LOW-CARBON FOOTPRINT CEMENTS

INCORPORATING HIGH VOLUMES OF

BAUXITE RESIDUE
D. Ariño-Montoya1,2, M. Katsiotis1, G.
Giannakopoulos1, R. I. Iacobescu2, Y. Pontikes2
1
TITAN Cement Company, S.A., Group Research,
Development & Quality, Greece
2
KU Leuven, Department of Materials Engineering,
Leuven, Belgium
ICSOBA Hamburg, 2 – 5 October 2017
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 Presenter’s Bio
• Name: David Ariño-Montoya

• Degrees earned: MSc Concrete Engineering, Spain (2010)

• Affiliation: TITAN Cement Company S.A., KU Leuven,

Materials Engineering

• Present position: PhD candidate – TITAN Cement; 2016 –

ongoing [Greece]

• Work experience:
– 2012 – 2015: Senior concrete technician; Bath University [UK]
– 2012: Research assistant; Novacem Ltd. [UK]
– 2007 – 2009: Concrete area manager; Horaing, S.A. [Spain]
ICSOBA Hamburg, 2 – 5 October 2017
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 Contents

• Introduction

• Research goals

• Results and discussion

• Conclusion

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 Introduction

Bauxite residue

0.8 – 2 t of BR per 1 t alumina

4 Mt used out of 150 Mt per year
> 3000 Mt stored worldwide

Source: aluminiuminsider.com

ICSOBA Hamburg, 2 – 5 October 2017

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 Introduction

Why low-carbon cements?

Cement demand outgrew 4500
earlier forecast by 20%
4000
What about CO2
emissions? 3500

Quantity (MT)
3000

2500

2000
TITAN Cement Plant, Thessaloniki (Greece) 2005 2020 2035 2050
Year
ICSOBA Hamburg, 2 – 5 Cement
Source: European October 2017
Research Academy (2006) and USGS
Cement Mineral Commodity Summary 5
 Introduction

Bauxite residue for cement production

Wt (%)
CaO 65
SiO2 21 New mix
Al2O3 5 designs to
Fe2O3 3 allocate
Wt (%) higher
CaO 2–8 amounts of
SiO2 3 – 50 Fe2O3
Al2O3 10 – 20
Fe2O3 30 – 60
Na2O 2 – 10
Source: Handbook of Recycling (2014) and redmud.org

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 Introduction

Why low-carbon cements?

Lower burning temperature Limestone calcination

~ 200 °C CaCO3 → CaO + CO2

ICSOBA Hamburg, 2 – 5 October 2017

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 Research goals

• Production of 2 families of low-carbon cements:

– Aluminoferrite
– Ferrobelitic

• Use of 50 wt% BR in raw meal composition.

• Study of the produced phases.

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Research goals

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Raw materials composition

Calcined Clay Bauxite

limestone (wt %) residue
(wt %) (wt %)
CaO 87.32 1.86 9.66
SiO2 6.02 64.50 4.03
Al2O3 2.62 14.00 22.11
Fe2O3 1.24 6.13 46.38
Other 2.74 2.86 7.93
LOI 0.00 10.59 9.81
Total 99.94 99.94 99.92

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 Clinker modelling Aluminoferrite

System BR – cLS – Al2O3 BR50 cLS48 Al2O302

100%

100% 14 Ca2SiO4
90%
Ca2SiO4
Melilite 80%
6 Ca3Ti2O7
80%

CaO 3 CaO
70%
9 Ca3Al2O6
60%
Ca3Al2O6
Weight (%)

50%
Na2CaAl4O8 60%

40%

30%
40%
20%

10%
65 Ca2AlxFe2-xO5
0%
Ca2AlxFe2-xO5
0 1 2 3 4 5 6 7 8 9 10 20%
Al2O3 content (wt%)

Bauxite residue constant at 50 wt%

Calcined limestone substituted by Al2O3 0%

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 Clinker modelling Ferrobelitic

System BR – cLS – Cl BR50 cLS46 Cl04

100%

100%

90%
Ca2SiO4 22 Ca2SiO4
80% 80%
5 Ca3Ti2O7
70%
CaO Melilite
5 Na2CaAl4O8
60%
Weight (%)

60%
50%

40%

30% Na2CaAl4O8
40%
20%
Ca2AlxFe2-xO5
10%
66
0% Ca2AlxFe2-xO5
0 1 2 3 4 5 6 7 8 9 10 20%
Clay content (wt%)

Bauxite residue constant at 50 wt%

Calcined limestone substituted by clay 0%

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 Clinker production

Aluminoferrite
BR50 cLS48 Al2O302

Heating rate: Target

10 °C/min temperature
1200 °C
1250 °C
1300 °C
800 °C 30 min
30 min Ferrobelitic
BR50 cLS46 Cl04

ICSOBA Hamburg, 2 – 5 October 2017

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 Clinker free-lime study

8.0

7.0

6.0

5.0
Free lime (wt%)

BR50 cLS48 Al2O302

4.0 BR50 cLS46 Cl04
BR50 cLS45 Cl05
3.0 BR50 cLS44 Cl06
BR50 cLS43 Cl07
2.0

1.0

0.0
1200 1250 1300
Temperature (°C)

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 Clinker free-lime study

8.0

7.0

6.0

5.0
Free lime (wt%)

BR50 cLS48 Al2O302

4.0 BR50 cLS46 Cl04
BR50 cLS45 Cl05
3.0 BR50 cLS44 Cl06
BR50 cLS43 Cl07
2.0

1.0

0.0
1200 1250 1300
Temperature (°C)

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Clinker X-ray diffraction (1250 °C)

Aluminoferrite
BR50 cLS48 Al2O302

Ferrobelitic
BR50 cLS43 Cl07

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Clinker Rietveld analysis (1250 °C)
Aluminoferrite Ferrobelitic
BR50 cLS48 Al2O302 BR50 cLS43 Cl07
100%
4 Ca3Al2O6 100% 2 Ca3Al2O6
8 Other 12 Other
80%
10 Ca2SiO4 80%

29 Ca2SiO4
60% 60%

58 Ca2AlxFe2-xO5
40% 40%
32 Ca2AlxFe2-xO5

20% 20%

21 Ca2Fe2O5 18 Ca2Fe2O5
0% 0%

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Scanning Electron Microscopy

Aluminoferrite Ferrobelitic
BR50 cLS48 Al2O302 BR50 cLS43 Cl07

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 Scanning Electron Microscopy

Ferrobelitic: BR50 cLS43 Cl07

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 Scanning Electron Microscopy

Aluminoferrite: BR50 cLS48 Al2O302

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 Mechanical Strength

Clinker mixed with 10 wt% gypsum

Flexural Compressive
Aluminoferrite
(MPa) (MPa)
2 days 1.6 4.5 ± 0.1
28 days 2.5 8.7 ± 0.4
BR50 cLS48 Al2O302

Flexural Compressive
Ferrobelitic
(MPa) (MPa)
2 days 2.7 10.5 ± 0.8
28 days 2.6 10.2 ± 0.6
BR50 cLS43 Cl07
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 Conclusions

• Production of cement clinker with 50 wt% BR is

feasible.

• Further studies are necessary to understand the

influence of minor elements in the clinker and
hydrated phases.
– Mechanical properties are promising.

• Performance of Fe-rich cements can be optimized

with the use of additives and optimization tools.

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 European Training Network for
Zero-Waste Valorisation of Bauxite
Residue (Red Mud)

Bauxite residue is:

• SOURCE of Fe, Al, Ti, Sc and REE
• RAW MATERIAL for construction materials

http://etn.redmud.org
@ etn_msca_redmud

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Thank you for your attention

http://etn.redmud.org
@ etn_msca_redmud

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 Introduction

Cement Cement Chemical Formulae

Name Abbreviations
Alite C 3S Ca3SiO5
Belite C 2S Ca2SiO4
Aluminate C 3A Ca3Al2O6
Ferrite C2(A,F) Ca2(AlxFe1-x)2O5

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