Powder Technology 166 (2006) 47 54

www.elsevier.com/locate/powtec

Properties and potential applications of zeolitic materials produced from fly

ash using simple method of synthesis
Arkadiusz Derkowski a,, Wojciech Franus b , Elbieta Beran c , Adriana Czmerov d
a

Institute of Geological Sciences, Polish Academy of Sciences, Senacka 1, 31-002 Krakw, Poland
Dept. of Geotechnics, Lublin University of Technology, Nadbystrzycka 40, 20-618 Lublin, Poland
c
Faculty of Chemistry, Wrocaw University of Technology, Gdaska 7/9, 50-334 Wrocaw, Poland
Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dbravsk cesta 9, 845-36 Bratislava, Slovakia
b

Received 12 July 2005; received in revised form 8 April 2006; accepted 19 May 2006

Abstract
Very low energy-consuming procedure is proposed for synthesis of zeolitic materials from fly ash. Three different zeolite materials (X, P and
S), rich in zeolite phases, NaX (FAU), NaP1 (GIS) and sodalite (SOD) were produced from F-class fly ash, using NaOH and NaCl solutions
under atmospheric pressure at temperature below 110 C.
Obtained zeolitic products were analysed for their composition and physicochemical properties then compared to the raw fly ash and
commercial adsorbents. The zeolitization results in a significant increase of CEC (from 5.5 up to 239meq 100g 1), and the high ability to adsorb
heavy metal ions (over 40 mg g 1) and retain complex and organic molecules (EGME), mostly evident for material X. Adsorptive purification of
waste and working lubricating oils using zeolitic products allow to provide their commercial applications in petroleum industry. Leachability of
toxic elements after standard post-reaction washing is environmentally safe.
2006 Elsevier B.V. All rights reserved.
Keywords: Zeolite; Fly ash; Hydrothermal synthesis; Refining of mineral oil; Microporous materials

1. Introduction
The fly ash from coal combustion processes is a waste very
attractive for recycling. It is used widely in various fields:
stabilization of soils, recultivation of landscapes, soil fertilization, production of geopolymers, it is applied as a backfill, in
building industry (ceramics and concrete production), as a
bottom layer in road construction, etc. (e.g. [1,2]). Some works
focus also on the utilization of fly ash as a cheap adsorption
material for water purification [3,4]. This last property of fly ash
can be enlarged by orders of magnitude by reacting fly ash into
a zeolitic material. The F-class fly ash (classification: see [5]) is
considered a good substrate for zeolite synthesis reaction
because of its composition dominated by aluminosilicate and
silicate phases. The transformation of fly ash in alkaline

Corresponding author. Tel.: +48 12 4221910.

E-mail address: ndderkow@cyf-kr.edu.pl (A. Derkowski).
0032-5910/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.powtec.2006.05.004

conditions is analogous to natural zeolitization of volcanic glass

and was confirmed experimentally (e.g. [6,7]). Production of
zeolites high-tech industrial products, by treatment of coal fly
ash with alkaline solutions is a well known technique,
described by many authors (review by [8]). Many methods of
reaction and products properties were reported during the last
dozen years. The synthesized zeolitic materials achieve very
high ion-exchange properties CEC up to 375meq 100g 1
[9,10], or even higher for pure zeolites produced from fly ash by
fusion method (460 meq 100 g 1; after [11]). They are being
used in sludge and water purification from heavy elements [12],
in gases separation and removing post-combustion gaseous
wastes: SOx and COx [13]. Thus, these zeolite materials can be
foreseen as commercially valuable commodities. The significant disadvantage of the mentioned techniques is a necessity of
a special treatment of fly ash before reactions.
One of the most promising application for zeolites produced
from fly ash, may be a refining of petroleum products. Clay
contacting method of adsorptive refining does not require a

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A. Derkowski et al. / Powder Technology 166 (2006) 4754

granular form of sorbent [14]. Powdery material can be used

directly for multifunctional purification of mineral oils [15] and
for adsorptive purification in reconditioning and regeneration of
used lubricating oils [16].
The present paper describes the composition and various
properties of three zeolitic materials containing high contents of
NaX (FAU), NaP1 (GIS) or sodalite (SOD) (nomenclature and
classification after [17]. These materials were produced at
atmospheric pressure, following simple synthesis procedures,
that can be directly applied in the conditions of industrial
synthesis. The proposed methodology is based on conclusions
of our previous studies [18,19] and allows to avoid initial fusion
of fly ash with hydroxides, which is energy- and costconsuming procedure. The yield of zeolite material per mass
of used fly ash is close to 100%. Beside the synthesis

techniques, the study presents results of microporous properties

of produced materials. The hydrothermal synthesis without
prior fusion step is suspected to produce zeolites with partially
closed micropores, which can limit their applications.
2. Materials
The samples of fly ash were collected from fresh ash
reservoirs of the Elektrociepownia Krakw (ECK) power
plant (Cracow, Poland). Mineral composition of the samples is
as following [18]: aluminosilicate glass (4050%), mullite
(below 30%), quartz (57%), unburned coaly matter (below
7.26% LOI limit), and, subordinately, Fe oxides, gypsum,
calcite, feldspars, apatite (Fig. 1A). The chemical composition
of the fly ash from the ECK power plant was determined by

Fig. 1. XRD pattern and the SEM general view of the ECK fly ash (A) composed mainly of glassy microspheres. Qtz quartz, Mu mullite, Cal calcite, Gy
gypsum. The rise of background line results of high content of amorphous phases. Big pleosphere (B), fulfilled with smaller microspheres (14m), grows on glassy
particle. EDS curve presents the chemical composition of the glass particle.

A. Derkowski et al. / Powder Technology 166 (2006) 4754

XRF (in wt.%): SiO2 47.31, Al2O3 25.19, Fe2O3 6.95, MnO
0.08, MgO 2.88, CaO 3.84, Na2O 1.24, K2O 2.65, TiO2 1.01,
P2O5 0.48. LOI = 7.26%. The SiO2/Al2O3 wt. ratio of fly ash is
ca. 1.88. Si/Al atomic ratio of aluminosilicate glass varies from
1.6 to 1.8 (EDS measurement: Fig. 1B). Other components and
properties of fly ash from ECK power plant, were determined
following EU specifications: content of reactive SiO2
26.2 wt.% (PN-EN 196-2:1996); and pH of abrasion in
leaching test 10.6 (PN-90/C-04540.01).
One synthetic zeolite A (4A) and two samples of pure natural
clinoptilolite from Ukraine (CL Ukr) and Slovakia (CL Sl),
commercially available as sorbents, were analyzed for their
some properties. Refining capacity of synthesized zeolitic
materials were compared with the following commercial
materials, common in petrochemical industry:
Attapulgus clay (natural rock composed of attapulgite and
smectite; Engelhard Minerals and Chemicals Co., USA),
Alumina sorbent Compalox 802, (with graining 0.32.0 mm,
manufactured by Martinswerk GmbH Germany),
Miltar standard bleaching earth smectite from Milowice
deposit (Poland), acid-activated,
Silica gel produced by Soda Mtwy SA (Poland), ground and
activated at 160180 C.
3. Conditions of synthesis
Based on the crystallization fields of zeolites synthesized
from ECK fly ash [18] and the simplified methods of production
of zeolitic materials [19], new procedures were developed. They
were designed to be easily applicable in industrial technologies
and to produce materials very rich in zeolitic phases. They are
fast and energy-effective hydrothermal reactions, resistant to
operator's mistakes.
10 g of homogenized raw fly ash, reaction time 24 h, and
atmospheric pressure were used in all experiments. All reactions
were carried out using polypropylene bakers. Details of zeolitic
materials preparations are following:
Material X fly ash + 200 ml of 3 M NaOH solution;
temperature: 75 C;
Material P fly ash + 200 ml of 1M NaOH solution + 100 ml
of 3M NaCl solution; boiling conditions (temperature: ca.
105 C);
Material S reagents: 10 g of fly ash + 400ml of 5 M NaOH
solution + 200 ml of 3 M NaCl solution; boiling conditions
(temperature: ca. 105 C).
After reactions the products were washed three times with
distilled water and dried.
4. Methods of investigating the products of synthesis
The mineral composition of all samples was determined by
X-ray diffraction (XRD) using Philips X'pert APD diffractometer with PW 3020 goniometer, Cu tube and graphite monochromator. The identification of phases was based on ICDD

49

PDF-2 database and on the collection of patterns recommended

by International Zeolite Association [20]. Random preparations
were made from 300mg of a sample ground in a mortar to ca.
<20 m.
Observations of the reaction products and analyses of
chemical composition in micro-range were carried out using
field emission scanning electron microscope (SEM) HITACHI
S-4700 equipped with energy dispersive spectrometry (EDS)
system VANTAGE NORAN.
The adsorption and desorption isotherms were determined
using sorption manostate, applying argon gas in liquid nitrogen
temperature. Samples were first outgassed with high vacuum
molecular pump until 10 5 mm Hg pressure was reached. The
specific surface area was calculated using the BET theory. The
specific volume of micropores was calculated with Dubinin
Radushkevich equation. The specific surface and volume of
mesopores were calculated using the 2nd variant of Dubinin
method [2123].
The cation exchange capacity (CEC) was determined using
various methods. Samples of fly ash, zeolitic material and
commercial zeolites were measured using simple and quick
method using hexamine cobalt(III) chloride, described by
Orsini and Remy [24]. Because of the crystallochemical
limitations ([25] and see results below), we were obliged to
apply other method for determination of CEC for zeolitic
samples. They were analyzed with procedure described by [26].
All exchangeable cations were leached by Ba2+ ion, their
concentrations were determined by atomic absorption spectroscopy (AAS), and the values of CEC were calculated. The
measurement was repeated several times. The averaged (error
< 2.5%) CEC values were re-calculated per weight of a
dehydrated sample.
Adsorption capacity of organic molecules was measured
using retention of ethylene glycol monoethyl ether (EGME)
after [27]. This method is being commonly applied for
estimation the surface area of soils. Direct calculation of surface
area from EGME retention should not be taken in the way while
studies of soils. There are structural limitations and likely
different adsorption surface factors between zeolites and clays
[28].
The control tests of leachability of ions from fly ash and
zeolite materials were carried according to the Polish standard
(PN-Z-15009) concerning the characteristics of toxicity of solid
wastes. A sample was mixed with ultra-clean water (solid/liquid
wt. ratio = 0.1) and shaken for 24 h. Then the suspension was
filtered through 0.45 m filter paper. The concentration of ions
in solution was measured using: ion chromatography (IC) for
Cl, NO3, SO42, atomic emission spectrometry with induced
coupled plasma (ICPAES) for Fe2+ and mass spectrometry
with induced coupled plasma (ICPMS) for Cd, Cr, Cu, Mn, Ni,
Pb, and Zn.
The potential of heavy metal removal from water solutions
was measured for raw fly ash and zeolitic materials as an
adsorption of Cd2+, Cu2+, Co2+, and Zn2+. Adsorption was
determined using pure solutions of chlorides or nitrates; 50 ml of
a solution containing 400 mg l 1 of each cation was mixed at
room temperature with 0.5g of a sample. After continuous

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A. Derkowski et al. / Powder Technology 166 (2006) 4754

Experiments were carried out by mixing the oil with studied

material at 20 : 1wt. ratio, 30min storage at 50C (transformer
oil) or 70 C (turbine oil). Refining efficiency (Eref; in %, for
calculations see Table 4) was calculated using two methods: as a
decrease of acidity and as a degree of bleaching. Acidity as
neutralization value was measured by procedure after ISO 6618,
that relates to amount of KOH sufficient for neutralization of
acidic compounds in oil. VIS spectrometry was applied to
measure the bleaching of the studied oils. Wavelength 455 nm
was chosen to determine the suitable values of absorbance for
exploited and refined oils. The content of water in oils was
determined in accordance to ISO 12937 using METLER
TOLEDO DL 36 KF Coulometer.
5. Results and discussion
5.1. Composition of zeolitic materials
5.1.1. Material X
The NaX zeolite phase is the main component of the reaction
product. The residual quartz, mullite and an amorphous phase
(noticeable as a slight rise of the XRD background line) occur in
minor amounts (Fig. 2). Calcite, which is present in trace
amounts, persists unaltered after high-pH reactions [18]. Average
cation ratios of the NaX zeolite are: (Na + K + Ca + Mg)/
Si = 0.59 and Si/Al = 1.10.
5.1.2. Material P
NaP1 phase is abundant in this material (Fig. 2). Mullite and
quartz occur in amounts that seem to be not significantly
different from the contents in the raw fly ash. A small content of
an amorphous substance can be noticed due to the slight rise of
the background line in the XRD pattern. Trace amount of
sodalite (SOD) was detected in by XRD (Fig. 2). Average cation

Fig. 2. XRD patterns of zeolitic materials produced from fly ash; natural (nat
without heating) and heated at 300C, 500C and 700 C. Abbreviations: Qtz
quartz, Mu mullite, Cal calcite, S sodalite (SOD), P NaP1 (GIS), CP
collapsed NaP1 unknown phase (PHI?), X NaX (FAU). The rise of
background line results of high content of amorphous phases.

stirring for 3h the mixtures were filtered and the solutions stored
at 4C [4,10]. The metal ion concentrations were determined by
AAS.
The thermostability of zeolite structures was checked at the
following temperatures: 300 C, 500 C, and 700 C. After 12h
of heating in an oven, zeolite materials were cooled and
analyzed by XRD.
Waste transformer oil (TRAFO collected in ZE Wrocaw,
Poland) and working turbine oil TU-46 (investigated during
service) were purified by clay contacting procedure [29].

Fig. 3. Argon adsorption/desorption isotherms of raw fly ash and zeolitic

materials.

A. Derkowski et al. / Powder Technology 166 (2006) 4754

Table 1
CEC, adsorption capacity, and textural parameters of raw fly ash and the zeolitic
materials produced from fly ash
Material

SBET

Vmic

Smez

Vmez

Fly ash
X
P
S
4A
CL Ukr
CL Sl

10
231
39
28

5
90
15
11

9
46
33
18

15
71
49
29

CECBa

CECCo

EGME

239.1
218.0
121.8
244.2
117.9
99.3

5.5
115.7
22.4
9.9
5.8
5.0
6.2

13.0
147.1
50.7
88.8
59.2
61.8

SBET specific surface [m2 g 1]; Vmic specific volume of micropores

[mm3 g 1] calculated using Dubinin Radushkevich equation; Smez specific
surface of mesopores [m2 g 1] calculated using 2nd variant of Dubinin method;
Vmez specific volume of mesopores [mm3 g 1] calculated using 2nd variant of
Dubinin method; CECBa cation exchange capacity [meq100g 1] determined
using Ba2+ ion; CECCo cation exchange capacity [meq100g 1] determined
using [Co(NH3)6]3+ ion; EGME retention of ethylene glycol monoethyl ether
[mgg 1].

ratios of the NaP1 phase are: (Na + K + Ca + Mg)/Si = 0.45 and

Si/Al = 1.43.
5.1.3. Material S
Sodalite (SOD phase, with Cl anion) is an almost
monomineral product of this synthesis reaction (Fig. 2). A trace
amount of calcite is the only residual phase. All aluminosilicate
substrates have been dissolved. The EDS analyses show that the
content of chlorine in sodalite crystals is quite substantial.
Average cation ratios of sodalite are: (Na + K + Ca + Mg)/Si = 1.06
and Si/Al = 1.21.
5.2. Properties
5.2.1. Textural properties, CEC and ion-sieving
Fly ash isotherm (Fig. 3) belongs to type II in the IUPAC
classification, with H3 narrow hysteresis loop. The isotherm of
material X follows Langmuir's curve, isotherm type I with H4
hysteresis loop and it is characteristic of microporous
adsorbents [30]. Materials P and S represent mixed types I
and II, with unexpectedly low general level of Ar adsorption.
Textural properties of the studied materials are given in Table 1.
The significant difference between the measured specific
surface of X type material and the remaining zeolitic
materials (Table 1) results from the dimension of Ar molecule
(0.384 nm; [31]) with respect to the pore size. Micropores of
NaX zeolite are wide enough (> 0.74nm) to accept argon

51

molecules. Too narrow channels dimensions of NaP1 (ideal

form: 0.31 0.44 nm 2 and 0.28 0.49 nm 2 ) and sodalite
(0.22 nm) block the adsorption of Ar inside the pores
[17,31]. For this reason the calculated specific volumes of
micropores in materials P and S increase only slightly in
relation to the raw fly ash. Those structures can adsorb Ar
atoms only on crystal edges and at defect sites. The specific
surface of fly ash increases substantially after the zeolitization
reactions. Significant increase of micropore volume (18 times)
for the material X is undoubtedly the main factor of its
specific surface enlargement and is caused by the crystallization of microporous NaX zeolite.
Ion-sieving effect was also found while measuring CEC
using [Co(NH3)6]3+ ion a common method being applied for
clay minerals [24]. Smaller Ba2+ ion in water solution can
access all (or the most of) exchange sites of synthesized zeolitic
structures and CEC measures the true increase of adsorption
properties during zeolitization of fly ash. Only in the case of
sodalite that the CEC value is doubted to be correct. A part of its
structure may be unavailable even for such divalent cation.
Hexamine cobalt ion is too large to enter inside the zeolitic
structures; only a part of NaX microporous system is wide
enough for [Co(NH3)6]3+ incorporation. The remaining structure of NaX and other zeolites show negligible values of
adsorption, close to fly ash. CECCo value of material P
slightly higher than one of raw material may be a result of
structural irregularities in NaP1, crystallization of smectite or
contamination of NaX phase.
Variability of EGME retention is undoubtedly the function of
micropores size. Internal surfaces of material P and commercial
zeolites are probably unavailable for EGME. Pure, synthetic
zeolite A adsorbs more EGME. The highest retention is reached
by material X, due to the wide micropores occurring in zeolite
NaX. Despite containing only ca 50% of NaX phase,
material X adsorbs EGME significantly more than the
remaining studied materials.
Comparing to the commercial products, synthesized zeolitic
materials reach quite good cation exchange capacities and
adsorption properties. Materials X and P show CECBa values
(CEC for big divalent cations) higher than natural clinoptilolites
and very close to synthetic, pure phase A. The CECBa of
material S reaches a value similar to that of natural zeolites.
The fact that material X adsorbs large molecules inside the
structure, not only on external surfaces suggests its broader
application compared to the remaining materials.

Table 2
Results of leaching test
Material

Cl

NO3

SO4

Cd

Cr

Cu

Fe

Mn

Ni

Pb

Zn

X
P
S
Sludgea
Drinking waterb

0.74
42.6
14.1
1000
250

0.26
0.094
0.074
133
50

10.5
5.21
2.35
500
250

0.000077
0.00031
0.000032
0.05
0.005

0.103
0.018
0.070
0.5
0.05

0.010
0.0086
0.0087
0.1
2.0

0.069
0.20
0.12
10
0.2

0.0011
0.0035
0.0024
No limit
0.05

<0.0001
0.00041
0.00018
0.1
0.02

0.00063
0.00092
0.00027
0.1
0.01

0.0018
0.0036
0.0018
2
No limit

Data given in [mgl 1].

a
The most restrictive limits of concentrations for industrial sludge, Polish standard.
b
The limits for drinking water, EU standard.

52

A. Derkowski et al. / Powder Technology 166 (2006) 4754

Table 3
Adsorption of heavy metal cations on zeolite materials, in mg g 1 and % of
metal content in initial solution
Material Cd2+

Co2+

Cu2+

Zn2+

decomposition after heating at 770 C [31]. Sodalite is

extremely thermally stable with no traces of structural
deformation at 700C. It is expected to be stable up to 900 C
[31].

mgg 1 % sol. mgg 1 % sol. mg g 1 % sol. mgg 1 % sol.

Fly ash
X
P
S

8.15 15.6
>40.10 100.0
38.55 99.8
29.76 72.4

<0.01
35.66
18.05
19.07

0.00
84.0
42.5
44.9

13.37
38.40
32.39
22.38

25.5
95.2
83.4
55.5

7.56
35.69
26.55
21.13

15.3
93.8
72.4
55.5

Sign > means that whole metal ion content from initial solution was adsorbed.

5.2.2. Leachability
None of the leached components from any of the zeolitic
materials (Table 2) goes beyond the limits established for
sludge (Polish Water Law Act 1974 [43,44]). Only the
concentration of Cr goes beyond the limit value for drinking
water [42]. Thus, these zeolitic materials can be stored and
used in natural systems and environmentally neutral conditions
without any special treatment. Standard washing procedure
after synthesis reaction is sufficient to save leachability of ions
in safety range.
5.2.3. Thermostability (Fig. 2)
At elevated temperatures NaP1 zeolite structure is the least
stable. Below 300C, it alters probably into the Na-PHI type
structure (PDF-2 No 24-1046), although the results of
experiments carried on pure P zeolite, suggest that ca. 16% of
P structure collapses (contracts) at 165C, the remaining part
persists, and then crystallization of a new phase at 530C (see
[24,31]) will take place. In our experiment this new PHI
(contracted P?) phase disappears between 500 C and 700C.
No crystalline phase derived from NaP1 can be detected after
heating at 700 C. The traces of SOD phase which was found in
XRD pattern, crystallized during the synthesis reaction, not
during the transformations at elevated temperatures. The NaX
zeolite structure starts collapsing near 700C, which can be
observed as a slight decrease of NaX reflections. This data
agrees with pure synthetic phase investigations, that recorded a
first step of structure degradation at 660C and ca. 50%

5.2.4. Heavy metal removal

Examination of the raw fly ash shows its heavy metals
adsorption potential [4] that may exist due to the fine-particle
structure and the content of coaly matter and aluminosilicate
glass (Table 3). However, results of CEC measurements do not
confirm sufficient ion exchange capacity of fly ash (Table 1).
We postulate other reasons for decreasing the heavy metals
content in solution after mixing with fly ash. The pH of abrasion
for raw ash material is very high (see Materials) and can
significantly heighten pH of metal solution shortly after mixing.
Only 1 h after mixing fly ash with distilled water (in ratio 0.5g /
50ml), suspension reached pH 9.5. During the alkalization of
solution, caused by a contact with fly ash, the heavy metal ions
may precipitate as hydroxides. Thus, process acting on contact
of heavy metal ion and fly ash should be called entrapment
as a combination of adsorption and precipitation. The only
exception is cobalt, which does not show even traces of
entrapment by fly ash.
All zeolitic materials show high ion selectivity for heavy
metals (Table 3), correlating generally with their CEC trends
(Table 1). It is obvious that heavy metal ions occupy only part of
exchange positions due to incomplete ion-exchange in one
mixing stage. The highest adsorption capacities were reached
by the material X, which consumed all or the most of ions
available in solution. Materials P and S show lower capacities,
respectively. The heavy metals entrapment capability, being
shown by fly ash, can be strengthened by the zeolitization, with
an extreme change for cobalt adsorption. Zeolitic materials bind
heavy metals in a general trend, Cd2+ > Cu2+ Zn2+ > Co2+,
following their atomic weights.
5.2.5. Oil refining
Waste transformer oil and working turbine oil, used in
present test differed with their characteristics (Table 4).

Table 4
Results of adsorption refining of mineral oils using various materials
Waste transformer oil

Turbine oil TU-46 (in service)

Aciditya

Bleachingb

Moisture

Aciditya

Bleachingb

Xrawc

0.113

0.449

110

0.340

0.303

Adsorbent

Xrefc

Erefc

Xrefc

Erefc

H2O ppm

Xrefc

Erefc

Xrefc

Erefc

Attapulgus clay
Al2O3 compalox
Miltar standard
Silica gel
Material X
Material P
Material S

0.074
0.084
0.063
0.073
0.062
0.046
0.066

35
26
44
35
45
59
41

0.144
0.136
0.168
0.070
0.197
0.202
0.231

68
70
63
84
56
55
48

46
55
40
20
28
21
n.d.

0.047
0.075
0.104
0.055
0.101
0.070
0.080

86
78
69
84
70
79
76

0.141
0.300
0.194
0.126
0.234
0.222
0.278

53
1
36
58
23
27
8

a
b
c

Xraw and Xref values given in mgKOH/g (ISO 6618), Eref values given in %.
Xraw and Xref values given as absorbance units (01), Eref values given in %.
Eref [%] = [(Xraw Xref) / Xraw] 100%; Xraw value determined before refining; Xref value determined after refining.

A. Derkowski et al. / Powder Technology 166 (2006) 4754

Transformer oil was darker and showed lower content of acid

molecules, than turbine oil. All zeolitic materials occur at high
refining capabilities. The transformer oil yielded better
neutralization of acidity while using zeolitic materials than
while using commercial adsorbents. Close or slightly lower
decrease of acid content was found during refining of turbine oil
with zeolitic materials instead of commercial ones. Zeolitic
materials show generally worse bleaching capacities. Impurities, which blacken mineral oils, contain much organic
compounds: condensed aromatic polymers, resins, etc. [32].
Their molecules are too large to be adsorbed on internal surfaces
of zeolites; wider micropores are necessary to retain such
compounds.
Studied oils contain probably different sets of impurities
within groups determined as acidity and color. Commercial
sorbents, as well as zeolitic materials, show distinctive values of
refining efficiency, while contacting with two types of oil.
Application the Al2O3 Compalox sorbent is an extreme
example: bleaching efficiency varies between 70% and 1%,
and acidity neutralization efficiency between 26% and 78%,
giving reverse relationship for transformer oil and turbine one.
Removal of moisture is an application dedicated to zeolites.
Materials P and X (S was not measured) adsorb water as
efficiently as the best commercial product silica gel, and much
better than synthetic or activated clays. Narrow zeolitic
micropores prefer water molecules instead of large organic
compounds of oil.
Among the studied zeolitic materials, material P appeared to
be the best in refining. Materials P and X are generally
comparable with commercial adsorbents used in oil refining
industry.
6. Conclusions and potential applications of zeolitic
materials
Zeolitic materials, produced and analyzed in our study,
turned to be very useful commercial materials. The production
of these materials requires significantly less energy and reagents
than the traditional hydrothermal synthesis of zeolites from pure
reagents or by fusion. No limitation of properties of synthesized
zeolites was observed, compared to pure phases produced with
conventional methods, after an allowance that non-zeolitic
impurities are present. Instead of lower quantity of synthesized
active phase than zeolites synthesised traditionally, zeolites
produced from fly ash could replace them as cheaper material in
technological applications which do not demand the highest
purity. We propose two general applications for zeolitic
materials produced by simple reactions: removal of heavy
metal ions from water and adsorption refining of used
lubricating oils. High CEC values and ion-sieving properties
may be used in separation of different sizes molecules.
The material X contains high proportion (ca. 50%) of NaX
zeolitic phase (FAU) which is only rarely received as
monomineral product from fly ash [8] and can be a substitute
of commercially available product 13X. Material X, due to
wide micropores of zeolite and high thermostability, can be a
good gas adsorbent. Previous experiments confirmed high

53

adsorption of SO2, CO2, and NH3 on 4A-X zeolites synthesized

from fly ash [13]. Due to its high CEC and potential of heavy
metal adsorption, this material can be applied for technological
water purification and for remediation of soil [33], as well as for
137
Cs entrapment [34].
NaP1 phase occurs in the material P. This zeolite is a
common product of fly ash hydrothermal transformation under
alkaline conditions (i.e. [35,36]. Most often it is used for the
adsorption of metal ions from sludge [37] and soil [38]. Material
P appeared to be almost ideal adsorbent for oil refining, even
better than commercial products. Too narrow micropore
windows limit its application for the adsorption of gases. Very
high CEC value of the material P makes it useful as a
geosynthetic liner and it was also applied successfully in
groundwater remediation [12]. The alteration of NaP1 structure
below 300 C should be explained and the properties of the high
temperature phase have to be checked before attempting an
application of the material P at elevated temperatures.
Sodalite is the most underestimated product of the zeolitization reactions of fly ash. The synthesis of hydroxysodalite
(sodaliteOH), often called sodalite in papers, requires a
similar effort as the synthesis of NaX or NaP1 zeolites, but
results in the production of low CEC and BET material [8,13].
The transformation of entire fly ash sample into real sodalite
sodaliteCl (up to 100% in the product) turned out to be very
simple to achieve by lowering the H2O/NaOH ratio [31] and
adding the Cl ion to the reaction solution [39]. The sodalite
structure presents the highest cubic, sodalite cage content per
volume unit. These cages contain very small (ca. 0.22nm)
micropores too narrow for all gaseous molecules but
hydrogen, thus sodalite was projected for hydrogen storage
[40]. Due its very high thermostability (up to 900 C; [31]),
sodalite is examined in mixtures with borosilicate glass (75/25)
as high-level nuclear waste matrix [41].
Acknowledgments
The authors thank Jan rodo and Marek Michalik for their
helpful suggestions and reviews of the manuscript. This work
was financially supported by the Polish State Committee for
Scientific Research (KBN) Grant No. 3 P04D 008 23. A.
Czmerov acknowledges a financial support from the Slovak
Grant Agency for Science VEGA (Grant No. 2/3102).
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