Material p59 62

27/12/02

12:28 pm

Page 1 Paul Pauls Hard Drive:Desktop Folder:Paul s share file:ICR January 2003:Article or

PLANT PERFORMANCE

Alternative
materials
ortland cement concrete is the
most widely used material in
today's
construction
industry
because of its structural properties, durability and economy. More than
100Mt of cement is consumed annually in
the United States, and about 45Mt, in
Central America. This places the cement
industry among the largest process industries in terms of the output.
There are several factors that make the
industrys environmental impact quite significant (Tresouthick, Mishulovich, 1990).
Considerable energy consumption and raw
material requirements of approximately
1.6t per tonne of product are the most significant, along with the attendant CO2
emissions. Other emissions, such as sulphur
and nitrogen oxides, particulates (dust)
etc, are controllable within the regulation
limits but nevertheless not negligible.
The conservation efforts of the cement
industry have been directed toward the use
of alternative fuels and raw materials
derived from industrial byproducts.
Alternative developments have been concerned with the wider introduction of supplementary cementitious materials partially
replacing cement in concretes thereby
reducing the cement consumption.

Portland cement
composition
Portland cement is produced by pulverising
clinker consisting essentially of hydraulic
calcium silicates, usually containing one or
more of the forms of calcium sulphate as
an addition (ASTM, 1995). Typical chemical
composition of portland cement is as follows (Kosmatka, 1996):
SiO2
19 22 per cent
Al2O3
3.5 6.5 per cent
Fe2O3
2.0 5.0 per cent
CaO
60 66 per cent
It is interesting to note that the five
chemical elements comprising about 99 per
cent of the clinker chemical composition

by Alex Mishulovich, Construction Technology Laboratories Inc

In the foreseeable future Portland cement or its derivatives will remain the
basis of structural concrete. Therefore, finding the ways of the energy and
material conservation in the cement industry attain the first-rate
importance, both from the economic and ecological standpoints. In this
paper, presented at APCAC XIX Technical Conference, Alex Mishulovich
looks at alternative materials for the cement industry.
(O, Si, Al, Fe, Ca) are the most abundant
elements of the Earths crust. It means that
the cement industry depends only on the
most common mineral resources. Moreover,
these elements are found in the material
streams of other high-tonnage industries.
As we know, the principal crystalline
phases of Portland cement clinker are: tricalcium silicate (C3S), dicalcium silicate
(C2S), tricalcium aluminate (C3A), and
tetracalcium alumoferrite (C4AF). They are
present in clinker in the following proportions:
C3S
37 68 per cent
C2S
9 - 32 per cent
C3A
4 12 per cent
C4AF
6 13 per cent
A source of calcium is represented in
the greatest proportion in the cement raw
mix. Typically, it is one of calcareous rocks
(limestone, chalk, etc). Calcium carbonate
is the only calcium compound that can be
found in natural deposits large enough to
provide cement plants with long-term
resources. Not only does calcium carbonate
emit CO2 during calcination, but this reaction requires about 1850kJ/kg (800Btu/lb)
Table 1: composition of metallurgical slags

Blast furnace slag Steel slag Arc furnace slag

SiO2
33-42
16-19
23-26
Al2O3
10-16
2-3
7-9
Fe2O3
0.5-2.0
10-23
2-7
CaO
36-45
40-55
38-40
MgO
3-12
6-15
11-13

from the combustion of fuel. This is why

even a partial replacement of carbonates
with calcium-containing industrial byproducts may be beneficial.

Alternative raw materials

The clinker compounds are produced as a
result of chemical reactions during hightemperature treatment in a rotary kiln.
Calculations known as mix design take into
account only the chemical (oxide) composition of the ingredients, not their physical
or mineralogical form. Therefore, the rocks
such as limestone are usually chosen as the
principal source of lime only because of
their wide availability. Any other sources
can be used in this capacity, provided they
have a sufficiently high-calcium content
and are competitive with limestone in
terms of costs and sufficient supply.
Examples of such byproducts are metallurgical slags. Not unlike Portland cement
clinker, slags are products of high temperature processing of mixes containing natural
calcium carbonates. Their further use,
therefore, would not involve calcination,
which consumes energy and generates CO2.
Typical slag compositions (percentages) are
presented in Table 1 (Mishulovich, 1994).
Comparison of this data with the
Portland cement compositions demonstrates that many slags are close to
cements and therefore can be easily fitted
into cement raw mixes. Blast-furnace slags
are often added into raw mixes with other
mix ingredients. Steel-making slags are
even closer chemically to cement clinkers.

INTERNATIONAL CEMENT REVIEW / JANUARY 2003

59

Material p59 62

27/12/02

12:28 pm

Page 2 Paul Pauls Hard Drive:Desktop Folder:Paul s share file:ICR January 2003:Article or

PLANT PERFORMANCE
However, steel slags often contain
a significant amount of finely dispersed metallic iron, which makes
grinding more difficult. This
obstacle has been overcome in a
patented process by which
coarsely crushed steel slag is
added to the kiln feed separately
from the rest of raw meal (Young,
1995).
Elements in cement clinker
Slags are an example of
byproducts that can be utilised
with major benefits for the
cement industry. Another group of
waste materials is not so much
essential for cement manufacturing,
but
their
utilisation
relieves the generating industries
from the expense of disposal.
These byproducts contain some of
the oxides that can be incorporated in the clinker composition.
Table 2 shows some of such
byproducts tested by CTL in the Elements in Earth crust
recent years.
Silica, alumina, and iron oxide are preThe significance of these materials in
sent in many byproducts that can be
the cement production process varies
utilised in cement mix designs to balance
widely depending on the chemical compothe mix composition. Addition of these
sition. For example, alumina byproduct (1)
ingredients in the range of 1-10 per cent
contained a relatively high amount of silmay be both environmentally friendly and
ica, which is required in some raw mix
cost effective. Such additions contain
designs. This silica was present in chemisometimes a considerable amount of carcally reactive microcrystalline form, which
bon or combustible organic matter that
made it especially valuable. The presence
contribute to the general fuel input. An
of fluoride in the product gives it some
example is high-carbon fly ash, which was
mineralising, or catalytic, properties. As a
successfully tested as an addition at one of
result, raw mixes containing this product
the Illinois cement plants (Bhatty et al,
could be burned at much lower (by 501998). Another example is spent pot liner
80C) temperatures than conventional
generated in large amounts by the alumixes. Another alumina byproduct conminum industry. It contains carbon in the
tained the three major oxides in the ratio
form of graphite and fluorides (Tresouthick,
close to that in normal clinker. It needed
1986).
only a relatively small addition of limeOrganic substances, such as wood
stone to form the required composition,
fibres and poly-hydrocarbon fillers, were
with the attendant advantages.
Table 2: examples of byproducts

Deinking sludge
Shredder fines
Alumina byproduct
Alumina byproduct
Spent pot liner
Oily residue
Coal fly ash
Food containers
Pigment byproduct

60

SiO2

Al2O3

Fe2O3

CaO

15
22
(1)
(2)
11
21
50

25
6
44
23

12
12
15

7
18
57

13

19
18

9
16

28
5
30
20

10

55

INTERNATIONAL CEMENT REVIEW / JANUARY 2003

Organic
matter
50
12

60
86
10
52

Heating value
BTU/lb
5000
2100

7500
1200
7300

contained in paper sludge and

food containers, respectively.
O
The mineral portion of those
Si
materials was readily accommodated by the mixes, whereas the
Al
energy contribution by burning
Fe
the organic portion was considCa
erable.
Others
It can be seen that the cement
industry offers an economical
and environmentally sound way
of waste management. However,
certain restrictions apply to the
O
use of byproducts by the industry. First is the available amount
Si
of a byproduct. Even an average
Al
cement plant uses daily about
3500t of raw materials, and the
Fe
waste stream should be large
Ca
enough to be considered for utilisation. Its composition and
Others
other properties should be reasonably stable. The material can
contain small amounts of elements that may be detrimental
to the product quality (Hewlett, 1998),
and extensive testing is recommended prior
to its introduction into the industry.
Contamination by toxic or otherwise deleterious substances always complicates the
process. Finally, transportation costs can
make the use of certain products prohibitively expensive.

Waste-derived fuels
Production of cement clinker in existing
rotary kilns is an energy-intensive process
requiring 0.1 to 0.2t/t of fuel of the product. Fuel cost, being the largest item
among all cement production costs, has
been the focus of attention of cement producers ever since the beginning of the
commercial cement production. In many
cases, utilisation of combustible and often
toxic waste is not only economically
advantageous, but in many cases presents
an environmentally sound alternative to
incineration.
According to the 2000 reports, eight
cement plants in the US used WDF as primary fuels exclusively (two plants) or with
other fuels (coal, coke, oil). In the same
period, 22 plants reported the use of WDF
as alternate fuels, with 26 more plants
using WDF as alternate mixed with other
fuels. In Canada, seven plants used WDF as
alternative fuels. The quantity of WDF
actually used is difficult to estimate.
Three groups of waste materials are
used as kiln fuels:

Material p59 62

27/12/02

12:28 pm

Page 3 Paul Pauls Hard Drive:Desktop Folder:Paul s share file:ICR January 2003:Article or

PLANT PERFORMANCE
1. liquid fuels (spent solvents, oils,
etc)
4000
2. used automotive tyres
3500
3. other solid wastes.
3000
Substitution of byproducts for 2500
more conventional fuels in the 2000
cement kiln may affect the production 1500
process and the environmental perfor- 1000
mance. Since the flame temperature
500
needs to be sufficient, it is desirable
0
1
2
3
to use fuels whose adiabatic flame
temperature (AFT) is high, and those
Cement
Fly ash
Slag
Aggregates
which generate of black body radiating species. On balance, higher car- Concrete ingredients
bon fuels tend to give higher AFT valsystem to an extent of about 99.85 per
ues. By contrast, higher hydrogen fuels
cent, and emissions from cement kilns
tend to be volatile, with low carbon conaveraged four per cent of the allowable
tents, and often are poor black body radialimit, with none greater than 22 per cent,
tors. If we apply these considerations to
even when maximising lead input.
waste fuel firing, several factors become
Cadmium is retained to an extent of about
apparent:
99.4 per cent, and the average emissions
1. High-hydrogen, high volatile fuels are
during these tests were again less than
suitable for the front end of the kiln, in
five per cent of the allowable, with none
the sintering zone. Very high moisture congreater than 40 per cent of the allowable.
tents are deleterious to obtaining and
Thallium emissions were at least three
maintaining the required high flame temorders of magnitude lower than any regulaperature.
tory limits, as were mercury emissions with
2. Some carbon and/or ash is desirable in
one exception. In US waste fuels, thallium
the sintering zone fuel, to carry out the
contents are often lower than in the fossil
desirable heat transfer via the black body
fuel they are replacing the same is also
radiation mechanism.
often true of arsenic, mercury, beryllium,
3. It is not desirable to fire low energy
and silver.
fuels in the sintering zone, as the heat will
Testing on dioxin and furan emissions
not be transferred at a high enough temhas generally shown that levels are fundaperature to ensure acceptable free lime
mentally unaffected by substitution of
values in the clinker.
waste fuels for fossil fuels. Emissions of
The balance of thermal processes in the
SO2 are usually significantly reduced when
rest of the kiln require relatively lowpotential heat. Many fuels not suitable for
waste is burned, unless the sulphur stems
use in the sintering zone are potentially
principally from the kiln feed. NOx emisvery useful when added to the calcining
sions are generally unchanged when fuel is
zone of the kiln. Here, the key issue is
burned only in the firing zone of the kiln.
ensuring complete burnout of the fuel.
When mid-kiln firing is practiced, reduced
The firing of fuel in the calcining zone has
NOx levels are often observed, since the
a number of advantages:
overall thermal load in the sintering zone
It reduces the thermal load in the sinis reduced (Miller, 2002).
tering zone, potentially improving refracIn conclusion, the use of waste fuels
tory life.
as a partial replacement for fossil fuels in
The reduced thermal load results in
cement manufacture has a number of
reductions in NOx generated in the sinterpotential benefits, economic and technical.
ing zone. The vast majority of dust emisFrom the technical perspective, product
sions from cement kilns are related to raw
quality may be improved, sulphur and
materials, not fuels. For this reason, stack
nitrogen oxide emissions may decrease,
emissions of particulates are only very
and added flexibility may permit increased
slightly influenced by the use of waste
production capacity. Recognising the
fuels. Of all the regulated metals, only
requirements of each zone of the kiln with
lead, cadmium, thallium, and mercury are
respect to the separate issues of heat and
volatile enough to be of any concern.
temperature will aid in selecting the proper
However, the practical experience has
firing location. Product quality may
shown that lead is retained in the kiln
improve when these decisions are made

properly, and in no case is there an

emissions risk that threatens to
cause any harm to human health and
the environment.

Supplementary
cementitious materials
An obvious way to reduce the power
consumption and CO2 emission in
cement manufacturing is partial
replacement of clinker with hydraulically reactive materials not requiring
pyroprocessing. In the US practice,
supplementary cementitious materials
are used in by cement manufacturers
in blended cements and by ready-mix
producers in concretes.
In general, active mineral additions or
supplementary cementitious materials for
use in blended cements or in concretes
may be subdivided into categories of
pozzolanic materials and latent hydraulic
cements. Pozzolans are siliceous or
siliceous and aluminous materials which in
itself possess no cementitious value but
which will chemically react with calcium
hydroxide at ordinary temperatures to form
cementitious compounds. Typical pozzolans
are some natural rocks (volcanic ashes,
tripoli) or industrial byproducts, the most
widely used being fly ash.
Latent hydraulic cements act as cementitious materials if mixed with water and a
minimal amount of certain activating
agents. Granulated blast-furnace slag is the
well-known example of a material that is
activated by alkali environment (Schroeder,
1968). Slag is produced in the ratio of
280-340kg/t of pig iron (USGS, 2002), and
its utilisation serves both cement manufacturing and steel making.
Hydraulic cements form the basis of
modern concrete construction, and
strength is their most essential property.
Ability of supplementary cementitious
materials to contribute toward the concrete performance is based primarily on
their chemical reactivity. Most pozzolans
contain amorphous or microcrystalline silica either as a natural ingredient, or as a
product of thermal decomposition of
hydrosilicates. Water-granulated molten
slag, as well as fuel ash, contains a high
amount of a vitreous phase (mineral glass).
The latter, being a supercooled liquid, is
thermo-dynamically unstable and, therefore, chemically reactive (Keil, 1958). In
mixes with Portland cement it is activated
by the solution of calcium hydroxide which
forms as a product of cement hydration.

INTERNATIONAL CEMENT REVIEW / JANUARY 2003

61

Material p59 62

27/12/02

12:28 pm

Page 4 Paul Pauls Hard Drive:Desktop Folder:Paul s share file:ICR January 2003:Article or

PLANT PERFORMANCE
As a result, the properly formulated
and manufactured supplementary cementitious materials are fully competitive with
Portland cement in terms of strength.
Another important advantage of blended
cements containing slags and pozzolans is
their ability to improve concrete durability
(Roy, 1985).
Aside from mechanical and physical
factors leading to degradation of concrete
in service, concrete durability can be
adversely affected by chemical reactions
involving a combination of some agents
present in the environment or in concrete
itself. The most common are reactions
between alkalies and concrete aggregates,
and reactions of the hardened cement
matrix with sulphate-bearing water
(Stark,1991). In both cases, reactive silica
present in the cements or concretes
containing supplementary cementitious
materials neutralises the aggressive ions
causing the concrete deterioration.

Conclusion
The cement industry by its sheer size
inevitably impacts the environment by
extraction of the natural raw materials and
generating solid and gaseous emissions.

62

On the other hand, due to the chemical

composition of its product, the industry is
able to absorb a substantial portion of
byproducts generated by other industries.
This not only minimises the industrys
impact on the environment but helps to
reduce the waste streams of the industrial
production in general.

References
American Society for Testing and Materials,
1995, Standard Specification for Portland
Cement C150
Bhatty, J, Detwiler, RJ, Miller, FM,
Mishulovich, A, 1998, Use of High Carbon
Fly Ash as a Component of Raw Mix, Report
#WO 566101, EPRI, Palo Alto, CA
Peter C Hewlett (Ed), 1998, Lea's Chemistry
of Cement and Concrete, Arnold Publishers,
London, UK
Keil, F and Locher, FW, 1958, Hydrulische
Eigenschaften von Glssen, ZementKalk-Gips, Nr 6, s 245-253
Kosmatka, S, 1996, Portland Cement: Past
and Present Characteristics, Concrete
Technology Today, Vol17, No2, pp1-4, PCA,
Skokie, Illinois, USA
Miller, FM, 2002, Private communication
Mishulovich, A, 1994, Reduction of CO2

INTERNATIONAL CEMENT REVIEW / JANUARY 2003

Emissions, Portland Cement Association,

Skokie, Illinois, USA
Roy, Della M, Luke, K, Diamond, S, 1985,
Characterisation of Fly Ash and its Reactions
in Concrete, Fly Ash and Coal Conversion
By-Products: Characterisation, Utilisation,
and Disposal I, pp 3-20, Materials
Research Society, Pittsburgh, Pennsylvania,
USA
Schroeder F, Blast Furnace Slags and Slag
Cements, The Fifth Int Symposium on the
Chemistry of Cements, Part 4, Tokyo, 1968.
Stark D, 1991, Handbook for the
Identification of Alkali-Silica Reactivity in
Highway Structures, SHRP-C-315, National
Research Council, Washington DC, USA
Tresouthick SW, 1986, Spent Pot Liner as a
Supplementary Fuel in Cement Production,
23d International Cement Seminar,
Chicago, Illinois, USA
Tresouthick SW, Mishulovich A, 1990,
Energy and Environmental Considerations
for the Cement Industry, Proceedings of
the Energy and the Environment in the
21st Century Conference, Cambridge, Mass
Young, Rom D, Method and Apparatus
for Using Steel Slag in Cement Clinker
Production, US Patent 5,421,880 (1995).
_________________________________