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Ru -der Bokovic
Institute, Division of Materials Chemistry, Laboratory for the Synthesis of New Materials,
Bijenic ka 54, 10000 Zagreb, Croatia
article info
abstract
Article history:
Received 6 October 2010
Received in revised form 20 December 2010
Accepted 21 December 2010
Available online 28 December 2010
Keywords:
Aluminosilicate hydrogels
Crystallization
Zeolite A
Crystal morphology
Crystal size
1. Introduction
A crystals. Since the mentioned investigatio ns were conducte d under very different and incomparableconditions,and mostly foAmong more than 200 different types of zeolites, zeolite Na-A, cused to only one property of system, the conclusions arising
also known as zeolite 4A is the most important for industrial
from the analysis of the obtained results are more general, e.g., that
applications D
. ue to applicati onsof zeolite A as absorbents[1]
alkalinity of reaction mixture has the most expressive effect on the
ion-exchanger s [2] and especiall y detergent builders [3] , many crystal
atsize [8,9,11] and that crystal habit of zeolite A can be modtempts were focused on the investigatio ns of various factors which
ied by the aluminum content in the reaction mixture [6,8] .
control the crystallization pathway and particulate properties of
Thus, although the results of numerous investiga tions gave very
the crystalline end product.
quality and worthy data, however, they do not offer a complete
Numerous studies [414] have shown that chemical composi- feature on the inuence of the chemical composition of the reaction of the reaction mixture (hydrogel) is the most important factor
tion mixture on crystallizati on pathway and the propertie s o f the
for controlling the particulate properties of zeolite A. In these studproducts, especially the particulate (crystal size distribution, crysies, special attention was paid to inuence of alkalinity
tal morphology ) ones. From this reason, we conducted systematic
[8,9,11,13,14] and the batch molar ratio Si/Al [68,12 14] , respecinvestiga tion of the inuence of the chemical compositi on of the
tively, of the reaction mixture on both the size and shape of zeolite
reaction mixture (hydrogel), entirely dened by the batch molar
ratios [Na2 O/H2 O]b , [SiO2 /Al2 O3 ]b and [SiO2 /H2 O]b , i n wide ranges,
Corresponding author. Tel.: +385 (0)1 46 80 123; fax: +385 (0)1 46 80 098. even these beyond the standar d chemical conditions of zeolite
A synthesis, on the duration of crystallization (detail kinetic
E-mail address:
subotic@irb.hr (B. Subotic
).
1387-1811/$ - see front matter 2010Elsevier Inc. All rights reserved.
doi: 10.1016/j.micromeso.2010.12.027
390
analysis will be published elsewhere), reaction yield, specic num- The aluminosi licatehydrogels, prepared as described above
ber of crystals, crystal size distribution (by both number and vol- were transferred into stainless-steel reaction vessel preheated at
ume) and crystal morphology.
crystallizati on temperature (80
C). The reaction vessel was proIn the rst part of our study [15] it was found that depending on
vided with a thermostated jacket and tted with a water-cooled
the alkalinity of the reaction mixture, the increase of aluminium reux condenser and thermom eter.The reaction mixture was
content in the reaction mixture (decrease of the batch molar ratioheated at crystallizationtemperatureunder stirring with a Tefy = [SiO
lon-coated magnetic bar driven by magnetic stirrer, until the entire
2 /Al
2 O
3 ]b ) causes not only appearanceof {0 1 1}crystal
planes of zeolite A and thus, formation of cubic crystals with trun-amount of the amorphous aluminosi licate (gel) is transformed into
cated edges[6,8] ,but also a gradual loss the individual crystal
zeolite. The end-point of crystallization,
tc =tc(end) (tc is the time
planes and formatio no f pseudo-sph erical,
face-lessparticles of
of crystallization) was determined by microscopic observation
zeolite A (zeolite FLA). Hence it is evident that morphology of zeo-(optical microscope with magnication of 1000is used for this
lite A crystals is not determinedby only the batch molar ratio
purpose) of the samples used from the reaction mixture at various
y = [SiO
A = [Na2 O/H2 O]b ,
times tc during the synthesis.As tc(end) is used the time tc for
2 /Al
2 O
3 ]b , but also by the batch alkalinity
and total batch silica concentratio tsc=
n,
[SiO
which some irregularly-sha pedparticles (gel) are not observed.
2 /H
2 O]
b or better to
say, by the entire chemical composition of the reaction mixture. The absenceof the gel phase in the products was additionally
From this reason, the inuence of chemical composition of the checked by X-ray diffraction.
reaction mixture (hydrogel) on the size (distribution )and morThe reaction yield,YR, (in wt.%, i.e. grams of zeolite obtained
phology of zeolite A crystals, obtained by hydrothermal treatmentfrom 100 g o f the reaction mixture) was determined as follows: So(heating at 80 C) of hydrogels,was investiga ted.The chemical
lid phase (zeolite A) of the reaction mixture tat
c P tc(end) is sepcomposition of hydrogels was varied by wide-range variations of arated from the liquid phase (supernatant) by centrifugation. After
the batch molar ratiosA (from 0.00507 to 0.0762) andtsc (from
removal of the supernatant, the solid phase was redispersed in dis0.00255to 0.03785) for two characteristic valuesy of
(1.3 and 2.0). tilled water and centrifuged repeatedly until the pH value of the liquid phase above the sediment was 910. The wet washed solids
were dried overnight at 105
C, were cooled in desiccato rs with sil2. Experimental
icagel and were weighed. From known amounts,
mR, o f the reaction
mixture and,mz, o f crystallized zeolite, the reaction yield,
YR, can
Aluminosili cate hydrogels having the batch chemical
be
calculated
by
the
simple
relation:
compositions :
System S1: 3.981Na
Al2O3 2SiO2z1H2O; [Na2O/Al2O3]b = con2 O
stant = 3.981; [SiO2/Al2O3]b = constant = 2.0;[Na2O/SiO2 ]b =
constant = 1.990
System S2: 2.588Na2 OAl2O 3 1.3SiO2 z2H2O; [Na2O/Al2O3]b =
constant = 2.588; [SiO
/Al
O/SiO
]
2
2 3Ob ]= constant = 1.3; [Na
2
2 b=
constant = 1.9905
mz =mR
z1
z2
tsc
H1.1./H2.1.
H1.2./H2.2.
H1.3./H2.3.
H1.4./H2.4.
H1.5./H2.5.
H1.6./H2.6.
H1.7./H2.7.
H1.8./H2.8.
H1.9./H2.9.
H1.10./H2.10.
785.11
376.23
241.27
173.79
133.29
106.09
86.84
72.44
61.32
52.19
509.17
244.72
156.85
112.97
86.56
68.89
56.44
47.04
39.79
33.90
0.00255
0.00532
0.00829
0.01151
0.01500
0.01885
0.02315
0.02761
0.03262
0.03785
0.00507
0.01058
0.01650
0.02291
0.02986
0.03750
0.04585
0.05500
0.06500
0.07620
whereNi is the number frequency of the crystals having the size betweenD and DD, Di =D + DD/2, D is measured equiva lent spherical
3
diamete r andq = 2 g/cm
is the density of zeolite A.
3. Results and discussion
The solid phases (X-ray amorphous aluminosilicate gels) of all
hydrogels (see Table 1 ) were completely transformed into crystalline ones during hydrothermal treatment at C.X-ray
80
diffraction
analysis revealed that all the crystalline end products obtained by
hydrothe rmal treatment of hydrogels H1.1.H1.7. and H2.1.H2. 8.,
are pure, fully crystalline zeolite A (see XRD patterns in Supplements 1 and 2). However, due to the tendencyof spontaneou s
transformat ionof zeolite A into hydrohysodalite(HS) at higher
alkalinities [14,17] , traces of HS were found in the crystalline end
391
tc(end) (min)
Sample (No.)
YR (wt.%)
D (l m)
Ns
H1.1./H2.1.
H1.2./H2.2.
H1.3./H2.3.
H1.4./H2.4.
H1.5./H2.5.
H1.6./H2.6.
H1.7./H2.7.
H1.8./H2.8.
H1.9./H2.9.
H1.10./H2.10.
10,000/6980
2640/2050
524/410
360/260
230/210
180/160
145 /130
95/130
90/90
80/60
s1.1./s2.1.
s1.2./s2.2.
s1.3./s2.3.
s1.4./s2.4.
s1.5./s2.5.
s1.6./s2.6.
s1.7./s2.7.
s1.8./s2.8.
s1.9./s2.9.
s1.0./s2.10.
2.482/2.436
5.036/4.872
7.342/7.368
9.587/9.470
12.127/11.907
14.536/14.176
16.593/16.352
19.042/18.483
21.210/20.518
23.334/22.470
1.448/1.404
1.488/1.610
2.069/1.945
2.201/1.935
1.934/1.409
1.086/1.198
1.031/1.104
1.360/1.256
0.476/1.248
0.787/1.634
1.05
1.86
6.25
5.85
1.83
3.85
4.10
1.94
1.71
4.93
/g)
1010/5.25 1010
1010/5.82 1010
1010/6.82 1010
1010/8.59 1010
1011/2.01 1011
1011/3.16 1011
1011/3.40 1011
1011/2.43 1011
1012/2.26 1011
1011/7.57 109
392
Fig. SEM
1. images of the crystalline end products (zeolite A) obtained by hydrothermal treatment of hydrogels H1.1. (s1.1.), H1.2. (s1.2.), H1.3. (s1.3.), H1.4. (s1.4.), H1.5.
(s1.5.), H1.6. (s1.6.), H.17. (s1.7.) and H1.8. (s1.8.).
99% (by number) of all the crystals formed from hydrogel H1.1, its
and decreases the size ranges and the peak sizes of the larger-size
portion in the total mass of the formed crystals is less than 10%; crystal populations (see the CSD curves s1.1., s2.1., s1.2. and s2.2. in
more than 90% of the mass is yielded by less than 1% (by number)
Fig. 3 ) o f zeolite A obtained from low-alkaline hydrogels H2.1. and
of the crystals having the size in the range 650
H2.2.: For example, the size range and the peak size in the largerl m. Thus, it is
obvious that the CSDs by number of these products are determined
size crystal population of zeolite A obtained from hydrogel H1.1.
by the large number of crystals having the size in the range 0.5 (y = 2.0) are 2.756
l m and 18.7l m (see the CSD curve s.1.1. in
2 l m (see the CSD curves s1.1., s2.1., s1.2. and s2.2. in Fig. 3 ) and
Fig. 4 ), and the correspondi ng values of zeolite A obtained from
that the larger crystals (>6l m) dominate si n the SEM images
hydrogel H2.1. y
( = 1.3) are 2.730l m and 8.2l m (see the CSD
(see the SEM images s1.1.and s1.2.
in Fig 1 as well as s2.1. and
curve s.2.1. in Fig. 4 ).
s2.2. in Fig. 2 ).
Now, taking into considerati on that:
While the excess of aluminiumy( = 1.3) does not markedly
inuence the CSDs, either by number (see the CSD curves s1.3.
(i) zeolite nuclei are formed in the gel matrix during its precips1.10. and s2.3.s2. 10. in Fig. 3 ) o r by volume (see the CSD curves itation [3136] ,
s1.3.s1.10. and s2.3.s2.10. in Fig. 4 ), of zeolite A obtained from (ii) number and distribut ion of nuclei in the gel matrix considerhydrogels H1.3.H1.8. and H2.1.H2.8., the excess of aluminium
ably depend on the chemical composition of hydrogel and
considerably increases specic number,
Ns, o f crystals (see Table 2 )
the mode of its preparation [3537,9,38,39 ] ,
393
Fig.
SEM
2.images of the crystalline end products (zeolite A) obtained by hydrothermal treatment of hydrogels H2.1. (s2.1.), H2.2. (s2.2.), H2.3. (s2.3.), H2.4. (s2.4.), H2.5.
(s2.5.), H2.6. (s2.6.), H2.7. (s2.7.) and H2.8. (s2.8.).
(iii) nuclei cannot grow in the gel matrix, but can start to grow [4446] where AlOH4 anions preferent ially react with largest silafter their releasing from the gel dissolved during crystal-icate anions [47] , results in the forma tion (precip itation) of amorphous phase (gel) having the molar ratio [SiO
/Al3 O
]
than
lization, i.e., when they arein full contact with the liquid
2
2
g higher
is the batch molar ratio y = [SiO
phase [4,26,34,37,39, 40] ,
2/Al 2O 3] b [4850] ,i.e., for y = 2.0
] > 2.0. Or in the other words, number of
(iv) specic number of crystals,
Ns, correspond s t o the number of (system S1), [SiO
2 /Al
2 O
3 g
SiOSi bonds in the gel matrix increasesand at the same time
active nuclei from which growth the crystals are formed
number of SiOAl bonds in the gel matrix decreases with increase
[11,34,9] and
of y, and vice versa. Since for zeolite A are immanen t SiOAl and
(v) CSD depends on the number and distribut ion of nuclei in the
not SiOSi bonds (i.e., Si/Al = 1 in zeolite A framewo rk [20] ) zeolite
gel matrix [34,37,39,41,42 ] ,
A nuclei can be rather formed in SiOAl than in SiO Si environthe considerable differe nces of the particulate properti es (specicment. From this reason number of the nuclei formed in the gel matrix is proportio nal to the content of aluminum in the gel and thus,
number,Ns, o f crystals; see Table 2 , CSD by volume; see Fig. 4 )in
determine d b y the value of [SiO
the products obtained from hydroge lsH1.1. (y = 2.0)and H2.1.
2
2/Al
3O
g ] . O n the other hand, since
the value of [SiO2/Al2O3] g decreaseswith decreasingvalue of y
(y = 1.3) can be explained as follows: Reactio no f monomeri c
AlOH4 anions [43,44] from aluminate solution with higher-p oly- [4850] , number of nuclei formed per unit mass of the solid phase
of hydroge ls H2.1. and H2.2.
y =(1.3) are higher than the number of
merized silicate anions present in low alkaline silicat esolution s
394
Fig. 3. Crystal size distributions (CSD) by number of the crystalline end products Fig. 4. Crystal size distributions (CSD) by volume of the crystalline end products
obtained by hydrothermal treatment of hydrogels H1.1. (s1.1.), H2.1 (s2.1.), H1.2.
obtained by hydrothermal treatment of hydrogels H1.1. (s1.1.), H2.1 (s2.1.), H1.2.
(s1.2.), H2.2. (s2.2.), H1.3. (s1.3.), H2.3 (s2.3.), H1.4 (s1.4.), H2.4. (s2.4.), H1.5. (s1.5.),
(s1.2.), H2.2. (s2.2.), H1.3. (s1.3.), H2.3 (s2.3.), H1.4 (s1.4.), H2.4. (s2.4.), H1.5. (s1.5.),
H2.5. (s2.5.), H1.6. (s1.6.), H2.6. (s2.6.), H1.7. (s1.7.), H2.7. (s2.7.), H1.8. (s1.8.),H2.5.
H2.8.(s2.5.), H1.6. (s1.6.), H2.6. (s2.6.), H1.7. (s1.7.), H2.7. (s2.7.), H1.8. (s1.8.), H2.8.
(s2.8.), H1.9. (s1.9.) H2.9. (s2.9.), H1.10 (s1.10.) and H2.10. (s2.10.). The solid curves
(s2.8.), H1.9. (s1.9.) H2.9. (s2.9.), H1.10 (s1.10.) and H2.10. (s2.10.). The solid curves
(s) corresponds to the CSDs of the products crystallized from system
y = 2.0)
S1 ( and
(s) corresponds to the CSDs of the products crystallized from system
y = 2.0)
S1 ( and
the dashedcurves (d) correspond tothe CSDsof the products crystallized from
the dashed curves d)
( correspond tothe CSDsof the products crystallized from
system S2 (y = 1.3).ND is number percentageof crystals having the spherical
system S2 (y = 1.3).VD is volume percentageof crystals having the spherical
equivalent diameter
D.
equivalent diameter
D.
nuclei formed per unit mass of the solid phase of hydrogels H1.2. tween the correspond ingcrystal size distribut ions(see Figs. 3
and H2.2. y
( = 2.0). Thus, the speci c number of crystals,
Ns, i n the
and 4) and (iii) marked changeof particle (crystal) morphology
(see Fig. 5 ).
crystalline end products obtained from low-alkaline hydrogel s
H2.1. and H2.2. (sampless2.1. and s2.2.)are consider ablyhigher
The increase of specic number,
Ns, o f crystals with increase of
than the specic number of crystals in the crystalline end productsalkalinity (simultaneous increase of free+Na
and OH ions) can
obtained from low-alka line hydroge ls H1.1. and H1.2. (samples s1.1.
be readily explained by the action of structure -forming +
Na
ions
and s1.2.; see Table 2 ).
[32,51,52 ] which induces the formation of nuclei in the gel matrix
The formation of two particle (crystal) populations during crys-[4,11,32, 34,36] . In addition, the increase of alkalinity increases the
tallization of zeolite A form low-alkaline hydrogels can be exconcentr ationof lower-polymer izedsilicate anions (monomers,
plained by specic distribut ion of nuclei in the gel matrix; most dimmers) [4446] ;this governs the reactions between silicate
of nuclei are formed in the centers of the gel particles and lower
and aluminate ions to formation of the gels with higher aluminum
part of nuclei are formed at the surface and subsurface regions ofcontent (decrease in the molar ratio, [SiO
O ] , o f gel) [50] and
2
2/Al
3 g
gel particles [37,9,38,39] . Since the nuclei positioned in the surface
thus, additionally facilitates the formation on nuclei in the gel maand subsurface regions of gel are released from the gel matrix and
trix. Finally, forA > 0.01 the excess of aluminum in the reaction
start to grow at the beginning of crystallization process,their
mixture (y > 2 ) has not a considerably inuence on the molar ratio
growth consumes most of aluminosilicate material before the nu- [SiO2/Al2O3] g [49] , so that the vales N
ofs for both the systems (S1
clei positioned in the centers of gel particles are released from and S2) become close for
A P 0.0165(see Tables 1 and 2 ). Almost
the gel matrix.
the same crystal size distribut ions of the crystalline end product
Simultaneous increase ofA and tsc (A/tsc= 1.99 = constant for obtained at given alkalinity (01656 A 6 0.046) for y = 1.3and
both systems) causes at least three effects; (i) increase of specicy = 2 (see Figs. 3 and 4 ) indicate that not only number of nuclei,
number,Ns, o f zeolite A crystals in the product of crystallization but also their distribut ion in the gel matrix does not considerably
(see Table 2 ) and conseque ntly, decrease of crystal size (see Figs.
depend on excess of aluminum in the reaction mixture at higher
14 ),(ii) decreasein the differenc ebetweenspecic number of
alkalinities of the reaction mixture.
crystals in the products obtained by hydrothermaltreatmentof
The great inuence of the excess of aluminum in the reaction
correspondi ng hydrogels of systems S1
y=
( 2.0) and S2 y( = 1.3.;
mixture at low alkalinity A( <0.01) on the specic number of cryssee Table 2 ) and conseque ntly, decrease in the difference the betals (see Table 2 ) and crystal size distribution (see Figs. 3 and 4 )is
395
s1.3. and s2.1.s.2 .3. in Fig. 5 ) with simultaneous increase of alkalinity, A, and total silica concentration,
tsc, indicate that not only
the value ofy, but also the values of
A and tscinuence the growth
rate inh0 1 1i direction relative to the growth rate h
in
0 0 1i direction. Now, keeping the thesis that the decrease of crystal growth in
h0 1 1i direction and thus, developing of {0 1 1 } crystal planes of
zeolite A is caused by distortion of the terminal SiO
4 tetrahedra
in the presence of aluminate ions [15,53] , the above mentioned effects can be readily explained by the fact that, the ratio,
L [Al/Si] ,in
the liquid phase of hydrogel increases with increasing alkalinity
[50] . Since, on the other hand, for given valuesAofand tsc, [Al/
Si]L increases with decrease yof[48,49] the higher edge-to-face aspect ratios of zeolite A obtained from system S2
y=
( 1.3) than of
these obtained from the correspond ingbatches of system S1
(y = 2.0), was expected .
Further simultaneou sincrease of A (A P 0.02291) and tsc
(tscP 0.01151) causes rounding of the crystal edges and apexes
(see SEM images s1.4., s2.4., s1.5 and s1.6. in Fig. 5 ) following by
partial (fory = 2.0,A P 0.0375and tscP 0.01885; see SEM images
s1.5. and s1.6. in Fig. 5 ) o r complete loss of individua l crystal faces
(for y = 1.3,A P 0.02291and tscP 0.01151; see SEM images s2.5
s2.7. in Fig. 5 also see Fig. 6 ). The rounding of the crystal edges
and apexes can be explained by surface nucleation [15] , as postulated by Unemura et al. (see Fig. 2 i n Ref. [54] ), caused by increase
of supersaturation level with simultaneou s increase Aofand tsc
[21,22] . On the other hand, since the loss of individua l crystal faces
is connectedwith the pseudo-sph ericalshape of the particles
(crystals) of zeolite A (see Fig. 6 ) one can assume that, under the
given chemical conditionsA(P 0.02291,tscP 0.01151for y = 1.3
and A P 0.0375, tscP 0.01885 for y = 2.0),the growth rate is
approximat ely the same in all directions. However, since there is
not a theoretical basis or even an experime ntal evidence for such
an assumption, it is more realistic to assume that a gradual rounding of zeolite A crystals and formation of the pseudo-sph erical
particles of zeolite A i s caused by intensive surface nucleation at
high supersaturati on characteristic for the above mentioned condition. On the other hand, the absence of identiable individual crystal planes accompani ed by high roughness of particles surfaces (see
Fig. 6 ) indicates that the intense surface nucleation [54] was probably followed by a rapid growth [15] of the formed surface nuclei.
In this context, the complete disappearingof individual crystal
Fig. 5. SEM images of the crystalline end products obtained by hydrothermal
planes at lower values of
A (0.02291) andtsc(0.01151) fory = 1.3
treatment of hydrogels H1.1. (s1.1.), H2.1 (s2.1.), H1.2. (s1.2.), H2.2. (s2.2.), H1.3.
(s1.3.), H2.3 (s2.3.), H1.4. (s1.4.), H2.4. (s2.4.), H1.5. (s1.5.), H2.5. (s2.5.), H1.6. (see
(s1.6.)SEM image s.2.5 in Fig. 5 ) relative to only partial disappearing
H2.6. (s2.6.), H1.7. (s1.7.), H2.7. (s2.7.), H1.8. (s1.8.), H2.8. (s2.8.), H1.9. (s1.9.), H2.9.
(s2.9.), H1.10 (s1.10.) and H2.10. (s.2.10.).
396
397
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