Waste Manag Res OnlineFirst, published on August 10, 2010 as doi:10.

1177/0734242X10379494

Research Paper

Magnetic separation of coal fly ash from Bulgarian power plants

Annie S. Shoumkova

Waste Management & Research 0(0) 112 ! The Author(s) 2010 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav DOI: 10.1177/0734242X10379494 wmr.sagepub.com

Abstract Fly ash from three coal-burning power plants in Bulgaria: Maritza 3, Republika and Rousse East were subjected to wet low-intensity magnetic separation. The tests were performed at different combinations of magnetic field intensity, flow velocity and diameter of matrix elements. It was found that all parameters investigated affected the separation efficiency, but their influence was interlinked and was determined by the properties of the material and the combination of other conditions. Among the fly ash characteristics, the most important parameters, determining the magnetic separation applicability, were mineralogical composition and distribution of minerals in particles. The main factors limiting the process were the presence of paramagnetic Fe-containing mineral and amorphous matter, and the existence of poly-mineral particles and aggregates of magnetic and non-magnetic particles. It was demonstrated that the negative effect of both factors could be considerably limited by the selection of a proper set of separation conditions. The dependences between concentration of ferromagnetic iron in the ash, their magnetic properties and magnetic fraction yields were studied. It was experimentally proved that, for a certain set of separation conditions, the yields of magnetic fractions were directly proportional to the saturation magnetization of the ferromagnetic components of the ash. The main properties of typical magnetic and nonmagnetic fractions were studied.

Keywords Coal fly ash, magnetic separation, solid waste, Bulgaria

Date received: 5 March 2010; accepted: 4 July 2010

Introduction
Coal y ash (FA) are generally aluminosilicate materials, containing also Fe, Ca, Mg, Na, K, Ti, mainly in oxide forms, unburned carbon, and tens of other elements in micro or trace concentrations, some of which are toxic (Turner, 1981) or radioactive (Papp et al., 2002). In recent years a very large number of investigations worldwide have been devoted to the characterization of FAs, in order to estimate the potential environmental impact of FA waste, and its signicance as a material resource for dierent industrial applications (Bayat, 1998; Iyer and Scott, 2001; Goodarzi, 2006; Kostakis, 2009). A signicant number of the methods and technologies already elaborated for FA utilization includes a magnetic separation step, applied not only when the purpose of the reprocessing is to obtain Fe-containing products (Brown, 1980; Aldrich, 1984; Dobbins and Murtha, 1983; Orlov et al., 1999; Sripriya et al., 2003), but also in cases when iron is an undesirable ingredient for instance in Al2O3

production (Cohen and Mercier, 1976; McDowell and Seeley, 1981; Styron and Abiodun, 2001), or when limitations on its concentration in the nal products exist (Boybay and et al., 1996; Demirel, 1982; Molina and Poole, 2004; Paya Prakash et al., 2001). Magnetic separation can be carried out by very dierent methods, with respect to the aims of its application, requirements for the quality of the nal products, properties of raw materials, etc. With regard to iron concentrate extraction, wet low-intensity magnetic separation, performed in one (Hurst and Styron, 1978; Murtha and Burnet, 1978; Baitenev and Murzaeva, 1984) or two stages (Hwang, 1993;

Institute of Physical Chemistry, Bulgarian Academy of Sciences, Sofia, Bulgaria. Corresponding author: Annie S. Shoumkova, Institute of Physical Chemistry, Bulgarian Academy of Sciences, bl. 11 Acad. G. Bonchev Str., 1113 Sofia, Bulgaria. Email: ashoumkova@ipc.bas.bg

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Orlov et al., 1999), usually provides magnetic fractions, having two to six times higher iron content, at yields of 1030% of the feed material. Wet high intensity magnetic separation is generally applied for separation of ironlean (0.26% Fe) fractions, at typical yields of 7080% (Hurst and Styron, 1978; Prakash et al., 2001). The process of wet magnetic separation of some Bulgarian FAs has also been explored (Shumkov and Shoumkova, 2002, 2004; Shoumkova, 2006b). All these investigations demonstrate that the eciency of the magnetic separation and the quality of the resulting fractions depends to a high degree on the separation conditions. Therefore a profound study of magnetic separation process, the abilities of its management and optimization is of great importance for the practice, as it would contribute to the increase of protability of the reprocessing technologies and their practical application. The main aims of the present study were to characterize the physical and chemical properties of three types of Bulgarian FAs, to explore the applicability of the low-intensity magnetic separation process and to check the possibilities for its management by investigating the inuence of the main technological parameters on separation eciency.

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directly in the geometric centre of the matrix using a Teslameter Model 310A, Thorn Emi Technology GmbH. Real ow velocity (V) is calculated from apparent ow velocity (Vm) and free volume in the matrixes. The FAwater suspensions were prepared by intensive stirring (for 5 min, at 2000 rpm) of 100 g of ash in 1000 g water. Then the slurry was passed through the working camera of the separator where strongly magnetic particles were captured onto the matrix, forming the magnetic fraction (MF), while weakly magnetic ones passed through it to form the non-magnetic fraction (NF). The MF was then washed by water while the magnetic eld was switched on in order to prevent the mechanical capture of particles in the camera. The separately collected MF and NF were dewatered, dried, weighed and analysed. The main quantitative and qualitative parameters for magnetic separation process eciency estimation were dened as follows: yield of magnetic (YMF) or non-magnetic (YNF) fraction, the quantity of this fraction obtained, expressed as wt.% of the initial sample; recovery (RFe), the quantity of Fe, extracted in MF or NF, expressed as wt.% of its quantity in initial sample; enrichment factor (FFe), the ratio of concentration of Fe in MF or NF to that in the initial FA; selectivity (SFe), the dierence between the concentration of Fe in MF and NF.

Materials and methods Materials

Coal ashes from three Bulgarian power stations: Maritza 3 (FAM3; 120 MW), burning local lignite coals, Republika (FAR; 460 MW), burning local sub-bituminous coals and Rousse East (FARE: 400 MW), burning foreign bituminous and anthracitic coal, were investigated. The FAM3 and FAR are taken directly from electrostatic precipitators, and the FARE represents a mixture of FA and slag. In some studies also FAs from power plants Varna (FAV), Bobovdol (FAB) and Maritza East 1 (FAME1) were used.

Analytical methods and equipment

In the present study, the chemical composition of FA was investigated by a combination of standard silicate analysis for macro elements Si, Al, Fe, Ca and Mg, and atomic absorption spectroscopy (AAS; Perkin-Elmer Model 306 AA spectrophotometer) for microelements K, Na and Ti. The content of unburned carbon (including organic matter) and sulfur was estimated on the base of the parameter loss on ignition at 1073 K (LOI1073K), determined by thermogravimetric analysis (TGA; using (Setaram 92 16.18 apparatus). The mineralogy of the samples was studied using X-ray diraction (XRD; Siemens Diractometer D 5000 with CuKa radiation at scanning speed 1 /min). For Mo S electromechanical spectrometer Wissenschaftliche Elektronik GmbH working at regime of constant acceleration at 293 K, 57Co/Rh radiation (Activity$10 mCi), with standard -Fe was used. Magnetic properties were determined on the basis of the magnetization curves obtained by SQUID (Model MPMS). The morphology was observed by a scanning electron microscope (SEM; Jeol Superprobe 733 and Jeol JSM -5800LV) with an energy dispersive X-ray detector (EDX) for chemical analyses. Particle size distribution data were obtained by laser analyser (Beckman Coulter LS 230) working in a combined centrifugalgravitational regime. Specic weight was determined by electron pycnometer (Micrometrics AccuPyc 1330). Specic surface and micro- and mezzo-porosity were measured by inert gas adsorption using a Micrometrics ASAP 2010.

Procedure
The FA materials were pretreated by dry sieving and the fractions <0.125 mm (representing 20% for FAM3, 94% for FAR, and 85% for FARE), were collected and analysed. Then they were subjected to wet low-intensity magnetic separation in a laboratory solenoid magnetic separator of matrix type, because it provided high repeatability and an additional instrument for process managementgradient variation. In the separator the gradient is generated by a matrix of steel spheres and can be approximately calculated by the formula: gradB % 2jBj:d1 (Svoboda, 2004), where B is the magnetic ux density, d is the diameter of the matrix elements. The matrix exhibits low remanent magnetization (0.004 T) and mechanical capturing capacity (0.20.8% depending on d and V). It is situated in a cylindrical canister (radius 0.025 m and height 0.125 m). Magnetic induction is measured

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iron-bearing crystal phases in FAs were impure maghemite, hematite and Ca-Fe oxide. Unfortunately, the low-intensity and overlapping of characteristic peaks of magnetite, and maghemite complicated their denitive recognition and quantitative determination by XRD (Figure 2). That is the reason why, although the sets of peaks in obtained XRD-patterns tted better to maghemite, it could be assumed that impure magnetite was present in addition or instead of it, because the Mo ssbauer spectroscopy (Mo S) (Figure 2) identied sextets with parameters closer to magnetites standard. This analysis showed that iron ions were in third and second oxidation states, high-spin and octahedral or tetrahedral coordination, but, unfortunately, it provided only some approximate information about the mineralogy of Fe-containing minerals, because some of the determined parameters did not correspond exactly to those of the pure mineral standards, but denoted the existence of non-stoichiometric iron compositions, solid solutions, partially substituted iron oxides, etc. That is why the most important information extracted from the Mo S was the relative weight of strongly magnetic (magnetite or maghemite), weakly magnetic (hematite and goethite) and non-magnetic (pyrite, Fe-bearing aluminosilicate crystal and glass phases) iron compounds, estimated on the basis of the sum

Results and discussion Initial fly ash samples

The studied FAs represented inhomogeneous powders, consisting of particles of dierent shapes, from almost ideal spherical to highly irregular with dierent texture and surface formations (Figure 1). The chemical composition and physical properties of the initial FA samples (Table 1) were close to previously reported (Vassilev et al., 2001; Vassilev and Vassileva, 2009) values. Particle size analyses showed that the FAs had a quite inhomogeneous composition, which, in addition to the complicated hydrodynamics of the magnetic separation process, made the available magnetic separation models (Svoboda, 2004) inapplicable, and the results of the separation dicult to predict. According to the number statistics, all the samples consisted exclusively (>99.9%) of respirable size particles (<10 mm) and predominantly (>80%) of submicron particles. The mineralogical composition of the three FAs studied was complicated, but in general it matched the theoretical expectations based on the composition of parent coals and burning regimes (Mitchell and Gluskoter, 1976; Hatt and Bull, 1990; Vassilev and Vassileva, 1996; Vassilev et al., 1996; Jak et al., 1998; Demir et al., 2001). The main

Figure 1. SEM micrographs of fly ash particles FAM3 (a), FAR (b) and FARE (c).

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Table 1. Chemical composition and physical properties of the initial ashes Material Chemical compositiona SiO2 (wt.%) Al2O3 (wt.%) Fe2O3 (wt.%) CaO (wt.%) MgO (wt.%) K2O (wt.%) Na2O (wt.%) TiO2 (wt.%) LOI 1273J (wt.%) Physical properties Specific weight, , (kg m3) Bulk density (kg m3) Specific surface (m2 g1) Pores volume (pm3 g1) Colour Particles size distribution (%), statistic by Equivalent diameter (mm) 0.5 1.0 5 10 20 40 60 80 100 150 d50 Magnetic properties and characteristics Saturation magnetization of ferromagnetic components, Ms (A m2 kg1) Remanent magnetization, Mr, (A m2 kg1) Coercive force, Hc (A.m1) Paramagnetic contribution in M at 796 kA m1 (%) Paramagnetic contribution in M at 2389 kA m1 (%) Strongly magnetic iron, as Fe2O3 (%) Weakly magnetic iron, as Fe2O3 (%) Non-magnetic iron, as Fe2O3 (%)
a

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FAM3

FAR

FARE

42.12 19.92 12.89 10.74 3.07 1.20 1.12 2.20 6.3 2363 1980 15.4 3.6 Dark grey Volume 0.11 1.25 8.01 15.3 28.7 55.0 72.2 81.0 92.4 100 35.7 Number 24.3 83.1 99.5 99.9 99.97 100 0.64 2.78 0.61 11943 3.8 10.9 6.06 1.16 5.67 Volume 0.3 3.8 18.9 35.7 57.3 80.4 89.9 100 16.3

57.13 27.63 5.82 3.24 1.04 2.47 0.28 2.27 1.13 2180 960 15.3 3.5 Grey Number 28.0 87.9 99.6 99.9 100 0.56 1.04 0.18 8758 5.8 15.3 1.16 0.84 3.82

54.57 29.54 4.36 3.48 2.33 1.82 0.66 1.43 0.28 2635 2340 6.8 1.6 Dark grey Volume 0.73 7.05 22.9 30.7 40.2 59.0 65.2 75.2 98.3 100 34.58 Number 28.0 89.9 99.9 99.98 100 0.58 1.38 0.07 5971 9.3 23.1

Obtained values for metal content are recalculated as oxides content and are not normalized to 100%.

of the relative weights (g) of the corresponding partial components. The obtained values are shown in Table 1 along with the data for magnetic properties, estimated on the basis of the magnetization curves (Figure 3). The total magnetization of the FA samples was determined by the magnetization of ferromagnetic (magnetite and maghemite), paramagnetic (pyrite, etc.) and ferrimagnetic (Ca- and Mg-ferrites) and antiferromagnetic (hematite, goethite, etc.) constituents, all having dierent characters of magnetization

curves. Actually, at room temperature, hematite exhibits paramagnetic and parasitic ferromagnetic behaviour (Svoboda, 2004). Below Neels temperature (403 2 K) goethite also exhibited weak ferromagnetism and its magnetic susceptibility was strongly eld-dependent (Svoboda, 2004). All magnetization curves had light hysteresis character due to the presence of small quantities of ferromagnetic components and probably to the presence of ne hematite powder (Svoboda, 2004).

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(a) FAM3

Q C A H A AA Q M

H M

H C

CH

Q MH

Q FAR

Q MI

MI MI MI MIMI Q MI MI Q Q Q Q MI Q

FARE CF

CF CF

10 (b) Relative transmittance (%) 100 99 98 97

20

30

40 2-theta-scale

50

60

70

FAM3 96 10 8 6 4 2 0

FAR 2 4 6 8 10 10 5 0 5 s1) 10

Velocity (mm s1)

Velocity (mm

Figure 2. (a) XRD patterns of FAM3, FAR and FARE. Legend: Q, quartz (SiO2); M, maghemite (g-Fe2O3); H, hematite (a-Fe2O3); C, calcite (CaCO3), A, Ca-Al silicate (Ca0.88Al1.77Si2.23O8); Ml, mullite (3Al2O3.2SiO2), CF, calcium iron oxide (CaO.FeO); (b) Mo ssbauer spectra of FAM3 and FAR. The curve passing through data points is a least-square fit composed of Lorentzian shaped components, drawn as lighter curves (3 sextets and 2 doublets for FAM3; 4 sextets and 2 doublets for FAR).

This made the correct measurement of magnetic susceptibility of the samples extremely complicated, because although the magnetic susceptibility of paramagnetic materials was independent of the magnetic eld, paramagnetic minerals containing admixtures of magnetically ordered minerals exhibited eld-dependent magnetic susceptibility (Svoboda, 2004). This phenomenon can seriously alter the predictions for the results of magnetic separation based on the eld-independent magnetic susceptibility (Svoboda, 2004). That is why magnetic susceptibility is not discussed in the investigation, but an attempt for approximate

evaluation of ferromagnetic and paramagnetic contributions on specic magnetization has been made on the basis of the data obtained (Table 1). The maximum magnetization values and the widest hysteresis loop were observed for the FAM3 sample having the highest iron content among the three FAs studied. The data obtained now and previously, for another three Bulgarian FAs, show almost linear (Figure 3) correlation between the concentration of ferromagnetic iron and the saturation magnetizations (Ms). Only FAV was found to possess lower Ms than the expected one, but since it consisted almost entirely

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(a) 4.0
FAM3

(b) 3.5
FAR FARE

3.0 Magnetization (A m2 kg1) 2.0 1.0 0.0 1.0 2.0 3.0

Saturation magnetization of ferromagnetic components (A m2 kg1)

3.0 2.5 2.0 1.5 1.0 0.5

From left to right: FAR, FAB, FAME1, FAM3 OFAV

4.0 3000 2000 1000

1000

2000

3000

0.0 0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

Magnetic field strength (kA m1)

Concentration of strongly magnetic iron (as Fe2O3) (%)

Figure 3. (a) Magnetization curves, obtained at 293 K; (b) Saturation magnetization of ferromagnetic components as a function of their concentration.

of spherical particles (Shoumkova, 2006a), this phenomenon could be explained by the demagnetization eect of the particles shape. Although in all of the y ashes Ms was achieved at magnetic eld strength of 700800 kA m1, actually, more than 90% of Ms was reached at about 240 kA m1 which determined the applicability of the low-intensity magnetic separation process.

Magnetic separation results

The experimental conditions, yields and compositions of some MF and NF are shown in Table 2. The comparison between some YMF obtained at similar V/B ratio showed that only two pairs of experiments (No.6No.8 and No.9No.45) conrm Svobodas (2004) model, supposing that at equal other conditions the yield of MF depends only on V/B. However, the data obtained (Figure 4(a)) showed good correlation between the concentration of ferromagnetic iron and YMF for all sets of experimental conditions. The dependences were quite similar to those shown in Figure 3; again the values for FAV were much lower than the expected ones. Figure 4(b) illustrates clearly that for closer prediction of the YMF, the obtained data for saturation magnetization (Ms) of ferromagnetic constituents could be used. The experimental data for all series separated in the interval 0.0220.088 T showed that the increasing magnetic induction and/or the decreasing of ow velocity led to improving RFe and the YMF, but at the expense of Fe2O3 content in the MF. These dependencies have already been observed

(Shoumkova, 2006b) and could be explained by the fact that at higher magnetic eld intensity and gradient, the selectivity of iron separation gets worse, owing to the retaining of more weakly magnetic particles (having Fe < 25%) on the matrix (proved by SEM-EDX for all FAs). The comparison between the test pairs No.1No.4 and No.3No.5 shows that MFs separated at the lowest B had less Fe content, which could be explained by the supposition that at such weak magnetic eld the magnetic force acting on the nest iron-rich particles was too small, while the hydrodynamic force, being considerably stronger, led to their involvement in the NF. This hypothesis is also conrmed by the observation that the inuence of the velocity on the yield of MF was more signicant at lower magnetic inductions. This last statement was valid for all FAs, but to a dierent extent. For all FA samples the highest selectivity and enrichment factors were achieved at B 0.022 T and V 0.325 m s1. This observation matched the results from previous studies (Shoumkova, 2006b), but generally, the magnetic separation results were worse, as under the same conditions the Fe2O3 content in FAV, FAB and FAME1 were 36.3% (FFe 4.2), 31.9% (FFe 3.5) and 37.7% (FFe 1.4), respectively. The most likely reason for the low eciency of separation of FARE was the uniform distribution of iron in the volume of material, proved by SEM-EDX studies. Another possible reason for poor selectivity and low level of extraction was the presence of large amounts of Fe, incorporated in the glass phases. Additional negative impact on magnetic separation of all FAs may be associated with the presence of agglomerates and aggregates of phases, rich and poor in iron, observed by SEM-EDX in all samples (Figure 5).

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Table 2. Magnetic separation conditions and results
Test no. Separation conditions FA B (Tesla) 0.011 0.011 0.011 0.022 0.022 0.022 0.044 0.044 0.044 0.088 0.088 0.011 0.022 0.044 0.088 0.022 0.022 0.022 0.022 0.022 0.044 0.044 0.044 0.044 0.088 0.088 0.044 0.044 0.088 0.088 0.022 0.022 0.022 0.022 0.044 0.044 0.044 0.044 0.088 0.088 0.022 0.022 0.022 Vo (m.s1) 0.130 0.087 0.025 0.130 0.025 0.012 0.130 0.025 0.012 0.130 0.087 0.130 0.130 0.130 0.130 0.130 0.130 0.087 0.025 0.012 0.130 0.087 0.025 0.012 0.130 0.087 0.087 0.087 0.087 0.087 0.130 0.087 0.025 0.012 0.130 0.087 0.025 0.012 0.130 0.087 0.087 0.087 0.087 d (mm) Grad B (T m1) 7.3 7.3 7.3 14.7 14.7 14.7 29.3 29.3 29.3 58.7 58.7 7.3 14.7 29.3 58.7 3.7 14.7 14.7 14.7 14.7 29.3 29.3 29.3 29.3 58.7 58.7 17.6 8.8 35.2 17.6 14.7 14.7 14.7 14.7 29.3 29.3 29.3 29.3 58.7 58.7 8.8 4.4 3.7 YMF (%) 16.9 21.08 40.3 24.8 49.7 55.0 40.6 54.3 63.1 45.2 57.7 6.5 11.2 14.0 22.1 6.0 5.0 6.5 14.0 22.0 6.4 7.8 16.0 25.4 11.4 12.6 7.2 5.7 9.5 8.4 6.0 10.2 24.0 41.6 15.1 19.8 46.0 65.1 20.8 33.8 4.8 2.7 2.1 Chemical composition of MF, (wt.%)a SiO2 Al2O3 Fe2O3 CaO MgO Magnetic separation efficiency RFe (%) 30.1 35.2 57.2 48.3 79.6 84.9 18.8 29.0 28.7 40.8 14.9 12.4 13.3 13.4 22.5 33.2 18.5 14.9 16.5 16.7 22.0 9.1 13.7 25.1 12.4 13.1 12.5 FFe SFe (%) 12.1 11.0 9.1 16.2 15.4 15.6 26.4 23.2 15.7 14.0 20.4 9.1 6.7 4.5 2.8 2.4 3.1 6.8 11.7 4.9 10.3 2.4 0.7 0.3 7.3 17.3 22.1

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 Test no.

FAM3 FAM3 FAM3 FAM3 FAM3 FAM3 FAM3 FAM3 FAM3 FAM3 FAM3 FAM3 FAM3 FAM3 FAM3 FAM3 FAR FAR FAR FAR FAR FAR FAR FAR FAR FAR FAR FAR FAR FAR FARE FARE FARE FARE FARE FARE FARE FARE FARE FARE FARE FARE FARE

3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 12 3 3 3 3 3 3 3 3 3 3 5 10 5 10 3 3 3 3 3 3 3 3 3 3 5 10 12

39.32 39.40 42.33 37.16 40.20 40.90 30.91 32.83 37.36 39.34 33.96 50.88 52.97 54.49 55.50 56.08 55.32 52.21 49.30 53.61 51.03 54.48 54.09 54.53 45.24 42.54 39.7

18.82 18.86 20.70 17.68 18.46 19.65 15.16 17.28 18.19 19.08 17.1 25.26 26.23 26.01 26.85 27.33 27.00 25.56 24.01 26.12 24.54 26.27 28.37 29.02 22.32 20.21 17.88

22.95 21.61 18.31 25.07 20.66 19.91 37.51 33.53 26.41 23.82 32.03 14.43 12.10 9.98 8.20 7.61 8.52 12.12 16.80 10.21 15.22 6.58 4.97 4.55 11.3 21.2 26.0

12.17 11.73 11.84 11.67 11.82 11.80 10.53 9.42 10.61 10.19 11.3 3.98 3.32 2.72 3.25 3.34 3.14 3.68 4.24 3.01 3.62 3.95 3.57 3.50 3.24 3.21 2.90

2.72 3.28 2.98 3.22 2.58 2.66 3.54 3.73 3.85 3.87 2.43 1.85 2.35 2.17 2.00 1.45 1.95 2.26 1.65 2.22 2.36 2.52 2.25 2.30 2.21 2.33 2.35

1.8 1.7 1.4 1.9 1.6 1.5 2.9 2.6 2.1 1.9 2.5 2.5 2.1 1.7 1.4 1.3 1.5 2.1 2.9 1.8 2.6 1.5 1.14 1.04 2.6 4.8 6.0

Separation conditions FA B (Tesla) 0.088 0.088 0.088 Vo (m.s1) 0.025 0.025 0.025 d (mm) 3 3 3 Grad B (T m1) 58.7 58.7 58.7 YNF (%) 26.9 71.7 64.0

Chemical composition of NF, (wt.%)a SiO2 44.78 65.39 57.31 Al2O3 20.32 29.72 31.66 Fe2O3 8.41 3.43 4.31 CaO 10.80 2.25 2.71 MgO 2.40 0.81 2.12

Magnetic separation efficiency RFe (%) 17.6 42.2 63.3 FFe 0.65 0.59 0.98 SFe (%) 6.1 8.5 0.2

44 45 46
a

FAM3 FAR FARE

The analytical results are recalculated as oxides and are not normalized to 100%.

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(a) 80 70 60 YMF (%) 50 40 30 20 10 0 0.5

Series 1-0.088T, 0.062 ms1 Series 2-0.088T, 0.0325 ms1 Series 3-0.044T, 0.0325 ms1 Series 4-0.022T, 0.0325 ms1 From left to right: FAR, FAB, FAV, FAME1, FAM3

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

6.5

Concentration of strongly magnetic iron (as Fe2O3) (%) (b) 80 70 60 YMF (%) 50 40 30 20 10 0 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 Ms of ferromagnetic components (A m2 kg1)
Series 1-0.088T, 0.062 ms1 Series 2-0.088T, 0.0325 ms1 Series 3-0.044T, 0.0325 ms1 Series 4-0.022T, 0.0325 ms1 From left to right: FAR, FAV, FARE, FAB, FAME1, FAM3

Figure 4. (a) Dependence between concentration of strongly magnetic particles and yield of magnetic fraction; (b) dependence between magnetic separation of ferromagnetic components of fly ashes and yield of magnetic fraction.

In order to explore the opportunities for improving the eciency of separation by limiting the negative impact of the presence of poly-mineral aggregates and agglomerates in the ash, a series of additional experiments (Table 2, Tests 1215), including wet preliminary milling (15 min in planetary ball mill) of the material was carried out. The results show 1.8 to 2.9 times decreased yields of MF (in comparison with those for unground ash under the same conditions), but signicantly higher iron content in MFs; therefore the inuence of pre-milling of FA can be estimated as positive. A comparison between Test 1 and Test 15 proved that the proper selection of separation conditions can lead to an increase in both quantity and quality of the obtained fractions and thus it is very important for the magnetic separation process. Tests 13 and 14, in which equal quantities of iron were extracted in MFs of dierent volumes, conrm the same conclusion. The increasing size of matrix elements can also prevent the undesired mechanical capturing of large aggregates and agglomerates. Additionally, it would inuence the magnetic separation process by decreasing the magnetic eld gradient

that takes part in the calculation of the magnetic force. The inuence of matrix spheres diameter on magnetic separation eciency was studied in a few additional experiments (Table 2), performed with matrixes of steel balls of 5, 10 and 12 mm in diameter. The comparison of results of magnetic separation tests provided at equal other conditions (B and Vo) but using ball matrixes of dierent size showed substantial dierences in the yields and chemical composition of the obtained fractions. Generally, the increasing diameter of the balls had a positive eect on magnetic SFe and FFe, but led to a reduction of YMF and RFe. Its quantitative inuence was dierent for dierent materials, since the change of size of balls had a complex eect: it mainly aected the eld gradient, but also the ow velocity, mechanical capturing and loading capacity of the matrix.

Magnetic and non-magnetic fractions

From the comparison of typical MFs (Tests 4, 17 and 43) and typical NFs (Tests 44, 45 and 46) it could be deduced that wet

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Figure 5. SEM images of: (a) aggregates of (1) silicon-rich crystal (Si > 99%) and (2) iron-rich matter (Fe > 90%), observed in magnetic fraction, FAM3; (b) aggregates of (1) Ca-rich crystals and iron-rich matter (Fe > 85%), observed in magnetic fraction, FAM3; (c) aggregates of particles with (1) moderate content of iron (Fe 44%) and (2) aluminosilicate particle (Fe 0%), observed in magnetic fraction, FAR; (d) aggregates of particles with (1) moderate content of iron (Fe 32%) and low content of iron (Fe 5.1%), observed in magnetic fraction, FAR; (e), (d) large agglomerates of particles, observed in magnetic fraction, FARE.

low-intensity magnetic separation was a good method for separating ash fractions with dierent chemical compositions and properties (Table 2, Figure 6). All magnetic fractions had darker colour and higher specic weight (), due to the magnetite enrichment in magnetic fractions, and negligible LOI1273K. The average size of the particles (d50) of typical MFs was bigger than that of the non-magnetic ones, conrming previous investigations (Hower et al., 1999; Blaha et al., 2008). The MFs also had a lower volume percentage of particles under 2030 mm and very low content of submicron particles which could be a result of the signicant eect of hydrodynamic forces on particles of smaller size. The comparison of chemical compositions of typical MFs and NFs, showed slight enrichment in Ca and noticeable (up to twofold) enrichment in Mg in all MFs which can be explained by the presence of magnetic minerals containing Ca and Mg, such as ferrites and partially substituted magnetite, as has been reported by Gomes et al. (1999). The XRD patterns of the MFs and NFs (Figure 6(a)) are a little bit clearer than those of the initial samples. Pure or impure magnetite, maghemite and hematite are the typical minerals for FA magnetic concentrates (Hower et al., 1999).

In the present samples maghemite (or magnetite) was available in all MF. The presence of the non-magnetic minerals, quartz, mullite, Ca-Al-silicate, in the MFs was expected and it was determined by the existence of poly-mineral aggregates with strongly magnetic minerals (Hower et al., 1999). Such were often observed in magnetic fractions. Additionally, SEM-EDX analyses of MFs also showed the existence of poly-mineral particles, having an Si or Si-Al core and Fe-rich shell, most probably formed by secondary crystallization of iron oxides (Gomes et al., 1999) on the surface of quartz or mullite kernels. Quartz is the most important crystal phase in NFs. Temperatures above 14731573 K for more than 30 min and oxidizing conditions led to glass formation from quartz (Mitchell and Gluskoter, 1976). That was the case of FARE, where the XRD patterns showed a very high amorphous halo in the initial and NF fraction. On the base of the Mo ssbauer spectrum of the MF of FAM3 (Test 4) it was calculated that under the separation conditions about 69% of iron oxides (magnetite and hematite), and about 22% of Fe-bearing aluminosilicate minerals and amorphous phases were collected in the MF. The partial

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Waste Management & Research 0(0)

FAM3 MF
r = 2850 kg m3 Q A A M Q H A A M K K H K

M H

8
H M

7 6 Volume %
H

FAM3 NF d50 = 29.7 mm FAM3 MF d50 = 48.5 mm

M H Q MH

5 4 3 2 1

QA

FAM3 NF
r = 2315 kg m3 S QA A

C H H

CH Q

0 0 20 40 60 80 100 120 140 Particle size (mm)

FAR MF
r = 2228 kg m3 Q MI MI

8 7
M FAR NF d50 = 8.2 mm FAR MF d50 = 69.6 mm

6 Volume %
M Q MI Q MI Q MI Q Q MI Q MI M Q

5 4 3 2 1

FAR NF
r = 2143 kg m3 Q MI MI MI MI MI Q Q MI Q MI Q

0 0
Q Q Q MI Q MI QQ

20 40 60 80 100 120 140 160 180 200 Particle size (mm)

8 7
M M MI M M M M FARE NF d50 = 30.3 mm FARE MF d50 = 54.7 mm

FARE MF
r = 3120 kg m3

6 Volume % 5 4 3 2 1 0 0 20 40 60

FARE NF
r = 2595 kg m3 CF

20

30

40 2 - theta - scale

50

60

80 100 120 140 160 180

Particle size (mm)

Figure 6. (a) XRD patterns of magnetic and non-magnetic fractions. Legend: Q, quartz (SiO2); M, maghemite (g-Fe2O3); H, hematite (a-Fe2O3); C, calcite (CaCO3); A, Ca-Al silicate (Ca0.88Al1.77Si2.23O8); Ml, mullite (3Al2O3.2SiO2); CF, calcium iron oxide (CaO.FeO); S, silicon oxide (Si96O192); K, potassium iron oxide (K6Fe2O5); (b) particle size distribution in magnetic and non-magnetic fractions.

extraction of paramagnetic iron by low-intensity magnetic separation was probably due to its coexistence with ferromagnetic iron minerals in the particles.

Conclusions
On the basis of the analyses carried out in the present study, several conclusions can be summarized. 1. Magnetic properties correlate directly to the concentration of ferromagnetic iron in FAs. The total magnetization in the studied interval of magnetic elds is determined mostly by ferromagnetic components, but the relative contribution of paramagnetic magnetization at more intensive magnetic elds could be signicant.

2. Wet low-intensity magnetic separation is a good method for separating ash fractions having dierent and controllable chemical composition. All the technological parameters investigated: magnetic eld intensity, suspension ow velocity and the size of matrix elements, aect magnetic separation eciency, but their inuence is interlinked and is determined not only by the properties of the material, but also by the combination of other conditions. 3. For a certain set of separation conditions, the yields of magnetic fractions are directly proportional to the saturation magnetization (Ms) of the ferromagnetic components of the FAs. This allows reliable predictions of magnetic separation yields (YMF) to be made only on the basis of magnetization curves, while the pre-estimation based on

Shoumkova
the concentrations of ferromagnetic components could sometimes be less accurate. 4. The concentrations of iron in the richest magnetic concentrates obtained for FAM3, FAR and FARE respectively were 37.5% (RFe 18.8%, SFe 26.4%), 16.8% (RFe 16.5%, SFe 11.7%) and 26% (RFe 12.5%, SFe 22.1%). Although these results are not satisfactory enough for the direct utilization of MFs as ironbearing raw materials, the additional tests indicated that after further optimization of the separation conditions, small yields of higher grade magnetic concentrates could be obtained. 5. The observations indicate that the mineralogical composition and the distribution of minerals in particles are fundamental parameters in the determination of the applicability of magnetic separation. The main factors limiting the process are: (1) the presence of paramagnetic Fe-containing mineral and amorphous matter; (2) the existence of poly-mineral particles and the existence of aggregates of magnetic and non-magnetic particles. The rst factor cannot be managed, but its inuence can be pre-estimated on the base of chemical, XRD and Mo S analyses. The second factor can be aected by the application of appropriate pre-treatment (seeding, grinding, physical or chemical de-agglomeration, etc.). It was experimentally proven that the negative eect of both factors could be considerably limited by the selection of proper sets of separation conditions. 6. For the extraction of more concentrated iron fractions, further optimization should be performed at low magnetic eld induction 0.01 < B < 0.02 T, high suspension ow velocity (0.2 < V < 0.4 m s1), moderate eld gradients (3 < Grad B < 30 T m1), and suitable pre-treatment. FAR FARE FAV LOI1073K MF Mo S NF SEM SQUID TGA TPS XRD fly ash from TPS Repulika fly ash from TPS Rousse East fly ash from TPS Varna loss on ignition at 1073 K magnetic fraction Mo ssbauer spectroscopy non-magnetic fraction scanning electron microscope superconducting quantum interference device thermogravimetric analysis thermopower station X-ray diffraction

11

References
Aldrich RG (1984) Separation of high grade magnetite from fly ash, US Patent 4432868. Baitenev N and Murzaeva G (1984) Magnetic concentrate preparation from Ekibaztuss ash. Kompleksnoe Izpolzovanie Mineralnovo Suirja 7: 3638. (, (in Russian). Bayat O (1998) Characterisation of Turkish fly ashes. Fuel 77: 10591066. Blaha U, Sapkota B, Appel E, Stanjek H and Rosler W (2008) Micro-scale grain-size analysis and magnetic properties of coal-fired power plant fly ash and its relevance for environmental magnetic pollution studies. Atmospheric Environment 42: 83598370. Boybay M and Demirel T (1982) Process for preparing cryolite from fly ash, US Patent 4362703. Brown JW. (1980) Process for recovering magnetite from fly ash. US Patent 4191336. Cohen J and Mercier H (1976) Recovery of alumina from non-bauxite aluminium-bearing raw materials. Light Metals 2: 318. Demir I, Hughes RE and DeMaris PJ (2001) Formation and use of coal combustion residues from three types of power plants burning Illinois coals. Fuel 80: 16591673. Dobbins MS and Murtha MJ (1983) Recovery of iron oxide from coal fly ash. US Patent 4386057. Gomes S, Franc ois M, Abdelmoula M, Refait PH, Pellissier C and Evrard O (1999) Characterization of magnetite in silico-aluminous fly ash by SEM, TEM, XRD, magnetic susceptibility, and Mo ssbauer spectroscopy. Cement and Concrete Research 29: 17051711. Goodarzi F (2006) Characteristics and composition of fly ash from Canadian coal-fired power plants. Fuel 85: 14181427. Hatt RM and Bull DL (1990) Mineral Matter and Ash Deposition from Coal. In: Bryers R and Vorres K (eds.), New York, USA: Engineering Foundation. Hower JC, Rathbone RF, Robertson JD, Peterson G and Trimble AS (1999) Petrology, mineralogy, and chemistry of magneticallyseparated sized fly ash. Fuel 78: 197203. Hurst VJ and Styron RW. (1978) Fly ash beneficiation process. US Patent 4121945. Hwang JY (1993) Wet process for fly ash beneficiation. US Patent 5227047. Iyer RS and Scott JA (2001) Power station fly ash - a review of valueadded utilization outside of the construction industry. Resources Conservation and Recycling 31: 217228. Jak E, Degterov S, Hayes PC and Pelton AD (1998) Thermodynamic modelling of the system Al2O3SiO2CaOFeOFe2O3 to predict the flux requirements for coal ash slags. Fuel 77: 7784. Kostakis G (2009) Characterization of the fly ashes from the lignite burning power plants of northern Greece based on their quantitative mineralogical composition. Journal of Hazardous Materials 166: 972977. McDowell WJ and Seeley FG (1981) Recovery of aluminum and other metal values from fly ash, US Patent 4252777.

Acknowledgements
Part of the reported data have been included in the PhD thesis, High gradient magnetic separation of coal y ashes (Shoumkova, 2006a, b) elaborated at the University of Chemical Technology and Metallurgy, Soa, Bulgaria, with the kind support of Professor Dr I. Grancharov and Associate Professor Dr S. Shumkov. riaux Jean Roxel (Nantes, The help of the Institut de Mate France) Laboratoire de Physique Cristalline for the analyses of physical properties, XRD, Mo S and microscopic studies is greatly appreciated.

List of frequently used abbreviations and acronyms

AAS EDX FA FAB FAM3 FAME1 atomic absorption spectroscopy energy dispersive X-ray detector fly ash fly ash from TPS Bobov dol fly ash from TPS Maritza 3 fly ash from TPS Maritza East 1

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Mitchell RS and Gluskoter HJ (1976) Mineralogy of ash of some American coals: Variations with temperature and source. Fuel 55: 9096. Molina A and Poole C (2004) A comparative study using two methods to produce zeolites from fly ash. Minerals Engineering 17: 167173. Murtha MJ and Burnet G (1978) The magnetic fraction of coal fly ash: its separation, properties, and utilization. Proceedings of Iowa Academy of Science 85: 1013. Orlov S, Entelis I, and Smirnoff B (1999) Method of iron concentrates preparation. RU 2148093. czy S (2002) Significant radioactive contamiPapp Z, Dezs Z and Daro nation of soil around a coal-fired thermal power plant. Journal of Environmental Radioactivity 59: 191205. J, Monzo J, Borrachero MV and Peris-Mora E (1996) Paya Comparisons among magnetic and non-magnetic fly ash fractions: Strength development of cement-fly ash mortars. Waste Management 16: 119124. Prakash S, Mohanty JK, Dass B and Venugopal R (2001) Characterisation and removal of iron from fly ash of talcher area, Orissa, India. Minerals Engineering 14: 123126. Shoumkova AS (2006a) Physico-chemical characterization and magnetic separation of coal fly ash from Vrna, Bobov dol and MaritzaEast I power plants, Bulgaria, Part I Physico-chemical characterization. Journal of the University of Chemical Technology and Metallurgy 41: 175180. Shoumkova AS (2006b) Physico-chemical characterization and magnetic separation of coal fly ash from Vrna, Bobov dol and MaritzaEast I power plants, Bulgaria, Part II Magnetic separation. Journal of the University of Chemical Technology and Metallurgy 41: 181186.

Waste Management & Research 0(0)

Shumkov S and Shoumkova A (2002) Magnetic separation of coal fly ash. Journal of the University of Chemical Technology and Metallurgy 35: 565570. Shumkov SH and Shoumkova AS (2004) Magnetochemical treatment of coal fly ash. Bulgarian Chemistry and Industry 75: 3740. Sripriya R, Rao PVT, Bapat JP, Singh NP and Das P (2003) Development of an alternative to magnetite for use as heavy media in coal washeries. International Journal of Mineral Processing 71: 5571. Styron RW and Abiodun KS (2001) Method of making mineral filler and pozzolan product from fly ash, US Patent 6242098. Svoboda J (2004) Magnetic Methods for the Treatment of Minerals. Kluwer Academic Publishers. Dordrecht, The Netherlands. Turner R (1981) Oxidation state of arsenic in coal ash leachate. Environmental Science and Technology 15: 10621065. Vassilev S, Eskenazy G and Vassileva C (1996) Occurrence, abundance and origin of minerals in coals and coal ashes. Fuel Processing Technology 48: 85106. Vassilev S, Eskenazy G and Vassileva C (2001) Behavior of elements and minerals during preparation and combustion of the Pernik coal, Bulgaria. Fuel Processing Technology 72: 103129. Vassilev S and Vassileva C (1996) Mineralogy of combustion wastes from coal-fired power stations. Fuel Processing Technology 47: 261280. Vassilev S and Vassileva C (2009) A new approach for the combined chemical and mineral classification of the inorganic matter in coal. 1. Chemical and mineral classification systems. Fuel 88: 235245.