800 iso 90 8C 4.1(4) 5.2(1)
dis 800 iso 100 8C 3.9(2) 5.0(1)
ported in Table 1 and displayed in Fig. 6. The Avrami
ord 600 iso 70 8C 6.0(4) 7.3(3) equation with proper values of n is utilized to fit the
ord 600 iso 80 8C 6.1(3) 7.0(2) kinetic curves (a range within 0.10.9) and to derive the
ord 600 iso 90 8C 4.8(4) 6.0(2) values of the rate constants k (Brown et al. 1980). The
ord 600 iso 100 8C 4.8(6) 6.0(3) results of the analysis are reported in Table 2 in terms of
rate constants, relative standard deviations, and fit coef-
ficients. The reproducibility check performed on the
crystallization rate increases. Such plots provide the val- isothermal run at 100 8C of KGa1-800 resulted in values
ues of the kinetic order (q), which are reported in Table of n55.3(2) and of k50.0501(5), which are perfectly
1 for the various isotherms. The numerical value of expo- consistent with the values reported for the 100 8C
nent q is a function of nucleation and growth mechanism. isotherm in Tables 1 and 2.
When q53 the nucleation is heterogeneous, when q54 The rate constants k from the isothermal runs at 70
the nucleation is is homogeneous in the case of linear, 100 8C are utilized in the Arrhenius equation k5
size-independent growth. When q is larger than 4, the Aexp(2EyRT) in the logarithmic form ln (k) vs. 1yT for
nucleation rate increases (autocatalytic nucleation) dur- the calculation of the apparent activation energy Ea of the
ing the crystallization process (Subotic and Graovac process from the slope of the linear plot and the pre-ex-
196

Fig. 6 Variation of the order of the reaction n with the temperature Fig. 8 Arrhenius plots from the induction periods for the calcula-
of the isothermal experiment tion of the activation energy for the nucleation process for KGa-1
activated at 800 8C, Kga-2 activated at 800 8C, and KGa-1 acti-
vated at 600 8C

Table 3 Results of the parametrization of the Arrhenius equation:

apparent activation energies, frequency factors and fit coefficients

KGa-1-800 KGa-2-800 KGa-1-600

Ea (kcalymole) 8.7(5) 8.0(2) 4.2(2)

A (min21) 5.73103 2.03103 1.83102
R 0.990 0.994 0.996

Table 4 Activation energies of the nucleation process calculated

from the induction periods

KGa-1-800 KGa-2-800 KGa-1-600

Fig. 7 Arrhenius plot for KGa-1 activated at 800 8C, KGa-2 acti- T8C t0 (min) t0 (min) t0 (min)
vated at 800 8C and KGa-1 activated at 600 8C
70 195 195 89
80 108 112 64
ponential frequency factor A from the constant term. We 90 60 69 40
left out the run at 110 8C because of the presence of 100 28 48 39
hydroxy-sodalite which is likely to affect the kinetics of En (kcalymole) 16.2(9) 13.3(3) 7.0(4)
the reaction. The resulting values are reported in Table 3 A (min21) 1.13107 1.53106 3.03102
R 0.992 0.998 0.994
together with the relative standard deviations and the fit
coefficients. Figure 7 reports the Arrhenius plots for
KGa1-800, KGa2-800, and KGa1-600.
Table 4 reports the measured induction periods to for shows the resulting Arrhenius plot for the three experi-
each experiment. These values are employed in an ments.
Arrhenius-like plot of ln (to) vs. 1yT in order to calculate From SEM observations it is known that the average
the values of the activation energy En of the process of size of the zeolite A crystals formed at various tempera-
nucleation and the frequency factor A. This method was tures is 2 mm. Figure 9 a shows an intergrowth of cubic
successfully applied by Joshi et al. (1990) in the kinetic zeolite A crystals. No hydroxy-sodalite is observed for
analysis of the formation of zeolite L [LTL]. Figure 8 this product. Figure 9 b shows a particular of the cubic

Table 2 Results of the kinetic

analysis using the Avrami KGa-1-800 KGa-2-800 KGa-1-600
equation: rate constants and fit
coefficients T(8C) k R k R k R

70 0.01744(3) 0.995 0.01533(5) 0.998 0.0355(3) 0.996

80 0.02285(7) 0.992 0.02121(8) 0.998 0.0435(2) 0.975
90 0.03519(5) 0.997 0.0298(1) 0.990 0.0502(2) 0.991
100 0.04720(1) 0.990 0.0393(3) 0.970 0.0590(3) 0.990
110 0.05390(4) 0.998 0.0450(1) 0.980 0.0881(5) 0.982

Fig. 9 A, B SEM images (A)
sample KGa1-800 after iso-
thermal run at 80 8C, 15 kV
electron beam, 34000 magni-
fication; (B) particular of the
crystals of zeolite A reacting
after the isothermal run at
110 8C from sample KGa1-800
(magnification534000)
Fig. 10 Plot of a vs. time for zeolite A (triangle) and hydroxy-
sodalite (rhombus) during the isothermal experiment at 100 8C of
Kga1-800
zeolite A crystals reacting at 110 8C to form hydroxy-so-
dalite. The image is similar to the ones shown in Rees
and Chandrasekhar (1993) where new crystals are form-
ing on older crystals, indicating that secondary nucle-
ation is occurring instead of Ostwalds ripening. Al-
though Fig. 9(b) is clear evidence that some kind of crys-
tal dissolution and recrystallization takes place, the ki-
netic analysis discussed above, and the curves of conver-
sion factors vs. time of the two phases (Fig. 10) indicate
that the main process is simultaneous nucleation and
growth, with competition between the two phases. As
evidenced in Fig. 10, zeolite A crystals start to dissolve
well after most of hydroxy-sodalite has crystallized al-
ready. Therefore we are inclined to believe that a sec-
ondary nucleation of hydroxy-sodalite takes place and
that this process has direct influence on the kinetics of
zeolite A formation (sharp decrease of the nucleation
rate, showing down of the reaction and progressive later
dissolution).
197
Discussion
The plot of the time when the conversion factor is 50%
vs. T(8C) of formation of zeolite A (Fig. 4) displays sim-
ilar trends for the two kaolinites activated at 800 8C and
the reaction and kinetics parameters for the two samples
reported in Tables 1 to 3 shows only slight differences.
Thus, to a first instance, we might say that the reaction is
independent upon the structural state of the starting ma-
terial. Albeit it is a little artificious, we can speculate on
such slight differences and say that, since the reaction
rates are faster for the disordered sample (KGa2-800),
the transition to thermodynamically stable hydroxy-so-
dalite is faster. Accordingly, the disordered kaolinite dis-
plays larger crystallization % of forming hydroxy-so-
dalite in the same temperature ranges with respect to the
ordered one and, at 100 8C, hydroxy-sodalite formation is
favoured and the rate of formation of zeolite A is de-
creased.
A significantly higher reactivity of KGa-1 activated at
600 8C clearly shows that the thermal activation history
has great influence on the kinetics of formation of zeolite
A. As a matter of fact, significant differences in the
product phase, crystallization %, and kinetics of forma-
tion of zeolite A from natural kaolinite depending upon
the thermal treatment (600 and 800 8C) have been report-
ed in Alberti et al. (1994) and Rocha et al. (1991). The
higher reactivity for the sample prepared at 600 8C can
indeed be explained in terms of the structural difference
between the precursor materials activated at different
temperatures. At about 600 8C, the metakaolinite struc-
ture displays ...-Al-O-Si-O-Al-... chains with the Al
atoms mainly in four fold coordination (Gualtieri 1995).
At 800 8C and above the metakaolinite structure collaps-
es into a pseudo-amorphous material which is the pre-
cursor for the mullite formation in which the Al atoms
are increasingly six coordinated. Zeolite A formation is
198
therefore favoured in the case of the metakaolinite pre-
cursor.
The process leading to the crystallization of zeolite A
from kaolinite can be summarized in terms of a step-by-
step reaction: (1) dissolution of the pre-existing short
range ordered Si-Al polyhedral framework by alkali
leaching at low temperature, (2) condensation and poly-
merisation of an amorphous precursor with ...AlySi-O-
Si... bonds, (3) nucleation of zeolite A germs, (4) 3-di-
mensional growth of zeolite A crystals.
The kinetic orders q calculated from the various
isotherms are similar for the three samples and, until
100 8C, q is constantly greater than 4. The rate limiting
step of the reaction is the dissolution of the pre-existing
short range ordered Si-Al polyhedral framework by al-
kali leaching at low temperature followed by the poly-
merisation of the amorphous precursor. The apparent ac-
tivation energy refers to this process. Assuming that the
quasicrystalline phase in contact with the liquid phase
become new nuclei after the release from the gel, the
consequent increase in the number of nuclei accelerates
the rate of the gel dissolution and therefore the rate of
formation of new nuclei. At higher temperatures, there is
a rapid decrease of the nucleation rate (q has a tendency
to drop) because hydroxy-sodalite is more stable than
zeolite A (Ostwalds law).
Our data confirm that the rate of formation of zeolite
A from natural kaolinites is fairly different from the rate
of formation in a reaction mixture prepared from an
amorphous sodium aluminosilicate gel and aqueous
NaOH (Kerr 1966). The apparent activation energies
here obtained for the two samples treated at 800 8C (8.7
and 8.0 kcalymole) are lower than the values reported for
the formation of the zeolite from a mixture of gels. Bar-
rer (1982) found activation energies of about 15 kcaly
mole which are comparable to the activation energy for
the depolymerization of silica at about 50 8C (21.5 kcaly
mole). The rate limiting step for that reaction is the gen-
eration of precursor species undergoing condensation-
polymerization at the crystal surface (Barrer 1982; Bar-
rer 1985). Our values show instead that the kinetics of
the reaction is different: in the case of formation of zeo-
lite A from metakaolinite, the more favorable dissolution
of the starting alumino-silicate promotes the fast poly-
merization of aluminosilicate species in solution and the
formation of a gel where the Si and Al species are in four
fold coordination, and minor atomic rearrangements
originate the zeolite germs. The tetrahedral coordination
of Si and Al in metakaolinite and in the zeolite A germs,
and probably a similar short-range poymerization state
in the precursor and in the zeolite are the reason for the
very low value of activation energy observed for the zeo-
lite formation from metakaolinite (KGa1-600, Table 3).
The amorphous precursors obtained from kaolinite acti-
vated at 800 8C are assumed to be structurally (less Al
atoms in four fold coordination) and chemically (more
silica segregated) much harder to organize in zeolite
germs (Rees and Chandrasekhar 1993; Rocha et al.
1991). The analysis of the induction times confirm the
above speculations. The Arrhenius-like plot of ln (t0) vs.
1yT shown in Fig. 8, and the calculated values of En
reported in Table 4 again indicate lower values for the
kaolinite heated at 600 8C.
Conclusions
The present work reports a systematic in-situ study on
the formation kinetics of zeolite A from natural kaolin-
ites activated at different temperatures, in order to evalu-
ate the influence of the structural state of the starting
kaolinite and of the activation temperature of the precur-
sors on the crystallization process. Image Plate (IP) dif-
fraction data in transmission geometry were used for the
first time in the calculation of kinetic parameters. The
results can be summarized as follows: 1) the mechanism
of formation of zeolite A from activated natural kaolin-
ites, which at least in the early stages of the reaction is
controlled by autocatalytic nucleation, is better de-
scribed by the population model, even in its reduced
form instead of the Avrami model; 2) there is no depen-
dence of the process upon the density of defects of the
starting kaolinite material; 3) the thermal history of the
precursor is fundamental: the higher reactivity of
metakaolinite with respect to the high temperature pre-
cursors is due to the short range structural similarity
between metakaolinite and the crystalline zeolite germs;
4) metastable zeolite A crystals react at the higher inves-
tigated temperatures to form thermodynamically stable
hydroxy-sodalite (Ostwalds law): although the occur-
rence of an Ostwalds ripening process can not be com-
pletely ruled out, a secondary nucleation process of hy-
droxy-sodalite is evidently influencing the kinetics of
zeolite A formation by competing nucleation; 5) the ki-
netic order q calculated from the various isotherms is
constantly greater than 4, indicating that the reaction is
autocatalytic. The rate limiting step of the reaction is the
dissolution of the pre-existing short range ordered Si-Al
polyhedral framework by alkali leaching at low tempera-
ture followed by the polymerisation of the amorphous
precursor; 6) our results yield as well some important
indications for the synthesis and production of zeolite A
from natural kaolinite-based clays. The temperature of
activation of kaolinite should not be higher than 600 8C
(production of metakaolinite) and any increase of activa-
tion temperature neither accelerates the rate of formation
of zeolite A nor lowers the induction times of the reac-
tion.
Acknowledgements This research is supported under contract
DE-AC02-76CH00016 with the US Dept. of Energy by its Divi-
sion of Chemical Sciences, Office of Basic Energy Sciences and
by the Danish Natural Science Research Council. A. Gualtieri
benefited from a grant from Fullbright USA-Italy Cultural Ex-
change Commission. G. Artioli acknowledges funding from Ital-
ian MURST and CNR. The authors are indebted to Dr. A. Tombesi
(CIGS, Univ. di Modena) and Prof. E. Galli (Univ. di Modena) for
the SEM analyses and to Dr. B. Subotic for useful suggestions and
comments.

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