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Energy 113 (2016) 85e94

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Energy
journal homepage: www.elsevier.com/locate/energy

Properties of ash generated during sewage sludge combustion: A


multifaceted analysis
Aneta Magdziarz a, *, Małgorzata Wilk a, Marcin Gajek a, Dorota Nowak-Wo
zny b,
Agnieszka Kopia a, Izabela Kalemba-Rec a, Janusz A. Kozin ski c
a
AGH University of Science and Technology, Mickiewicza Av. 30, 30-059 Krakow, Poland
b
Wroclaw University of Technology, Wybrzeze Wyspianskiego 27, 50-370 Wroclaw, Poland
c
York University, Lassonde School of Engineering, Toronto, M3J 1P3, ON, Canada

a r t i c l e i n f o a b s t r a c t

Article history: This paper presents chemical properties of sewage sludge ashes required for determining their thermal
Received 2 April 2016 characteristics. A novel approach, linking selected advanced analytical techniques with FactSage
Received in revised form modelling, was developed and applied to obtain new information on deposit formation mechanisms that
9 June 2016
contribute to fouling and slagging. The mineral matter and fusion temperatures were investigated using
Accepted 6 July 2016
Available online 16 July 2016
a variety of analytical techniques including XRF, ICP-MS, XRD, SEM-EDX and AFT. The slagging and
fouling indices were calculated and the sintering properties were predicted. The studied ashes were rich
in P2O5, CaO, SiO2 and Fe2O3, but their concentrations slightly differed. Phase analyses suggested the
Keywords:
Sewage sludge ashes
existence of calcium and phosphorus as main phases. Thermal behaviour of ashes was studied focusing
XRD on the mass loss, temperature peaks and thermic effects with the increasing of temperature up to
ICP-MS 1200  C under air atmosphere. The changes in concentration of ash compounds contributed to differ-
SEM ences in ash fusion temperatures. FactSage thermochemical equilibrium calculations were used to pre-
Ash fusion temperature dict the amount of liquid slag and solid phases, giving information about slagging properties of ashes.
Thermodynamic calculations The general conclusion based on experimental studies is that sewage sludge ashes cause the slagging and
fouling hazard while they reveal low corrosive effect.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction the treatment of household and industrial wastewaters. In its dry


form, sewage sludge could be considered as renewable fuel due to
Environmental protection and new EU legislation drive the use the high quantity of organics of sufficiently high calorific value,
of renewable fuels for energy production. Biomass and sewage which can be thermally utilized. On the other hand, it contains
sludge are known alternative energy sources. In addition, increases microorganisms and harmful substances including heavy metals,
in the amount of sewage sludge have been affecting the environ- poorly biodegradable organic compounds, bacteria, viruses, phar-
ment, which has resulted in legislation changes in Poland. In the maceuticals, hormones and dioxins [12]. There are several thermal
view of the recent legal regulation (7/16/2015) regarding the technologies utilizing municipal sewage sludge to obtain useful
criteria and procedures for releasing wastes to landfilling, the energy. They include pyrolysis, gasification, combustion, and co-
thermal disposal of sewage sludge is important due to its gross combustion processes [13e17] Currently, as many as 11 plants in
calorific value, which is greater than 6 MJ/kg, and the problems that Poland use sewage sludge as fuel. This technology is expected to be
result from its use and application [1,2]. While biomass combustion further developed while considering the benefits of co-combustion
or co-combustion processes are commonly used [3e9], sewage with other fuels [18]. The combustion of sewage sludge can cause
sludge combustion is rather new technology especially in large- operating problems due to high moisture content and a large
scale devices [10,11]. Sewage sludge is the residual matter from amount of ash. Additionally, gaseous pollutants (CO, CxHy, NOx, SOx,
PAHs, dioxins and furans) and particulate matter are generated
[19,20].
* Corresponding author. AGH University of Science and Technology, Al. Mick- The advantages of thermal processes are the large reduction in
iewicza 30, 30-059 Krakow, Poland volume, the thermal destruction of toxic organics and the recovery
E-mail address: amagdzia@metal.agh.edu.pl (A. Magdziarz).

http://dx.doi.org/10.1016/j.energy.2016.07.029
0360-5442/© 2016 Elsevier Ltd. All rights reserved.
86 A. Magdziarz et al. / Energy 113 (2016) 85e94

of the energy from organic compounds present in the sludge. influence the calculated mineral phases. The sewage sludge ash is a
However, burning sewage sludge generates a large amount of ash very complex material in terms of physical and chemical properties.
containing mineral compounds (more than 30%) creating problems It consists of particles of different shape, a different chemical
when other fuels are substituted by sewage sludge. The main ele- composition and phase. The intergranular boundaries and chemical
ments in the sewage sludge ash are silicon, phosphorus, potassium, composition of individual grains are significant impact on the sin-
calcium, sulphur, chlorine and sodium [19]. Potassium content is tering process. Moreover, physical and chemical properties of ash
important because it indicates a potential ash fusion and deposition grains influence on the viscosity and line tension of intergranular
by vaporization and condensation. In renewable fuels combustion boundaries (surface and volume diffusion of mobility ions), but
K and Cl can be released in gas such as HCl, KCl and potassium exists viscosity and line tension of intergranular boundaries determine
as potassium silicate, aluminosilicate and sulphate. During the the sintering mechanism [31]. Therefore, thermodynamic analysis
cooling process the gaseous potassium may condense on the coarse is interesting as a complement to standard and nonstandard ash
fly ash as KCl and K2SO4 [21]. Some of the gaseous potassium tests that give detailed information about physical and chemical
directly forms aerosols. The potassium, sulphur and chlorine en- transformation of the ash.
richments in ash are very harmful because of corrosion risk. In the The multifaceted description of sewage sludge ashes using
case of sewage sludge, the presence of heavy metals such as Pb, Cd, advanced instrumental methods and supported by FactSage cal-
Cr, Cu, and Ni is a significant problem during the combustion pro- culations with special emphasis on precise physico-chemical
cess [22]. Alkali metals associated with sulphur and chlorine give characteristics is exactly what this paper has to offer.
serious operating problems such as slagging, fouling and corrosion
of metal surface limiting heat transfer. The term of slagging is used 2. Materials and methods
to describe the formation and accumulation of slags on the furnace
sections (refractory walls, water walls, and grates). The reactivity of 2.1. Materials
slags and bed agglomerations depends on the chemical reaction
between ash components in particularly silica, alkali, alkaline earth Materials considered for this study consisted of four kinds of
metals and other inorganic compounds present in the environment sewage sludge ashes. The samples were denoted as A_1, A_2, A_3,
[23,24]. The term fouling is used to indicate the formation of ash and A_4, respectively. The sewage sludge samples were taken from
deposits on heat transfer surfaces in the convective parts of the four existing municipal wastewater plants in Poland. Ash samples
furnace. were obtained from existing energy units where the sewage sludge
Although sewage sludge combustion is applied in several loca- is combusted. Current knowledge of the ash formation mechanisms
tions with good efficiency, ash deposition is a new problem, which and interactions between the ingredients is insufficient to suc-
requires new solutions. There are many papers concerning the in- cessfully avoid slagging and fouling of ashes on boiler surfaces.
fluence of chemical composition of biomass ash on deposition and Various analytical methods determining physical and chemical
corrosion processes e.g. Refs. [21,25,26]. The formation and trans- characteristics of biomass and sewage sludge ashes are required in
formation of sewage sludge ash are presented elsewhere [27,28], order to better understand the driving forces contributing to
but details regarding mechanisms associated with deposit forma- fouling/slagging.
tion that contribute to slagging and fouling are still being studied.
In order to better understanding of the mineral matter trans- 2.2. Experimental procedures
formation at high temperatures, a FactSage Thermodynamics
Model was used. The FactSage is based on minimization of the The X-ray fluorescence (XRF, Riau ZSX Primus II) has been used
Gibbs energy of a system. The Gibbs energy minimization algo- to determine the main chemical composition of sewage sludge
rithms identify amount of various phases and the composition of ashes (expressed as oxides in Table 1). There were two kinds of
the solution phases. Gibbs energy can be calculated from what is oxides then the chemical properties were taken into account. The
known of the chemical potential of the component by Ref. [29]: basic oxides are Na2O, K2O, MgO, CaO and Fe2O3, and the acid ox-
ides are SiO2, Al2O3 and TiO2.
X
G¼ ni Gi (1) TGeDSC technique (Thermogravimetry and Differential Scan-
i ning Calorimetry) was conducted using Netzsch STA 449 F3 Jupiter.
The samples were heated in alumina crucibles from ambient tem-
where: the ni amount of the component i. Assuming some con- perature to 1200  C at a constant rate of 10  C/min and at a 40 ml/
straints such as p, T and overall composition, the Gibbs energy min flow of air. The mass of sample was 35 mg, pan capacity was c.a.
minimization algorithms find the amount of various phases and the 113 mm3. The evolved gaseous products from decompositions were
composition of solution phases which give a global minimum in the identified on-line using mass spectrometry (QMS Netzsch). The
total Gibbs energy of the system [30]. The Gibbs energy can be following ions, which are characteristic of the molecules of interest,
expressed as: were monitored: 18, 44, and 64 H2O, CO2 and SO2, respectively.
The fusibility analysis was performed by a LECO AF700 Ash
0  1
ZT ZT Fusion Determinator. Pre-prepared ash cones were mounted on a
Cp ðT
GðTÞ ¼ DH298 þ Cp ðTÞdT  T D@S298 þ dT A ceramic tray and placed into a high-temperature and rampable
T furnace. The tests were done under air atmosphere. The specially
298 298
prepared pyramids are heated up to 1500  C. The heating process of
(2)
the ash cones was observed and monitored via video camera to
The values of DH298 , S298 and Cp ðTÞ are from thermodynamic determine deformation temperatures (a deformation temperature
databases. (IDT), a softening temperature (ST), a hemispherical temperature
Thermochemical calculations can indicate chemical composi- (HT) and a flow temperature (FT)). IDT is the temperature at which
tion in equilibrium, show amount of liquid slag and solid phases, the first rounding of the apex of the cone occurs. ST is the tem-
and give information about slagging properties of ashes. The perature at which the cone has fused down to a spherical lump and
transformation and fusion of ash takes place at high temperatures, the height becomes equal to the width of the base. At HT temper-
and kinetic limitations, mass transport, chemical potentials have all ature the height becomes one-half of the width of the base. FT is the
A. Magdziarz et al. / Energy 113 (2016) 85e94 87

Table 1
Ash composition expressed as oxides, wt % (XRF method).

Ash SiO2 Al2O3 Fe2O3 TiO2 CaO MgO K2O Na2O MnO P2O5 SO3 Cl

A_1 17.8 7.11 15.6 e 20.4 4.5 2.84 1.99 0.16 26.8 2.76 0.02
A_2 14.4 8.05 15.4 1.07 23.2 4.85 2.23 0.6 0.15 26.3 3.78 -*
A_3 22.1 8.39 11.05 1.07 22 4.4 1.97 0.79 0.28 22.4 4.98 -*
A_4 15.5 7.67 9.94 0.87 33.6 3.48 1.17 1.19 0.39 19.5 6.57 0.19

*- Below detection level.

temperature at which the fused mass has spread out in the nearly contribute to forming low melting point eutectics, which can cause
flat layer with a maximum height of 0.0016 m. slagging and bed agglomeration. For A_1 and A_4 samples we
The phase analysis of the sewage sludge ash was examined by X- found the presence of chlorine, which together with sulphur and
ray diffraction (XRD) using PANanalytical EMPYREAN DY 1061 with alkali metals forms very corrosive agents. Comparing sewage
Cu Ka radiation in Bragg-Brentano geometry. Operating conditions sludge ashes to biomass ashes from the point of view of corrosion
of the XRD were 40 KV and 40 mA Cu Ka (l ¼ 1.54 Å) radiation and caused by potassium and sodium, it seems that the problem may
step-scanned in the range 2Q ¼ 10e90 , step 0.06 , time 10 s. For not be as critical. Biomass ashes can contain above 10% of K2O and a
phase identification, a data base PDF-4þ product of ICDD was used. significant amount of chlorine [9,14].
A Scanning Electron Microscopy with Energy Dispersive Spec- Generally, there are two kinds of oxides of which the chemical
trometry (SEM-EDX) was applied to perform microanalysis of ash properties need to be taken into account. The base oxides are Na2O,
samples. The FEI Quanta 3D FEG Dual Beam microscope was used. K2O, MgO, CaO and Fe2O3, and the acid oxides are SiO2, Al2O3, and
The microanalysis (EDX) determined the proportion of the con- TiO2. The base-to-acid ratio is the simplest index allowing to pre-
stituents in the samples. SEM-EDX analyses were conducted for the dict the tendency of ash slagging and sintering. The basic com-
studied ashes to obtain information about the morphology and to pounds of ash (RB) reduce ash fusion temperatures while acidic
semi-quantitatively analyze its elemental composition. The sam- oxides (RA) increase them. The presence of Fe2O3 and P2O5, addi-
ples were observed in a high vacuum mode by secondary electrons tionally influences the sintering properties of ash. In the case of
(SEM) using the accelerating voltage - 1 kV. P2O5 we should expect a decrease in melting temperature (melting
The FTIR (Fourier Transform Infrared Spectrometry) spectra point of P2O5 is 569  C). It was confirmed for A_1 and A_2 ashes
were recorded using Bruker Alpha FT-IR Spectrometer. The spectral
region from 4000 to 400 cm1 was investigated. An infrared
spectrum presents absorption peaks, which correspond to the fre- Table 2
quencies of vibrations between the bonds of the atoms making up Slagging and fouling indices and fusion temperatures of ashes.
the material. The size of the peaks in the spectrum was used for
Ash RB RB/A SR RS Fu Fe2O3/CaO IDT ST HT FT
direct indication of the amount of material present.
A_1 45.34 1.12 30.53 1.56 5.42 0.76 1170 1200 1240 1260
A_2 30.88 1.31 24.89 1.69 3.97 0.66 1110 1170 1190 1230
2.3. Methodology of FactSage calculations A_3 40.21 1.27 37.11 1.77 3.51 0.5 1140 1210 1250 1280
A_4 49.38 2.05 24.79 4.12 4.84 0.29 1210 1300 1320 1360
In the present work, FactSage 6.4 thermochemical software and
databases were used [29,32]. The chemical equilibrium was calcu-
lated be considering Gibbs energy of all phases and minimizing the
total Gibbs energy of the system. The FactSage modelling program
can be used to interpret processes taking place during sintering of
an ash sample, to predict the chemical composition at equilibrium
state, as well as to predict the AFTs (Ash Fusion Temperatures). In
particular, the ‘equilibrium module’ and FToxid, FTmisc, ELEM and
FactPS databases were used. A possibility of two immiscible slag
phases was assumed. Chemical compositions of sewage sludge ash
samples (Table 1) were used as input data for thermodynamic
calculations. The thermodynamic calculations were performed at
the temperature range from 600 to 1500  C at 1 atm pressure.

3. Results and discussion

3.1. Chemical and physical properties of sewage sludge ashes

The chemical composition of the mineral matter of sewage


sludge ashes is presented in the oxide form in Table 1. The con-
centration of main oxides varies because of their different origin.
However, the main compounds of the ash are P2O5, CaO, SiO2,
Fe2O3, Al2O3, MgO, K2O, and Na2O. Since sewage sludge contains
high amounts of phosphorus, it is not surprising to see a similar
effect in the sewage sludge ashes. All of ashes possess considerable
calcium content. As compared to woody biomass ashes, sewage Fig. 1. Characteristic temperatures of sewage sludge ashes in oxidizing atmosphere
sludge ashes are rich in Fe2O3 and contain less K and Na oxides. The (IDT - initial deformation temperature, ST - softening temperature, HT - hemispherical
presence of even relatively low concentration of K and Na may temperature, and FT - flow temperature).
88 A. Magdziarz et al. / Energy 113 (2016) 85e94

Fig. 2. X-ray diffraction patterns of sewage sludge ashes a) A_1, b) A_2, c) A_3, d) A_4, where: 1-Fe2O3, 2-SiO2, 3-CaSO4, 4-Na2SO4, 5-Ca9Fe(PO4)7, 6-Fe3O4, 7-CaCO3.

Fig. 3. SEM images of sewage sludge ashes: a) A_1; b) A_2; c) A_3; d) A_4.

with the higher concentration of P2O5. correlating the functional temperature and standardized chemical
The formation of deposits depends mainly on the fuel quality, composition of ashes, thus making it possible to predict ash
the boiler design and its operation. The presence of this material behaviour and deposition tendencies. Slagging and fouling during
reduces the heat transfer and combustion efficiency, and damages sewage sludge combustion are very complex phenomena
combustion chambers when large particles break off. The most depending on chemical composition of the ash, as well as com-
important problems associated with inorganic deposits are slag- bustion conditions. Ash behaviour (transformation of inorganic
ging, fouling and corrosion. Different correlations and methodolo- compounds) and deposition tendencies can be predicted by using
gies have been used for predicting the slagging and fouling empirical indices. The following formulas (1e5) have been used in
tendencies of solid fuel ashes. There are some empirical indices order to predict ash fusibility based on chemical composition of
A. Magdziarz et al. / Energy 113 (2016) 85e94 89

ashes [33] (RB e basic constituents RB/A - (baseetoeacid) charac- dominated by Ca and P-base minerals in the form of Ca9Fe(PO4)7
terizes the ash fouling tendency, SR e viscosity index, RS e slagging and CaSO4, due to the high content of calcium and phosphorus
index, Sd e the percentage of S in dry fuel, Fu e fouling index): naturally occurring in sewage sludge. Phosphorus is present as
calcium and iron phosphates. Silicates were not detected, although
RB ¼ (Fe2O3 þ CaO þ MgO þ Na2O þ K2O) (3) they would likely be generated in the reaction between Al2O3, SiO2,
and CaO. Iron mineral compounds are present as hematite (Fe2O3)
RB/A ¼ (Fe2O3 þ CaO þ MgO þ Na2O þ K2O)/(SiO2 þ Al2O3 þ TiO2)(4) and magnetite (Fe3O4). Iron oxides have been reported to cause ash
melting and fouling. Iron oxides can react with SiO2 and Al2O3 to
SR ¼ 100SiO2/(SiO2 þ eq(Fe2O3) þ CaO þ MgO) (5) form low melting eutectics (~900  C).
These forms can be amorphous and non-detected by XRD ana-
RS ¼ RB/ASd (6) lyses. XRD analyses indicate only one phase Na2SO4 that can cause
the corrosion of the metal surface (others like K2SO4, NaCl and KCl
Fu ¼ RB/A(Na2O þ K2O) (7) were not detected). It could be the result of not high enough con-
centration of K, Na, S and Cl in the ashes.
As can be seen from Table 2, A_4 ash has the highest RB and The SEM-EDX method allows for investigating particle
consequently RB/A. The base-to-acid ratio depicts the fouling ten- morphology, surface structure and elemental distribution in ashes.
dency of ashes. All ashes studied, show high sintering tendency of Fig. 3 presents morphology of studied ashes. The ashes differ
deposits (0.6 < Fu  40 - a high fouling inclination), but the mainly in the size of individual particles. The A_1 ash consists of the
increasing amount of SiO2 and Al2O3 in ash decreases the fouling finest particles with a variety of shapes. The angular fragments with
tendency. Slagging index RS suggests extremely high slagging developed surface as well as rounded particles were observed. The
inclination for ash A_4 (RS > 2.6), and a medium one for other particle size and shape of A_2 and A_3 ashes are similar. Addi-
samples (RS ¼ 0.6e2.0). To conclude, the ratio of alkali metals to tionally in the A_2 ash round elements are visible. Amount of these
SiO2 determines the tendency to fouling or slagging. The slag's globules is larger than in A_1 ash. Moreover, their diameters are
viscosity index depends on SiO2 and Fe2O3. The highest value of SR higher. The surface of angular particles is characterized by signifi-
has the A_3 ash. Low melting points eutectics of SiO2 and Fe2O3 cant roughness and porosity. The A_4 ash grains are the biggest
may have the highest impact on bed agglomeration. During the from among the analyzed ashes. The shape and structure of parti-
sintering process the iron can react with quartz and aluminium cles is rather similar to those observed for other ashes. A scant
silicates forming iron silicates and iron aluminium silicates which volume of ball-shape fragments was detected. The general distri-
can melt at lower temperatures. The highest iron content has A_1 bution of elements (based on EDX analysis) in sewage sludge ashes
ash. The reactions between P, Mg and Ca with Si also enhance is listed from the highest to the lowest values:
deposition of ash. The ratio of Fe2O3/CaO confirms the possibility of O > P > Ca > Si > Fe > Al > Mg > K > Na > Cl > S > Ti > Mn. When
containing or enhancing slag formation eutectics. comparing the results obtained from XRF and SEM-EDX, clear dif-
The chemical composition influences the melting point of ash, ferences are observed because of the heterogeneity of the ashes
especially its basic compounds. The differences between defor- (that is why EDX alone is not an accurate enough a technique).
mation (IDT), softening (ST), hemispherical (HT) and flow temper- Based on the EDX results it is not possible to discuss quantitatively
atures (FT), which affect the sewage sludge slag mobility, are the chemical composition of the ash and its impact on deposition
presented in Table 2 and shown in Fig. 1. It shows similar temper-
atures for most ashes, but ash A_4 has clearly higher fusion tem-
peratures, especially for FT. For A_4 the larger temperature interval
from 1210  C to 1360  C was identified between the IDT and FT. It
indicates the presence of high melting temperature compounds.
The A_4 contains the highest amount of CaO (33.6%) between
studied ashes, then it contains in descending order of its amounts
SiO2, Al2O3, Fe2O3, but the lower content of alkali metals and P2O5.
For A_1 and A_2, lower temperature intervals were identified be-
tween DT and FT. Analyzing the differences in DT with respect to
CaO and MgO contents, it was found that the deformation tem-
perature increases with the increase of the CaO þ MgO content and
it should be emphasized that initial deformation temperature (IDT)
is dependent on the proportions of the elements in sewage sludge
ash. Additionally, a correlation was observed between RB and KAl ¼
SiO2/Al2O3 and the softening temperature. The minimum of ST
corresponds to the lower RB and the highest ratio KAl. The effect of
base to acid ratio RB/A on the deformation temperature was
observed for A_4. IDT increases with the increasing of ratio RB/A.
The crystalline mineral species in ash samples were identified
by XRD and are shown in Fig. 2 (X-ray patterns). It should be noted
that only main crystalline phases were observed by XRD in all
samples. Since there were too little amounts of amorphous mate-
rials and crystalline phases, it was not possible to identify them. For
all ashes, the main identified mineral phases are Ca9Fe(PO4)7, Fe2O3,
CaSO4, Fe3O4, SiO2 and CaCO3. The important differences between
ashes were observed only in the content of phases indicating an
important role of chemical composition.
The main characteristic of sewage sludge ashes is that they are Fig. 4. FTIR spectra of sewage sludge ashes.
90 A. Magdziarz et al. / Energy 113 (2016) 85e94

Fig. 5. TG and CO2 (m/z ¼ 44) evolution profiles (monitored using MS) of sewage sludge ashes during thermal process under air atmosphere.

Fig. 6. DSC and SO2 (m/z ¼ 64) evolution profiles (monitored using MS) of sewage sludge ashes during thermal process under air atmosphere.

processes. SEM is generally a good technique for morphology study results are quantitatively similar in all studied cases but differ in
but it is only semi-quantitative method in the case of heteroge- relative intensity of absorbance bands. The most intensive changes
neous material such sewage sludge ash. in the absorption bands are observed in the range of
Fig. 4 presents the FTIR spectra of four sewage sludge ashes. FTIR 400e1100 cm1. Silica absorption bands appear at 466, 794 and
A. Magdziarz et al. / Energy 113 (2016) 85e94 91

Fig. 7. Mass percentage of slag liquid phases at different temperatures for sewage sludge ashes calculated by FactSage 6.4.

Fig. 8. Stable solid phases in equilibrium with the slag phase for A_1 sewage sludge ash.

1028 cm1; but the most intensive broad absorption band appears some calcium compounds by CO2 produced via combustion of
in the characteristic silica region with the maximum at 1028 cm1. organic matter, as seen in TGA and XRD tests.
The other strong band during 400e550 cm1 is caused by SieO or TG and DTG graphs connected with emissions of CO2 and SO2
AleO bending vibration [34]. The strong absorption band appears are presented in Figs. 5 and 6. For all ashes the thermal behaviour
at 970 cm1 due to anti-symmetric SieOeSi or SieOeAl stretching up to 1200  C can be divided into three steps. The first step con-
vibrations. The absorption band of P-containing compounds ap- cerns moisture release, which was absorbed on the ash surface
pears at 552 cm1 due to PeO bending vibration. A weak peak during storage and preparation for investigations. The mass loss
appears at around 560 cm1 which is attributed to FeeO (they are was not significant; A_1: 0.62%, A_2: 1.1%, A_3: 0.59%, A_4: 0.02%,
only slightly visible for A_3 and A_4). Moreover, carbonate ab- respectively. The highest mass loss for A_2 ash was confirmed in
sorption bands at about 1500 and 880 cm1 are also detected, but the form of thermal effect via DSC curve. However, this effect could
the carbonate band is weaker for A_3 and nearly disappears for A_4. be related to the decomposition of gypsum.
After incineration at 550  C, the absorption bands of organic matter The second step, between the temperature range 120e900  C, is
disappear while that of carbonate appears due to carbonation of attributed to the decomposition of carbonate compounds (CaCO3)
92 A. Magdziarz et al. / Energy 113 (2016) 85e94

Fig. 9. Stable solid phases in equilibrium with the slag phase for A_2 sewage sludge ash.

Fig. 10. Stable solid phases in equilibrium with the slag phase for A_3 sewage sludge ash.

and organic residues. A peak corresponding to the emission of CO2 obtained by XRD analysis. Above 900  C, the liquid phase appears.
is observed, while 3.47% and 1.32% mass losses were detected for At 1200  C, the ashes revealed glassy surface and assumed darker
A_3 and A_4 (no noticeable thermal effects were seen in DSC colour (brown). Changes in the colour may be due to a high amount
curves). In this stage, there could be simultaneously endothermic of iron residue in the ashes.
and exothermic effects resulting in competing with each other. The
highest mass loss, 7.48%, was observed for A_1 ash. It was linked 3.2. FactSage equilibrium calculations
with exothermic effect at 437  C indicting carbon content. For A_2
no changes in TG and DSC curves were observed. Fig. 7 shows the relative amounts of liquid slag formation for
The third stage, above 900  C, corresponds to the decomposition A_1 to A_4 ashes under oxidizing conditions.
of other compounds, probably due to phosphates and sulphates Fig. 7 shows the mass present of slag phases (relative to ash
(SO2 emission was detected by MS analysis). In this stage the mass amount) as a function of temperature for A_1-A_4 samples. It can
losses were more significant; A_1: 4.28%, A_2: 1.35%, A_3: 4.30%, be seen that the slag liquid phase starts to form at 840  C for A_1
and A_4: 5.07%. In addition, the endothermic effects were observed. sample, at 920  C for A_3 sample, at 980  C for A_4 sample and at
There is a relation between mass losses and crystalline phases 1020  C for A_2 sample, respectively. It is interesting that the
A. Magdziarz et al. / Energy 113 (2016) 85e94 93

amount of slag phase does not increase with temperature for all the increasing of phosphorus content in ash. Potassium phosphates
samples and that the maximum amount of slag phase is not did not appear but it could indicate with low content of potassium
correlated with the starting temperature. For example, for sample in ash and its evaporating property. Obtained results have showed,
A_1 slag liquid phase starts to form at visibly lower temperature that it is difficult to compare XRD results with FactSage calcula-
than for sample A_4 but its maximum mass amount is also visibly tions. XRD analysis of ashes presents the phase composition in ash
lower. It means that not only the starting temperature of slag for- taken from boilers and the analysis was done at cooling samples. It
mation is important but its kinetics, as well. Therefore, the differ- should be noted that only crystalline phases were observed by XRD
ence in the slag phase forming process is revealed in the form of in ash sample. Amorphous materials and crystalline phases with
selected characteristic temperatures. Based on Fig. 7, the charac- too little amount were not identified. FactSage calculation show the
teristic temperatures at which slag phase starts to form (t0), reaches possible phases with the increasing of temperature calculated
the value of 15% wt (t15) and 25% wt (t25) of total ash mass can be based on chemical composition of ash, what allows to predict
defined. The lowest t0 has A_1 at 840  C and t25 at 1080  C. The slag possible routes and reactions of ash at higher temperatures.
liquid phases appeared at the highest temperatures for A_2. No It should be emphasized that phosphorus plays an important
clear correlations have been obtained between ash fusion tem- role in sewage sludge ashes. From the ash microstructure point of
peratures and phase transitions estimated by FactSage equilibrium view, the characteristic temperatures are very important when
calculations. It could indicate a different size of the ash particles. phase transitions or chemical reactions occur. These temperatures,
The microstructure of ash is an important factor in the process of together with transitions in solid state, are listed in Table 3. It can be
sintering except the chemical composition of the ash. Slag phase observed that the slag phase formation (kinetics and formation
predicted by FactSage has been started to form at highest tem- temperature) and phase transitions at solid state that occur at
perature for A_2 samples whereas the ash fusion temperature for lower temperatures, strongly depend on ash composition.
these samples was the lowest. This unusual behaviour is clear
because of the visible smaller ash grain sizes for A_4 sample than 4. Conclusions
for A_3 and A_4.
The slag phase formation depends on the processes in solid state This paper aimed to present a comprehensive analysis of sewage
that take place at lower temperatures. Therefore, FactSage 6.4 was sludge ashes using a number of analytical techniques. In addition,
used for the prediction of solid state phase transitions and re- the thermodynamic equilibrium modelling was used to predict the
actions. Figs. 8e11 present the major solid phases that occur in A_1 percentage of melt phases in the combustion environment and
and A_2 ash samples below the slag formation temperature. It can possible solid phases existing at different temperatures. These re-
be observed that in all samples there exists a relatively large sults revealed the principal properties that should be taken into
amount of calcium phosphate, which confirms XRD results, and it is account to characterize the sewage sludge ash.
the main solid species. FactSage results showed that phosphorus A novel approach, linking selected advanced analytical tech-
can exist as phosphates of calcium (Ca3(PO4)2) for all of ashes and niques with FactSage modelling, was developed and applied to
magnesium (Mg3P2O8) for A_2 and aluminium (AlPO4) for A_3 ash. obtain better understanding of deposit formation mechanisms, as
The existing of calcium, magnesium and phosphorus phases was well as new information on fouling and slagging during sewage
confirmed by both methods, experimental and calculation. The sludge combustion.
effect of phosphorus on ash-related problems is connected with Considering the chemical composition data, the major elements
presence of silica and the formation of silicates and phosphates. The of ashes differ slightly. The following were clearly dominant in the
presence of phosphorus in ash increases the risk of ash sintering inorganic matter: P, Ca, Si and Fe. It was observed that the main
and melting behaviour. The melting temperatures decrease with mineral phases came from phosphorus- and calcium-based

Fig. 11. Stable solid phases in equilibrium with the slag phase for A_4 sewage sludge ash.
94 A. Magdziarz et al. / Energy 113 (2016) 85e94

Table 3 [5] Krzywan  ski J, Rajczyk R, Nowak W. Model research of gas emissions from a
Characteristic temperatures for solid phase of ash transformation processes. lignite and biomass co-combustion in a large scale CFB boiler. Chem Pro Eng
2014;2:217e31.
Sample Temp.,  C Process [6] Werther J. Potentials of biomass co-combustion in coal-fired boilers. In: 20th
International Conference on fluidized bed combustion; 2009. p. 27e42. Xi'an
A_1 680 KAlSi2O6 formation
China. China, May 18-21.
700e710 AlPO4 phase transition
[7] Saidur R, Abdelaziz EA, Demirbas A, Hossain MS, Mekhilef S. A review on
760e770 K2SO4 phase dissapearance biomass as a fuel for boilers. Renew Sustain Energy Rev 2011;15:2262e89.
K3Na(SiO4)2 formation [8] Fernandez RG, García CP, Lavín AG, de las Heras JLB. Study of main combustion
800e810 K2Ca2(SiO4)3formation characteristics for biomass fuels used in boilers. Fuel Process Technol
A_2 680 KAlSi2O6 phase transition 2012;103:16e26.
720e730 Al2SiO5 phase transition [9] Vassilev SV, Baxter D, Vassileva CG. An overview of the composition of
890e900 Al2SiO5 dissapearance biomass ash. Part 1. Phase-mineral and chemical composition and classifica-
Mg2Al4Si5O18 increase tion. Fuel 2013;105:40e76.
A_3 680 KAlSi2O6 phase transition [10] Fytili D, Zabaniotou A. Utilization of sewage sludge in EU application of old
705 AlPO4 phase transition and new methods - a review. Renew Sust Energ Rev 2008;12:116e40.
725 Al2SiO5 phase transition [11] Wzorek M. Characterisation of the properties of alternative fuels containing
792 Al2SiO5 dissapearance sewage sludge. Fuel Process Technol 2012;104:80e9.
[12] Manara P, Zabaniotou A. Towards sewage sludge based biofuels via thermo-
Mg2Al4Si5O18 formation
chemical conversion - a review. Renew Sustain Energy Rev 2012;16:1081e7.
868 SiO2 phase transition
[13] Judex JW, Gaiffi M, Burgbacher HC. Gasification of dried sewage sludge: status
A_4 680e690 KAlSi2O6 phase transition of the demonstration and the pilot plant. Waste Manag 2012;32:719e23.
730e740 CaSiTiO5 dissapearance [14] Garcia G, Aruazo J, Gonzalo A, Sanchez JL, Abrego J. Influence of feedstock
CaAl2Si2O8 increase composition influidised bed co-gasification of mixtures of lignite, bituminous
CaTiO3 formation coal and sewage sludge. Chem Eng J 2013;222:345e52.
760e770 Mg2SiO4 formation [15] Chun YN, Kim SC, Yoshikawa K. Pyrolysis gasification of dried sewage sludge
CaMgSi2O6dissapearance in a combined screw and rotary kiln gasifier. Appl Energy 2011;88:1105e12.
CaAl2Si2O8 increase [16] Magdziarz A, Werle S. Analysis of the combustion and pyrolysis of dried
Mg4Al10Si2O23 decrease sewage sludge by TGA and MS. Waste Manag 2014;34:174e9.
[17] Wilk M, Magdziarz A, Kalemba I. Characterisation of renewable fuels' torre-
faction process with different instrumental techniques. Energy 2015;87:
259e69.
[18] Magdziarz A, Kosowska-Golachowska M, Kijo-Kleczkowska A, Sroda  K,
minerals. XRD analysis had confirmed the presence of the Fe2O3,
Wolski K, Richter D, et al. Analysis of sewage sludge ashes from air and oxy-
SiO2, CaSO4, Na2SO4, Ca9Fe(PO4)7, Fe3O4 and CaCO3 in a crystalline fuel combustion in a circulating fluidized-bed, Book of Abstracts, the Inter-
forms. This information can be supplemented by the thermo- national Conference on the Susainable Energy and Environmental Develop-
chemical calculations that predict the solid-solid chemical and ment; 2016, 191.
[19] Obernberger I, Brunner T, Barnthaler G. Chemical properties of solid biofuels
physical transitions. It is characteristic that Na, Fe, Si and Ca ele- e significance and impact. Biomass Bioenergy 2006;30:973e82.
ments, during sintering at higher temperatures occur mainly in the [20] Batistella L, Silva V, Suzin RC, Virmond E, Althoff CA, Moreira RFPM, et al.
form of silicates. The ashes were characterized by high tendency to Gaseous emissions from sewage sludge combustion in a moving bed
combustor. Waste Manag 2015;46:430e9.
fouling and slagging, which, in practice, contributes to the limita-
[21] Niu Y, Zhu Y, Tan H, Wang X, Hui S, Du W. Experimental study on the coex-
tion in heat flow, between ash deposit and metal surface. Never- istent dual slagging in biomass-fired furnaces: alkali- and silicate melt-
theless, corrosion should not have a dramatic effect because of a induced slagging. Proc Combust Inst 2015;35:2405e13.
[22] Nowak B, Aschenbrenner P, Winter F. Heavy metal removal from sewage
low content of potassium, sodium and chlorine. This is a clear
sludge ash and municipal solid waste fly ash e a comparison. Fuel Process
advantage of sewage sludge ashes versus biomass ash. Technol 2013;105:195e201.
One of the key outcomes of this work is better understanding of [23] Wang L, Skjevrak G, Hustad JE, Gronli MG. Sintering characteristics of sewage
mechanisms governing deposit formation, which is linked with sludge ashes at elevated temperatures. Fuel Process Technol 2012;96:88e97.

[24] Ohman M, Nordin A, Skrifvars B-J, Backman RM, Hupa M. Bed agglomeration
risk-related issues. In addition, new data was obtained on fouling characteristics during fluidized bed combustion of biomass fuels. Energy Fuels
and slagging during sewage sludge combustion. It is worth 2000;14:169e78.
mentioning that a novel approach of this study is related to linking [25] Díaz-Ramírez M, Frandsen FJ, Glarborg P, Sebastia n F, Royo J. Partitioning of K,
Cl, S and P during combustion of poplar and brassica energy crops. Fuel
selected advanced analytical techniques with FactSage modelling. 2014;134:209e19.
The presented methodology of renewable fuels and their ash in- [26] Vassilev SV, Baxter D, Vassileva CG. An overview of the behaviour of biomass
vestigations could be helpful during design of new energy units during combustion: part II. Ash fusion and ash formation mechanisms of
biomass types. Fuel 2014;117:152e83.
focused on the selection of metallic materials. [27] Luan C, You C, Zhang D. Composition and sintering characteristics of ashes
from co-firing of coal and biomass in a laboratory-scale drop tube furnace.
Acknowledgment Energy 2014;69:562e70.
[28] Magdziarz A, Dalai AK, Kozin  ski JA. Chemical composition, character and
reactivity of renewable fuel ashes. Fuel 2016;176:135e45.
The research leading to these results has received funding from [29] Lindberg D, Backman R, Chartrand P, Hupa M. Towards a comprehensive
the Polish-Norwegian Research Programme operated by the Na- thermodynamic database for ash-forming elements in biomass and waste
combustion d Current situation and future developments. Fuel Process
tional Centre for Research and Development under the Norwegian
Technol 2013;105:129e41.
Financial Mechanism 2009e2014 in the frame of Project Contract [30] Nel MV, Strydom CA, Schobert HH, Beukesa JP, Bunt JR. Reducing atmosphere
No Pol_Nor/208189/105/2015. ash fusion temperatures of a mixture of coal-associated minerals d the effect
of inorganic additives and ashing temperature. Fuel Process Technol
2014;124:78e86.
References [31] Ristic MM, Milosevic SDj. Frenkel's theory of sintering. Sci Sinter 2006;38:
7e11.
[1] Werle S. Sewage sludge-to-energy management in Eastern Europe: a Polish [32] Bale CW, Belisle E, Chartrand P, Decterov SA, Eriksson G, Hack K, et al.
perspective. Ecol Chem Eng S 2015;22:459e69. FactSage thermochemical software and databases d recent developments.

[2] Kijo-Kleczkowska A, Sroda K, Kosowska-Golachowska M, Musiał T, Wolski K. Calphad 2009;33:295e331.
Mechanisms and kinetics of granulated sewage sludge combustion. Waste [33] Pronobis M. Evaluation of the influence of biomass co-combustion on boiler
Manag 2015;46:459e71. furnace slagging by means of fusibility correlations. Biomass Bioenergy
[3] Demirbas A. Potential applications of renewable energy sources, biomass 2005;28:375e83.
combustion problems in boiler power systems and combustion related envi- [34] Saikia BJ, Parthasarathy G. Fourier transform infrared spectroscopic charac-
ronmental issues. Prog Energ Combust 2005;31:171e92. terization of kaolinite from Assam and Meghalaya, Northeastern India. J Mod
[4] Basu P. Biomass gasification, pyrolysis and torrefaction. Practical design and Phys 2010;1:206e10.
theory. 2nd ed. San Diego: Elsevier; 2013.