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Shoumkova Annie 1*, Tsacheva Tsenka 2, Stoyanova Valeria 2, Grancharov Ivan 1, Shumkov
Stefan 1 and Marinov Miko 2
University of Chemical Technology and Metallurgy,
8 Kliment Ohridski Blvd, 1756 Sofia, Bulgaria, e-mail: annnie@abv.bg
Institute of Physical Chemistry, Bulgarian Academy of Sciences,
Acad. G. Bonchev Str. Bl.11, 1113 Sofia, Bulgaria, e-mail: valeria@ipc.bas.bg
A detailed investigation of chemical, physical and morphological properties of fly ash from coal-
burning power plant Varna, Bulgaria, was carried out applying a variety of analytical technique.
A series of wet magnetic separation tests were performed in order to investigate the influence of the
main technological parameters on separation efficiency. At the optimal regime magnetic fraction
with Fe2O3 content more than four times higher than that in the feed was obtained at selectivity of
about 32 %. The distribution of 45 trace elements in magnetic fractions was examined. It was
established that some of these elements trend to be concentrated in discrete particles. The existence
of very fine particles, enriched in such toxic elements in available forms, suggests that fly ash might
have a more deleterious impact on environment and health than it could be suggested from bulk
analytical data.
Key words: coal fly ash, magnetic separation, analysis, EPXMA, solid waste
Fly ash represents the finest fraction noncombustible residue from coal burning, which is being
collected in gas purification facilities. It is generally oxide material of alumino-silicate type but it
also may contain different amounts of Fe, Ca, Mg, Na, K, Ti, C and many other elements including
heavy and radioactive metals in micro or trace concentrations. The total quantity of fly ash
produced in the world is approximately 370 million tones per year [13]. In Bulgaria annually coal-
firing power plants generate about 5.5 million tons of this waste and less then 25% of it is utilized
in concrete production. The rest is being disposed in landfills creating serious risk of air, soil,
ground- and surface water pollution with toxic and/or untypical elements. The enrichment of some
harmful fly ash ingredients in respirable size (diameter < 10 m) particles [4,6,7,15] involves an
additional health risks. That is why the deposition taxes increase from year to year and the
elaboration of effective and low-cost methods and technologies for their utilization is of great
practical interest [1,2,3,5,9,12,16,17,20,21].
Big part of these technologies includes magnetic separation step [1,3,5,14]. The optimization of this
process would contribute for increasing the economical efficiency of the technology and would
facilitate its introduction into practice. That is why one of the aims of the present study was to
explore the applicability of magnetic separation process in fly ash treatment. The investigation of
chemical and physical properties of the fly ash used also takes an important place in this study,
because it is the only routine providing reliable information about potential environmental impact
and its significance as a material resource.
2.1. Materials
Fly ashes from electrostatic precipitation utilities in one of the biggest power station in Bulgaria -
Varna (2000MW), burning different coals from local and foreign deposits have been used.
2.2. Procedure
The initial fly ash was pretreated by dry sieving in order to remove coarser (>0.125mm) particles,
which represented about weight 3% of the feed material and consisted mainly of unburned carbon.
The material was then examined by a combination of different analytical methods (see 2.3). After
that fly ash water slurries with solid/liquid ratio 1:10 were prepared and then were subjected to wet
high gradient magnetic separation (HGMS) by using a laboratory size device of solenoid type. The
magnetic separation process is described and investigated in more details in previous papers
[18,19], but briefly, it was realized by passing the slurry through the working camera of the
separator, where strongly-magnetic particles were retained onto the matrix, forming so called
magnetic fraction (MF), while weakly magnetic ones passed through it, forming so called
nonmagnetic fraction (NM). After that, both separately collected fractions were flocculated,
dewatered, dried, weighed and analyzed.
HGMS tests were performed at different magnetic field intensities and suspension flow velocities in
order to investigate the influence of these factors on some parameters evaluating the magnetic
separation applicability - yield of MF (YM) - as wt. % of the initial sample; iron recovery (R) -
quantity of Fe, extracted in MF as wt. % of its quantity in initial sample and iron enrichment factor
(F) the ratio of Fe concentration in MF to that in NF.
2.3. Analytical methods and equipment
In the present study chemical composition was investigated by combination of standard chemical
Silicate Analysis (SA) for macro elements Si, Al, Fe, Ca and Mg; Atomic Absorption
Spectroscopy (AAS) (Perkin-Elmer Model 306 AA spectrophotometer) for micro elements K and
Na, and X-Ray Luminescence Energy Dispersive Analyses (XRL, Oxford ED 2000) for trace
elements. Because of the low sulfur concentration, unburned carbon (including the organic matter)
content was determined thermo-gravimetrically (Setaram TGA 92 16.18) as loss on ignition at
1073K. Water soluble (W.S) constituents are determined as weight loss after 24 hours extraction by
distillated water (10 g fly ash/ 100 ml H2O) at room temperature and intensive stirring.
The mineralogical composition was determined by X-Ray Diffraction Analyses (XRD) using
Siemens Diffractometer D 5000 using CuK radiation at scanning speed 1/min. Additional
information about mineralogy of the Fe-content phases was obtained by Mssbauer Spectroscopy
(MS, Wissenschaftliche Elektronik GMBN, 293K, Co/Cr radiation, -Fe standard). Magnetic
properties were determined from magnetization curves obtained by SQUID (Model MPMS) at
constant temperature of 293K and magnetic induction interval of 3 Tesla. Particle size distribution
data were obtained by laser analyzer (Beckman Coulter LS 230). Specific weight was determined
by electron pycnometer (Micrometrics AccuPyc 1330). Specific surface and porosity (micro- and
mesopores volume) were measured by inert gas adsorption using Micrometrics ASAP 2010. The
morphology of fly ash samples was observed by Scanning Electron Microscope (SEM) and the
individual particles were studied by means of Electron Probe X-Ray Micro-Analysis (EPXMA)
with JEOL Superprobe 733. X-Ray analysis was performed by an energy-dispersive X-ray detector
(EDX) at a distance of 11 mm from the sample and 25 KeV electron beam.
3.1. The initial fly ash sample
Initial fly ash material represents fine light tan powder consisting mainly of single spherical
particles (microspheres) with smooth surface (Figure 1-left). They may be hollow (cenoshperes)
(Figure 1- middle) or solid (Figure 1- right). Particles of irregular shape, disturbed spheres, as well
as aggregates are rarely observed in this sample.

Figure 1. SEM micrographs of fly ash particles Varna

The elemental composition of initial fly ash sample, expressed as oxides was determined as follows:
SiO2 46.70 %, Al2O3 23.50 %, Fe2O3 8.62%, CaO 5.16 %, MgO 2.97 %, K2O- 2.91 %,
Na2O- 0.85 %, LOI (carbon) 9.83 %, W.S. 0.2 %. The specific weight was 2456 kg/m3, specific
surface - 3m2/g and pores volume - about 0.68cm3/g. Analytical data for particle size distribution
showed that 78 % of volume was occupied by particles with diameter of 10 m or less (volume d50
=5.32 m). If expressed by number of particles statistic would show that 100% were finer than 10
m and d50 was just 0.59 m. The SEM observations confirmed the presence of significant quantity
of submicron particles. The fact that the sample consisted mainly of respirable size particles is very
important from health risk assessment point of view [4,6,7].
The mineralogical composition of fly ashes depends on parent coals petrography, boiler type,
combustion temperature, rate of cooling etc. More than 55 minerals have been identified in fly ash
samples [8,10,11,23,24], but most of them ordinary present in negligible quantities and do not
influence fly ash properties. As it can be seen from XRD pattern (Figure 2) of the initial fly ash
sample, it has considerable amorphous halo and only the presence of quartz (SiO2), mullite
(3Al2O3.2SiO2), hematite (-Fe2O3) and very likely maghemite (-Fe2O3) could be clearly detected
by this method. The existence of the last two minerals was confirmed by MS studies, as well, but
the presence of some magnetite (Fe3O4) and pyrite (FeS2) was only supposed on the base of some
characteristic parameters, such as wide, not Lorentzian picks, values untypical for the clear minerals
etc., obtained from MS.

Figure 2. XRD patterns of initial fly ash Varna

The information about magnetic properties of the initial fly ash was taken from magnetization
curves obtained at constant temperature of 293K in magnetic induction interval of 3 Tesla. Their
values were determined as follows: mass magnetic susceptibility () - 1.11emu/g, saturation
magnetization of ferromagnetic component (s) - 1emu/g (at 0.4 Tesla), remnant magnetization
(Mr) - 0.111emu/g and coersitive force - (Br) 0.007 Tesla. It was established that ferromagnetic
components almost reach their saturation magnetization at magnetic field intensity of 0.2-0.3 Tesla.
After that fly ash magnetization increases very slowly and mainly on the expense of the
paramagnetic ingredients, such as quartz, aluminosilicates, that is why the upper limit for magnetic
field intensity in magnetic separation tests was fixed at about 0.3T.
3.2. Magnetic separation
Low intensity HGMS was performed in order to extract partially iron from the fly ashes. In series of
previous experiments [19] matrix of steel spheres 3 mm in diameter was chosen as the most suitable
magnetic filter for our purposes, due to its commercial production, low price, easy maintenance and
good performance. The influence of magnetic induction (B) and flow velocity (V) on separation
efficiency was studied by providing the separation at 20 different combinations of these factors. The
experimental data for MF yields are plotted in Figures 3, while chemical compositions of some
magnetic fractions are given in Table 1.

80 80
70 B=0,27T 70 cm/s
60 60 V=21,7
50 B=0,022T cm/s
YM , %

YM, %
40 V=6,2
20 cm/s
10 V=1,5
0 cm/s
0 5 10 15 20 25 30 35 0
0 0,05 0,1 0,15 0,2 0,25 0,3
V, cm/s B, Tesla

Figure 3. Yields of MF, as a function of magnetic induction and flow velocity

Table 1. Chemical composition initial ash and MFs and separation efficiency parameters,
V, Chemical composition, % Efficiency parameters
, Tesla
m/s SiO2 Al2O3 Fe2O3 CaO MgO R F S
Initial ash 46.70 23.50 8.62 5.16 2.97 - - -
0.022 32.5 33.70 17.17 36.26 4.43 4.16 20.2 4.2 29.0
0.022 21.7 33.76 16.66 34.02 6.47 5.11 22.5 4.0 26.9
0.022 6.2 42.70 23.39 19.67 6.06 4.38 28.1 2.3 12.6
0.022 3.0 43.16 22.97 16.54 5.44 4.88 39.3 1.9 10.0
0.047 32.5 38.64 19.46 29.17 4.72 3.63 27.8 3.4 22.4
0.047 21.7 38.33 20.60 27.91 4.90 4.46 30.8 3.2 21.3
0.088 21.7 41.04 20.92 25.41 4.59 4.48 37.7 3.0 19.3
0.270 32.5 44.57 21.57 19.34 4.62 3.79 38.8 2.2 13.1
0.270 21.7 45.00 22.54 18.46 7.44 3.51 40.5 2.1 12.1

The experimental data for all series showed that increasing the magnetic induction and decreasing
the flow velocity, increase iron recovery and YM, but Fe2O3 content in it goes down. These
dependencies could be explained by the fact that at higher magnetic field intensity the selectivity of
the separation gets worse, owing to the retaining of more weakly magnetic particles (having less Fe-
content) in the matrix. Contrariwise, the increasing of flow velocity upgrades the magnetic
concentrate quality by preventing the mechanical capture of weakly or nonmagnetic particles in the
filter. The biggest iron enrichment factor (F= 4.2) and the best selectivity (S= 29%) were achieved
at high V=0.325m/s and B=0.022T, although iron content in this fraction is not very high (36.2%).
These results last could be explained by the presence of some aggregates and/or agglomerates of
magnetic and nonmagnetic particles, affecting separation selectivity, but according to our SEM
observations it is not the main factor, limiting magnetic separation process. Our investigations
showed that it is more likely, the relatively low selectivity to be a result from the presence of multi-
mineral particles, heterogeneous crystal phases and especially of paramagnetic iron-containing
compounds, such as aluminosilicates, pyrite and the like. The third group of factors, which have
negative impact on magnetic separation efficiency, includes processes of mechanical capturing and
magnetic flocculation, but as the material used was very fine and suspensions solid/liquid ratio was
low enough to avoid undesirable interactions among particles, in the carried out experiments they
could not affect strongly magnetic separation process.
3.3. Trace elements distribution
It XRL analyses results for some trace- and micro- elements concentration in initial samples and
magnetic fraction, obtained at B= 0.185T and V= 0.179 cm/s, are shown at Table 2.
Table 2. Trace elements concentration in MF and initial fly ash
Content, ppm in fly ash from
Element Initial MF Element Initial MF Element Initial MF
Ag 4 6 Hg 19 0 Sc 317 138
As 458 365 I 18 5 Se 64 60
Ba 1773 1476 In 0 0 Sn 56 59
Bi 101 34 La 106 105 Sr 3926 2190
Br 61 15 Mn 3373 5349 Ta 119 100
Cd 4 6 Mo 57 30 Te 10 97
Ce 236 147 Nb 76 48 Th 20 47
Cl 136 84 Nd 19 113 Ti 17300 7800
Co 799 1083 Ni 539 712 Tl 36 24
Cr 35 47 P2O5 749 1712 U 32 0
Cs 48 43 Pb 426 223 V 541 418
Cu 740 662 Pr 34 0 W 193 229
Ga 164 109 Rb 653 333 Y 194 141
Ge 20 9 S 18000 5300 Zn 979 1159
Hf 280 650 Sb 24 30 Zr 1090 659

It was established that among 45 elements examined, Co, Cr, Ni, Mn, Hf, Nd, Te, Th, W and Zn are
more concentrated in magnetic fraction, having enrichment factors up to ten, typically between 1.2
and 2.5. The enrichment of first raw transition elements (V, Cu, Cr, Co, Ni and Mn) is widely
discussed in the literature [10,11,15,26] and the most possible explanation of the phenomenon is the
formation of partially-substituted magnetite (Fe 3-xMxO4 ,M=Co ,Ni ). In the present investigation
no enrichment of V and Cu in MF was detected. Their content in nonmagnetic fraction was even
higher, that is why we deduced that these elements probably are concentrated in discrete
nonmagnetic particles, which fact was confirmed by EPXMA (see 3.4). The enrichment of Hf, Nd,
Te, Th and W could be explained by the association of these elements with pyrite in parent coals.
Most of trace elements (As, Ba, Bi, Ce, Ga, Ge, Hg, Mo, Nb, Pb, Pr, Rb, S, Sc, Sr, Ti, Tl, U, V and
Zr) were less concentrated is magnetic fraction. Their content in MF was 1.2 3.0 times lower than
in initial ash. Some of them like Hg, Pr and U were even no detected in this fraction. The specific
of the distribution of these elements could be referred to their association with clay minerals and
organic compounds in feed coals. The rest elements were relatively uniformly spread in magnetic
and nonmagnetic fractions.
3.4. Individual particle analysis
More than 200 individual particles were analyzed by EXPMA. 160 of them were chosen in BEI
(formed by back-scattered electrons) regime, where particles with mean atomic number higher than
this of the background alumosilicate matter are visualized as bright ones (Figure 4). Such
particles usually have high heavy metal content therefore their investigation is of great importance
from ecological point of view. About 76% of bright particles analyzed were iron-rich ones. They
were classified in two groups, according to Fe content, as it is shown in Table 3 where the
concentration variations of their major constituents are shown, as well.

Figure 4. SEM images of fly ash Varna in SEI (first raw) and BEI (second raw) regime

Table 3. Typical composition of iron rich particles

Element Bright (85% of particles) Semi-bright (15% of particles)
Fe > 65 % 25-65 %
Si 2.5-14 % 17-37 %
Al 3-18 % 6-20 %
Ca 0.2- 4.% 0.5-5.5 %
Mg 0-6 % 0-6 %
K 0.2-1.5 % 0.8-4 %
S 0-1 % 0-4 %
Ti 0-2.5 % 0-1.3 %
Mn 0-5.5 % 0-5 %
Cr 0-0.6 % 0-0.3 %
About one quarter of bright particles observed was iron - lean, but rich in heavy metals. 67 % of
them were characterized with high Ba content (19-69%), typically accompanied by Sr (3-43%), Cu
(7-35%) - or by a combination of Cu and Tl (7-27%) and higher content of Ca (8-10%). In single
cases Ba-La-Ce and Ba-Cu-Tl-Pb particles were detected. Another characteristic feature of Ba-rich
particles was the present of S - up to 19% and/or Cl - up to 2% in their composition. It should be
mentioned that Tl was found only in Ba-rich particles, but it is not impossible to present in other
ones in trace concentrations. In addition to Ba-Cu rich particles, which represents about 7% of all
bright objects analyzed, some copper containing particles with high chlorine content (13-15%)
were observed. These results overlap almost fully those, obtained for fly ash from Bobovdol power
plant [18], therefore it could be concluded that such combinations of elements are not an exception
in fly ashes. Strontium is the third often met element - in 35% of iron lean bright particles.
Although in most of cases it was found in combination with Ba, six pure Sr (37-76%) particles
with about 4% of sulfur and traces (0.5 2%) of V and Ti, and one Ca rich (22%) Mn-containing
(5.7%) were analyzed. Traces of V were detected in lead-rich particles, having 60-78% Pb, as well.
In fly ash sample investigated Mn, Cr, Co and Ni were not found in discrete particles, but usually
presented in Fe-rich particles in low concentration (up to 1.5%), which fact confirm the hypothesis
that these elements are integrated in the crystal lattice of Fe-oxides. The compositions of some
bright, rare elements rich particles are shown in Table 4.
Table 4. Composition of rare elements rich particles
Content, % in particle
Fe 3.9 8.8 5.8 6.5 0.7 9.2 - 1.8 - -
Si 22.1 11.9 29.7 34.7 6.5 20.3 3.0 13.3 1.5 2.5
Al 16.8 7.7 16.8 25.4 6.2 8.7 3.2 10.5 1.6 2.8
Ca 1.1 4.2 2.8 1.7 8.6 2.4 - - - -
K 2.7 3.9 3.6 2.2 - 3.6 - - - -
S 2.4 6.6 2.1 2.3 - - - - - -
P 10.3 - 6.9 - - - - - - -
Ti - 1.0 - - - 0.6 - - - -
Ba - - - - 49.4 - - - - -
Cu - - - - 13.7 - - 0.6 - -
Zr - - - - - 49.5 - - - -
Zn - - - - - - - 0.3 - -
Y - 51.8 4.4 - - 4.1 - - - -
La - - 6.6 6.8 10.3 - - - - -
Ce 18.0 - 14.2 13.1 4.7 - - - - -
Nd 13.2 - 8.21 7.3 - - - - - -
Sm 4.1 - - - - - - - - -
Gd 2.3 4.2 - - - - - - - -
Ag - - - - - - 93.8 73.5 96.0 94.1
Particle size, m 1.5x2 2x2.5 1x1 3.5 10x15 1.5x1.5 2x3 2x3 3.5x3 1x2.5
Major elements distribution in 30 single particles profiles was investigated by spot-mode analysis
of the chemical composition in the center and on the periphery of spherical particles with diameters
from 3 to 15m. In 65 % of particles an enrichment of Fe on the surface of the microshpreres was
established, in 20% no important differences were found and only in 14 % the iron content in the
center was bigger than on the surface of the particle. The enrichment (ratio of elements
concentrations in the periphery and in the center) varied from 1.2 to 8.5 with an average level of
2.2, and it was mainly on the expense of Al and Si content. Due to the high temperatures (above
2000K) at which the ash was obtained, a secondary mineral formation by crystallization of iron
oxides onto aluminosilicate kernels could be an explanation of this phenomenon. Other major
elements did not show any trends to be enriched in the shell or inside the spheres, but the results for
iron distribution may be very important in context of the affinity of iron oxides to absorb some toxic
elements [22].
On the base of magnetic separation tests and analyses carried out in present study, it was established
that in reference of iron extraction the best results were obtained at less intensive magnetic field
(=0.022) and the highest flow velocity (V=32.5cm/s). The concentration of iron in the richest
magnetic concentrate obtained were 36.3 at selectivity of about 30% and yield 50 kg per tone fly
ash. XRD, MS, SEM and EPXMA have confirmed that the selectivity of the magnetic separation
process is limited mainly by the presence of iron containing aluminosilicates and at less extent by
the presence of agglomerates of magnetic and nonmagnetic particles in the ashes.
XRL analyses have showed that Co, Cr, Hf, Mn, Nd, Ni, P, Te, Th, and Zn are enriched in magnetic
phase, while As, Ba, Bi, Ce, Ga, Ge, Hg, Mo, Nb, Pb, Pr, Rb, S, Sc, Sr, Ti, Tl, U, V and Zr are less
concentrated in it. On the base of the analytical information obtained by EPXMA, it can be
presumed that some of the trace elements (Ba, Sr, Cu, Pb, Zr, Y, Ag, La, Ce and Nd) in the studied
fly ash trend to be concentrated rather in discrete particles. The existence of very fine particles of
respirable size, enriched in such toxic elements in available forms, suggests that fly ash might have
a more deleterious impact on environment and health than it could be suggested from bulk
analytical data.
Part of investigations was carried out with the financial support of Section for Scientific Researches
in UCTM, Project 10063. For the analyses of physical properties and XRD the help of Institut de
Matriaux Jean Roxel (France) - Laboratoir de Physique Cristalline and personally of Dr. Gerard
Froyer is highly appreciated. The electron microscope investigations were carried out with the
financial support of the National Fund Scientific Researches at the Ministry of Education and
Science in the framework of Project F 1008/00.
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