8

RESOURCES
PROCESSING
Manufacture of Eco-friendly and Energy-efficient Alinite Cements
from Flyashes and other Bulk Wastes

Pradip and P.C. Kapur

Tata Research Development and Design Centre 54B, Hadapsar Industrial Estate, Pune 411 013, India

Abstract
Based on the chemistry of alinite compound, we have successfully converted a wide variety of fly-
ashes and other mineral, industrial and municipal waste materials into a new class of hydraulic setting
alinite cements. Three case studies are presented for producing good quality alinite cements from rep-
resentative samples of flyash from a thermal power plant in India, tailings sands from an Indian gold
processing plant and chloride rich municipal incinerator ash obtained from South Korea. The process
parameters optimized include raw mix composition—represented by lime index and chloride
content—clinkering temperature schedule and clinker grinding fineness.

Introduction producing a value added product of mass con-

Large quantities of solid wastes, many of which
are toxic, hazardous and/or voluminous, are gen-
erated during the cradle-to-grave cycles for min-
erals, materials and metals. As for example, it is
estimated that typically a Canadian base metal ore
mine rejects 42% of total mined material as waste
rock, 52% as mill tailings and 4% as smelter slag.
Only 2% is recovered as valuables for subsequent
processing. This prodigious rate of generation of
solid wastes cannot be sustained indefinitely un-
less technologically sound and economically via-
ble ways and means are found for their manage-
ment. Because of high tonnage consumption,
building materials are perhaps the most attractive
option for recycling and utilization of mining, in-
dustrial and municipal wastes. For instance, sev-
eral waste materials such as flyash and blast fur-
nace slags are used world wide quite extensively
as admixtures in different grades of Portland–
pozzolana cements [1]. Also, mine wastes and fl-
yash are routinely employed in the production of
bricks, building blocks, filters, aggregates, glass
ceramics and zeolites.
It is evident that a preferred solid waste man-
agement strategy should be based on a benign
technology solution–that is, low energy con-
sumption and minimal environmental impact–for
Accepted 13 January 2004
sumption. It turns out that a class of hydraulic set-
ting cements could be a highly attractive option
for meeting these stipulations. By exploiting the
chemistry of alinite and sulfo-aluminate type ce-
ments, we have successfully converted a wide va-
riety of mineral, industrial and municipal waste
materials such as fly ashes, fertilizer chalk wastes,
tailings sands, lime sludges and rice husk ash into
hydraulic setting cements. In this communication,
we present some salient findings of our extensive
work on alinite cements made almost wholly from
waste materials.
Alinite phase, which belongs to the CaO-SiO2-
MgO-Al2O3-CaCl2 system, was discovered by
Noudelman et al. [2] in the erstwhile USSR. A
characteristic of alinite is that oxygen ions are
partially substituted by chlorine and silica by alu-
mina [3–5] in its crystal structure, which is other-
wise similar to the alite, the well-known tri-
calcium silicate (C3S) phase of the Portland ce-
ment. Because of its solid solution type structure,
alinite is remarkably tolerant of various impuri-
ties. Consequently, coupled with its hydraulic set-
ting property, alinite is ideally suited for waste re-
cycling and utilization.
Three case studies are presented here. In first
case alinite cements were made from fly ash ob-
tained from a captive pulverized coal fired power
plant and steel plant wastes, namely, limestone
fines, mill scale (Fe2O3) and magnesite (MgCO3)
dust. Second study employed tailings sands from

RESOURCES PROCESSING
 Manufacture of Eco-friendly and Energy-efficient Alinite Cements from Flyashes and other Bulk Wastes
a gold ore processing plant along with a low grade
limestone available locally with waste hydrochlo-
ric acid and/or calcium chloride as a flux. Inciden-
tally, the alinite cement produced in this case was
shown to be an excellent substitute for Portland
cement binder for pelletization of tailings for heap
leaching of residual gold. In third case, alinite ce-
ment was produced from a sample of chloride rich
municipal incinerator fly ash (finer fraction hav-
ing as high as 20% chloride in the form of alkali
chlorides) and bottom ash (coarse fraction) with
limestone and Degana siliceous gravel ore as a
source of silica. Commercial grade calcium chlo-
ride was used as a flux material whenever needed.
Experimental
The following standard procedure was fol-
lowed in the laboratory for preparing alinite ce-
ment clinkers. Finely divided raw materials were
mixed with calcium chloride solution, hand moul-
ded into 10 cm cubes, dried and fired in a silicon
carbide furnace, typically at 1150°C for 4 hours.
For larger production of a few kg cement per
batch, the blocks were fired in a gas fired furnace.
Large scale trials were conducted by clinkering
the dried raw mixed bricks (15 × 15 × 10 cm) in a
chamber kiln having a capacity of 5 tons material
per batch. The soft and readily friable alinite clin-
kers were ground in a ball mill with steel balls
grinding media.
The alinite cement samples were tested exten-
sively as per the relevant standards for specific
gravity, specific surface area, consistency, setting
times and cement-sand (1 : 3) mortar compressive
strength. All the compressive strength data pre-
sented in this paper were collected as per IS 4031
(Indian standards specifications for methods of
physical tests for hydraulic cements).
Fig. 1 Compressive Strength of Alinite Cements as a function of Lime Index; Cements produced from flyash (left) and
from gold tailing sands (right)
Vol. 51, No. 1 (’04–Spring)
9
Results and discussion
Raw Mix Design
Based on our extensive work on the optimum
design of raw mix for the manufacture of alinite
cements [6,7], we have concluded that lime index
and calcium chloride content are the two crucial
parameters for the formation of the alinite phase
during clinkering. Lime index LI defined as LI =
%CaO / (%SiO2 + %Al2O3 + % Fe2O3) must be
greater than 1.5. As shown in Fig. 1, the strength
properties increase with an increase in LI, at least
up to a LI of 2. It is moreover inferred from
Fig. 2, that the optimum quantity of chloride con-
tent in the raw mix is seemingly around 8% by
weight.
As discussed elsewhere [2,5,8], alinite phase
contains up to 4.1% chloride in the structure and
belinite can accommodate as high as 9.1% chlo-
ride. Good quality alinite cements produced from
different waste materials in our investigations are
invariably rich in alinite phase only and typically
contain 4% chloride, even though the raw mix
may contain much higher amounts of chloride. It
would seem that depending on the raw mix design
as well as the level of other impurities present, a
significant proportion of chloride volatilizes. This
is the reason that much higher chloride content is
needed in the raw mix. However, in a continuous
plant operation where flue gases are recycled, the
chloride content needed to achieve the desired
amount of alinite phase in the final clinker would
be somewhat lower. It is interesting to note that
the Korean incinerator ash sample contained very
high levels of alkali chlorides (as high as 18%).
Even then these amounts of chlorides are not suf-
ficient to form alinite cement since alkali chlo-
 10 Pradip and P.C. Kapur

Fig. 2 Effect of Calcium Chloride Addition on the Compressive Strength of Alinite Cements; Cements produced from
flyash (left) and from gold tailing sands (right)

rides tend to volatilize easily. Additional calcium
chloride, to the extent of 3% by weight in the raw
mix, must be incorporated to achieve an accept-
able level of alinite phase in the final clinker. In
the absence of alinite phase, the strength proper-
ties are inferior to those obtained with tri calcium
silicate (alite) phase in Portland cement.
Blaine specific surface area of the ground alin-
ite cements
The alinite clinkers are always observed to be
soft and friable. In the absence of alinite phase,
the clinkers are relatively harder and therefore the
friability of clinkers is a useful and convenient in-
dicator of the formation of alinite phase during
clinkering. Considering the easy grindability of
these clinkers, alinite cements of greater fineness
than Portland cements can be produced with sig-
nificantly lower energy consumption. The en-
hanced specific surface area imparts, as expected,
superior workability to cement pastes as well as
higher strengths, as shown in Fig. 3.
Gypsum addition
It is a standard practice to add 4 to 5% gypsum
to Portland cements, which acts as a set retarder.
Based on our investigations on different kind of
alinite cements, we have established that unlike
Portland cements, addition of gypsum does not af-
fect the set properties but it does lead to a signifi-
cant improvement in strength. We add up to 8%
gypsum in alinite cements in order to achieve

Fig. 3 Effect of Blaine Specific Surface Area on the Compressive Strength of Alinite Cements; Cements produced from
flyash (left) and from gold tailing sands (right)

RESOURCES PROCESSING
 Manufacture of Eco-friendly and Energy-efficient Alinite Cements from Flyashes and other Bulk Wastes 11

higher strengths, particularly long term strength. compared with specifications of Portland cement
Characterization of alinite cements in Fig. 5. It will be observed that alinite cements
The X-ray diffraction is perhaps the most reli- are at least as good as Portland cements so far as
able and convenient tool for ascertaining the the physical properties are concerned. Moreover,
formation of alinite phase in clinkers. Figure 4 it turns out that alinite cements are completely
shows the characteristic finger print of good qual- compatible with Portland cements [6]. In addi-
ity alinite cements with three most prominent tion, it is possible to make good quality alinite
peaks for Cu Kα radiation at 2.808 A° (100% rela- pozzolana cements, similar to Portland pozzolana
tive intensity), 2.618 A° (26%) and 3.235 A°
(22%) at 2θ equal to 31.8, 34.2 and 27.5 degrees,
respectively.
Solid state MAS NMR studies have also been
carried out on alinite cements. The characteristic
shifts observed for alinite cements are distinctly
different from that observed for Portland cements
[8,9]. The NMR results confirm the presence of
Q0 distribution of silicate ions in alinite cements.
The spectra of Portland cements show greater
structure due to at least three in-equivalent silicon
positions in the alite structure [8].
Compressive strengths
The compressive strength (as per IS 4031) of
standard 1 : 3 cement-sand mortar cubes of alinite
cements made from different waste materials is

Fig. 4 X-Ray Diffraction Patterns for Alinite Cements;
Cements produced from Korean Municipal Incin-
erator Ash (C1), Coal flyash (C2) and from gold
tailing sands (C3) as compared to Portland
Cements (P1 & P2)
Fig. 5 Compressive Strength of Alinite Cements pro-
duced from flyash (bottom), gold tailing sands
(middle) and Korean Incinerator Ash (top) as
compared to Indian standard specifications for
Portland Cements

Vol. 51, No. 1 (’04–Spring)

 12 Pradip and P.C. Kapur

cements, by inter-grinding the clinker with up to
20% fly ash by weight [6]. The advantages of the
low temperature clinkering route described here
over conventional Portland cements are given in
Table 1.
Applications and Field Trials
The alinite cements made almost exclusively
from waste materials require much lower clinker-
ing temperatures thus resulting in significant sav-
ings of thermal energy. Another distinguishing
feature of alinite clinker is its soft and friable na-
ture as compared to Portland cement clinkers.
Electrical energy consumption during grinding is
therefore considerably lower even though the ce-
ment produced is much finer. Consequently, alin-
ite possess better workability, rapid hardening and
higher strength characteristics. Our experience
shows that the constituent alinite phase is much
more tolerant of the impurities that are inevitably
present in waste materials.
We have also produced these cements on ton-
nage scale. 10 tonnes of alinite cement was made
from fly ash and other steel plant wastes and ex-
tensively tested by in field application such as
concrete road making, RCC Construction etc. So
far as the physical properties and applications are
concerned, these cements were found to be no dif-
ferent from regular Portland cements.
Alinite Cements were made from tailings sands
of Bharat Gold Mining (BGML) operation. These
were used as a binder substitute for Portland ce-
ment in pelletizing of tailings sands in a balling
drum for heap leaching. Detailed investigations
were carried out in our laboratories to compare

Table 1 A comparison of Portland Cements with Low Temperature Alinite Cements produced from industrial and other
wastes at TRDDC.
Low Temperature Alinite Cements
Ordinary Portland
Parameter/Criteria Municipal
Cement Flyash Tailings Sands
Incinerator Ash
Composition (Wt %)
CaO 62–67 45–55 55–60 60.5
SiO2 18–24 13–19 18–21 17.8
Al2O3 4–8 9–12 2–5 2.3
Fe2O3 1.5–4.5 4–10 4–7 2
MgO 0.5–4 1–10 4–6 2.9
Cacl2 — 6–18 4–9 8.6 (total)
Gypsum addition (% by wt 5 8 8 8
of cement)
Calcareous component in 75–90 60–70 72–73 65
the raw mix (% by weight)
Raw materials used for man- Limestone and clay Flyash, limestone, Tailings, sands, Incinerator flyash
ufacture millscale magnes- limestone and cal- and bottlemash,
ite dust and calcium cium chloride limestone, calcium
chloride chloride
Lime Saturation Factor 0.66–1.02 ~ 0.7 ~ 0.7 ~ 0.7
Lime Index >2 1.5–2.0 1.5–2.0 2.7
Clinkering temperature 1400–1500 1100–1200 1100–1200 1100–1200
Major phases C3S, C2S, C3A, C4AF Alinite Alite, C3A Alinite, Alite, C4AF Alinite C11A7Cacl2
β-C2S
Blaine specific surface cm2/g 2000–3200 4000–7000 4000–7000 6000
Compressive strength, Kg/cm2 (as per IS 4031)*
3 days > 160 145–420 100–260 207
7 days > 220 200–475 160–330 263
28 days > 330 300–500 235–450 402
Energy Consumption
Electrical (KWH/t) 110–135 Estimated Savings 50–80%
Thermal (Kcal/t) 800–1100 Estimated Savings 30–60%
Raw Material Sensitivity Stringent quality Amenable to waste recycling, more tolerant of impurities
constraints
* The corresponding specifications for high strength Portland cement are 220, 330 and 430 Kg/cm2 for 3, 7 and 28 days
respectively when tested as per Indian Standard Specifications IS 4031.

RESOURCES PROCESSING
 Manufacture of Eco-friendly and Energy-efficient Alinite Cements from Flyashes and other Bulk Wastes
the properties of pellets bonded by alinite cement
and ordinary Portland cement. The pellet
strengths were comparable and hence the alinite
cements could readily substitute for conventional
Portland cements.
Similarly, we have produced and tested alinite
cements from Korean Municipal incinerator ash
and a judicious combination of other waste mate-
rials to satisfy the raw mix design indices.
Concluding remarks
In all three cases described here, significantly
lower temperatures of the order of 1150°C are
sufficient to achieve the desired proportion of
alinite phase in the final cement product, as
against temperatures of the order of 1450°C re-
quired in the manufacture of ordinary Portland ce-
ment. X-ray diffraction studies of cements show
alinite as the principal phase with presence of rel-
atively minor amounts of other phrases such as
belite and calcium alumino-chloride
(11CaO.7Al2O3.CaCl2). Incorporation of gypsum
during clinker grinding invariably has a beneficial
effect on the quality of cement produced. The
alinite technology offers considerable potential
for energy saving both at the clinkering stage, be-
cause of lower temperatures employed, and at the
grinding stage, due to highly friable nature of the
alinite clinker.
Several groups around the world are currently
active in research on alinite cements [5–12]. Over-
all, this process offers an economically attractive,
energy-efficient and eco-friendly solution for re-
cycling and utilization of chloride rich municipal
incinerator ashes (also fly ashes) as well as other
mining, mineral and metallurgical waste materi-
als, which currently are of considerable nuisance
value.
Acknowledgements
The authors are grateful to our sponsors Tata
Steel and Bharat Gold Mines Ltd. for their initial
financial support for the program. We express sin-
cere thanks to our colleagues D. Vaidyanathan,
D.J. Dasgupta, Maneesh Singh, Ajay Panjwani
and Vijay Pujar for their valuable contributions
during their association with this research pro-
gram at our centre. We thank Prof. E.C. Subbarao
and Prof. Mathai Joseph for their unfailing en-
couragement, interest and support during the
Vol. 51, No. 1 (’04–Spring)
13
course of this work.
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