International Journal of Arts & Sciences,

CD-ROM. ISSN: 1944-6934 :: 6(3):391396 (2013)

c 2013 by UniversityPublications.net
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HYDROTHERMAL TECHNOLOGY OF ZEOLITE MATERIALS

SYNTHESIS FROM FLY ASH
Wojciech Franus and Magorzata Franus
Lublin University of Technology, Poland
Magdalena Wdowin
Mineral and Energy Economy Research Institute of The Polish Academy of Sciences, Poland
In this paper the conversion technology of F-class fly ashes into Na-P1 zeolite material has
been presented. In the proposed solution four process stages can be distinguished: a stage of
the reactor loading, a reaction stage, a stage for separation of reaction products, and a stage for
final processing of the obtained material. The prototype line was the basis for obtaining
a zeolite material, in which Na-P1 type was a dominant phase. For synthesis processes the
following conditions were applied: 20 kg fly ash, 12 kg NaOH, 90 dm3 water, a reaction
temperature of 80 C and reaction duration of 36 hours. The content of pure zeolite phase in
the reaction product was 81% with a BET surface area increasing from 15 to 75 m2g-1. A high
conversion rate of the fly ash into the Na-P1 zeolite indicates the necessity of industrial
research into the construction of a processing line capable of manufacturing zeolite material in
industrial conditions.
Keywords: Fly ash, Synthesis of zeolites, Technical line.

Introduction
Synthetic zeolite materials can be prepared with chemical reagents in the reaction of sodium
silicate and sodium aluminate, minerals resources include: clay minerals, minerals from the silica
group, and some Circumstantial Combustion Products CCP (such as fly ash) [1-4].
The paper presents a method for producing zeolite material on the basis of the hydrothermal
reaction of Class F fly ash and NaOHaq at technical scale based on designed technical line [58].
The main component of the line is the reaction vessel about the total volume of 1.3 m3. This
vessel is equipped with a three heaters, the probe to control of reaction temperature, the sensor of
reactor filling level, a mechanical stirrer and a membrane pump. Above the reservoir the weight
tank is placed that is suspended on the tensometric weight where the synthesis reaction substrates
(fly ash and NaOH) are weighted. Water required for the synthesis is dispensed through the flow
meter. After loading the reactor is started heating system and control of process conditions.
After completion of the reaction cycle, the conversion of fly ash products are directed to a
hydraulic press in which the zeolite material is rinsed with excess NaOHaq and then subjected to
a drying process in order to activate the surface properties of the obtained material. The proposed

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technical solution the fly ash conversion into the zeolite material is fully automated and
controlled by both the PC as well as the touch screens from the various components of the line.
Using the following conditions of the synthesis process: 20 kg fly ash, 12 kg NaOH, 90 dm3
water, temperature 80 C and the duration of the reaction 36 h, can be obtain Na-P1 zeolite type
about total conversion level into the zeolite material up to 81%.
The high degree of conversion and textual and ion-exchange properties point to a broad
spectrum of applications of received zeolite materials in industrial and environmental
engineering.
Materials and Methods
F-class fly ash used for synthesis was obtained by combustion of coal at the Kozienice power
plant. The chemical composition of the fly ash is predominately SiO2 (52%) and Al2O3 (32%)
with Fe2O3 (5%) respectively. The rest of the chemical components occur in insignificant
amounts [5, 9].
The mineral composition is dominated by spherical forms of aluminosilicate glass (68%)
and mullite (22%). In addition quartz and iron oxides occur in the form of magnetite and
hematite on the aluminosilicate spheres (Fig. 1).

Figure 1. SEM images of fly ash used for the synthesis. 1) magnification 5000X, 2) magnification 10000X.

Chemical and mineral composition of all substrates and products of the reaction were
thoroughly characterized by X-ray diffraction and scanning electron microscopy. Textural
properties were determined by low temperature N2 isotherms.
Mineral composition were characterized by using a Philips Xpert APD diffractometer with
PW 3020 goniometer, Cu lamp and graphite monochromator. Analysis was performed in an
angular range of 5 65 (2 ) and the collected data was analyzed by XPert Highscore softwere.
Identified mineral phases were compared with the PDF-2 release 2010 data base formalized by
ICDD.
Morphology and chemical composition in the field of main mineral components of the
investigated materials was examined by scanning electron microscope SEM FEI Quanta 250
FEG, equipped with EDS.
The chemical composition of the fly ashes used for synthesis reactions was determined by
XRF method. With a X-ray tube equipped with dual Cr-Au anode with a maximum power of
3kW was the excitation source.

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Wojciech Franus et al.

technical solution the fly ash conversion into the zeolite material is fully automated and
controlled by both the PC as well as the touch screens from the various components of the line.
Using the following conditions of the synthesis process: 20 kg fly ash, 12 kg NaOH, 90 dm3
water, temperature 80 C and the duration of the reaction 36 h, can be obtain Na-P1 zeolite type
about total conversion level into the zeolite material up to 81%.
The high degree of conversion and textual and ion-exchange properties point to a broad
spectrum of applications of received zeolite materials in industrial and environmental
engineering.
Materials and Methods
F-class fly ash used for synthesis was obtained by combustion of coal at the Kozienice power
plant. The chemical composition of the fly ash is predominately SiO2 (52%) and Al2O3 (32%)
with Fe2O3 (5%) respectively. The rest of the chemical components occur in insignificant
amounts [5, 9].
The mineral composition is dominated by spherical forms of aluminosilicate glass (68%)
and mullite (22%). In addition quartz and iron oxides occur in the form of magnetite and
hematite on the aluminosilicate spheres (Fig. 1).

Figure 1. SEM images of fly ash used for the synthesis. 1) magnification 5000X, 2) magnification 10000X.

Chemical and mineral composition of all substrates and products of the reaction were
thoroughly characterized by X-ray diffraction and scanning electron microscopy. Textural
properties were determined by low temperature N2 isotherms.
Mineral composition were characterized by using a Philips Xpert APD diffractometer with
PW 3020 goniometer, Cu lamp and graphite monochromator. Analysis was performed in an
angular range of 5 65 (2 ) and the collected data was analyzed by XPert Highscore softwere.
Identified mineral phases were compared with the PDF-2 release 2010 data base formalized by
ICDD.
Morphology and chemical composition in the field of main mineral components of the
investigated materials was examined by scanning electron microscope SEM FEI Quanta 250
FEG, equipped with EDS.
The chemical composition of the fly ashes used for synthesis reactions was determined by
XRF method. With a X-ray tube equipped with dual Cr-Au anode with a maximum power of
3kW was the excitation source.

Hydrothermal Technology of Zeolite Materials Synthesis...

393

Textural properties study of fly ash and zeolite material were investigated by using an ASAP
2020, Micromeritics. Parameters such as specific surface area, pore size distribution and pore
volume were evaluated by analyzing the Nitrogen adsorption/desorption isotherm. Measurement
was carried out at -194,85 C in liquid Nitrogen. Prior to analysis the sample was degassed under
high vacuum at 250 C for 24 h (10-3 hPa). The specific surface area was estimated using BET
theory and pore size distribution by BJH method.
Technological Line for Conversion of Fly Ashes into Zeolites

Figure 2 presents a photography of the device for producing zeolites for technical scale. In this
test arrangement 4 process stages can be distinguished: a stage of the reactor loading, a reaction
stage, a stage for separation of reaction products, and a stage for final processing of the obtained
material.

Figure. 2. The prototype line for the synthesis of zeolites from fly ash.

The stage for the reactor loading consists of two storage tanks, where granulated NaOH and
fly ash are stored. These tanks are connected with two worm gears with a weight tank, the
purpose of each worm gear is the transport of fly ash and sodium hydroxide granules from the
storage tank to the weight tank.
The tank is made of stainless steel with the symbol 316L. It has the shape of a converse cone
head ended by a roller. In order to avoid an excessive dustiness of the room the tank is closed by
cap. To provide suitable amount of substrates for the synthesis reaction, the tank is mounted on
three weight stain gauges sensors. In order to improve the dump of substrates (NaOH, fly ash) to
the synthesis reaction tank the worm gears and the weight tank are equipped with pneumatic
piston vibrators.
The main component of the described line is a reaction tank, where the conversion process
of fly ash into zeolites is carried out. Total volume of the tank is 130 dm3 (working volume is
100 dm3). The tank is equipped with a system of three heaters (2 kW each), a probe for
controlling the reaction temperature, and the level of tank filling probe, and a stirrer which is

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sequentially switched on and is responsible for the homogenization of the material and prevents
the aggregation of the material during the reaction process. At the tank outlet a pneumatic
membrane is installed that pumps the zeolitic material during and after reaction. The separation
of the products block consist of a filter press, and two tanks in which the post-reaction aqueous
solution of NaOH as well as materials rinsing solution are stored. The aqueous solution from the
first rinsing of the reaction products is directed to the storage tank and then pumped back to the
reactor for further synthesis. A solution from rinsing is returns to its original composition and is
directed to the next reaction cycle.
The volume of water during loading and the volume of solution after modification process
and recycling are controlled by flowmeters.
The final processing stage consists of a ribbon feeder and the rotary furnace. The drying step
of the zeolitic material is obtained by filtration of the solution and calcination is using a rotary
furnace.
The whole process is fully automated and controlled by a computer or touch screens located
in the cabinets of each technological blocks.
Results
A series of zeolite synthesis reactions were carried out thanks to the proposed technological
solution. For obtaining a monomineral zeolite Na-P1 the following conditions of the conversion
process were applied: 20 kg of fly ash, 12 kg NaOH, 90 dm3 H2O, temprerature of the process 80
o
C and duration 36 hours. Obtained zeolite materials were fully characterized by scanning
electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS), powder X-ray
diffraction and N2 adsorption-desorption isotherm.

Figure 3. XRD patterns of the studied materials.

Diffractograms that show the mineral composition of the zeolite material are presented in
figure 3. A presence of Na-P1 zeolite phase in the reaction products was determine based on the
characteristic interplanar distances dhkl = 7,10; 5,01; 4,10; 3,18 . The content of the pure zeolite
phase in the product obtained under given conditions was 81%.

Hydrothermal Technology of Zeolite Materials Synthesis...

395

Figure 4. SEM images of Na-P1 zeolite material 1) magnification 6000X, 2) magnification 30000X.

The morphologies of the fly ash used for the synthesis reaction and the obtained zeolite NaP1 are shown in figure 4. Chemical analysis in the microarea revealed that sodium is the main
exchange cation in the zeolite structure, which balances the charge of aluminosilicate framework.
Averaged ratios of individual cations obtained by EDS are as follows: Na+K+Ca+Mg/Si = 0,44;
Si/Al = 1,42.
Nitrogen adsorption-desorption isotherms and pore size distributions (PSD) obtained by
BJH method are presented in figure 5. Fly ash has a low specific surface area (15 m2 g-1), while
zeolite obtained on the basis of fly ash, showed much better textural parameters, where a specific
surface area is 75 m2g-1. Nitrogen adsorption-desorption isotherm for fly ash represents type II
isotherm in IUPAC classification and is characteristic for meso- and macroporous materials with
relatively small specific surface area. In addition, pore size distribution scheme indicates a low
porosity of fly ash.

Figure 5. Nitrogen adsorption-desorption isotherms (77 K) and pore size distribution of the studied materials,
1- fly ash, 2-Na-P1 zeolite material.

Zeolite material Na-P1 obtained on a basis of fly ash has higher specific surface area. An
isotherm shape can be classified as I type in IUPAC classification. It indicates presence of
micropores (the Langmuir isotherm, monolayer adsorption by micropore filling) and also
mesopores (a hysteresis loop in the range of p/p0 = 0,4). The hysteresis loop is the most similar

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to the H4 type in IUPAC classification, that is characteristic for mesopores in the shape of
narrow slits. The pore size distribution by BJH indicate an mesoporous structure of the material.
Conclusions
The proposed technological solution allows to achieve a high level of fly ash conversion into
zeolite material, where the content of pure zeolite phase is 81%. The mineral composition is
dominated by Na-P1 zeolite type. Porous structure of the obtained material as well as its textural
properties indicates the possibility of using it as a sorbent for various types of environmental
contamination, for example, petroleum substances, heavy metals, radionuclides from mine water
and ammonium from wastewater.
This researches are financed by NCBIR within Project no PSB1/A2/7/2012 and WNDPOIG.01.03.01-06-146/09.
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