Fuel Processing Technology 72 Ž2001.

103–129
www.elsevier.comrlocaterfuproc

Behaviour of elements and minerals during

preparation and combustion of the
Pernik coal, Bulgaria
Stanislav V. Vassilev a,) , Greta M. Eskenazy b,
Christina G. Vassileva a
a
Central Laboratory of Mineralogy and Crystallography, Bulgarian Academy of Sciences,
Acad. G. BoncheÕ Str., Bl. 107, Sofia 1113, Bulgaria
b
Department of Geochemistry, Sofia UniÕersity, 15 Tzar OsÕoboditel Str., Sofia 1000, Bulgaria

Received 1 June 2000; received in revised form 1 February 2001; accepted 1 February 2001

Abstract

The chemical and mineral composition, including major ŽAl, Ca, Fe, K, Mg, S, Si, Ti., minor
ŽNa, P. and trace ŽBr, Cl, Co, Cr, Cu, Li, Mn, Ni, Pb, Rb, Sr, Zn. elements and different minerals,
of the Pernik subbituminous coals and their preparation and combustion solid waste products were
studied. Feed coals, upgraded coals Žhigh-grade and low-grade coals. and their waste products,
namely coal slimes and host rocks generated from the Pernik coal preparation plant, as well as
combustion waste products such as bottom ashes, fly ashes and lagooned ashes resulted from the
Republica coal-fired thermoelectric power station were characterized. The occurrence and be-
haviour Žpartitioning, volatilization, condensation, capture and retention. of the above-mentioned
elements and various minerals during coal preparation and combustion are described. The results
indicate some technological problems and possible environmental pollution of the air, water, soil
and vegetation with certain elements in the areas surrounding both thermoelectric power station
and coal preparation plant. q 2001 Elsevier Science B.V. All rights reserved.

Keywords: Coal; Waste products; Mineral and chemical composition; Trace elements

)
Corresponding author. Present address: Instituto Nacional del Carbon-CSIC, La Corredoria srn Apartado
73, 30380 Oviedo, Spain. Fax: q34-98-5297662.
E-mail address: stan@incar.csic.es ŽS.V. Vassilev..

0378-3820r01r$ - see front matter q 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 8 - 3 8 2 0 Ž 0 1 . 0 0 1 8 6 - 2
104 S.V. VassileÕ et al.r Fuel Processing Technology 72 (2001) 103–129

1. Introduction
Coal, as a sedimentary rock, is a complex mixture of organic and inorganic matter,
containing intimately mixed solid, liquid and gaseous phases, which have allothigenic
and authigenic origins. Comprehensive data on contents, concentration trends, distribu-
tions, organic–inorganic affinities and modes of occurrence of major, minor and trace
elements in various coals have been reported w1–11x. The variety of mineral occurrences
in coal, as well as their proportions, morphologies and genesis have also been widely
discussed and summarized w1,5,12–24x. The inorganic constituents in coal, comprising
dominantly minerals and to a lesser extent amorphous phases and fluid inclusions, are
responsible for a series of technological and environmental problems related to coal
mining, coal processing such as preparation, combustion, pyrolysis, gasification and
liquefaction, and utilization of coal wastes. For this purpose, studies on the behaviour of
different elements and to a lesser extent some minerals during coal beneficiation have
been conducted w7,19,25–28x. Further, extensive investigations on combustion solid
waste products Žin particular fly ashes. originated from coal-fired thermoelectric power
stations ŽTPSs. worldwide have been also carried out. For example, studies on the
contents and concentration trends of various elements in these products have been
performed w11,29–46x. The phase-mineral composition, morphological–microstructural
characteristics and some genetic phase peculiarities of combustion wastes have been also
characterized w36,42,44,47–64x. Additionally, investigations on the behaviour and mate-
rial balance of different elements in TPS have been conducted to some extent w11,29–
46,65–70x.
Despite the above-listed numerous studies, the behaviour Žpartitioning, volatilization,
condensation, capture and retention. of different minerals and trace elements during coal
preparation and combustion are still uncertain or incompletely understood and additional
investigations are required. Even more, this behaviour may differ significantly for
various coals. The present work provides a systematic investigation on the geochemistry
and mineralogy simultaneously of the Pernik coals ŽBulgaria. and their preparation and
combustion products generated from the Pernik coal preparation plant ŽCPP. and the
Republica TPS, respectively. Such detailed knowledge could be important in:
1. Determination of content, migration, concentrationrdepletion trends, distribution
and modes of occurrence of elements, minerals and phases.
2. Elucidation of elemental and mineral behaviour during coal upgrading and burn-
ing.
3. Characterization and evaluation of economically valuable components occurring in
coals and coal waste products.
4. Elucidation of products’ formation during coal processing.
5. Prediction, elucidation, reduction or elimination of various problems resulting from
preparation and combustion of coal, namely:
( Technological problems such as agglomeration, abrasion–erosion, corrosion,
slagging, fouling, processing of inert material, oxidation;
( Local environmental impacts such as pollution of the air, water, soil and
plants by gas, liquid and solid emissions, namely fly ashes, acidic or alkaline
solutions, toxic and potentially toxic elements and compounds.
 S.V. VassileÕ et al.r Fuel Processing Technology 72 (2001) 103–129 105

The purpose of the present work is to elucidate most of the above-listed problems
associated with the Pernik coals and their preparation and combustion products.

2. Materials and methods

Five types of samples from the Pernik subbituminous coals and their preparation
products generated from the Pernik CPP were examined. They include: feed coal ŽFC.;
low-grade coal ŽLGC., after coal sieving ŽF 30 mm.; high-grade coal ŽHGC., after coal
sieving and dense media separation; and waste products, namely coal slime ŽCS. and
host rock ŽHR.; taken from the bunkers and depositories at the Pernik CPP. The LGC is
used as a source of energy after burning in the pulverized coal-fired systems of the
Republica TPS. The common characteristics of this fuel are 47–60% A ar , 6–14% War
and about 21% VM ar , 74% C daf , 16% Odaf , 5% H daf , 3% Ndaf , 1% S daf and 2100–2200
kcal kgy1 Q daf .
Three major types of samples from combustion solid waste products, originated from
the dry-ash discharge boilers in the Republica TPS, were also examined. They include:
bottom ash ŽBA. from under the combustion chambers; fly ash ŽFA. recovered from the
hoppers of mechanical collectors ŽFA1., and first ŽFA2. and second ŽFA3. fields of the
electrostatic precipitator chains in TPS; and lagooned ash ŽLA. taken from the disposal
sites near TPS. The BA and FA samples were collected simultaneously from two boilers
in TPS. The above-listed samples were composed of a large number of single portions.
The high-temperature ash ŽHTA. of coal was prepared in an electric furnace under
atmosphere of static air at 5008C for 12 h. Sieving and magnetic separations, as well as
hand picking under a binocular microscope were applied to concentrate the minerals and
phases present. Some extraction procedures were also conducted. Dry water-soluble
residues ŽDWSR. were generated from 100 g material of FA3 and ground ŽF 100 mm.
LGC. Each sample was placed in a glass tank with 1 l distilled water for 24 h. The
suspension was periodically stirred and after that filtered. The pH value was potentio-
metrically measured in the generated water solution, and then the solution was placed in
a drying furnace at 808C until resulting DWSR. A sample of LA was also leached
sequentially with CH 3 COONH 4 Ž1 N., HCl Ž2 N. and HF Ž48%..
Polarizing microscopes were used for optical observations under reflected and
transmitted light. Powder X-ray diffraction ŽXRD. patterns were recorded for all
samples and their separated fractions using a diffractometer with CuK a and CoK a
radiation. Scanning electron microscopy ŽSEM. studies were carried out on a micro-
scope equipped with an energy dispersive X-ray analyzer ŽEDX.. The procedures for
optical and SEM observations, as well as for XRD analysis have been described earlier
w24,56x. Semi-quantitative and quantitative determinations of the mineral and phase
proportions in samples were performed using separation and ashing procedures, light
microscopy Žpoint counting method., XRD Žsemi-quantitative analysis. and SEM Žmi-
cromorphometric particle analysis..
The major, minor and trace elements in HTA, combustion waste products and
fractions were analyzed by wet chemical methods for Al, Ca, Fe, Mg, P, S, Si, Ti and
106 S.V. VassileÕ et al.r Fuel Processing Technology 72 (2001) 103–129

atomic absorption spectroscopy ŽAAS. for Co, Cr, Cu, Li, Mn, Ni, Pb, Rb, Sr, Zn. The
chemical analyses for Cl and Br were conducted by X-ray fluorescence ŽXRF. on
pelletized coal samples and standards w71x. SEM equipped with EDX was also used for
some elemental determinations.

3. Results and discussion

3.1. Chemical and mineral composition of the Pernik coal and preparation products

The contents of major, minor and trace elements studied in coals and coal waste
products from the Pernik CPP are given in Table 1. A number of elements such as Al,
Co, Cr, Cu, Fe, K, Li, Mg, Ni, P, Pb, Rb, and Zn, in the high-ash FC have
concentrations greater than the respective Clarke values for coals ŽTable 1.. The
comparison is evaluated by an enrichment factor ŽEF., namely as a ratio of the element
content in coal samples to the Clarke value for coals. For instance, the highest over
Clarke concentrations ŽEF G 3. in FC show Rb Ž12., Cu Ž11., Pb Ž6., Co Ž5., Zn Ž4., Ni
and Cr Ž3.. Such a comparison reveals elements that have the greatest potential for
environmental impacts andror for possible resource recovery during coal processing.
The regulated toxic and potentially toxic trace elements from combustion systems
comprise more than 22 elements w68,72x. They include Cl, Co, Cr, Cu, Mn, Ni, Pb, and
Zn studied in the present work. Hence, the above-listed over Clarke and hazardous
elements, in particular chalcophile and siderophile ones, should have a more detailed
environmental and economical concern.
The total chemical composition of coal or HTA is insufficient for a reliable
explanation of element behaviour during coal formation or coal processing. Most
important are the modes of element occurrence Žminerals and phases., their amount,
origin and behaviour in coal or coal products. The major minerals in FC are quartz,
kaolinite and feldspars Ždominantly K feldspar and to a lesser extent plagioclase., while
the minor minerals include illite, chlorite, calcite, pyrite, gypsum, siderite and muscovite
ŽTable 2.. Many other minor and accessory minerals also occur in the Pernik coals
w24,73x, but they are not under consideration in the present study because of their
complicated identification, quantification and comparison, and commonly subordinate
significance during coal preparation.
The elements in coal occur in both organic and inorganic constituents including the
fluid inclusions associated with them. According to the ash yield ŽTable 1., the studied
five samples were divided in three groups for relative comparison, namely with low
Ž18.9%., moderate Ž54.9–59.9, mean 57.5%. and high Ž72.4%. ash values ŽFig. 1.. It
can be seen that there is a positive correlation between ash yield and Si, Al, Mg, K, Li,
Rb, Cr, quartz, calcite, and a negative correlation between ash yield and S, Cl, Br,
kaolinite, chlorite, K feldspar, gypsum, pyrite in coal and coal ash. For the other
elements and minerals these trends are more complicated due to the occurrence of
subtrends based on the mixed influence of organic matter, authigenic and detrital
 S.V. VassileÕ et al.r Fuel Processing Technology 72 (2001) 103–129 107

Table 1
Mean chemical composition and trace element contents in coals and coal waste products from the Pernik CPP
Component FC HGC LGC CS HR Clarke
ar a ab b ar a ab b ar a ab b ar a ab b ar a ab b Coal Ash
Major and minor elements (%)
SiO 2 32.72 56.60 7.20 38.10 34.92 58.26 29.78 54.21 42.15 58.23 54.65 c
Al 2 O 3 14.74 25.50 3.98 21.06 15.66 26.13 13.44 24.47 17.43 24.08 23.54 c
Fe 2 O 3 4.29 7.42 2.28 12.06 3.30 5.50 5.41 9.85 5.73 7.92 6.63 c
CaO 1.34 2.32 1.13 5.97 1.34 2.24 1.66 3.02 1.82 2.51 6.26 c
SO 3 1.23 2.13 3.12 16.51 1.08 1.80 1.40 2.55 0.74 1.02 3.46 c
MgO 1.23 2.13 0.42 2.22 1.12 1.87 1.26 2.29 1.69 2.33 1.68 c
K 2O 1.17 2.02 0.26 1.38 1.35 2.25 1.13 2.06 1.60 2.21 1.51c
TiO 2 0.58 1.00 0.23 1.22 0.58 0.97 0.58 1.06 0.70 0.97 1.14 c
Na 2 O 0.24 0.41 0.10 0.53 0.44 0.73 0.18 0.33 0.30 0.41 0.81c
P2 O5 0.27 0.47 0.18 0.95 0.15 0.25 0.09 0.16 0.23 0.32 0.26 c
LOI d 43.54 0.00 82.20 0.00 39.93 0.00 44.60 0.00 27.49 0.00 0.00 c
Total 101.35 100.00 101.10 100.00 99.87 100.00 99.53 100.00 99.88 100.00 99.94 c

Trace elements (ppm)

Lithophile elementse
Li 38 66 9 48 37 62 35 64 42 58 20 f 80f
Rb 58 100 12 63 66 110 54 98 59 82 5f 46f
Sr 107 185 54 286 94 157 89 162 165 228 130 f 1100f
Siderophile elementse
Cr 35 61 11 58 33 55 31 57 42 58 12 f 70f
Mn 65 112 101 534 86 144 224 408 433 598 100 f 510f
Co 14 24 11 58 14 23 14 26 15 21 3f 20f
Ni 27 47 23 122 24 40 29 53 29 40 8f 51f
Chalcophile elementse
Cu 87 151 24 127 71 119 66 120 78 108 8f 48f
Zn 74 128 27 143 63 105 66 120 70 97 18 f 100f
Pb 17 29 9 48 24 40 15 27 20 28 3f 53f
Non-metal elementse
Cl 53 92 74 392 26 43 56 102 46 64 614 g 4690g
Br 9 16 8 42 6 10 8 15 7 10 17 g 130g
Ash Ž%. 57.8 100.0 18.9 100.0 59.9 100.0 54.9 100.0 72.4 100.0
nh 4 4 4 4 4 4 4 4 4 4
a
As received.
b
Ash basis. The oxides are normalized to 100% without loss on ignition.
c
Mean value for 41 coal ashes worldwide Žbased on Ref. w85x.. The mean MnO value is 0.06%.
d
Loss on ignition Ž5008C..
e
Mineralogical classification of elements w87x.
f
Clarke for subbituminous coals and coal ashes w8x.
g
Clarke for US coals and coal ashes w23x.
h
Number of samples and analyses.

minerals. The ash in coal comprises a sum of various genetic ash classes and subclasses
and their distribution in coal should be considered separately in understanding the actual
element association and affinity in coal w74x. For example, the authigenic minerals
108 S.V. VassileÕ et al.r Fuel Processing Technology 72 (2001) 103–129

Table 2
Mineral proportions in coals and coal waste products from the Pernik CPP, %
Mineral FC HGC LGC CS HR
ar a ab b ar a ab b ar a ab b ar a ab b ar a ab b
Silicates
Quartz 20 35 5 32 30 50 21 39 31 43
Kaolinite 13 22 3 19 11 19 11 20 9 12
Illiteqmuscovite 3 5 1 6 4 6 3 5 4 6
Chlorite 3 5 2 8 2 4 3 6 3 4
Plagioclase 3 5 1 4 1 2 2 3 3 4
K feldspar 6 10 2 8 2 3 4 7 3 4

Sulphates
Gypsum 2 4 1 5 1 2 2 4 2 3

Carbonates
Calcite 3 5 1 6 4 6 3 5 10 14
Siderite 2 4 2 8 3 5 3 6 4 6

Sulphides
Pyrite 3 5 1 6 2 4 3 5 3 4

Total 58 100 19 102 60 101 55 100 72 100

nc 1 1 1 1 1 1 1 1 1 1
a
As received Žthe crystalline matter is assumed to be the ash yield..
b
Ash basis.
c
Number of samples and analyses.

dominate most low-ash Ž8–10%. coals, whereas the proportion of detrital minerals
increases with increasing ash yield w75x. In general, the qualitative composition, mode of
localization and supposed dominant genesis of the minerals in coal show that sulphides,
sulphates, carbonates, chlorides, and some phosphates and clay minerals Žmainly kaolin-
ite and occasionally illite. are commonly authigenic in origin w24x and the present study
confirms these observations. Therefore, the informative ratio between an element
concentration in HR Ž72.4% ash yield. and HGC Ž18.9% ash yield. shows approximately
the dominant association of this element with detrital minerals or organic matter and
authigenic minerals in coal. The ratio values reveal:

Ø Elements with strong affinity to organics and authigenic minerals in coal ŽF 0.4.
—S ) ŽCl, Br. ) ŽP, Ni. ) ŽCa, Co.;
Ø Elements with predominant affinity to organics and authigenic minerals in coal
Ž0.5–0.8. —Pb ) Fe ) Zn ) ŽTi, Na, Sr.;
Ø Elements with equivalent affinity to organics–authigenic minerals and detrital
minerals in coal Ž0.9–1.1. —Al, Cr, Cu, Mg, Mn;
Ø Elements with predominant affinity to detrital minerals in coal Ž1.4–1.2. —Rb ) Li;
Ø Elements with strong affinity to detrital minerals in coal ŽG 1.5. —K ) Si.
 S.V. VassileÕ et al.r Fuel Processing Technology 72 (2001) 103–129 109

Fig. 1. Correlation trends between ash yield and some chemical components Ž'—as received; v —ash basis.
and minerals ŽB—crystalline matter basis. of the Pernik coals and high-temperature ashes.

The organic affinity of Co, Na, Ni, Pb, Sr, and Zn were also emphasized in another
study w73x and previous investigations of the authors for a great number of samples from
the Pernik coals.
 110 S.V. VassileÕ et al.r Fuel Processing Technology 72 (2001) 103–129

The generated water solutions from LGC studied earlier w76x and in the present study
show pH 4.1–6.3 Žacid to slightly acid., whereas the amount of the resulted DWSR is
0.3–1.2% Žsalty total mineralization.. The chemical composition of DWSR includes:

01 Ø Major elements Ž%. —Ca Ž13.4–15.8., S Ž15.7. Mg Ž6.3–7.2., Na Ž4.6–6.6., K

18/08/2015 Ž0.9–1.7., and Fe Ž1.4.;
a Gomez Rojas
Ø Minor elements Ž%. —Si Ž0.9., Al Ž0.4., and Cl Ž0.1.;
Ø Trace elements Žppm. —Mn Ž150–524., Cu Ž88–141., Zn Ž115–121., Li Ž68., Ni
Ž62., Co Ž44., Rb Ž26., Br Ž24., and Pb Ž9–19..

The water-extractable proportions of some elements from LGC are 24% Cl, 13% S,
0.4–3.8% Cu, 0.5–2.4% Zn, 0.5–2.0% Mn, 0.1–1.5% Pb, 0.9% Co, 0.8% Ni, 0.6% Li,
and 0.1% Rb. This leaching indicates that substantial Cl and S parts in LGC are related
to the presence of water-soluble salts and organic materials. In contrast, the behaviour
02 for Br, Co, Cu, Li, Mn, Ni, Pb, Rb, and Zn can be explained by their occurrence in
18/08/2015 strongly bound organic and inorganic water-insoluble forms. The XRD study shows that
a Gomez Rojas
this DWSR is composed by gypsum and traces of calcite. Both minerals are also
originally present in this coal ŽTable 2..

3.2. BehaÕiour of elements and minerals during preparation of the Pernik coal

The above results emphasize some characteristic features of this subbituminous coal,
namely: very high ash yield; abundance of detrital quartz and feldspars, and authigenic
kaolinite, siderite and pyrite; enrichment of Co, Cr, Cu, K, Mg, Ni, P, Pb, Rb, and Zn;
depletion of Br, Ca, Cl, Na, S, and salts; predominant affinity to organics and authigenic
minerals of Br, Ca, Cl, Co, Fe, Na, Ni, P, Pb, S, Sr, Ti, and Zn; predominant detrital
affinity of K, Li, Rb, and Si; significant occurrence of water-soluble Cl and S. These
peculiarities are of great importance in the elucidation of elemental and mineral
behaviour during preparation and combustion of the Pernik coal.
It can be seen that there are some informative element and mineral redistributions
Žash basis. during FC beneficiation ŽTables 1 and 2.. For example, HGC shows a
relative enrichment of Fe, Ca, S, Mg, Ti, P, Sr, Mn, Co, Ni, Zn, Pb, Cl, Br, illite,
chlorite, gypsum, calcite, siderite and pyrite, and reduction of Si, Al, K, Li, Rb, Cu, ash
yield, quartz, kaolinite and feldspars in comparison with FC. LGC reveals a relative
enrichment of Si, Al, K, Na, Rb, Mn, Pb, quartz, illite, calcite, and siderite, and
reduction of Fe, S, Mg, P, Sr, Cr, Ni, Cu, Zn, kaolinite, chlorite, feldspars, gypsum, and
pyrite in comparison with FC. The HGC is abundant in authigenic minerals and organic
matter and elements associated with them. Such constituents are commonly disseminated
intimately with each other in coal and their physical isolation Žseparation by screening
and dense media. is limited during coal cleaning. On the other hand, the LGC, CS and in
particular HR, are normally enriched in physically separable detrital and authigenic
Žquartz, illite, mica, chlorite, calcite, siderite. coal minerals, and especially in rock
fragments Žsandstones, sandy clays, sandy limestones and argillites from intra-seam
layers, roof and floor strata. fallen in the FC during coal mining. Despite the general
above-mentioned observations, it should be stated that some finely dispersed detrital
 S.V. VassileÕ et al.r Fuel Processing Technology 72 (2001) 103–129 111

coal minerals such as quartz, clay minerals and feldspars remain in HGC, whereas some
other authigenic coarse-grained and gangue minerals, namely siderite, calcite and pyrite
pass to LGC, CS and HR. Hence, the major fuel beneficiation during coal preparation in
the Pernik CPP is related to the reduction of ash yield in HGC and some S, Cl and pyrite
in LGC.

3.3. BehaÕiour of elements and minerals during combustion of the Pernik coal

3.3.1. Occurrence and partitioning

The combustion wastes ŽFig. 2a,b. comprise original and newly formed inorganic and
organic constituents characterized in detail earlier w56x. The chemical and mineral
composition of the BA, FA, LA and separated size fractions studied are listed in Tables
3–7. The inorganic part consists of different amorphous components ŽFig. 2c–f. and to a
lesser extent of crystalline phases ŽFig. 3a. represented by various minerals. The
inorganic composition includes mainly glass, quartz, feldspars, mullite, clay minerals,
hematite and magnetite, and to a lesser extent cristobalite, anhydrite-gypsum, calcite,
and lime. The organic constituent is represented by unburnt coal components Žchar. such
as slightly changed, semi-coked and coked petrographic ingredients ŽFig. 3b–d..
Different element Žash basis. and mineral concentration trends in these waste
products were observed ŽTables 3–7.; however, the trends are commonly not very
distinct. BA is relatively enriched in Fe, Ca, Mg, Cr, Mn, Cu, quartz, illiteq muscovite,
calcite, char ŽTables 3 and 6. and glass in comparison with FA. Hence, BA is abundant
in products originated dominantly from coal carbonates Žcalcite, siderite., pyrite and
quartz, and associated them with trace elements. It can be seen that the concentrations of
Si, Al, Ni, cristobalite, mullite, hematiteq magnetite, lime, and Ca sulphates are higher
in the finest-grained BA fraction Ž- 0.25 mm., while the contents of Fe, Ca, Mg, Ti,
Na, Sr, Cr, Mn, Cu, Zn, Pb, char, clay minerals, feldspars, and calcite are higher in the
coarsest-grained BA fraction Ž) 1 mm. ŽTables 4 and 7.. A characteristic feature of BA
is also the relatively higher proportions of refractory and unmelted quartz and
kaolinite–metakaolinite aggregates ŽFig. 2a..
FA is relatively enriched in Si, Al, K, Ti, Na, Sr, Zn, kaolinite, K feldspar, mullite,
hematiteq magnetite, and lime, in comparison with BA ŽTables 3 and 6.. Hence, FA is
abundant in products generated predominantly from clay minerals and feldspars in coal.
FA from the mechanical collectors ŽFA1. is concentrated in Al, Fe, Ca, Sr, Mn, char,
cristobalite, kaolinite, illite q muscovite, and mullite ŽTables 3 and 6. in comparison
with FA from the electrostatic precipitators ŽFA2 and FA3.. It can be seen that the
concentrations of Si, Rb, Sr, Mn, Co, Ni, Cu, Pb, K feldspar, mullite, Ca sulphates, and
calcite are higher in the finest-grained FA fraction Ž- 0.10 mm., while the contents of
Al, Ca, Mg, Na, Li, Cr, Zn, char, quartz, clay minerals, and hematiteq magnetite are
higher in the coarsest-grained FA fraction Ž) 1 mm. ŽTables 5 and 7.. The finest FA
ŽFA3. shows maximum concentrations of Mg, Ti, Na, P, Rb, Cr, Co, Ni, Cu, Zn, and Pb
in comparison with FA1 and FA2 ŽTable 3.. A characteristic feature of FA is also the
relatively lower proportions of microspheres ŽFig. 2b. due to the limited fusion of
original mineral matter composed dominantly by resistant quartz and kaolinite ŽFig. 3a..
112 S.V. VassileÕ et al.r Fuel Processing Technology 72 (2001) 103–129

Fig. 2. Ža. SEM image of a general view of bottom ash from the Republica TPS. Secondary electrons. Žb. SEM
image of a general view of fly ash from the Republica TPS. Secondary electrons. Žc. SEM image of an
aluminosilicate glass particle in fly ash from the Republica TPS. Secondary electrons. Žd. SEM image of a
surface detail from the above aluminosilicate glass particle Žc. in fly ash from the Republica TPS. Secondary
electrons. Že. SEM image of an aluminosilicate glass cenosphere in lagooned ash from the Republica TPS.
Secondary electrons. Žf. SEM image of an aluminosilicate glass plerosphere in fly ash from the Republica
TPS. Secondary electrons.

The above listed changes in concentrations are related to the partitioning and
redistribution of phases among BA, FA and stack emissions during combustion of coal.
Processes such as Ž1. intensive particle agglomerationrdesintegration and fractionation
Table 3
Mean chemical composition and trace element contents in combustion waste products from the Republica TPS
Component BA FA1 FA2 FA3 FA2 q 3 FA LA
a b a b a b a b a b a b
ar ab ar ab ar ab ar ab ar ab ar ab ar a ab b
Major and minor elements (% )
SiO 2 54.75 59.37 57.70 59.36 58.65 59.91 58.67 59.88 58.66 59.91 58.34 59.72 56.36 59.89

S.V. VassileÕ et al.r Fuel Processing Technology 72 (2001) 103–129

Al 2 O 3 22.26 24.13 24.46 25.16 24.12 24.64 24.20 24.70 24.16 24.68 24.26 24.84 23.41 24.88
Fe 2 O 3 7.57 8.21 7.24 7.45 7.00 7.15 6.85 7.00 6.92 7.07 7.03 7.20 6.48 6.89
CaO 2.27 2.46 2.28 2.35 2.25 2.30 2.18 2.22 2.21 2.26 2.23 2.29 2.26 2.40
MgO 2.00 2.17 1.87 1.92 2.01 2.05 2.06 2.10 2.03 2.07 1.98 2.03 2.04 2.17
K 2O 1.99 2.16 2.20 2.26 2.33 2.38 2.31 2.37 2.32 2.37 2.28 2.33 2.06 2.19
TiO 2 0.81 0.88 0.91 0.94 0.97 0.99 1.06 1.08 1.02 1.04 0.98 1.00 0.89 0.95
Na 2 O 0.29 0.31 0.29 0.30 0.33 0.34 0.37 0.38 0.35 0.36 0.33 0.34 0.39 0.41
P2 O5 0.29 0.31 0.25 0.26 0.23 0.24 0.26 0.27 0.24 0.24 0.24 0.25 0.21 0.22
LOI c 7.27 0.00 2.29 0.00 1.61 0.00 1.70 0.00 1.66 0.00 1.87 0.00 5.52 0.00
Total 99.50 100.00 99.49 100.00 99.50 100.00 99.66 100.00 99.57 100.00 99.54 100.00 99.62 100.00

Trace elements (ppm )

Lithophile elements
Li 59 64 61 63 65 66 65 66 65 66 64 66 57 61
Rb 102 111 103 106 109 111 111 113 110 112 107 110 99 105
Sr 140 152 159 164 159 162 154 157 156 159 157 161 129 137
Siderophile elements
Cr 57 62 49 50 50 51 54 55 52 53 51 52 58 62
Mn 353 383 327 336 229 234 202 206 216 221 253 259 246 261
Co 22 24 18 19 22 22 23 23 22 22 21 21 26 28
Ni 49 53 41 42 57 58 66 67 61 62 54 55 45 48
Chalcophile elements
Cu 117 127 107 110 122 125 132 135 127 130 120 123 108 115
Zn 118 128 101 104 205 209 259 264 232 237 188 192 90 96
Pb 41 44 30 31 36 37 60 61 48 49 42 43 24 26
Ash Ž% . 92.2 100.0 97.2 100.0 97.9 100.0 98.0 100.0 97.9 100.0 97.7 100.0 94.1 100.0
nd 2 2 2 2 2 2 2 2 4 4 6 6 4 4

a
As received.
b
Ash basis. The oxides are normalized to 100% without loss on ignition.
c
Loss on ignition Ž5008C ..
d

113
Number of samples and analyses.
114 S.V. VassileÕ et al.r Fuel Processing Technology 72 (2001) 103–129

Table 4
Mean chemical composition and trace element contents in size fractions of bottom ashes from the Republica
TPS
Component BA )1 mm BA 1–0.5 mm BA 0.5–0.25 mm BA - 0.25 mm
Ž5.0%. a Ž14.3%. a Ž45.4%. a Ž35.3%. a
ar b ab c ar b ab c ar b ab c ar b ab c
Major and minor elements (%)
SiO 2 36.89 56.70 49.62 59.07 56.98 60.37 57.42 59.24
Al 2 O 3 15.41 23.69 19.57 23.30 21.85 23.15 24.00 24.76
Fe 2 O 3 6.17 9.48 6.96 8.29 7.23 7.66 7.42 7.66
CaO 2.54 3.91 2.69 3.20 2.32 2.46 2.40 2.48
MgO 1.51 2.32 1.52 1.81 1.95 2.06 1.99 2.05
K 2O 1.40 2.15 2.05 2.44 2.24 2.37 2.13 2.20
TiO 2 0.66 1.01 0.84 1.00 0.89 0.94 0.92 0.95
Na 2 O 0.30 0.46 0.49 0.58 0.45 0.48 0.37 0.38
P2 O5 0.18 0.28 0.26 0.31 0.48 0.51 0.27 0.28
LOI d 34.63 0.00 15.80 0.00 5.63 0.00 2.88 0.00
Total 99.69 100.00 99.80 100.00 100.02 100.00 99.80 100.00

Trace elements (ppm)

Lithophile elements
Li 42 65 53 63 60 64 61 63
Rb 66 101 90 107 101 107 100 103
Sr 120 184 166 198 144 153 129 133
Siderophile elements
Cr 35 54 46 55 44 47 48 50
Mn 412 633 445 530 328 347 384 396
Co 17 26 20 24 22 23 26 27
Ni 43 66 52 62 49 52 86 89
Chalcophile elements
Cu 96 147 104 124 106 112 113 117
Zn 91 140 120 143 106 112 107 110
Pb 26 40 31 37 30 32 32 33
Ash Ž%. 65.1 100.0 84.0 100.0 94.4 100.0 96.9 100.0
ne 2 2 2 2 2 2 2 2
a
Fraction yield.
b
As received.
c
Ash basis. The oxides are normalized to 100% without loss on ignition.
d
Loss on ignition Ž5008C..
e
Number of samples and analyses.

in the combustion chambers, electrostatic precipitators and mechanical collectors, Ž2.

limited melt flow in the boilers, and Ž3. some element volatilization in boilers and
subsequent complete or partial condensation downstream on FA take place during coal
burning Žsee below..
The generated water solution from FA3 shows pH 8.5 Žslightly alkaline., whereas the
amount of the resulted DWSR is 0.8% Žsalty total mineralization.. The concentration of
some elements in DWSR is 28.2% Ca, 1.7% K, 1.1% Na, 0.8% Mg, 175 ppm Fe, 144
ppm Li, 73 ppm Cu, 54 ppm Zn, and 34 ppm Rb. The water-extractable proportions of
Table 5
Chemical composition and trace element contents in size fractions of fly ash from the mechanical collector ŽFA1. at the Republica TPS
Component FA1 ) 1 mm Ž0.2% . a FA1 1–0.5 mm Ž3.7% . a FA1 0.5–0.25 mm Ž58.6% . a FA1 0.25–0.10 mm Ž23.0% . a FA1 - 0.10 mm Ž14.5% . a
b c b c b c
ar ab ar ab ar ab ar b ab c ar b ab c
Major and minor elements (% )
SiO 2 45.04 59.18 56.59 60.73 58.62 60.40 58.09 59.35 58.78 60.32
Al 2 O 3 19.23 25.27 23.01 24.69 24.06 24.79 23.81 24.33 24.28 24.92

S.V. VassileÕ et al.r Fuel Processing Technology 72 (2001) 103–129

Fe 2 O 3 5.39 7.08 5.85 6.28 6.53 6.73 7.91 8.08 6.89 7.07
CaO 1.73 2.27 2.03 2.18 1.90 1.96 2.16 2.21 1.80 1.85
MgO 1.67 2.19 2.10 2.25 2.01 2.07 2.06 2.11 1.93 1.98
K 2O 1.73 2.27 2.14 2.30 2.36 2.43 2.26 2.31 2.19 2.25
TiO 2 0.76 1.00 0.84 0.90 0.94 0.97 0.92 0.94 0.95 0.97
Na 2 O 0.43 0.57 0.46 0.49 0.49 0.50 0.51 0.52 0.46 0.47
P2 O5 0.13 0.17 0.17 0.18 0.15 0.15 0.15 0.15 0.17 0.17
LOI d 24.11 0.00 6.39 0.00 2.39 0.00 1.60 0.00 2.06 0.00
Total 100.22 100.00 99.58 100.00 99.45 100.00 99.47 100.00 99.51 100.00

Trace elements (ppm )

Lithophile elements
Li 51 67 63 68 46 47 60 61 55 56
Rb 78 102 92 99 77 79 100 102 149 153
Sr 82 108 106 114 98 101 123 126 153 157
Siderophile elements
Cr 63 83 71 76 74 76 49 50 69 71
Mn 166 218 304 326 305 314 396 404 386 396
Co 15 20 21 23 23 24 20 20 22 23
Ni 26 34 39 42 25 26 30 31 39 40
Chalcophile elements
Cu 88 116 87 93 89 92 100 102 118 121
Zn 114 150 140 150 137 141 142 145 135 138
Pb 9 12 14 15 6 6 7 7 25 26
Ash Ž% . 76.1 100.0 93.2 100.0 97.1 100.0 97.9 100.0 97.5 100.0
ne 1 1 1 1 1 1 1 1 1 1

a
Fraction yield.
b
As received.
c
Ash basis. The oxides are normalized to 100% without loss on ignition.
d
Loss on ignition Ž5008C ..

115
e
Number of samples and analyses.
116 S.V. VassileÕ et al.r Fuel Processing Technology 72 (2001) 103–129

Table 6
Mean mineral proportions in the crystalline matter of combustion waste products from the Republica TPS, %
Mineral BA FA1 FA2 FA3 FA2q3 FA LA
Silicates
Quartz 58 49 55 53 54 53 53
Cristobalite 6 6 5 5 5 6 4
Kaolinite 3 5 4 4 4 4 5
Illiteqmuscovite 5 4 3 3 3 3 3
Plagioclase 4 4 4 4 4 4 8
K feldspar 4 6 6 4 5 6 4
Mullite 6 10 8 9 8 9 8

Oxides
Hematiteqmagnetite 6 6 7 6 7 7 5
Lime 4 4 4 4 4

Sulphates
Gypsumqanhydrite 5 6 4 6 5 5 4

Carbonates
Calcite 3 6

Total 100 100 100 98 99 101 100

na 2 2 2 2 4 6 1
a
Number of samples and analyses.

trace elements are 1.8% Li, 0.4% Cu, 0.2% Rb, and 0.2% Zn, which indicate that they
are in strongly bound inorganic and organic water-insoluble forms. The XRD study
shows that this DWSR is composed mainly by gypsum. Ca sulphates are also present in
FA ŽTable 6..
As expected, LA tends to show an intermediate chemical and mineral composition
between BA and FA. However, some distinctions can be pointed out, namely: increased
ŽNa, Co, kaolinite, plagioclase, calcite. or decreased ŽFe, P, Sr, Ni, Cu, Zn, Pb,
cristobalite, hematiteq magnetite. concentrations of some components; magnetite oxida-
tion and hydration; anhydrite hydration; lime hydration and subsequent carbonatization.
The reason for that are the redistribution, solution, migration and weathering of some
solid phases during the water transport, sedimentation and storage of FA, BA and LA.
The sequential extraction procedure on the studied LA ŽTable 8. for elucidating some
modes of occurrence w77x and leaching behaviour of different elements for possible
water pollution from disposal sites shows that:
Ø Significant Ž10–39%. proportions of Ca ) Sr ) Mn ) Zn ) Ni occur as adsorbed
and ion-exchangeable components onrin clay minerals, mica, char, and as water-soluble
sulphates, oxides, and organics Žassociated with functional groups such as carboxyls and
carbonyls. leachable by ammonium acetate.
Ø Dominant Ž54–64%. proportions of Co ) Mn and significant Ž16–48%. parts of
Ca ) P ) Cu ) Rb ) Sr ) ŽZn, Pb. ) Fe ) ŽTi, Ni. ) Li occur as carbonates, Fe–Mn
oxides, chelates, phosphates, or other oxides leachable by HCl.
 S.V. VassileÕ et al.r Fuel Processing Technology 72 (2001) 103–129 117

Table 7
Mean mineral proportions in the crystalline matter of size fractions from bottom ash and fly ash at the
Republica TPS, %
Mineral BA FA1
)1 1–0.5 0.5–0.25 - 0.25 )1 1–0.5 0.5–0.25 0.25–0.10 - 0.10
mm mm mm mm mm mm mm mm mm
Silicates
Quartz 48 55 51 50 47 53 39 44 42
Cristobalite 5 5 5 6 4 3 8 5 4
Kaolinite 10 8 5 5 9 6 4 3 6
Illiteq muscovite 5 4 4 3 6 5 3 5 6
Plagioclase 5 6 5 4 4 4 15 6 4
K feldspar 5 4 3 2 4 6 5 7 5
Mullite 5 3 6 8 8 4 6 8 9

Oxides
Hematiteqmagnetite 4 4 4 6 8 6 5 5 7
Lime 2 1 2 6 5 3 4 6

Sulphates
Gypsumqanhydrite 8 4 9 10 6 9 10 10 8

Carbonates
Calcite 6 4 5 5 2 5 5

Total 101 99 98 101 102 101 100 102 102

na 2 2 2 2 1 1 1 1 1
a
Number of samples and analyses.

Ø Dominant Ž50–86%. proportions of Cr ) Ti ) Fe ) Ni ) Zn ) Li and significant

Ž14–46%. parts of P ) Cu ) Rb ) Co ) Mn ) Sr occur as glass, silicates Žclay miner-
als, feldspars. or covalent organometallic complexes leachable by HF.
Ø Dominant Ž60%. proportions of Pb and significant Ž12–35%. parts of Rb ) ŽLi,
Sr. ) Cu ) Ni occur as insoluble inorganic Žmullite, oxides, barite, celestite, xenotime
and other fine-grained accessory minerals. or organic Žcomplexed elements. components
that were unaffected by the extraction procedures or were not exposed to the solvents.
3.3.2. Volatilization
The balance factor by Egorov et al. w65x was used in order to determine approxi-
mately the element proportions, which do not bind in the discharged FA and BA from
Republica TPS and show susceptibility to release into the atmosphere. The previous
w11,78,79x and present results for 49 elements reveal that up to 92% of Br, 53% of Na,
30–40% of Ce, Cr, Hf, Mo, and Sc, 20–30% of La, S, and Zn, 10–20% of Co and Eu,
and limited Ž- 10%. proportions of Al, As, Ba, Be, Cs, Cu, Ge, Pb, V, and Y initially
present in LGC were emitted in solid, liquid and gas states during combustion. The
reasons for this disbalance of elements could be:
Ø Partial volatilization Ževaporation and sublimation. of elements in the combustion
chamber and their incomplete condensation on FA;
118 S.V. VassileÕ et al.r Fuel Processing Technology 72 (2001) 103–129

Fig. 3. Ža. SEM image of a kaolinite–metakaolinite particle in fly ash from the Republica TPS. Secondary
electrons. Žb. SEM image of a Afusinoid-typeB char particle in fly ash from the Republica TPS. Secondary
electrons. Žc. SEM image of a Aspore-typeB char particle in fly ash from the Republica TPS. Secondary
electrons. Žd. SEM image of a char particle with well-developed porous surface in lagooned ash from the
Republica TPS. Secondary electrons.

Ø Migration of elements through the finest ash particles that have not been caught in
the cleaning equipments;
Ø Capture and remaining of elements on the TPS’s metal surfaces.

The first two reasons are dominant, while the last one has a negligible importance for
the total balance of elements during combustion. Technological processes and character-
istics such as fuel preparation, type of coal burning and waste removal, temperature and
gas environment, modes of element occurrence, size of minerals and phases and their
physico-chemical properties are principal factors for element migration.
The modes of element occurrence in coal may be a guide for the volatilization
behaviour of elements during combustion. For instance, elements with the highest
volatile behaviour in the studied TPS, namely Br, Co, Na, S, and Zn, show a tendency
for concentration in the easily decomposing organic matter and authigenic coal minerals
Žsulphides, carbonates, sulphates, hydrosilicates.. The bearing phases of these elements
probably exhibit high vapour pressure developed during the phase decomposition and
favour their mobility together with volatile sulphur, carbon, nitrogen, and other gases,
water vapour or their condensed products generated in TPS. Proportions of extremely
 S.V. VassileÕ et al.r Fuel Processing Technology 72 (2001) 103–129 119

Table 8
Sequentially leached elemental percentages with different solvents from the lagooned ash at the Republica
TPS, %
Element CH 3 COONH 4 HCl HF Residue
Fe 3 30 62 5
Ca 39 48 4 9
Ti 1 19 76 4
P 2 47 46 5
Li 3 16 50 31
Rb 2 36 27 35
Sr 23 32 14 31
Cr 1 9 86 4
Mn 16 54 25 5
Co 8 64 26 2
Ni 10 19 59 12
Cu 4 40 39 17
Zn 12 31 53 4
Pb 2 31 7 60

volatile gas species with low initial condensation temperature Ždew-points F 100–1508C.
of some trace elements Žfor example, Br components. may leave TPS as vapours without
condensation and capture w79x.
Characteristic volatile trace elements such as As, Ba, Br, Cl, Cu, Ga, Ge, Pb, Sb, Sn,
Sr, U, V, and Zn w67x may occur as newly formed and finely dispersed discrete
accessory phases and particles in FA and some of them were identified w56x. These
micrometer Ž1–10 mm. and dominantly submicrometer Ž0.01–1 mm. in size solid phases
are difficult to be caught in the cleaning equipment at TPS. Other non-volatile or slightly
volatile trace elements ŽCr, Cs, Li, Mn, Rb, REE, Sc, Th, Ti, Zr. may occur predomi-
nantly in original and relatively refractory minerals in coal such as clay minerals, mica,
feldspars, Fe and Ti oxides, apatite, zircon and other inert minerals that may undergo
weak changes during combustion process. Hence, their migration with particulates from
stack emissions could be referred to pre-existing fine mineral particles in coal that are
frequently also below 10 mm in size w24,56x. For example, both Al and Cr Želements
with increased affinity to detrital minerals in coal. with disbalance in the present study
could be referred by the migration of original or newly formed finely dispersed Al- and
Cr-bearing phases such as mullite, metakaolinite, glass microspheres and chromite,
identified in FA. Original or newly formed solid phases with a dimension - 10 mm in
size may escape easily the particulate control systems in TPS w58x. Therefore, the
behaviour of elements during combustion strongly depends on their modes of occurrence
in coals and their combustion products. The simplified findings related to the classifica-
tion of elements as non-volatile, semi-volatile or volatile depending only on their
volatility in elemental state with increasing temperatures could be quite unrealistic
without considering their actual modes of occurrence.
3.3.3. Condensation, capture and retention
The above-mentioned observations reveal that a number of highly mobile elements
such as As, Ba, Be, Bi, Cl, Cs, Cu, Ga, Ge, Ni, Pb, Sb, Sn, Sr, Ta, Tl, U, V, and Zn, do
 120 S.V. VassileÕ et al.r Fuel Processing Technology 72 (2001) 103–129

not show a great volatilization during combustion of the Pernik coal. These elements
were divided in groups 2 and 3, namely elements with volatilization–condensation
mechanism or remaining in the gas phase in TPS, respectively w67x. Most of the
aforesaid elements may occur as volatilized species in the furnace and condense and
adsorb downstream, preferentially on the finer inorganic and organic FA particles with
higher specific surface, as the temperature of the flue gas drops. Such volatilization–
condensation mechanism has been repeatedly discussed w11,29–35,37,39,40,42,44–
46,66–70x. This mechanism should take place for some volatilized species in the
Republica TPS because elements such as Co, Cr, Cu, Ni, P, Pb, Rb, Sr, Ti, and Zn show
informative higher concentration trends to the finest FA or fractions ŽTables 3 and 5..
Possible mechanisms between metal vapours and dispersed substrates have been
proposed elsewhere in order to capture and stabilize the most volatile elements in the
ash residue w80,81x. They include particle coagulation between metal nuclei and sorbent
particles, and condensation mechanisms that comprise physical film condensation and
reactive capture of metal vapour on substrates. An approach for metal emission control
is to minimize the formation of metal vapours during combustion by suppressing metal
volatilization and capturing volatilized metals using effective sorbents. The important
role of clay minerals, Ca-, Mg-, K-, Na-, and Fe-bearing oxyhydroxides, sulphates and
03 carbonates, or glass and char in the partial capture and retention of some trace elements
18/08/2015 has been emphasized w42,46,79,82x.
a Gomez Rojas
An interesting phenomenon in the Republica TPS is the relatively depressed
volatilization and increased capture and retention behaviour of some volatile and over
Clarke elements during the combustion process. For instance, the present results for 19
elements reveal that 53% of Na and only 5% of Al, 4% of Cr and 4% of Co initially
occurring in LGC were emitted during combustion. This phenomenon could be ex-
plained with:
Ž1. Limited loss of element proportions to the stack emissions Žliquid and gas.
because the volatile elements occur mainly in stable minerals in coal.
It seems that this factor is dominant for the depressed trace element volatilization
according to the mineral composition of coal and combustion wastes. Many original
silicates, oxides and phosphates in this high-ash coal are relatively stable phases at
higher temperatures Ž1200–15008C. and are commonly found in FA and BA. Hence, the
trace elements associated with the pre-existing refractory minerals should remain
dominantly in solid waste products.
Ž2. Capture and retention effects of the volatile elements in FA and BA by:
Ž2a. Original kaolinite highly enriched in this coal.
This factor has a major role for the capture and retention behaviour of trace elements.
The studied coal is highly enriched in kaolinite and this mineral undergoes dehydroxyla-
tion Žremoval of combined water from the hydroxyl groups and destruction of the
lattice. resulting in the formation of metakaolinite ŽFig. 3a. in the temperature range
450–6508C. The latter semi-amorphous phase is transformed to amorphous SiO 2 ,
mullite, spinel, cristobalite, corundum, and aluminosilicate glass above 9008C ŽFig.
2c,d.. It is well known that kaolinite possesses a good sorption capacity in the interlayer
space. Substitutions within the lattice of kaolinite, which result in unbalanced charges in
the structure, lead to the formation of ion-exchange positions on its surface w83,84x. This
 S.V. VassileÕ et al.r Fuel Processing Technology 72 (2001) 103–129 121

sorption capacity is probably activated additionally before Žloss of adsorbed water at

100–2008C. during Ž450–6508C. and after Ž650–9008C. the completed dehydroxylation.
The dehydration and dehydroxylation interval of kaolinite is parallel to the most
intensive oxidation of the Pernik coal at 200–5708C Žwith maximum at 350–5308C..
This oxidation interval is related to an intensive release of the most volatile trace
elements associated with organic matter and sulphides. The higher temperature interval
600–9008C is normally related to the liberation of trace elements associated with
carbonates, chlorides and some sulphates due to their decomposition, melting and
probably boiling. So, the finely dispersed original kaolinite and newly formed metakao-
linite with a high specific surface area could be effective sorbents and inertants for a
capture and retention of many volatile trace elements in the Republica FA and BA. The
possible mechanisms between the metal vapours and kaolinite–metakaolinite seem to be
mainly homogeneous or heterogeneous vapour nucleation, condensation, coagulation
and reaction within the solid clay particles, to a lesser extent physical and chemical
reactions on the solid clay particles, and limited solution reactions inron the melted clay
particles.
The exterior surface deposits are probably less important because there is a relatively
suppressed volatilization and subsequent condensation of volatile metals as salts on clay
substrates in this TPS. For example, the DWSR yield Žcomposed dominantly by
gypsum. from FA is only 0.2–0.8%. The solution reactions are quite limited because the
Pernik coal ashes have very high fusion temperatures. For instance, the hemispherical
and fluid temperatures are ) 15008 w85x and there is relatively limited glass formation.
Hence, the interior surfaces of original kaolinite in coal should provoke a successful
capture, stabilization and immobilization of various trace elements within the clay
particles. Consecutive processes, namely sorption captures accompanied by lattice
destruction and metakaolinite formation, and then amorphous SiO 2 formations and
crystallization of refractory silicate and oxide phases, induce pore blockage and solidifi-
cation in the substrate. Some of these transformations are clearly seen in former
kaolinite particles ŽFigs. 2c,d and 3a.. The Pernik coal is also enriched in illite and
chlorite, and some processes Žsimilar to kaolinite. such as release of interlayer water
Ž50–1508C., dehydroxylation Ž370–7508C., lattice destruction Ž820–9008C. and forma-
tion and crystallization of amorphous phase, spinel, cristobalite, olivine and mullite
Ž) 9008C. could also have a subsidiary role for capture and retention of trace elements
in FA and BA. The resulted DWSR and sequential leaching ŽTable 8. confirmed the
successful immobilization of trace elements.
Ž2b. Newly formed glass, Ca-, Mg-, and Fe-bearing sulphates, oxides and silicates.
This factor should have subordinate importance for the capture and retention be-
haviour of trace elements because the newly formed sulphates Žmainly anhydrite.,
hematite–magnetite, lime–periclase, Ca–Mg silicates ŽTables 6 and 7. and to some
extent glass, have a depressed occurrence in FA. Despite that some capture and retention
of volatile elements by these phases originated from solid-phase, gas–solid and liquid–
solid reactions in FA and BA may also occur. A part of the volatile elements can be
condensed, adsorbed andror reacted with the above-mentioned and surface deposited
phases. As a result, some elemental parts could be captured and retained onto and into
the aforesaid matrix crystalline phases and glass as impurities Žmainly as isomorphic
122 S.V. VassileÕ et al.r Fuel Processing Technology 72 (2001) 103–129

substitutions., very fine Ž- 1 mm. nucleation and cryptomere crystallization, and

discrete well-crystallized phases. For instance, the detected trace element concentrations
in DWSR from FA3 confirmed such limited retention effect for Cu and Zn in surface
salts of FA.
Ž2c. Newly formed porous char material.
This factor should have limited importance for the capture and retention behaviour of
trace elements because the char amount is about 7% in BA and 1.6–2.3% in FA. The
specific surface area of the studied FA is only 0.3–0.5 m2 gy1 . However, the porous
char material ŽFig. 3b–d. could be an effective sorbent for capture and retention of some
volatile trace elements due to its higher Žwithin orders of magnitude. surface area. For
example, the surface area of char in typical FAs was between 10 and 80 m2 gy1 Žsimilar
to most clay minerals., whereas the surface area of these samples after burning off the
char was between 0.03 and 0.08 m2 gy1 w42x. The present data show that the products
and fractions enriched in char material may be abundant in some trace elements ŽTables
3–5.. For a confirmation, 14 samples were arranged in three groups for comparison
ŽFig. 4., namely with low Ž1.6–2.9, mean 2.1%., moderate Ž5.5–7.3, mean 6.2%. and
high Ž15.8–34.6, mean 24.8%. values of loss on ignition ŽLOI.. The specified groups
were divided according to the LOI content proximities for the samples into each group
and to the distinct LOI content intervals between the groups divided. It can be seen that
positive correlation trends with char show Li, Sr, Cr, Mn, Ni, and Cu Žash basis.. Hence,
portions of these trace elements could be captured in the char and occur mainly in Fe-,
Ca- and Na-bearing minerals ŽFig. 4. and phases, probably as surface-deposited salts.
However, the bulk char material and DWSR yield are quite limited as pointed above. On
the other hand, samples highly enriched in char are also abundant in clay minerals ŽFig.
4. and some element capture could also be attributed to these minerals.
The data related to such limited trace element volatilization in TPS are of particular
interest because they are informative for the selective capture, retention and immobiliza-
tion of different toxic and potentially toxic components by originally present minerals
and organic ingredients in coal, newly formed inorganic phases and char in combustion
wastes, additives to coal, or selectively blended coals.
3.4. Technological and enÕironmental problems
The composition of the Pernik coal emphasizes some technological and environmen-
tal problems or advantages related to the coal beneficiation and combustion perfor-
mance. For example, the very high ash yield, originated particularly from detrital
minerals such as abrasive quartz, contributes greatly on the preparation, combustion,
transport and storage cost of a big amount of inert material and the wear down of
interior metal surfaces in CPP and TPS. On the other hand, the high ash-fusion
temperatures and low concentrations of S and Cl depress the problems connected with
fouling, slagging and corrosion of metal surfaces in TPS and formation of dangerous
heavy-metal chlorides and sulphates in FA, BA and LA. The low content of unburned
char Ž1.6–2.3%. in FA is informative for good combustion performance in TPS and
perspective utilization of this FA for some construction materials.
The contents of various elements in the wastewater, which transports FA and BA
from the studied TPS, may exceed significantly the respective Clarke values for surface
 S.V. VassileÕ et al.r Fuel Processing Technology 72 (2001) 103–129 123

Fig. 4. Correlation trends between loss on ignition ŽLOI. and some chemical components Ž'—as received;
v —ash basis. and minerals ŽB—crystalline matter basis. of the Republica FA, BA and LA.
124 S.V. VassileÕ et al.r Fuel Processing Technology 72 (2001) 103–129

waters. For example, the highest over Clarke concentrations ŽEF G 5. in this contami-
nated slightly alkaline water ŽpH s 8.0. show Br Ž3048., Ca Ž115., V Ž69., F Ž36., Na
Ž23., K Ž16., Zn Ž10., Cl and Mg Ž5. w11x. The reason for that is their occurrence in
water-soluble salts commonly with a surface particle association in FA. Such mobile
elements migrate inside and out of the pond disposals, and may contaminate the surface
and subsoil waters, soils and plants in the surrounding areas. Some elements in the
wastewater, namely Ca, Cl, F, V, and Zn, even exceed the maximum permissible
concentration for drinking water according to the EC, USA and other standards in some
European countries. The DWSR generated from FA contains water-soluble Ca, Cu, Fe,
K, Li, Mg, Na, Rb, S, Zn, and probably high concentrations of the above-mentioned
over Clarke elements according to the composition of this wastewater w11x. Further, the
DWSR originated from LGC contains water-soluble Br, Cl, Co, Cu, K, Li, Mn, Na, Ni,
Pb, Rb, S, Zn and other elements. Many of the above listed elements are regulated as
toxic and potentially toxic trace elements and their water-soluble forms are bioavailable
and could penetrate easily into the nutritious chain. To avoid or reduce such problems,
mineral sorbents like mixed–layered clay, montmorillonite and clinoptilolite may be
effectively used for purification of these contaminated wastewaters w86x. The water
recycling could improve significantly the environmental state around the pond disposals
of TPS. On the other hand, some elements in wastewaters may be of interest in terms of
their extraction and utilization.
Elements with disbalance ŽAl, As, Ba, Be, Br, Ce, Co, Cr, Cs, Cu, Eu, Ge, Hf, La,
Mo, Na, Pb, S, Sc, V, Y, Zn. in the studied TPS could also contaminate the soils near
TPS despite their limited volatilization behaviour. The contents of various elements in
soils near Republica TPS may exceed significantly the respective Clarke values for soils.
For example, the highest over Clarke concentrations ŽEF G 2. in these soils reveal Hf
Ž17., Pb Ž5., Ba, Co, Cu, La, Li, Mn and Sc Ž2. w11x. It should be stated that some of the
listed elements could be easily released into solutions from the soils near TPS. However,
the determination of such contamination is difficult because additional sources of
elements in the areas near TPS may also occur. For instance, the original over Clarke
contents in soil, the effect of other side contaminants Žexhausts of cars, other factories,
contaminated rainfalls, fertilizers. and the surface water migration could also contribute
to these element enrichments in soils. On the other hand, elements with environmental
concern such as Cl, Co, Mn, Ni, Pb, S, and Zn show enrichment in HGC Žash basis. and
could also provoke some problems during use of this fuel for home heating.
The contents of various elements in grass vegetation Žash. from the LA disposal sites
of this TPS may also exceed significantly the respective Clarke values for vegetation
Žash basis.. For example, the highest over Clarke concentrations ŽEF G 3. in this
vegetation show Bi Ž2000., Cd Ž1000., Sr Ž23., Pb Ž20., Yb Ž13., Ba Ž10., Sc Ž6., Ti and
V Ž3. w11x. Probably, some water-soluble portions of the aforesaid elements from FA,
BA and wastewater have been accumulated in this vegetation.

4. Conclusions
The characteristic features of the subbituminous Pernik coal include: very high ash
yield; abundance of detrital quartz and feldspars, and authigenic kaolinite, siderite and
 S.V. VassileÕ et al.r Fuel Processing Technology 72 (2001) 103–129 125

pyrite; enrichment of Co, Cr, Cu, K, Mg, Ni, P, Pb, Rb, and Zn; depletion of Br, Ca, Cl,
Na, S, and salts; predominant affinity to organics and authigenic minerals of Br, Ca, Cl,
Co, Fe, Na, Ni, P, Pb, S, Sr, Ti, and Zn; predominant detrital affinity of K, Li, Rb, and
Si; significant occurrence of water-soluble Cl and S.
The HGC is abundant in authigenic minerals and organic matter and elements
associated with them and these constituents are commonly disseminated intimately with
each other in coal and their physical isolation is limited during coal cleaning. The LGC,
CS and in particular HR, are normally enriched in physically separable detrital and
authigenic coal minerals and rock fragments. The major fuel beneficiation during coal
preparation is related to the reduction of ash yield in HGC and some S, Cl and pyrite in
LGC.
The depressed volatilization and increased capture and retention behaviour of some
volatile and over Clarke elements during combustion process in the Republica TPS
could be explained with: Ž1. limited loss of element proportions to the stack emissions
because the volatile elements occur dominantly in stable minerals in coal; and Ž2.
capture and retention effects of the volatile elements in FA and BA mainly by original
kaolinite, and to a lesser extent by newly formed glass, Ca-, Mg-, and Fe-bearing
sulphates, oxides and silicates, and porous char material.
The very high ash yield of the Pernik coal contributes greatly on the processing cost
of a big amount of inert material and the wear down of interior metal surfaces in CPP
and TPS. The high ash-fusion temperatures and low concentrations of S and Cl depress
the problems connected with fouling, slagging and corrosion of metal surfaces in TPS
and formation of dangerous heavy-metal chlorides and sulphates in FA, BA and LA.
The results indicate some possible environmental pollutions of the air ŽBr, Ce, Co,
Cr, Eu, Hf, La, Mo, Na, S, Sc, Zn., water ŽBr, Ca, Cl, F, K, Mg, Na, V, Zn., soil ŽBa,
Co, Cu, Hf, La, Li, Mn, Pb, Sc. and vegetation ŽBa, Bi, Cd, Pb, Sc, Sr, Ti, V, Yb. in the
areas surrounding the Republica TPS. Various elements with environmental concern
such as Cl, Co, Mn, Ni, Pb, S, and Zn show enrichment in HGC and could also provoke
some problems during use of this fuel for home heating. The present study emphasizes
that a monitoring and better understanding of the trace element and mineral behaviour
during coal preparation, coal combustion and waste storage are required in the large
TPSs and CPPs, and in the areas surrounding such factories.

Notation
A ar ash content, as received basis, %
ab ash basis
ar as received
AAS atomic absorption spectroscopy
BA bottom ash
C daf carbon, dry ash-free basis, %
CPP coal preparation plant
CS coal slime
DWSR dry water-soluble residue
EDX energy dispersive X-ray analyzer
EF enrichment factor
126 S.V. VassileÕ et al.r Fuel Processing Technology 72 (2001) 103–129

FA fly ash
FA1 fly ash from the mechanical collectors in TPS
FA2 fly ash from the first fields of the electrostatic precipitator chain in TPS
FA3 fly ash from the second fields of the electrostatic precipitator chain in TPS
FC feed coal
H daf hydrogen, dry ash-free basis, %
HGC high-grade coal
HR host rock
HTA high-temperature coal ash
LA lagooned ash from the disposal sites near TPS
LGC low-grade coal
LOI loss on ignition
n number of samples and analyses
Ndaf nitrogen, dry ash-free basis, %
Odaf oxygen, dry ash-free basis, %
Q daf calorific value, dry ash-free basis kcal kgy1
REE rare earth elements
S daf sulphur, dry ash-free basis, %
SEM scanning electron microscopy
TPS thermoelectric power station
VM ar volatile matter, as received basis, %
War moisture, as received basis, %
XRD powder X-ray diffraction
XRF X-ray fluorescence

Acknowledgements

The authors would like to express their gratitude to Mrs. M. Yossifova from the Sofia
University and Mr. G. Laskov from the Republica TPS for the assistance during
samples’ collection.

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Annotations

Behaviour of elements and minerals during preparation and

combustion of the Pernik coal, Bulgaria
Vassilev, S.; Eskenazy, G.; Vassileva, C.

01 Olga Patricia Gomez Rojas Page 8

18/8/2015 13:56
Afinidad de carbon subbituminoso y alto cz

02 Olga Patricia Gomez Rojas Page 8

18/8/2015 13:56
redistribución de elementos en las cz

03 Olga Patricia Gomez Rojas Page 18

18/8/2015 13:56
caolinita mineral q influye en enriquecimiento captura y retencion desarrolla capacida de absorción

04 Olga Patricia Gomez Rojas Page 19

18/8/2015 13:56
entre 600-900 se libera ET asociados con carbonatos, cloratos, sulfatos debido a descomposición,
fusión y ebullición . tambien son dispersados en la calolinita formando metacaolinita