High-temperature slag

engineering and how such a

process could deliver slags
for high value-added
applications

Theodoros Karachalios, Yiannis Pontikes

February 2018
 The goal
Take responsibility and move from awareness to implementing solutions

Even if the above approach is not perfect, it does indicate we live beyond
“sustainable, safe operating space”

Source: http://www.footprintnetwork.org
Taking action (?)
Paris Agreement
 A path forward: industrial symbiosis
Is linear
A large constant supply of raw materials is required
This system is unsustainable

Is partially cyclic
Reduced materials and energy required
Reduced waste produced
Characterises most present day industrial systems

Is highly integrated and closed

All by-products constantly used and
Yes, it can! recycled > apart from re-cycle think
See Kalundborg, also of out-cycle!
Denmark Represents a sustainable state
Is the ideal goal of Industrial Ecology

B.R. Allenby. “Achieving Sustainable Development Through Industrial Ecology.” International Environmental Affairs 4, no. 1 (1992): 56–68
A strategy
Foster industrial symbiosis and open collaboration/innovation/ecology

Industrial Symbiosis in Kalundborng, Denmark

 Implementing that in our region
Group Machiels, Houthalen
Metallo-Chimique, Beerse - slag: depends
- slag: 180 kt/year*

Umicore, Hoboken Aperam, Genk

- slag: 150 kt/year* - stainless steel: 900 kt/year*
- slag: 250 kt/year*
Metal Valley

ArcelorMittal, Gent
- steel: 4000 kt/year*
- BOF slag: 450 kt/year*

Aperam, Châtelet
- stainless steel: 700 kt/year*
- slag: 200 kt/year*
…and the vision

Transform local supply of residues towards new materials

Circular economy through zero waste processing
In practice

Additives

Granulation New slag

In practice

Granulation New slag

Innovation is the tool
Innovation is the tool
Stainless steel slags as a case study
Stainless steel production
 3-step process (before casting)
- EAF: scrap melting
- AOD/VOD: de-C and de-S
- Ladle refining: de-S

EAF slag AOD/VOD slag Ladle slag

125 kg/ton steel 180 kg/ton steel 20 kg/ton steel
Slag valorisation chain

Final solidified slag

Uses?
 Drives for valorisation

Slags are voluminous residues, typically >50.000t/y per slag type, per plant.

Cement production/use is “second to water”; actually third if aggregates are

included also. A solution could be to have slags mixed with cement (see
GGBFS). But as what? Filler or hydraulic component?
http://www.iea.org/papers/2009/Cement_Roadmap_targets_viewing.pdf
 Drives for valorisation
Slags are basic, i.e. high Ca/Si ratio.
SiO2
0
100

10
90

20
80
Trass brick
30
dust
70 pozzolana
40
60

50
50
CC
experimental 60
40

AOD 70
Blast furnace slag
30
experimental
80 Blast furnace slag cement
20
High
90
Portland alumina
cement cement
10

100
0
CaO+MgO 0 10 20 30 40 50 60 70 80 90 100 Al2O3+Fe2O3

CaO MgO Fe2O3 FeO MnO SiO2 Al2O3 CaF2

AOD slag 45-60 5-12 <1 <1 <1 30-40 <5 4-6
LM slag 60-70 ~ 10 <1 <1 <1 15-25 <1 8-12
Belite-rich clinker 60-63 <1 3-6 - - 25-30 3-7 -

Chemistry looks close to OPC and belite-rich clinkers but mineralogy no…
If we modify the mineralogy without affecting any metallurgical steps?
 Drives for valorisation
There are application for some slag qualities and landfilling is also an option(!)

Maximising the added value does not guarantee any profits for the residue-producer!
Yet, may justify the investments and accelerate the break-even.
Can we be the catalyst for a new more “green”, thinking mentality?

Jean-Marie Delbecq, Steel Slags as cementitious materials, Seminário Internacional – Aplicação de Escória de Aciaria, Belo Horizonte, Nov. 22 , 2010,
 Our approach

Do not change Do not change

anything and work only anything and work
downstream: only downstream:
mechanical activation chemical activation
(or mech+chem
activation; or
Stainless
carbonation)
steel slag

Change the Change the cooling

chemistry and the and do not change
cooling: replica BFS the chemistry:
or stable slag granulation

Hot stage; this presentation

Background thinking

 Methodologies of slag stabilisation

- Avoid C2S phase formation completely
- Avoid β- to γ-C2S phase transformation by:
* Doping * High cooling rates
(effect on matrix and grain size a.o.)

25
Background thinking

Add SiO2/Al2O3/CaO rich source Add B, P rich source

during/after tapping AOD slag during/after tapping AOD slag
 Background thinking

Addition at molten slag, with possible co-injection of air/O2

K. Wada, K. Yamaguchi, M. Fukuda, H. Takahashi, S. Naito, Y. Murakami; Seitetu Kenkyu, 301, 59, 1980; M. Kühn et al. In 2nd
European slag conference, 2000, Germany, 123-135; J. Li, Q. Yu, J. Wei, T. Zhang, Cem. Concr. Res. 41, 324.
 Chapter 1

Increasing the cooling rate to

secure β-C2S

Kriskova, L., Y. Pontikes, L. Pandelaers, Ö. Cizer, P. Jones, K. Balen, and B. Blanpain, Effect of High Cooling
Rates on the Mineralogy and Hydraulic Properties of Stainless Steel Slags. Metallurgical and Materials
Transactions B, 44 (2013), 1173-1184.
 High cooling rate solidification

Melting in an induction-heating set-up using graphite crucibles; RT to

1700 °C ± 30 °C within 7 min, followed by an isothermal step for 7 min.
The molten slag was released from the crucible by rising up the graphite
pin blocking the orifice in the bottom of the crucible. The melt was
granulated on a rotating copper wheel.
 High cooling rate solidification: starting
materials

I II III AOD LM
CaO 52.4 54.7 56.7 55.6 51.5
SiO2 32.7 30.4 28.4 31.7 28.3
MgO 6.5 6.5 6.5 9.8 11.3
Al2O3 1.3 1.3 1.3 1.2 1.2
TiO2 1.1 1.1 1.1 n.d. n.d.
Cr2O3 0.0 0.0 0.0 0.3 3.9
CaF2 6.0 6.0 6.0 n.d. n.d.
Others 0.0 0.0 0.0 1.4 3.8

The major phases in AOD and LM slag are γ-dicalcium silicate, γ-(CaO)2.SiO2,
merwinite Ca3Mg(SiO4)2, bredigite Ca1.7Mg0.3SiO4 and periclase MgO.
The γ-C2S is 36 wt.% in LM slag and 15 wt.% in AOD; merwinite and bredigite is
higher in AOD.
High cooling rate solidification: solid slag

I II III
Mineral phase
G G G
β-C2S 7 21 68
γ-C2S - 20 19
Merwinite 42 9 -
Bredigite 44 41 <1
Fluorite 2 4 5
Cuspidine 5 - -
Periclase - 5 8
 High cooling rate solidification: slag + H2O
8 250
I I-cml
7 II II-cml I

Cumulative heat release, J/g

Rate of heat release, J/h.g

III III-cml 200

6 IV IV-cml
II
5 150

DTG
III
4

3 100 IV
2
50
1

0 0
0 15 30 45 60 75 90 105 120 135 200 400 600 800 1000
Hydration time, h Temperature, °C
 Chapter 2

Addition of an Al-rich source

aiming for stabilization

Iacobescu, R.I., A. Malfliet, L. Machiels, P.T. Jones, B. Blanpain, and Y. Pontikes, Stabilisation and
Microstructural Modification of Stainless Steel Converter Slag by Addition of an Alumina Rich By-Product.
Waste and Biomass Valorization, 5 (2014), 343-353.
 XRF of raw materials
AOD*
CaO SiO2 Al2O3 MgO Cr2O3 Other*** C/S C/S**
Oxide, wt%
55.70 33.02 1.27 7.60 0.79 1.5 1.69 ~1.60
*F- – not included, ** - CaF2 excluded, *** - MnO, TiO2, Fe2O3

Valoxy*
Al2O3 MgO SiO2 CaO Fe2O3 F- CuO TiO2 SO3 Cl- Na2O K2O MnO
Oxide, wt%
75.78 9.17 7.15 1.93 1.44 1.3 0.5 0.8 0.3 0.3 0.5 0.7 0.4
*Dry weight

Boron source – dehybor (Na2B4O7)*

Component, wt.% Na2O B2O3
47 53
*Tm = 742 °C
 XRD/QXRD of raw materials

Identified Valoxy,
minerals wt%
Spinel 12.2
Identified AOD, Corundum 8.6
minerals wt% Other (phases with
Ti, Na, K, Cu, Cl-, S 8.5
Merwenite 22.4
and Mn elements)
Cuspidine 21.2
Quartz 0.8
γ-C2S 20.3
Fluorite 0.4
Bredigite 18 Amorphous* or
Periclase 8.1 69.5
unidentified
β-C2S 7.5 Total 100
* It contains mainly Spinel and
Wollastonite 2.1
Fluorite 0.3 Corundum
Total 100

35
Determine amount of Valoxy to stabilize slag

Validation of the
calculated phases with
measured phases:
- Amount of high T
structure (1000°C)
- Amount of low T
structure (700°C)

Model of slag structure

In collaboration with InsPyro

Determine amount of Valoxy to stabilize slag

Required amount to stabilize slag

<5% C2S

In collaboration with InsPyro

Determine amount of Valoxy to stabilize slag

In collaboration with InsPyro

Temperature effects of additions and FeSi
1 tonne of slag can be heated
200°C with an addition and burning
of 6 kg of FeSi is required

In collaboration with InsPyro

 Macroscopical characterisation

15 wt.% 12.5 wt.% 10 wt.% 5 wt.%

STABLE STABLE* Un-STABLE Un-STABLE

45

* More brittle (observed during polishing) compared to 15 wt% Valoxy

XRD/QXRD characterisation
Identified
AOD+ AOD+ AOD+ AOD+
minerals,
15Valoxy 12.5Valoxy 10Valoxy 5Valoxy
wt.%
Merwinite 45.7 33.3 42.4 40.2
Bredigite 14.4 27.9 18 27
Gehlenite 14.1 8.2 6.7 1.9
Spinel 12.2 12.1 13 6.1
Cuspidine 4.4 2.8 5 3.3
Periclase 2.6 2.8 3.5 5.3
γ-C2S 1.9 3.3 3.9 4.4
Lime 0.3 0.1 0.2 0
Calcite 0.3 3.7 0 0
Fluorite 0.6 0.5 1.5 1.6
Wollastonite 0.7 1.3 2.5 5.1
β-C2S 2.8 46
4 3 5
STABLE UN-STABLE
Vickers micro-hardness tests

Vickers micro-hardness of samples with Valoxy additions

 EPMA/WDS elemental maps
15wt.% 12.5wt.%

Merwinite Merwinite
Gehlenite Bredigite Bredigite
Spinel Gehlenite
Spinel

MgO MgO

Ref. Al Mg Si Ref. Al Mg Si
Ca F Ti Fe Ca F Ti Fe
Cr Mn Cr Mn
Cuspidine Cuspidine
48

Embedded in resin, polished surface, carbon coated

Summary: slag stability by B2O3 and
Valoxy additions

Summary on the volumetric stability of slag as a function of equivalent

B2O3 and Valoxy addition
 Chapter 3

Addition of an Al,Si-rich source

aiming for a new binder

Pontikes, Y., L. Kriskova, Ö. Cizer, P.T. Jones, and B. Blanpain, On a new hydraulic binder from stainless
steel converter slag. Advances in Cement Research, 25 (2013), 21-31.
 Addition of an Al+Si source

Table 1. Chemical composition of GGBFS slags, of GGBFS used and of

the three slag mixtures studied, in wt.%. GGBFS range after Bhatty, et
al., 2004 and references therein.

CaO SiO2 MgO Al2O3 Fe2O3 other

GGBFS range 30-50 27-40 1-10 5-15 <1 -
GGBFS used 41.9 35.5 9.2 9.5 0.4 3.5
FA22 46.9 31.6 6.3 6.1 1.5 7.6
FA30 43.3 32.7 6.2 7.8 2.0 8.0
FA38 39.8 33.9 6.1 9.5 2.5 8.2
Addition of an Al+Si source

FA30 and FA38 fully resemble GGBFS

Addition of an Al+Si source
And so does hydration
and mechanical
properties of the blended
cements synthesized
 Chapter 4

Addition of CaO aiming for a

new binder

Kriskova, L., M. Eroli, R.I. Iacobescu, S. Onisei, F. Vecchiocattivi, and Y. Pontikes, Transformation of stainless
steel slag toward a reactive cementitious binder. Journal of the American Ceramic Society, (accepted for
publication)
Chapter 4

Table 1 Chemical composition of synthetic AOD slag, in wt.%

I II III
CaO 57.6 59.4 61.0
SiO2 28.8 27.0 25.44
MgO 3 3 3
Al2O3 4.5 4.5 4.5
CaF2 6 6 6
Basicity (C/S) 2 2.2 2.4
 Chapter 4

XRD analysis of samples I, II, III subjected to both, WQ and AC, in wt.%

Water quenching Air cooling

Mineral phase Chemical formula
I II III I II III
Alite (C3S) Ca3SiO5 3 17 39 3 21 39
Olivine (γ-C2S) Ca2SiO4 2 3 <1 <1 <1 2
Belite (β-C2S) Ca2SiO4 67 50 48 78 57 40
Merwinite Ca3MgSi2O8 - <1 - - <1 <1
Fluorite CaF2 <1 <1 <1 2 2 2
Cuspidine Ca4Si2F2O7 9 6 5 <1 15 9
Bredigite Ca7MgSi4O16 <1 <1 <1 14 2 <1
Periclase MgO 1 <1 <1 <1 2 2
C3A Ca3Al2O6 <1 <1 1 <1 - <1
Krotite CaAl2O4 3 3 3 2 <1 4
Other/amorphous 13 17 2 n/a n/a n/a
 Chapter 4

Microstructure of samples with various C/S ratio, after AC and WQ: (A) ACI, (B)
ACII, (C) ACIII, (D) WQI, (E)WQII and (F) WQIII
Chapter 4

Main element distribution according to WDS mapping in the WQ2 sample. Last image
present the distribution of the C2S (light green) and the C3S (dark) phases.
 Chapter 4

Microstructure of hydrated WQ2 sample Energy requirements to keep various

mixtures of slag and CaO at various
temperatures. The initial temperatures
of slag and CaO were 1923 K (1650°C)
and 298 K (25°C), respectively.

Heat release during hydration of water

Chapter 5+

So many more options!

Chapter 5+

On many occasions, slag modification is not an option. That

raises the question about what is feasible to do with the
existing slags.

A number of options have been investigated.

Mechanical activation, alkali activation and carbonation

are all possibilities that deliver promising results.

Another option is to separate the finer fraction of the slag

(after self-pulverization) and use it as a raw material for
clinker production.
 Conclusions

Slag engineering concerns the adjustment of slag chemistry and solidification path
in order to achieve a preferable microstructure for certain applications.
There are many possibilities to achieve the above, each path with its own
challenges and opportunities. In all cases, however, such actions are meaningful if
the slags can be indeed valorized.
To achieve the above, the concept of industrial symbiosis is one of the possibilities,
where metallurgical and building material industries co-exist and grow adjacent to
each other. Such a scheme could bring the vision of circular economy closer to
reality.
Data presented herein testify that there are many opportunities and that the
technical barriers are not the impossible to overcome
Happening now!
• 2nd Conference on BR… > Athens
• RECOVER project to deliver mobile units by 2019
• 6th Slag Valorisation Symposium > April (?) 2019
• H2020 Remov.Al granted with most EU bauxite refineries
• JSM applies for IF in the next semester, 3rd year and going
strong…
Outreach/educate A new solar system…

SREMat

website
Thank you!