Materials Performance and Characterization Nevin Koshy, 1 Bhagwanjee Jha, 2 Srinivas Kadali, 3 and D. N. Singh 4 DOI: 10.1520/MPC20140053 Synthesis and Characterization of Ca and Na Zeolites (Non- Pozzolanic Materials) Obtained From Fly Ash–Ca(OH) 2 Interaction VOL. 4 / NO. 1 / 2015
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Synthesis and Characterization of Ca and Na Zeolites (Non-Pozzolanic Materials)
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Materials Performance andCharacterization
Nevin Koshy,1 Bhagwanjee Jha,2 Srinivas Kadali,3 and D. N. Singh4
DOI: 10.1520/MPC20140053
Synthesis andCharacterization of Caand Na Zeolites (Non-Pozzolanic Materials)Obtained From FlyAsh–Ca(OH)2 Interaction
VOL. 4 / NO. 1 / 2015
Nevin Koshy,1 Bhagwanjee Jha,2 Srinivas Kadali,3 and D. N. Singh4
Synthesis and Characterization of Caand Na Zeolites (Non-PozzolanicMaterials) Obtained From FlyAsh–Ca(OH)2 Interaction
Reference
Koshy, Nevin, Jha, Bhagwanjee, Kadali, Srinivas, and Singh, D. N., “Synthesis and
Characterization of Ca and Na Zeolites (Non-Pozzolanic Materials) Obtained From Fly
Over the years, fly ash from coal-based industries has been established as a potential
industrial by-product for waste valorization, especially because of the enormous
quantity being produced annually across the globe and the environmental pollution
associated with it. In this context, there has been a wide interest in using it for vari-
ous purposes such as pozzolanic cement manufacture using fly ash with Ca(OH)2[1–3], land reclamation [4], brick making [5], and soft soil stabilization [6]. Of late,
raw fly ash (RFA) has been used as a source material for synthesis of the polycrystal-
line meso- to micro-porous aluminosilicate minerals known as zeolites [7,8]. Inter-
estingly, natural form of such zeolites (i.e., the natural zeolites) has been used in
agriculture industry as a controlled release fertilizer [9,10] and for wastewater treat-
ment [11]. Zeolites (the commonly produced being sodium-based zeolites,
Nomenclature
AS ¼ autoclave systemBET ¼Brunauer-Emmett-TellerCEC ¼ cation exchange capacityEDX ¼ energy dispersive X-ray spectrometryFTIR ¼Fourier transform infrared spectroscopy
G ¼ specific gravityICP-AES ¼ inductively coupled atomic emission spectroscopy
RFA ¼ raw fly ashSEM ¼ scanning electron microscopySSA ¼ specific surface area
T ¼ interaction timeWS ¼water bath system
XRD ¼X-ray diffractionXRF ¼X-ray fluorescence
h ¼ temperature
KOSHY ET AL. ON SYNTHESIS AND CHARACTERIZATION 2
Materials Performance and Characterization
designated as Na-zeolites) synthesized from the fly ash have potential as an alterna-
tive to the natural zeolites, as they contain agro-friendly and fertilizer-specific ele-
ments (viz., soil nutrients like K, S, and P and micro-nutrients, such as Mg and Fe),
accommodated in the zeolitic pores after dissolution of the fly ash ingredients in the
alkali [12–14]. However, the impurities present in the Na-zeolites in the form of
unbounded/free sodium have been identified as an undesirable constituent in the
zeolites [15]. If used in large quantities for agriculture, this situation would cause
undesirable sodicity and salinity in the soil, which is detrimental to plant growth
because of soil-pore locking and flocculation, respectively [16,17]. In such circum-
stances, the most challenging task would be to synthesize Na-zeolite with no
free/unbounded Naþ using NaOH. Considering the incomplete interaction between
fly ash and NaOH, as reported by the previous researchers [7,8], the solution would
be to use an adequate quantity of NaOH for only maintaining pH. With this in view,
an agro-friendly alkali, i.e., Ca(OH)2, would prove to be a panacea for synthesis of
Ca-zeolites [18]. The presence of NaOH in the process along with Ca(OH)2 hints at
formation of a blend of zeolites, which may be dominated by Ca-zeolites inter-
mingled with some Na-zeolites as well, in the end products.
Also, other pertinent issues include cost of production of Ca-zeolites, require-
ment of their crystallinity, and cation exchange capacity (CEC) to be at par with
Na-zeolites. Based on a critical synthesis of literature, it has been shown that pure
phase of many zeolites (viz., epistilbite, gismondine, heulandite, levynite, phillipsite,
scolecite, thomsonite, and wairakite) are Ca exchanged zeolites, which may be syn-
thesized by using rhyolitic glass, basaltic glass (conforming to glass in the fly ash), ol-
igoclase, and nepheline under an alkaline environment of Ca(OH)2 and other
mineralizing mixtures of chemicals (viz., CaCl2 and NaOH) by hydrothermal treat-
ment under autogenous pressures at temperatures varying from 100�C to 250�C
[19]. Moreover, perlite, an amorphous, rhyolitic (volcanic) glass, has also been used
as a raw material for synthesis of Ca-zeolites (viz., epistilbite, heulandite, and gis-
mondine) as reported by Khodabandeh and Davis [20]. Interestingly, out of the
common types of Ca-zeolites mentioned above, wairakite (CaAl2Si4O12 � 2H2O) has
been reported as the most popular among various lime hydration products, obtained
from various syntheses procedures [19,21,22]. In addition, based on crystal structure
and comparable CEC, wairakite has been ascertained as the calcium analog of the
popular Na-zeolite, analcime (Na2Al2Si4O12 � 2H2O), which has usually been synthe-
sized by the previous researchers from alumina-silica gel under high pH conditions
[23]. The Ca-zeolites thus synthesized are expected to perform effectively as agro-
grade zeolites, as fertilizer, which may turn out to be quite economical over natural
zeolites. To meet large fertilizer demand, large-scale synthesis of Ca-zeolites would
be highly warranted at pilot plant scale. Furthermore, innovative efforts like using
seawater (i.e., water containing NaCl) for the synthesis of zeolites from the
RFA have been attempted in the recent past [24], which ascertains significant crys-
tallization of the end products and conversion of the RFA to Na-zeolites (viz.,
hydroxysodalite and Na-X) up to 88 %.
With this in view, to ensure large-scale production of the agro- and aqua-grade
zeolites and economic scaling up of the pilot synthesis unit in the future, the present
study is focused to employ (1) NaCl as a minor reagent, (2) high pH condition, by
dosing reaction mixture with traces of NaOH, and (3) Ca(OH)2, hydraulic lime, as
KOSHY ET AL. ON SYNTHESIS AND CHARACTERIZATION 3
Materials Performance and Characterization
major activating reagent. In addition, to establish a suitable process for low-cost pro-
duction of Ca- and Na-zeolites (the agro-grade zeolites), the present study is targeted
to undergo a comparative evaluation of two different types of synthesis methods: (1)
conventional hydrothermal activation under atmospheric pressure, and (2) autoclav-
ing the reaction mixture at autogenously set pressure and temperature under con-
trolled conditions. Furthermore, to monitor the micro-level transitions, which are
physico-chemical, mineralogical, structural, and morphological in nature, of the
RFA into the end product, various characterization tools (viz., Fourier transform
infrared spectroscopy, FTIR; X-ray diffraction spectroscopy, XRD; and scanning
electron microscopy-energy dispersive X-ray spectroscopy, SEM-EDX) have been
employed, and details of the methodology adopted are presented in this paper. It is
believed that this study would establish fly ash and its minor elements (viz., K, S, P,
Fe, and Mg conforming to micro-nutrients in a conventional fertilizer and manure)
as an agro-friendly resource material, as novel grade of fly ash zeolites [12–14]), and
in all, the study would be quite useful for scaling up the process to a commercial
(large-scale) production of fly ash zeolites for agriculture and water treatment. In all,
diversification of fly ash–Ca(OH)2 interaction from well-established formation of
pozzolanic cementitious materials to zeolites makes this study very interesting. To
grade the end products as an absorbent/adsorbent material, CEC has been identified
as a reference property of the end products [8].
Experimental Details
The RFA used for this study was obtained from the hoppers of the electrostatic pre-
cipitators of a coal thermal power plant in central Maharashtra, India. It is com-
prised of particle sizes ranging from 0.375l to 200 l. To remove major content of
unburned carbon particles, the raw fly ash was sieved through sieve No. 230 (aper-
ture size �63 l) as prescribed by ASTM E11-13 [25], and the quantity of the finer
ash passing through the sieve (designated as RFA) was employed. The activating
reagents, Ca(OH)2, NaOH, and NaCl, were procured from Merck Millipore (Mum-
bai, India). Before starting the synthesis, the initial pH of the reaction mixture was
maintained between 13 and 13.5, by adding traces of NaOH and homogeneously
mixing it with the help of a pitched blade turbine impeller (at 450 rpm). The
mixtures of different initial compositions (see Table 1) were treated in solution phase
(L/S¼ 2.54) by resorting to two types of hydrothermal treatments: (1) a Teflon-lined
5-l autoclave reactor, at controlled temperature (�100 to 175�C) and autogenously
set pressure (i.e., termed as an autoclave system, designated as AS), and (2) a water
bath (i.e., termed as water bath system, designated as WS) at controlled temperature
(�98 �C) and atmospheric pressure. Murayama et al. [26] have said that the higher
reaction rate occurs either at higher temperature or longer reaction times, and auto-
claving was carried out for short durations (1 to 6 h), whereas a water bath was set
for longer reaction times ranging from 4 to 24 h (see Table 1). After completion of
the targeted treatment, both the autoclave and the water bath were allowed to cool.
Subsequently, the end product (solid phase) was separated by vacuum filtration,
which was followed by oven drying of the end products at 60�C for 24 h. As shown
in Table 1, based on the variation in temperature, h, and the activation time, T, for
the two types of hydrothermal treatments, the end products have been designated as
Note: I, Impurities (¼FeþMg); -, below detection limit.
FIG. 5
The FTIR spectra of the RFA
and various end products of
the water bath system.
KOSHY ET AL. ON SYNTHESIS AND CHARACTERIZATION 10
Materials Performance and Characterization
pozzolanic materials in similar interactions reported by previous researchers [1,2].
Superiority of WS3 over WS4 and WS5 establishes that 10 h is more effective than
12 and 24 h for activation of the fly ash with Ca(OH)2. This is an improvement in
alkali–fly ash interaction as compared to previous reports on fly ash–NaOH interac-
tion, which ascertained longer interaction for obtaining higher CEC of the products
of an open system [8,15,26,27,29,30]. On the other hand, out of all the X-ray diffrac-
tograms of the products of the autoclaved system (see Fig. 2), AS1 to AS4 show
appreciable CEC (189 to 327 meq/100 g). Furthermore, prominent calcite peaks are
observed in AS1 and AS2, which can be attributed to their low CEC. Incidentally,
FIG. 6
The FTIR spectra of the RFA
and various end products of
the autoclave system.
FIG. 7
Particle size distribution of the
RFA and the most superior end
product, WS3.
KOSHY ET AL. ON SYNTHESIS AND CHARACTERIZATION 11
Materials Performance and Characterization
AS3 and AS4 are comprised of zeolite P and wairakite mainly, and have relatively
less peak intensity of calcite. These could be attributing factors for their high CEC.
Interestingly, both AS3 and AS4 could be graded as comparable products, as both
have nearly similar CEC (323 to 327 meq/100 g) and mineralogy. Incidentally, the
blend comprising wairakite, heulandite, zeolite P, and phillipsite, could be responsi-
ble for the higher CEC of the AS3 and AS4. The variation in CEC (see Table 2) and
phase transition in the XRD diffractogram (Fig. 2) are indicative of negligible effect
of change in temperature and time from 150�C to 175 �C and 1 to 2 h on the end
products, in the closed autoclaved system. To be more precise, it can be seen that the
amount of zeolitic formation (out of the total mineral phases) is highest for WS3
(¼28 %) and AS4 (¼36 %). Higher zeolitic content in AS4 could be because of sev-
eral crystalline Ca-zeolites (viz., heulandite and wairakite) peaks in the XRD diffrac-
tograms. However, its lower CEC can be attributed to lesser presence of Na-zeolites
(viz., zeolites P and phillipsite), which are more porous and are responsible for
imparting higher CEC, as in the case of WS3. The above-mentioned findings,
derived from the XRD diffractograms, are further substantiated from the SEM
micrographs of the various end products (see Figs. 3 and 4) and semi-quantitative
elemental heterogeneity on the crystal surface clarified by the EDX results (see
Table 3). It can be seen that the RFA (see Fig. 3(a)) consists of the majority of par-
ticles, which are <2lm, whereas fewer particles are �8lm in size, which are shaped
as spherules. These particles get converted to new morphology as bigger spheres of
wairakite and spherules of zeolite P (see Fig. 3(c)–3(e)), deposited on the end prod-
uct WS3, which are comprised of enhanced concentration of Na and Ca, as com-
pared to RFA, noted in Table 3. The noticeable peak of wairakite occurs at
2h¼ 26.299� (ICDD PDF No. 00-042-1451) in the XRD diffractogram, which indi-
cates the transformation of the mullite peak (2h¼ 26.287�, ICDD PDF No. 01-079-
1457) into zeolites (see Fig. 2).
The morphology of the superior products is clearly visible from the SEM micro-
graphs shown in Figs. 3 and 4. Figure 3(c) ascertains formation of fewer Ca-zeolite,
TABLE 4
Chemical composition (% by weight) of the raw fly ash and end products.
Oxide RFA WS3 AS1
SiO2 58.011 47.546 49.951
Al2O3 29.059 23.530 21.559
CaO 0.721 16.710 18.843
Fe2O3 6.091 4.311 2.952
TiO2 3.761 1.489 0.968
K2O 1.087 0.117 0.527
MgO 0.455 1.431 4.274
Na2O 0.183 3.138 0.741
P2O5 0.118 0.001 0.047
MnO2 0.050 0.035 0.034
SO3 0.038 0.001 0.047
SrO 0.034 0.027 0.031
KOSHY ET AL. ON SYNTHESIS AND CHARACTERIZATION 12
Materials Performance and Characterization
heulandite, as rhombohedral pellets of mineral phase, enriched in Ca (see Table 3), a
portion of which could be in the calcite phase as well as confirmed by the micro-
graph and the XRD diffractogram (see Fig. 1) of WS4. Incidentally, Fig. 3(c) also
exhibits large numbers of thin prismatic crystals, identified as Ca-zeolite, heulandite
(see EDX spectrum S4 in Table 3), and fewer crystals of phillipsite (a Na-zeolite),
present in the product, WS4. In view of the above observations, it can be seen that
the blend of zeolites identified in WS3, and WS5 (i.e., zeolites P and wairakite) are
remarkably different than WS4 (i.e., heulandite, phillipsite, and zeolite P). Moreover,
higher CEC of WS3 could result from higher Na-zeolites (zeolite P), present in this
product, than WS4. On the other hand, micrographs of AS1 (see Fig. 4(a)) and AS2
(see Fig. 4(b)) products show similar composition of the blend (i.e., zeolite P and
wairakite), as confirmed by the EDX results (see Table 3). Moreover, AS3 (see Fig.
4(c)) and AS4 (see Fig. 4(d)) exhibit many distinct crystals of heulandite and few big-
ger spherical wairakite crystals, also confirmed by their EDX results (see Table 3). A
comparison of micrographs of all the WS and AS superior products indicates that
wairakite grows more remarkably under higher temperature and pressure conditions
in the autoclaved (closed) system, whereas longer interaction time is effective in an
open system. In addition, AS3 reveals presence of calcite crystals, which could be a
deterrent for higher CEC of the product.
The transition in particle size and the crystallization of new minerals gets elabo-
rated from the FTIR spectra (see Figs. 5 and 6), which indicate formation of the new
bands at 3454 cm�1. These bands are broader and deeper in the WS products, in
general, and much more distinct in case of WS3 than the AS products. This can be
attributed to (1) asymmetric stretching of Si-OH (the silanol) bonds, and (2) higher
rate of zeolitization reactions between hydroxyl ion of the Ca(OH)2-NaOH (the
reagents) and the Si and Al (see Tables 3 and 4), present in the RFA, for the water
bath system. On the contrary, corresponding shallow bands in the AS products
could be a result of breakage of some of the OH� ions under pressurized and high
temperatures, which may lead to oxidation of the trace elements (viz., Fe, Mg, Mn,
S, P, Ti, etc., as listed in Table 4) of the RFA, and less existence of hydroxyl ion in
the AS. Furthermore, bands at 1663 cm�1 and 1485 cm�1 also establish formation of
improved products as a result of WS treatment, which gets reflected in the bands
obtained for WS3, which yields very high CEC (see Table 2) and consists of fewer
impurities (viz., carbonates and nitrates), respectively [29,30]. Incidentally, bands at
1015 cm�1 are revelations of more crystallinity of the AS products than the WS,
which is comprised of broader but shallower bands. The broader bands in the WS
product at 1015 cm�1 might indicate its soft crystal structure and Si-O-Si bonds
[8,27,29], as compared to the AS products. The soft structures of the crystals raise a
fresh issue regarding stability of the zeolites, present in WS3. The oxidation of the
trace elements as discussed above gets verified again because of the presence of
sharper and deeper bands at 875.6 cm�1 (corresponds to calcium phosphates),
609 cm�1 (corresponds to Fe bonded compounds), and 460 cm�1 (corresponds to
nitrates) in the AS products. Based on the above FTIR spectra, effectiveness of the
fly ash-Ca(OH)2 interaction gets more established for the most superior product
WS3 than its counterpart, AS4, which is comprised of maximum zeolitic content up
to 36 % in the end product. With all the above findings on WS3, efforts have been
made to determine its specific gravity and particle size. The specific gravity, G, of
KOSHY ET AL. ON SYNTHESIS AND CHARACTERIZATION 13
Materials Performance and Characterization
WS3 was found to be 2.637, a higher value as compared to that of RFA (¼2.224),which is in agreement with the findings of Kolay et al. [7]. This increase in G could
be because of the release of entrapped air in the cenospheres of the initial fly ash par-
ticles as a result of the surface-etching effects of the alkali reagents and their entry
into the core of the fly ash particles. Also, SSA of this product is seen to increase
from 0.5 m2/g (for RFA) to 75.4 m2/g. An increase of SSA by 150 times is indicative
of (1) the transitions in surface features of the RFA, and/or (2) formation of new
finer particles (see Fig. 7).
Moreover, the particle size distribution (see Fig. 7) for the most superior prod-
uct, WS3 shows that fly ash–Ca(OH)2 interaction results in an increase in particle
sizes of the product, as compared to those in the RFA, greater than 10lm. This
can be attributed to the crystallization on the surface of the fly ash particles after
interaction with the alkali. Subsequently, because of etching of the surface of the
particles present in the RFA (<10lm), their size in the most superior product,
WS3, gradually decreases [29]. The particles in this range could also contain zeo-
litic products, synthesized by the RFA-alkali interaction. Incidentally, the average
particle size of the conventional fertilizer falls in the range 1 to 5mm. Thus, WS3,
with <1mm size could be a better choice for application as fertilizer in
agriculture.
Based on above findings, the synthesized blend of zeolites is seen to have signifi-
cant presence of Ca with low Na concentration, which can be a better option for ag-
ricultural application and waste water decontamination. The major contribution of
this study lies in the agro-friendly ingredients present in the synthesized zeolites. In
this context, Table 3 highlights traces of K, S, and P in most of the superior products.
Incidentally, increased concentration of these elements in the most superior product,
WS3, makes it suitable to be used as agro-grade zeolites, i.e., as fertilizers in agricul-
ture [12–14]. Thus, WS3 can be shown to have double benefits like higher CEC and
agro-friendly elements in its pores, as revealed by the FTIR bands in the range of
600 to 400 cm�1 [27].
Conclusions
Based on the findings of the study, the following can be concluded:
1. The fly ash-Ca(OH)2 interaction, in an open system, is very effective for for-mation of blends of zeolite P and wairakite in a relatively less activation timeof 10 h at 98�C.
2. Higher temperature (150�C to 175�C) and less activation time (1 to 2 h) issuitable for the growth of wairakite zeolites in the products of an autoclaved(read “a closed”) system.
3. From the comparison of the CECs of autoclaved system products, it can beconcluded that the higher the NaCl, the lower the zeolitization of the fly ash.
4. Less CEC and FTIR bands corresponding to hydroxyl group in the products,from the autoclaved system, make them inferior with respect to their counter-parts from the water bath system.
5. The presence of S, K, and P in the blend of zeolites (viz., heulandites, waira-kite, zeolite P, and phillipsite) makes them suitable as agro-grade zeolites,which can be used as fertilizers.
KOSHY ET AL. ON SYNTHESIS AND CHARACTERIZATION 14
Materials Performance and Characterization
ACKNOWLEDGMENTS
The authors acknowledge the facilities availed by them at the Sophisticated Analyti-
cal Instrument Facility (SAIF) and the XRD Laboratory, Department of Earth Scien-
ces of IIT Bombay, during the course of this study.
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