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SEM-EDX and XRD Characterization of Zeolite NaA, Synthesized from Rice

Husk and Aluminium Scrap by Different Procedures for Preparation of the
Initial Hydrogel

Article  in  Journal of Porous Materials · January 2013

DOI: 10.1007/s10934-012-9594-x

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J Porous Mater
DOI 10.1007/s10934-012-9594-x

SEM–EDX and XRD characterization of zeolite NaA, synthesized

from rice husk and aluminium scrap by different procedures
for preparation of the initial hydrogel
Annie Shoumkova • Valeria Stoyanova

Ó Springer Science+Business Media, LLC 2012

Abstract A number of investigations have demonstrated Keywords Zeolite NaA
Rice husk
Waste aluminium

that zeolite NaA could be synthesized using Si, extracted SEM–EDX
from rice husk ash; however, experiments on direct
extraction of Si from rice husk (RH) are scarce. The main
objective of the present study was to explore the possibility 1 Introduction
to synthesize high-quality zeolite NaA from RH and waste
aluminium cans (as a source of Al), applying different Synthetic zeolite NaA (Na12Al12Si12O48
27H2O) was dis-
procedures for the preparation of initial hydrogel and a covered in the middle of the twentieth century by Milton [1].
unified procedure for crystallization of zeolite NaA. Since ‘‘Procter and Gamble’’ introduced zeolite NaA as a
Products were characterized by SEM–EDX and XRD water softening ‘‘builder’’ in laundry detergents [2], it has
analyses. The investigation demonstrated that Si could be become the most important synthetic zeolite, commercially
extracted directly from RH, avoiding the process of RH used in various (waste)water treatment and purification
burning. Practically complete dissolution of Si from RH processes [3]. Zeolite NaA has a growing global market,
was achieved by alkali treatment (with 10 % NaOH for estimated of about one million tons per annum, thus the
7 h) at boiling temperature and atmospheric pressure, i.e. elaboration of methods for its economical production is a
using refluxing system instead of autoclave for the prepa- subject of a great practical interest. Conventional synthesis
ration of Si-gel. Zeolite NaA samples synthesized from of zeolite NaA involves hydrothermal crystallization of
such Si-gels were pure, highly crystalline and white. Fur- aluminosilicate gels or solutions in the presence of sodium
thermore, it was found that the direct dissolution of Al in cations under alkaline environment. Zeolite NaA could be
Si-gel did not affect the quality of the final product. synthesized using variety of Al and Si chemicals, including
Although this investigation was not focused on the mech- aluminium, aluminium hydroxide, sodium aluminate,
anism of zeolite NaA crystallization, the results obtained sodium silicate, silica gels, reactive amorphous solid silica,
indicated clearly that the history of Si-gel preparation etc. For industrial production of zeolites, some cheaper
played an important role in the nucleation and growth of natural materials, such as clay minerals [4, 5] and natural
zeolite NaA crystals and influenced their yield, size, and zeolites [6], could be used as Si or Si–Al sources; however,
shape. Therefore, the optimization of Si-gel preparation their reprocessing usually involves some high energy-con-
procedure has to be considered as essential not only for the sumption processes like grinding, calcination and fusion [3].
economy of the synthesis of NaA from RH, but also for the On the other hand, some recent studies [7–12] have dem-
quality of the final product. onstrated that pure, commercial-grade zeolite NaA could be
successfully synthesized from silica-rich (85–98 % SiO2
[8]) rice husk ash (RHA), obtained by burning of rice husk
A. Shoumkova (&)
V. Stoyanova (RH), one of the largest agricultural wastes with annual
Rostislaw Kaischew Institute of Physical Chemistry, Bulgarian world production of about 130,000,000 t [13] (11,400 t for
Academy of Sciences, ‘‘Acad. G. Bonchev’’ Str., block 11,
1113 Sofia, Bulgaria
Bulgaria). The composition of RHA and its zeolitization
e-mail: [email protected] behaviour are dependent mainly on RH calcination

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temperature. The complete RH burning at high temperatures out that the Si/Al ratio (1–50), as well as the heating time
(850–1,200 °C) produces white, carbon-free, low-reactive (0–38 h), temperature (120–180 °C) and heating source
crystalline SiO2, while the incomplete roasting at lower affect the crystallinity and the size of zeolite. The maxi-
temperatures yields so-called carbonized RHA, containing mum crystallinity of NaA zeolite was obtained at Si/Al mol
carbonaceous material and highly reactive amorphous SiO2 ratio of 18 after 18 h heating (including 2 h microwave
[14]. The carbonized RHA is more easily dissolvable in irradiation) at 180 °C, while much longer time was needed
alkaline medium and thus is the preferred starting material to gain the same crystallinity by conventional heating.
for preparation of alkaline silicate solution, which is then Pseudo-spherical zeolite NaA particles were produced
mixed with aluminate solution, and processed by hydro- under all temperature regimes. Yusof et al. [13] also
thermal methods to produce zeolite [3, 10]. reported on successful synthesis of pure zeolite NaA, i.e.
Nur [10] experimented synthesis of zeolite NaA from without admixture zeolite phases, from RHA (obtained at
carbonized RHA and RH. Si was extracted from RH by 600 °C for 1 h). The silicate solution, prepared by heating
leaching with NaOH at 150 °C in autoclave, while RHA of RHA and NaOH solution at boiling temperature, was
was dissolved by heating at atmospheric pressure. Then the mixed with sodium aluminate solution to form hydrogel,
obtained solutions were mixed with sodium aluminate which was then subjected to crystallization for 6 h at
solution and subjected to crystallization for 5 h at 100 °C, 100 °C at autogenous pressure. Pimraksa et al. [14]
followed by calcination at 400 °C for 1 h. It was demon- experimented two synthesis methods, refluxing (at 100 °C)
strated that NaA zeolite can be synthesized directly from and autoclaving (at 130 °C), in the hydrothermal synthesis
both, RH and carbonized RHA, but the quality of NaA of zeolites directly from RHA and Al(OH)3. They found
zeolite obtained from RH was lower, due to the tendency out that the refluxing method did not result in any zeolite
for formation of amorphous phases and the presence of material, due to the insufficient reactivity of Al(OH)3 under
impurities, giving yellowish coloring of the product. Pet- the conditions tested (3 M NaOH, liquid to solid ratio of
kowicz et al. [11] also synthesized highly crystalline zeo- 8:1, reaction times of 24 and 48 h).
lite NaA products from carbonized at 600 °C RHA. The review of the studies, published in the last 1–2 decades,
Preliminary acid leaching of RH resulted in a lower crys- demonstrated that zeolite NaA could be successfully synthe-
tallinity of the product and in truncated edges of NaA sized from Si-gel prepared by alkali extraction of silica from
cubes. Foletto et al. [9] reported that cation exchange rice husk ash (RHA). However, just a couple of papers [7, 10]
capacity (CEC) of zeolite NaA, synthesized from RHA in discussing the direct extraction of Si from RH, i.e. avoiding
autoclave, decreased from 5.72 to 5.00 meq g-1 with the the preliminary burning of RH, were found. Both studies
increase of crystallization time from 3 to 12 h. The zeolite confirmed that Si could be extracted directly from RH, but the
particles seemed to be formed by random accumulations of obtained NaA zeolites were not as good in quality [10] and
crystallites and were of irregular shape. Wajima et al. [12] yield [7, 10] as those, synthesized using RHA. For this reason,
investigated the effect of experimental conditions on zeo- the main objective of the present study was to explore the
lite NaA synthesis from RHA, obtained by burning of RH possibility to synthesize high-quality crystalline zeolite NaA
at 650 °C for 2 h. The process was studied as a function of from Si, directly extracted from RH, and waste aluminium
NaAlO2 addition (SiO2/Al2O3 molar ratio = 1.7–2.8), cans (as a source of Al), applying several new simplified and
NaOH concentration (2–6 M), temperature (50–80 °C), economical procedures for the preparation of the initial
and reaction (0–48 h). Single-phase zeolite NaA was syn- hydrogels, and a unified crystallization regime.
thesized from RHA under all experimental conditions tes-
ted. High crystallinity was obtained rapidly when SiO2/
Al2O3 ratio, NaOH concentration and temperature were 2 Experimental
higher in the studied ranges of experimental conditions
variation. Azizi and Yousefpour [7] investigated the syn- 2.1 Materials
thesis of zeolite NaA using RHA obtained at 600 °C and
RH. The dissolution of the silica was assisted by heating at RH (sort ‘‘Halil B’’) was supplied by ‘‘Rice company’’
70 °C for 1 week. Crystallization of zeolite was carried out Ltd., Stara Zagora, Bulgaria, and used directly, i.e. without
by the two methods: conventional hydrothermal method any pre-treatment. Waste aluminium cans were taken from
and microwave-assisted method, in which the sample was the system for separate municipal solid wastes collection in
subjected to microwave irradiation for 2 h prior to the Sofia, Bulgaria. They were cut off, washed with water, put
heating by hydrothermal method. The authors reported that in 50 % H2SO4 for 5 s to remove the printed decoration,
the direct synthesis of zeolite NaA from RH as silica source rinsed with distilled water, and dried. Pure NaOH pellets
gave lower yield with respect to RHA; therefore the main and distilled water were used for the preparation of 10 %
experimental work was carried out using RHA. They found NaOH solution.

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2.2 Procedure Sample 5

Step 5.1 See Step 1.1.
2.2.1 General procedure Step 5.2 6 g RH was mixed with 60 ml 10 % NaOH and
kept at room temperature for 100 h at continuous stirring.
The reaction mixtures (hydrogels) were prepared according The indissoluble residue was separated from the obtained
to the described below specific procedures. The fresh Si-gel by filtration through glass filter and washing with
hydrogels were subjected to crystallization at 90 ± 5 °C 100 ml hot water.
for 5 h in a closed vessel, equipped with water-cooled Step 5.3 See Step 1.4.
reflux condenser, thermometer, and magnetic stirrer
(250 rpm). The obtained product was vacuum-filtered, 2.3 Methods and equipments
washed with distilled water until pH 8 was reached, dried
at 105 °C overnight, and analyzed. Morphology and elemental composition of initial materials,
intermediate and end products were examined by scanning
2.2.2 Specific procedures for hydrogels preparation electron microscope (SEM); model JEOL JSM6390, cou-
pled with energy-dispersive X-ray (EDX) analyzer, Oxford
Sample 1 Instruments. Average composition of the samples was
Step 1.1 1 g Al was added to 60 ml 10 % NaOH and left estimated on the base of so-called ‘‘integral spectra’’ taken
overnight at room temperature without stirring, in order to at low magnification (91000 for RH and by-products, 930
form Al-gel. for RHA and final products).
Step 1.2 6 g RH was burned in electric oven at 800 °C Particles (crystals) size distribution of the crystalline end
for 2 h, a regime selected in order to produce RHA, products (zeolite NaA) were estimated on the base of the
consisting of amorphous silica with low carbon content, spherical equivalent diameter of 300 individual particles of
according to [15]. each sample, determined from SEM micrographs.
Step 1.3 The RHA obtained was mixed with 60 ml 10 % Powder X-ray diffraction (XRD) data for phase identi-
NaOH, heated at 140–150 °C for 7 h in Teflon-sealed fication were collected by Philips PW 1050 automatic
autoclave (100 ml) under autogenous pressure without stirring. powder diffractometer, using CuKa filtered radiation and
The obtained Si-gel product was diluted with 100 ml water. Bragg–Brentanogeometry. Step-scan data were recorded in
Step 1.4 Al-gel was added to Si-gel (both gels freshly the angle interval 5°–80° (2h) with a step of 0.04° (2h) and
prepared) at room temperature under intensive stirring. accounting time of 2 s per step. Equal mass of powdered
samples and identical sample holders were used in all
Sample 2
measurements.
Step 2.1 See Step 1.1.
The reaction yields were expressed by the mass of dry
Step 2.2 6 g RH was mixed with 60 ml 10 % NaOH,
zeolite product, obtained from 6 g of RH.
heated at 140–150 °C for 7 h in Teflon-sealed autoclave
(100 ml) under autogenous pressure, without stirring. The
indissoluble residue was separated from the obtained Si-gel
3 Results and discussion
by filtration through glass filter and washing with 100 ml
hot water.
6 g RH yielded 1 g RHA with the following elemental
Step 2.3 See Step 1.4.
composition (normalized): SiO2—92.1 wt.%, K2O—4.4
Sample 3 wt.%, CaO—1.9 wt.%, MgO—1.0 wt.%, MnO—0.6 wt.%.
Step 3.1 See Step 1.1. RHA analysis confirmed that carbon had been completely
Step 3.2 6 g RH was mixed with 60 ml 10 % NaOH and burned during the thermal treatment of RH. The alkali
heated at 105 °C for 7 h under continuous stirring treatment of RH in autoclave produced 6.8 % indissoluble
(150 rpm) and vapor refluxing. The indissoluble residue residue, containing about 0.95 wt.% SiO2 (0.065 g) and
was separated from the obtained Si-gel by filtration through 0.27 wt.% CaO. The quantity of the residue, obtained in the
glass filter and washing with 100 ml hot water. refluxing system, was much greater—30 %. However, this
material contained only 0.19 % SiO2 (0.054 g) and 0.12
Step 3.3 See Step 1.4.
wt.% CaO, i.e. even smaller quantity of undissolved SiO2.
Sample 4 These results could be explained with the fact that SiO2
Step 4.1 Step 3.2. extraction from RH is a diffusion-limited process, assisted
Step 4.2 Si-gel was cooled, mixed with 60 ml 10 % by the intensified mass-exchange, resulting from the boil-
NaOH and 1 g Al, and kept at 25 °C overnight (16 h) ing and stirring in the refluxing system, while the higher
without stirring. temperature and pressure in the autoclave facilitate the

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conversion of the polysaccharides, participating in hemi- most probably hydrated (alkali) cellulose [17]. RHA
cellulose, into water-soluble monosaccharides (pentoses (Fig. 1b) kept the external relief of raw RH (Fig. 1a), due
and hexoses) [17], which increases the mass loss. SEM to the uniform distribution of SiO2 on its surface protective
observations showed that both residues looked quite similar layer.
in microstructure (see Fig. 1c), despite of the much lighter XRD patterns of the synthesized zeolite samples are
brown shade of the one, obtained in autoclave. An addi- presented in Fig. 2. The obtained diffractograms were
tional experiment at prolonged treatment (10 h) in auto- similar and matched zeolite NaA (PDF 00-039-0222).
clave produced 16.2 % white fiber product (see Fig. 1d), Admixture zeolite phases were not detected; however,

Fig. 1 SEM micrographs of:

a RH; b RHA; c indissoluble
residue from refluxing system
(7 h); d indissoluble residue
from autoclave (10 h)

Fig. 2 XRD patterns of the

synthesized zeolite NaA
samples

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Fig. 3 SEM micrographs of the

synthesized zeolite NaA
samples

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Sample 5 was found to be highly amorphous, with much ions in the solution will lead to the formation of cubic
less intensive characteristic peaks. The SEM observation of crystals with truncated edges, while at lower Al con-
the microstructure (Fig. 3) of the synthesized zeolite NaA centration regular cubes will crystallize. This hypothesis
samples confirmed that Samples 1–4 consisted predomi- fits to the results obtained for Sample 5 that was syn-
nantly of fine cubic crystals, while Sample 5 contains thesized at higher Al/Si ratio, due to the incomplete
significant quantity of amorphous-looking material and extraction of silica from RH, and for Sample 4, in which
relatively small amount of zeolite NaA crystals, homoge- zeolite NaA started to crystallize from a solution with
neously dispersed in it. lower Al/Si.
Shape and size of zeolite NaA crystals in the different The average elemental composition of the synthesized
samples varied. The crystal size distribution of the syn- zeolite NaA samples is presented in Table 1. Minor devi-
thesized zeolites is illustrated in Fig. 4. It is obvious that ations (max ± 2.8 %) from the theoretical elemental
Samples 1 and 2 (both obtained from silica, extracted in composition of zeolite NaA were observed for the elements
autoclave) are finer and have smaller deviations in the O, Na and Al. In all samples, Si content was a little bit
crystal size; however, further experiments are needed in higher (7–15 %) than theoretical, which may result in a
order to elucidate the nucleation and crystal growth phe- slight decrease in CEC from the value, calculated from the
nomena in the studied systems, and to find reliable expla- chemical formula of ideal zeolite NaA, in which the atomic
nation of the results obtained. The largest standard ratio of Si to Al is equal to 1.
deviation from the mean crystal size in Sample 4 was Zeolite yields varied and correlated almost directly with
expected and could be explained with the continuous the mean crystal sizes, which was indicative for the
nuclei formation and crystal growth during the Al disso- uncompleted crystallization process in some cases, e.g.
lution in the sodium silicate solution. Samples 2 and 5. In agreement with the results reported by
The shape of the zeolite NaA crystals (Fig. 3) was Azizi and Yousefpour [7], NaA zeolite from Si-gel pre-
found to vary from regular cubic crystals with sharp pared by RH treatment in autoclave (Sample 2) gave lower
edges and apexes toward cubic crystals with deeply yield than those prepared from RHA under the same con-
truncated edges in the following order: Sample 4, Sam- ditions (Sample 1). Sample 3 and Sample 4, both very light
ple 3, Sample 1, Sample 2, and Sample 5. Kosanovic and bulky materials, gave much higher yields that were
et al. [18] and Bosnar et al. [19], who investigated reproduced with small deviations of maximum ±2 %. It
systematically the influence of the batch molar ratio on was supposed that these samples might contain certain
the crystal morphology of zeolite NaA, synthesized from quantities of Al(OH)3; however, this conjecture was not
pure reactants, suggested that the formation of cubic confirmed by XRD analyses and SEM–EDX analyses of
crystals with truncated edges (formation of {011} crystal individual particles.
faces) was a result of the decrease of crystal growth in In discrepancy with Nur’s observations [10], the product
this direction caused by distortion of terminal SiO4 tet- synthesized from RHA (Sample 1) had yellowish colour-
rahedrons, positioned at crystal edges and apexes, in the ing, while those obtained directly from RH (Samples 2, 3,
presence of aluminate ions. Thus, it could be expected and 4) were white, which makes them applicable in
that at equal other conditions, the ‘‘excess’’ of aluminate detergent formulations.

Fig. 4 Size distributions of the

synthesized zeolite NaA crystals
in the different samples; d mean
particle size with standard
deviation

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Table 1 Average elemental composition of the synthesized zeolite NaA samples

Element, at. % Zeolite NaAa Sample 1 Sample 2 Sample 3 Sample 4 Sample 5

Si 10.8 12.0 12.0 11.6 12.4 11.7

Al 10.8 11.1 11.1 10.5 10.6 11.0
Na 10.8 10.9 11.2 10.6 10.5 11.0
O 67.6 66.0 65.7 67.3 66.5 66.3
Yield (g) – 2.6 1.7 3.9 3.6 2.2
a
Theoretical composition, calculated from the chemical formula of zeolite NaA

4 Conclusion Acknowledgments Authors express their gratitude to Mr. Ivan

Zaprianov, general manager of «Rice company» Ltd., for supplying
the RH material. The expert technical assistance of Mrs. Tsenka
Pure, highly crystalline zeolite NaA samples were suc- Tsacheva (SEM–EDX operator) and Mr. Georgi Avdeev (XRD
cessfully synthesized from alternative materials, operator) in the Institute of Physical Chemistry, Bulgarian Academy
untreated RH and waste aluminium cans, by means of of Sciences is highly appreciated.
simple, economical, and technologically feasible proce-
dures. The results obtained confirmed that silica could be
extracted directly from RH, avoiding the process of RH References
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spheric pressure, i.e. using refluxing system instead of 3. A. Shoumkova, Special issue of the research bulletin of the
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indicated that the process could be additionally opti- org/conf_papers/viewforum.php?f=45. Accessed 18 April 2012
mized towards significant reduction in the treatment time 4. C.A. Rı́os, C.D. Williams, M.A. Fullen, Appl. Clay Sci. 42, 446
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