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Combustion Science and Technology


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Utilization of Coal Combustion Ashes for


the Synthesis of Ordinary and Special
Cements
a a a
Milena Marroccoli , Maria Lucia Pace , Antonio Telesca , Gian
a b
Lorenzo Valenti & Fabio Montagnaro
a
Dipartimento di Ingegneria e Fisica dell'Ambiente , Università degli
Studi della Basilicata , Potenza, Italy
b
Dipartimento di Chimica , Università degli Studi di Napoli Federico
II , Naples, Italy
Published online: 08 Jun 2010.

To cite this article: Milena Marroccoli , Maria Lucia Pace , Antonio Telesca , Gian Lorenzo
Valenti & Fabio Montagnaro (2010) Utilization of Coal Combustion Ashes for the Synthesis of
Ordinary and Special Cements, Combustion Science and Technology, 182:4-6, 588-599, DOI:
10.1080/00102200903466210

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Combust. Sci. and Tech., 182: 588–599, 2010
Copyright # Taylor & Francis Group, LLC
ISSN: 0010-2202 print=1563-521X online
DOI: 10.1080/00102200903466210

UTILIZATION OF COAL COMBUSTION ASHES


FOR THE SYNTHESIS OF ORDINARY AND
SPECIAL CEMENTS

Milena Marroccoli,1 Maria Lucia Pace,1 Antonio Telesca,1


Gian Lorenzo Valenti,1 and Fabio Montagnaro2
1
Dipartimento di Ingegneria e Fisica dell’Ambiente, Università degli Studi
della Basilicata, Potenza, Italy
2
Dipartimento di Chimica, Università degli Studi di Napoli Federico II,
Downloaded by [New York University] at 20:02 15 May 2015

Naples, Italy

Raw mixes containing pulverized coal fly ash (with limestone and silica sand) or fluidized
bed coal combustion ash (fly and bottom, with added limestone, anodization mud, and, when
necessary, flue gas desulfurization gypsum), aimed at generating ordinary Portland or
calcium sulfoaluminate clinkers, respectively, were heated in a laboratory electric oven at
temperatures ranging from 1150 to 1500 C and submitted to X-ray diffraction analysis.
The former had the same qualitative phase composition as that of a reference mixture,
composed by limestone and clay; furthermore, they exhibited an excellent burnability on
the basis of their residual free lime contents, measured after heating at 1350 , 1400 ,
1450 , and 1500 C. The latter showed very good results in terms of conversion of reactants
and selectivity degree toward the main mineralogical constituent, calcium sulfoaluminate
(4CaO  3Al2O3  SO3), even if the behavior of a reference mixture consisting of limestone,
bauxite, and natural gypsum was slightly better. The introduction of a fluidized bed coal
combustion ash in the raw mix generating calcium sulfoaluminate clinker implies a saving
of bauxite and natural gypsum, which can be fully replaced through the addition of anodiza-
tion mud and flue gas desulfurization gypsum, respectively.

Keywords: Calcium sulfoaluminate clinker; Cement manufacture; Coal combustion ashes; Ordinary
Portland clinker; Waste utilization

INTRODUCTION
The cement industry consumes huge amounts of natural resources (Mehta, 1978)
and generates large quantities of pollutants, including also carbon dioxide responsible
for the greenhouse effect (Damtoft et al., 2008; Gartner, 2004; Hendriks et al., 1998)
and originating from both fossil fuel combustion and limestone thermal decompo-
sition; however, it can play a leading role in waste utilization, thus giving a significant

Received 13 March 2009; revised 21 September 2009; accepted 12 October 2009.


Address correspondence to Gian Lorenzo Valenti, Dipartimento di Ingegneria e Fisica
dell’Ambiente, Università degli Studi della Basilicata, Viale dell’Ateneo Lucano 10, 85100 Potenza, Italy.
E-mail: valenti@unibas.it

588
COAL COMBUSTION ASHES AND CEMENT SYNTHESIS 589

contribution to sustainable development. As an example, it represents in Italy the most


important field of potential use of nondangerous wastes as sources of raw materials.
Ordinary cements are hydraulic binders based on Portland clinker, namely the
burnt product, at about 1500 C, of a raw mixture mainly composed by limestone
and clay. Special cements are obtained from non-Portland clinkers; their peculiar
composition enables a technical performance better than that of ordinary cements
in particular fields of application.
In the present study, different coal combustion ashes, originated from pulver-
ized coal-fired power plants and a fluidized bed coal combustor, were investigated at
a laboratory scale as sources of raw materials for the synthesis of Portland cement
and calcium sulfoaluminate cement (one of the most interesting special binders),
respectively. For the latter, other industrial wastes, such as anodization mud and flue
gas desulfurization gypsum, were also used.
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PORTLAND CEMENT FROM PULVERIZED COAL FLY ASH


Among the ordinary cements, Portland cement is the most important hydraulic
binder. It consists of a blend of Portland clinker with a small amount of gypsum
(3–5%) as set retarder. The other ordinary cements are basically blended cements,
namely mixtures composed by Portland clinker, pozzolanic or hydraulic additions
(in significant amounts), and gypsum (3–5%).
The utilization of wastes and by-products as raw materials for the manufacture
of Portland and blended cements can occur in two different ways: (a) as constituents
added to the end products and (b) as components of the kiln raw feed.
The first use concerns fillers (added in small amounts to Portland clinker without
significantly affecting the cement properties) and pozzolanic or hydraulic additions,
which improve the cement technical performance, reduce clinker concentration, and
decrease limestone requirement, kiln thermal input, and generation of pollutants.
When utilized as components of the kiln raw feed for Portland clinker
manufacture, industrial wastes and by-products act as sources of calcium, silicon,
aluminium, and iron oxides, totally or partly replacing natural materials.
Pulverized-coal fly ash displays well-known pozzolanic properties; its use, as an
active addition in the manufacture of blended cements, is worldwide consolidated
(Antiohos et al., 2004; Malek et al., 2005; Newman & Owens, 2004; Pedersen
et al., 2008). However, the present need for environmental compatibility of coal-fired
power plants leads to lower combustion temperatures and results into the generation
of fly ash with a higher unburnt carbon content. These features can limit its use inas-
much as they promote a reduction of pozzolanic activity and an increase of water
demand by cementitious matrices as well as a fly ash higher ability to capture admix-
tures eventually added to concrete (Poon et al., 2004; Sakai et al., 2005). Therefore,
new application fields of pulverized-coal fly ash have to be searched for.

CALCIUM SULFOALUMINATE CEMENT FROM FLUIDIZED


BED COAL COMBUSTION ASH
The technical behavior of calcium sulfoaluminate (CSA) cements is regulated
by the ability of their key component, CSA (4CaO  3Al2O3  SO3), to generate
590 M. MARROCCOLI ET AL.

ettringite (6CaO  Al2O3  3SO3  32H2O) upon reaction with water, lime, or calcium
sulfate. According to its formation rate and microstructure, ettringite can promote
an expansive behavior or a rapid hardening (associated with dimensional stability).
These properties can be usefully exploited by shrinkage-compensating and
self-stressing cements (Kurdowski et al., 1986; Mehta, 1973; Muzhen et al., 1992)
or by high-performance cements (Bernardo et al., 2007; Glasser & Zhang, 2001;
Marroccoli et al., 2007a; Muzhen et al., 1997).
CSA cements are also worthy of consideration owing to the environmentally
friendly feature of their manufacturing process. In particular, for the formation of
their main component, lower synthesis temperature and calcium oxide (i.e., lime-
stone) requirement are needed, when compared to those necessary for the manufac-
ture of Portland cement; this implies a reduction of both thermal input to the kiln
and CO2 generation (Marroccoli et al., 2007b).
Depending on the synthesis temperature as well as the nature and the propor-
tioning of raw materials, CSA cements may contain, besides 4CaO  3Al2O3  SO3,
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a wide range of calcium silicates (2CaO  SiO2, 5CaO  2SiO2  SO3, 2CaO 
Al2O3  SiO2, CaO  Al2O3  2SiO2) and aluminates (12CaO  7Al2O3, 3CaO  Al2O3,
CaO  Al2O3, 4CaO  Al2O3  Fe2O3); among these components, dicalcium silicate is
the most important inasmuch as it contributes, as for Portland cement, to strength
and durability at medium and long ages (Beretka et al., 1992, 1993).
Fluidized bed combustion (FBC) ash is a blend of coal ash with exhausted sul-
fur sorbent. Its major oxides are: CaO, SiO2, SO3, and Al2O3. The reuse of FBC ash
in ordinary cement and concrete is generally made difficult by its chemical and min-
eralogical composition (Kurkcu et al., 2006; Odler & Zhang, 1997). Upon hydration,

Figure 1 Outline of possibilities of employing pulverized coal (PC) and FBC ash in the synthesis of
Portland and CSA cements.
COAL COMBUSTION ASHES AND CEMENT SYNTHESIS 591

exothermal, and expansive phenomena can occur (Liira et al., 2009); moreover, the
pozzolanic activity of FBC ash is poor, due to the low combustion temperatures
reached into the fluidized bed reactor. Hence, other fields of utilization have to be
found out (Barone et al., 2006; Fu et al., 2008; Jackson et al., 2009; Montagnaro
et al., 2005, 2006, 2008, 2009; Weinberg & Hemmings, 1997).
FBC waste has proved to be a very useful raw material for the synthesis of CSA
cements (Belz et al., 2006; Bernardo et al., 2003; Nobili et al., 2008): limestone, baux-
ite, and gypsum are the main natural materials involved in their manufacturing
process and the use of FBC waste as a raw mix component can enable a saving of
limestone and bauxite as well as a full replacement of gypsum. In order to enhance
the saving of an expensive natural material such as bauxite, the further addition of
an industrial waste with a relatively high Al2O3 content, such as anodization mud
(AM), is worthy of consideration. When necessary, flue gas desulfurization gypsum
can be also used as a source of calcium sulfate.
To summarize (see also Figure 1), the use of pulverized coal fly ash as constituent
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added to the end product is worldwide consolidated whereas that of FBC ash could
not be advisable due to its possible poor pozzolanic activity. Moreover, although a
pulverized-coal ash low in sulfates and a FBC ash high in sulfates could be not suitably
employed as raw materials for the synthesis of CSA and Portland cements, respect-
ively, the use of these pulverized coal and FBC ashes as raw feed components for
the synthesis of Portland and CSA cements, respectively, deserves investigation.

EXPERIMENTAL
Materials
Tables 1 and 2 show the chemical composition of natural materials and
industrial wastes used in this investigation, respectively. Raw mixes generating
Portland and CSA clinkers contained clay and silica sand as well as bauxite and
natural gypsum, respectively. Limestone was utilized in both categories of raw mixes.

Table 1 Chemical composition of natural materials (mass %)

Compound Limestone Clay Silica sand Bauxite Gypsum

CaO 54.7 8.9 — 1.7 31.7


SO3 — — — — 45.3
Al2O3 — 11.9 — 55.2 —
SiO2 — 51.8 99.0 6.5 —
MgO 0.3 — — — —
SrO — — — — —
P2O5 — — — — —
TiO2 — — — 2.3 —
Fe2O3 — 4.9 — 6.3 —
Mn3O4 — — — — —
Na2O — — — — —
l.o.i. 42.6 19.0 — 27.7 20.4
Total 97.6 96.5 99.0 99.7 97.4
592 M. MARROCCOLI ET AL.

Table 2 Chemical composition of industrial wastes (mass %)

Compound X Y F B FGD AM

CaO 5.5 6.2 24.2 43.1 32.0 7.7


SO3 — — 12.8 25.9 45.8 8.3
Al2O3 28.0 29.0 13.7 5.9 0.1 45.3
SiO2 47.0 47.0 23.2 18.4 0.1 2.9
MgO 1.4 1.3 1.0 1.0 0.4 2.7
SrO — — — — — —
P2O5 — — — — — —
TiO2 — — 0.8 0.5 — —
Fe2O3 4.4 4.1 6.7 3.2 — 2.8
Mn3O4 — — 0.1 0.1 — —
Na2O — — — — — —
l.o.i. 8.2 8.1 16.3 1.4 20.6 30.3
Total 94.5 95.7 98.8 99.5 99.0 100.0
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Pulverized coal fly ashes (X and Y), fluidized bed combustion ash, available in
two fractions, F (fly) and B (bottom), and flue gas desulfurization gypsum (FGD)
were kindly supplied by the ENEL Research Centre of Cerano (Brindisi, Italy);
AM came from a factory of anodized aluminium elements located in the Potenza
area in Italy. X and Y, on the one hand, as well as F, B, FGD, and AM, on the other,
were used as components of Portland and CSA clinkers generating raw mixes,
respectively.

Proportioning and Synthesis of Raw Mixes


Six raw mixes (MP, M1, M2, MS, M3, and M4) were submitted to thermal
treatments in a laboratory electric oven at temperatures ranging from 1150 to
1500 C. MP, M1 and M2 were utilized for the synthesis of Portland clinker; MS,
M3, and M4 were employed for that of CSA clinker. MP and MS, containing only
natural materials, were used as reference terms. The composition of the six raw mix-
tures is indicated in Table 3. The blend F þ B had a mass ratio (fly=bottom) equal to
1.5, close to that of the corresponding rates generated in the fluidized bed reactor.

Table 3 Composition of raw mixtures (mass %)

Product MP M1 M2 MS M3 M4

Limestone 72.60 77.00 78.00 25.27 32.35 30.62


Clay 27.40 — — — — —
Silica sand — 7.25 7.25 — — —
Bauxite — — — 42.14 — —
Gypsum — — — 32.59 — —
X — 15.75 — — — —
Y — — 14.75 — — —
FþB — — — — 44.37 37.04
FGD — — — — — 4.12
AM — — — — 23.28 28.22
COAL COMBUSTION ASHES AND CEMENT SYNTHESIS 593

MP, M1, and M2 were conceived in order to obtain a hydraulic modulus


(CaO=(SiO2 þ Al2O3 þ Fe2O3)) equal to 2.2 (a value commonly employed in the
cement industry). Both pulverized-coal fly ashes enabled a full replacement of clay
through a limited addition of silica sand. MS, M3, and M4 were proportioned by
assuming that (a) Al2O3 and SiO2 react to give only 4CaO  3Al2O3  SO3 and
2CaO  SiO2, respectively; (b) one half of CaSO4 is involved in the calcium sulfoalu-
minate formation and the second half is present as anhydrite useful for both stabiliz-
ing 4CaO  3Al2O3  SO3 in the thermal treatment and reacting with it during the
cement hydration; and (c) solid solution effects are neglected. M3 and M4 allowed
a complete substitution for both bauxite and natural gypsum. Table 4 shows the
potential concentration values of 4CaO  3Al2O3  SO3, 2CaO  SiO2, and CaSO4 in
the burning products of the three mixtures.
Thermal treatments on MP, M1, and M2 were aimed at burnability measure-
ments. The burnability of a raw mix for Portland cement manufacture can be defined
as the ease with which calcium oxide derived from limestone calcination reacts in the
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kiln with silicon, aluminum and iron oxides contained in the argillaceous material to
give the clinker; according to a fixed heating cycle, burnability is evaluated by either
the amount of unreacted calcium oxide (free lime) present after a given treatment
duration or by the burning time needed to reduce the free lime content to some
specific value (Taylor, 1997). The test adopted in this investigation (Bernardo
et al., 2004), aimed at obtaining a burnability index (BI) for each raw mix, was based
on the following thermal treatment: (a) first step at 105 C for 120 min; (b) second
step at 600 C for 30 min; and (c) third step at the final temperature (1350 , 1400 ,
1450 , or 1500 C) for 15 min. The burnability index is given by the formula:

BI ¼ 3:73  ðA þ B þ 2C þ 3DÞ=ðA  DÞ1=4 ð1Þ

where A, B, C, and D are the free lime contents in the product burnt at 1350 , 1400 ,
1450 , and 1500 C, respectively. A low BI value reveals good burnability; further-
more, BI values lower than 60 indicate a very satisfactory behavior.
Thermal treatments on MS, M3, and M4 were carried out for 2 hr at tempera-
tures between 1150 and 1300 C in order to evaluate conversion and selectivity of the
reacting systems.

Procedures and Techniques


The chemical composition of raw materials was determined through X-ray
florescence analysis by using a BRUKER Explorer S4. Both raw mixes and their
burnt products were ground in a laboratory mill to pass the 90-mm sieve.

Table 4 Potential concentration of 4CaO  3Al2O3  SO3, 2CaO  SiO2 and CaSO4 in the burning products
of mixtures MS, M3 and M4 (mass %)

Compound MS M3 M4

4CaO  3Al2O3  SO3 66.58 43.41 46.83


2CaO  SiO2 11.23 42.14 35.66
CaSO4 14.85 7.61 9.00
594 M. MARROCCOLI ET AL.

The mineralogical composition of synthetic clinkers was evaluated by X-ray


diffraction (XRD) analysis; a PHILIPS PW1710 diffractometer, operating between
5 and 60 2h (Cu Ka radiation), was used.
The free CaO concentration in Portland clinkers was measured by the Franke
method (Shelb & Ludwig, 1978), based on lime extraction with organic solvents,
followed by chemical titration.
As far as calcium sulfoaluminate clinkers are concerned, XRD analysis was
used from both a qualitative and quantitative point of view. In particular, the
XRD intensity of the main peak of 4CaO  3Al2O3  SO3 was monitored as a function
of the synthesis temperature.

RESULTS AND DISCUSSION


Figure 2 indicates the free lime concentration in the burnt products of the
mixtures MP, M1, and M2 as a function of the temperature reached at the end of
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the last step of the burnability test. As expected, the CaO content decreases as the
temperature increases. BI values for MP, M1, and M2 were, respectively, 7.34,
28.04, and 23.51; therefore, both waste-based mixes exhibited a very good burnabil-
ity, even if slightly worse than that of the reference mixture.
The qualitative phase composition of the synthetic clinkers obtained from M1
and M2, heated at 1500 C, is almost identical: in particular, peaks related to trical-
cium silicate (3CaO  SiO2), dicalcium silicate (2CaO  SiO2), tricalcium aluminate
(3CaO  Al2O3), and tetracalcium iron aluminate (4CaO  Al2O3  Fe2O3) were
detected. Figure 3 illustrates the XRD pattern of the burnt product of the mixture
M1. The qualitative phase composition of the synthetic clinker obtained from MP,
heated at 1500 C, is very similar to that of M1 and M2 (Figure 3).
Regarding sulfoaluminate clinkers, it has been found that the influence of
the synthesis temperature on the selectivity of the reacting systems toward
4CaO  3Al2O3  SO3 is quite significant (Figure 4); the best results were obtained at

Figure 2 Free lime concentration vs. final temperature of the burnability test.
COAL COMBUSTION ASHES AND CEMENT SYNTHESIS 595
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Figure 3 XRD patterns of mixtures MP and M1 burnt at 1500 C: a ¼ 3CaO  SiO2, b ¼ 3CaO  Al2O3,
c ¼ 4CaO  Al2O3  Fe2O3, d ¼ 2CaO  SiO2.

1300 C for the reference mixture and at 1250 C for the others. At all the investigated
temperatures it has been observed that (a) M3 and M4 have almost the same phase
composition, (b) the conversion of reactants is complete, (c) 4CaO  3Al2O3  SO3 is
the main mineralogical phase, and (d) the best selectivity toward 4CaO  3Al2O3  SO3
concerns the mixture MS.
Figure 5 shows the XRD patterns for mixtures MS and M3 heated at the best
synthesis temperatures. The most important secondary phases were 2CaO  SiO2,

Figure 4 XRD intensity (counts per second, cps) of the 4CaO  3Al2O3  SO3 main peak for the burning
products of mixtures MS, M3, M4 vs. synthesis temperature.
596 M. MARROCCOLI ET AL.
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Figure 5 XRD patterns of mixture MS burnt at 1300 C and mixture M3 burnt at 1250 C: b ¼ 3CaO  Al2O3,
c ¼ 4CaO  Al2O3  Fe2O3, d ¼ 2CaO  SiO2, e ¼ 4CaO  3Al2O3  SO3, f ¼ CaSO4, g ¼ 5CaO  2SiO2  SO3.

CaSO4, 4CaO  Al2O3  Fe2O3, 5CaO  2SiO2  SO3 (calcium sulfosilicate), and
3CaO  Al2O3.

CONCLUSIONS
Suitable application fields have to be searched for both pulverized coal fly ash
and fluidized bed coal combustion ash.
The former has generally an excellent pozzolanic behaviour and is extensively
used, but the recent tendency to reduce the combustion temperatures in the
traditional coal-fired power plants leads to the generation of fly ash with a lower
pozzolanic activity and a higher unburnt carbon content. This latter result implies
an increase of water demand by the cementitious matrices and an enhanced fly
ash ability to capture valuable admixtures added to concrete.
Due to its chemical and mineralogical composition, fluidized bed coal combustion
ash has poor pozzolanic behavior; furthermore, its use in ordinary cements and concrete
is hindered by exothermal and expansive phenomena occurring upon hydration.
This investigation has assessed that pulverized coal fly ash and fluidized
bed coal combustion ash enable a substantial saving of clay as well as bauxite
and natural gypsum, when used as raw mix components for the manufacture of Port-
land and calcium sulfoaluminate cements, respectively. A further saving of bauxite
and natural gypsum can be obtained through the use of AM and flue gas desulfur-
ization gypsum as additional constituents of the raw mixes generating CSA cements.

ACKNOWLEDGMENTS
The research activity concerning the utilization of pulverized-coal fly ash was
performed under the Collaboration Agreement between CNR=DET (Consiglio
COAL COMBUSTION ASHES AND CEMENT SYNTHESIS 597

Nazionale delle Ricerche=Dipartimento Energia e Trasporti) and DIFA


(Dipartimento di Ingegneria e Fisica dell’Ambiente—Università degli Studi della
Basilicata) within the Project ‘‘New technologies for enhancing the environmental
performance of pulverized-coal fired power plants,’’ following the Programme
Agreement MSE (Ministero dello Sviluppo Economico—CNR [Gruppo Tematico:
Carbone Pulito]).

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