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1
Utilization of Industrial By-Products
and Waste in ECO- Cement
Konstantin SOBOLEV, European University of Lefke, Civil Engineering Department, Lefke – TRNC
Metin ARIKAN, Middle East Technical University, Civil Engineering Department, Ankara - Turkey
Abstract
This paper presents a new approach to the production of High Volume Mineral
Additive (HVMA) or ECO- cement. ECO- cement technology is based on the
intergrinding of portland cement clinker, gypsum, mineral additives, and a special
complex admixture, Supersil ica. This new method increases the compressive strength
of ordinary cement to 140 MPa and also permits the util ization of a high volume (up
to 60%) of indigenous mineral additives in the cement composition.
The research results demonstrate that a high volume of natural materials (natural
pozzolans, alumosilicates, l imestone, sand) and industrial by-products (granulated
blast furnace slag, fly ash) and waste (chemical wastes, broken glass and ceramic)
can be used as mineral additives in ECO- cement. The maximum quantity of mineral
additives in ECO- cement depends on the type of mineral admixtures and the
desired strength/durability level. The optimization of the composition of ECO- cement
allows the production of the cement with maximal strength and at minimal cost.
2
Introduction
In the past 25 years, there has been considerable interest in realizing the potential of
construction materials for the util ization of industrial by-products and waste (IBPW) [1-
5]. Following industrial development the volume of IBPW has significantly increased
and will dramatically expand in the future; this is creating a number of economical
and ecological problems. Consequently, there is a demand for the development
and application of technologies to reduce IBPW and transform it into useful products.
There are many examples of the successful util ization of industrial by-products in the
cement industry: burning organic waste including scrap tires as cement kiln fuel and
using blast furnace slag and fly ash in cement [4-11]; highway construction: blast
furnace/steel slag, glass and waste ash as aggregate in hot mix asphalt and
base/sub-base fil ler material [2, 12-18]; dam construction: using blast furnace slag
and fly ash [14]; and ready mix and precast concrete industry: util ization of fly ash
and sil ica fume [3, 7, 9-14].
The following IBPW have been successfully used in construction [2-30]:
• Blast furnace slag
• Coal fly ash
• Coal bottom slag
• Flue gas desulfurization waste
• Glass
• Mining tailings
• Municipal waste combustion ash
• Plastic
• Reclaimed concrete and asphalt
• Scrap tires
• Steel slag
• Waste rock
• Carpet fiber wastes
• Waste Paper
3
Many processes for recycling of industrial waste and contaminated soil (Fig. 1) util ize
cement, bentonite, zeolite or l ime for this purpose [19-23]. The final products of the
process have been marketed as soil cement, cement treated base (CTB), bentonite
mix and roller compacted concrete. Generally, the use of industrial by-products to
replace cement is strictly defined by existing standards [7, 9]. The requirements for
by-products or mineral admixtures are summarized in separate standards. According
to current standards, the IBPW or mineral admixtures must demonstrate the binding
or pozzolanic properties providing a synergetic effect and compatibil ity with
portland cement. Cement-based materials have demonstrated excellent combining
properties in incorporating radioactive and hazardous waste. Extensive research
demonstrated the ability of immobilization of different types of IBPW including
nuclear isotopes and heavy metals in cement hydrates, especially, in the structure of
C-S-H gel [19].
At the same time, for many types of industrial by-products and waste the rate of
util ization is l imited by less than 5% [19, 22-24], mainly because of the destructive
nature of the IBPW. In this case, the compatibil ity of the product and cement system
in respect of simultaneous reactions and structure formation is a most important
criterion for the util ization of IBPW. It is challenging problem to provide IBPW
compatibil ity and at the same time increase the util ization rate.
The combination of certain mineral and chemical admixtures has been found to be
very effective in solving this problem [7-10]. The application of sodium sil icate (liquid
glass) in combination with granulated blast furnace slag (GBFS) was recognized as
very effective in reducing permeability, which is essential for the util ization of the
IBPW at high volumes [20-26]. The mechano-chemical approach presented in [31] for
improving properties of the cement has been successfully applied in util ization of
alum waste and spent chromium-bauxite catalyzer [4]. When the maximal loading of
these products in conventional cement was limited to 10-15%, a high performance
cement blended with 15% waste had no reduction in strength; and up to 30-45% of
waste was util ized in binders with strength of normal cement (Fig. 2).
4
In d u s t ria lB y -p ro d u c ts
& W a s teIB P W
H P C e m e n t
L im e
C la yB e n to n ite
G y p su m
P o r tla n dC e m e n t
P o ly m e rs
P h o s p h a teB in d e r
M a g n e s iu mB in d e r
L iq u idG la s s
Fig. 1. Binding Materials Used for IBPW Stabilization/Immobilization
Normal UseConcrete
Control ledLow StrengthConcrete/Fil l
Shotcrete
LWA/CellularConcrete
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
Co
mp
ress
ive
Stre
ngth
, MPa
Mineral Additive Content, %
HighPerformance
Cement
10 20 30 40 50 60 70 80 90
High StrengthConcrete
Special Concrete
Repairing Mortars
ArchitecturalConcrete
HighPerformance
Concrete
Fiber Concrete
Custom-MadeCement
HighPerformance
Cement Type A HighPerformance
Cement Type B
High VolumeMineral Additive
Cement
ControlledLow Strength
Binders
TCLP-ControlledBinders
Waste StabilizingBinders
Industrial Waste
Industrial By-products& Natural Minerals
Fig. 2. Products Based on HP Cement Technology
5
High-Performance Cement
A newly developed technique using a special admixture during the cement grinding
process helps to significantly improve the properties of ordinary cement. This
approach resulted in the formulation of a new high-tech product: High-Performance
(HP) Cement. The main idea of HP Cement is the addition of a new reactive sil ica-
based complex admixture, Supersil ica, during the grinding of the portland cement
(Fig. 3). Thus, in the case of HP Cement, the clinker is ground in a ball mill together
with mineral additives, gypsum and Supersil ica. The resulting cement is then available
for making a wide range of concrete including high-performance concrete (Fig. 2).
The use of the specially formulated admixture provides the following effects:
• pulverization of cement clinker and mineral additives;
• formation of optimal size distribution of cement;
• creation of highly active amorphous structures;
• physical and chemical modification of the minerals.
Fig. 3. High-Performance Cement Technology
Clinker IBPW
ComplexAdmixture Gypsum
Ball Mill
VICONHigh
PerformanceCement
Technology Enhancement
6
HVMA Cement
Importantly, in the production of HP Cement the amount of expensive and energy
consuming clinker can be drastically reduced. Even at high volumes of mineral
additives the special qualities of the Supersil ica admixture provide a blended HP
Cement that is far superior to ordinary cement.
As a result, HP Cement can be made to order: from super-strong cements with
rugged durability to low cost cements with up to 70% mineral additives. To use a high
volume of mineral additives (sand, l imestone or various industrial by-produs) has an
important economic and ecological impact. The following indigenous mineral
additives were applied successfully in the HVMA cement:
• natural pozzolanic materials;
• natural sand;
• l imestone;
• granulated blast furnace slag;
• fly ash;
• glass or ceramic breakage.
Two possible approaches to HVMA cement production: optimal and economical are
presented in the Fig. 4.
HVMA Cement/ IBPW Utilization
High PerformanceCement
Economical:Supersilica
Content 5-15% of
Clinker/OPC
Optimal:Supersilica
Content 5-15% in Total
HVMA Cement
Fig. 4. Types of High Volume Mineral Additive (HVMA) Cement
7
Experimental Program
The following materials were used in the experimental program:
• portland cement (NPC);
• complex admixture Supersil ica;
• finely ground mineral additives (FGMA): l imestone, natural sand, perlite, fly
ash, blast furnace slag, waste glass, spent catalyzer, waste of alum process.
The NPC had the following Bogue's composition:
• C3S-64%,
• C2S-14%,
• C3A-14%,
• C4AF-4%.
The fly ash had an intermediate activity according to Pozzolanic Potential Index
(PPI=0.74) and corresponded to class F according to the ASTM C618. All FGMA were
ground up to the Blaine specific surface area of 400-850 m2/kg in the laboratory
vibrating mill (LVM).
The composition of HVMA cement included a ternary blend of NPC, Supersil ica, and
FGMA. HVMA cement was manufactured by intergrinding all components in LVM for
20 minutes in order to realize the mechano- chemical activation.
Two major groups of HVMA cement were investigated:
• with optimum content of Supersil ica at 15% of Supersil ica in HVMA cement;
• with economical content of Supersil ica at Supersil ica to NPC ratio of 15:85.
FGMA content in HVMA cement was varied from 15% to 60%.
The strength characteristics of HVMA cements were determined in accordance with
a specially developed accelerated test procedure: the strength of mortar consisting
of cement, standard sand and water (in quantity, required to obtain flow of 106-115
mm) at a cement : sand ratio of 1:1 using 4x4x16 cm prismatic samples, cured for 8
hours at 80 0C in a steam chamber.
8
Strength Properties of HVMA Cement
It was found that the optimum content of Supersil ica in HP Cement is 15% [4]. This
amount of Supersil ica ensures the maximum strength of HP Cement: compressive
strength of 135.4 MPa and flexural strength of 18.1 MPa (at W/C of 0.14) [4,8].
The replacement of the portland cement component in HP Cement by FGMA at
optimal Supersil ica content provides an increase in compressive strength (Table 1-3):
• 135.8 MPa at limestone content of 60% (Fig. 5);
• 140.5 MPa at sand content of 60% (Fig. 5);
• 145.2 MPa at fly ash content of 15% (Fig. 6);
• 165.6 MPa at waste glass content of 30% (Fig. 7).
Further increase in the FGMA content above these limits leads to a proportional
reduction of strength (Fig. 5-7).
Compressive Strength, MPa
FGMA Content, %
0 15 30 45 6020
40
60
80
100
120
140
160
180
0 15 30 45 60
LimestoneSandPerlite
Supersilica:Optimal
Supersilica:Economical
Fig. 5. Effect of M ineral Additives on the Compressive Strength of HVMA Cement
9
Table 1. Effect of M ineral Additives on HVMA Cement Compressive Strength
Compressive Strength, MPa @ Volume of M ineral Additive, %
Mineral Additive
Type
0 15 30 45 60 Economical 135.4 129.7 108.5 82.1 79.4 Limestone Optimal 135.4 134.2 132.7 133.9 135.8 Economical 135.4 121.1 112.7 89.9 81.2 Sand Optimal 135.4 133.3 131.9 136.1 140.5 Economical 135.4 121.4 95.7 79.9 42.3 Perlite Optimal 135.4 131.1 122.2 110.3 85.9
Table 2. Effect of Fly Ash and GBFS on HVMA Cement Compressive Strength
Compressive Strength, MPa @ IBPW Content, % Mineral Additive
Type 0 15 30 45 60 90
Fly Ash Economical 135.4 121.5 84.2 73.1 61.4 35.2 Optimal 135.4 145.2 128.0 104.0 94.5 - GBFS Economical 135.4 117.2 82.3 71.9 54.7 Optimal 135.4 124.1 119.8 111.5 82.3
20
40
60
80
100
120
140
160
180
0 15 30 45 60
Fly Ash
GBFS
Compressive Strength, MPa
FGMA Content, %
0 15 30 45 60
Supersilica:Economical
Supersilica:Optimal
Fig. 6. Effect of Fly Ash and GBFS on the Compressive Strength of HVMA Cement
10
Table 3. Effect of IBPW on HVMA Cement Compressive Strength
Compressive Strength, MPa @ IBPW Content, %
IBPW Type
0 15 30 45 60 Economical 135.4 136.6 131.2 89.8 43.4 Waste
Glass Optimal 135.4 157.7 165.6 149.4 80.7 Economical 135.4 130.7 104.5 50.5 - Spent
Catalyzer Optimal 135.4 141.3 125.9 111.8 - Economical 135.4 101.5 77.1 45.9 - Alum
Waste Optimal 135.4 115.9 87.4 62.3 -
Financial analysis demonstrated that HVMA cements can be produced at a
reduced cost using FGMA in HVMA cement at an economical Supersil ica content
(Supersil ica to NPC ratio of 15:85) [4]. It was found that the HVMA cements with a
strength level of normal cement can be manufactured with up to 45% of FGMA and
with economical Supersil ica content.
20
40
60
80
100
120
140
160
180
0 15 30 45 60
Compressive Strength, MPa
FGMA Content, %
0 15 30 45 60
Supersilica:Economical
Supersilica:Optimal
Waste GlassSpent CatalyserAlum Waste
Fig. 7. Effect of IBPW on the Compressive Strength of HVMA Cement
11
CONCLUSIONS
1. The results of the research have demonstrated that the application of HP Cement
technology and Supersil ica admixture provides:
• control of the properties of the HVMA /ECO- cement;
• use a high volume of indigenous materials in the cement without strength loss;
• the production of super-high strength cement using selected IBPW.
2. The technology of HP Cement provides an opportunity for using a wide range of
by-products and waste.
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