Journal Pre-proofs

An integrated process for iron recovery and binder production from bauxite
residue (red mud)

Tobias Hertel, Amy Van den Bulck, Bart Blanpain, Yiannis Pontikes

PII: S0167-577X(19)31905-6
DOI: https://doi.org/10.1016/j.matlet.2019.127273
Reference: MLBLUE 127273

To appear in: Materials Letters

Received Date: 18 December 2019

Accepted Date: 27 December 2019

Please cite this article as: T. Hertel, A. Van den Bulck, B. Blanpain, Y. Pontikes, An integrated process for iron
recovery and binder production from bauxite residue (red mud), Materials Letters (2019), doi: https://doi.org/
10.1016/j.matlet.2019.127273

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An integrated process for iron recovery and

binder production from bauxite residue (red mud)

Tobias Hertel*, Amy Van den Bulck, Bart Blanpain, Yiannis Pontikes

KU Leuven, Department of Materials Engineering, Kasteelpark Arenberg 44, 3001 Leuven,

Belgium

*Corresponding author: Tobias.Hertel@kuleuven.be

Abstract

Bauxite residue, the waste product from the Bayer process, typically consists of approximately

40 wt% Fe2O3, which makes it a potential resource for Fe. This study presents an integrated

process in which Fe is extracted in a first stage, followed by valorisation of the remaining

residue towards alkali-activated binders. About 75 wt% of residue was melted with the addition

of C, B2O3 and SiO2 at 1250 °C. During this treatment, and after water quenching, a significant

amount of Fe was formed as well as an almost fully vitrified slag. The slag was used to produce

inorganic polymers with satisfactory compressive strengths. However, tincalconite, a boron salt

eventually precipitated, demonstrating limited incorporation of B in the binder.

Keywords

Boron oxide; bauxite residue; red mud; iron recovery; inorganic polymer; geopolymer

1. Introduction

The global move toward more sustainable management of industrial residues creates an

opportunity for bauxite residue (BR) generated during alumina production to be utilised in

various processes. As the residue’s chemistry is dominated by Fe2O3, recovery of Fe has been

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the focus of much research programmes and is reviewed elsewhere [1]. In most studies,

energy-intensive reductive smelting, usually at a temperature above 1500 °C, was applied in

combination with suitable fluxes, such as silica and lime. This high smelting temperature and

fluxing leads to a low viscosity melt and satisfactory metal-slag separation. The remaining

material can be used for other processes, e.g. alkali-activated inorganic polymers (IP) [2].

Roasting at lower temperatures is an alternative Fe-recovery method [1]; however, the

remaining fraction is relatively unreactive for use as binder precursor. Kavas et al. [3]

demonstrated the vitrification potential of using boron-containing wastes as fluxes for the

production of fired BR-derived bricks. The firing temperature was decreased significantly and

mechanical properties increased with higher boron content. Boron is known to be a powerful

glass former and an effective flux in glass making [4]. Previous works demonstrate the

incorporation of B into alkali-activated binders, e.g. made from borosilicate glass [5], silica fume-

borax-NaOH IPs [6], or IPs made from fly ash and borax additions to the Na-silicate activator

[7]. Trigonal boron was shown to transform into fourfold-coordinated B, and so incorporated in

the structure replacing Al and/or Si, forming a boroaluminosilicate network.

Here, we use B2O3 with C and SiO2 as fluxes for BR in an integrated process at a treatment

temperature of 1250 °C. The aim is the recovery of Fe and the production of IPs from the

remaining vitrified slag. We further assess the role of B in the binder.

2. Experimental Methods

BR (Rusal Aughinish) was used as raw material that consisted of 43.4 wt% Fe2O3, 19.5 wt%

Al2O3, 11.8 wt% SiO2, 5.2 wt% CaO, 9.0 wt% TiO2 and 8.8 wt% Na2O. The loss-on-ignition

(1000 °C) was 10 wt%.

The composition and loss-on-ignition were used as input for thermodynamic calculations

(FactSage 7.2, databases: FactPS-FToxid-FTstel) to assess the influence of C and B2O3

additions to BR at 1250 °C. The aim was to identify the optimum additions for a maximal Fe-

recovery and iron-depleted melt formation, and to use over 70 wt% BR. A constant silica

addition of 13.2 wt% was used, as previous work demonstrates its suitability as a flux [8].

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The slag was produced as described elsewhere [9], but at a temperature of 1250 °C. The

resulting material was crushed by a hammer, sieved and manually separated. The material was

then ground to ~10 mm, sieved and separated magnetically. The different fractions were

weighed to determine the recovery rate of iron. The non-magnetic fraction (i.e. slag) was milled

to a surface area of 5000 cm2/g (EN 196-6). The crystallinity of the slag was investigated using

quantitative X-ray diffraction and the bond structure of the material was investigated with

Fourier-transformed infrared spectroscopy (FTIR) as described elsewhere [9].

The chemical composition of slag and metal fragments was determined using an electron probe

microanalyser (EPMA, JEOL-JXA-8530F) with wavelength dispersive X-ray spectroscopy

(Voltage 15 kV, current 50 nA, defocused beam) and suitable standards.

IP pastes were prepared by mixing Na-silicate solution (molar ratio SiO2/Na2O=2.0, H2O

content=65 wt%) to a liquid-to-solid ratio of 0.5. The samples were cured at 20±2 °C for 28 d.

The hardened pastes were used for EPMA and FTIR analyses and compared to the slag. The

hydrolytic stability of the pastes was assessed by immersing 1 g of ground IP for 24 h in 100 ml

of water. After filtration, the leachate was analysed using an ICP-OES (Varian 720 ES). Solids

were investigated using XRD and FTIR.

Mortar samples were prepared on the basis of the EN197-1. The Na-silicate solution was used

with a liquid-to-slag ratio of 0.56 in order to achieve workability. The mortars were wrapped with

film and cured at 20±2 °C until the day of strength testing on 4x4x16 cm³ prisms.

3. Results and Discussion

Thermodynamic calculations at 1250 °C showed that increasing additions of B2O3 and C to BR

(with constant addition of 13.4 wt% silica) lead to a considerable increase in iron-depleted melt

and the formation of metallic Fe(s) (Figure 1). Based on these results, BR was mixed with

additions of 13.2 wt% SiO2, 12.1 wt% B2O3 and 8.7 wt% C (all based on 100 wt% BR).

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 Figure 1: Thermodynamic calculations; BR+SiO2+additions, modelled amount of a) melt, b)

Fe(s). The mix composition is marked with a cross.

Experimentally, a mass fraction of 77.7 wt% slag and 22.3 wt% Fe(s) was obtained. This result

was close to the modelled proportions (Figure 1). A recovery of approximately 92 wt% of Fe was

achieved. The slag was almost fully vitrified with 1 wt% anorthite, 1 wt% spinel and <1 wt% Fe

(Figure S1). The composition of the amorphous phase, determined by EMPA-WDX, was 27.2

wt% SiO2, 24.8 wt% Al2O3, 10.1 wt% TiO2, 7.2 wt% Na2O, 17.7 wt% B2O3, 6.9 wt% CaO and 6.1

wt% FeO. FTIR analysis indicated the presence of BO3 units (1200-1500 cm-1) as well as BO4

units (850-1200 cm-1) [10], the latter overlapping with the signal of Si-O bonds [11]. No boron

was detected in the metallic fraction that was dominated by Fe (95.7-100 wt%), with some Cr

(≤4.3 wt%) and Ni (≤0.4 wt%), a composition that might be interesting for steelmaking.

The compressive strength of the mortars was satisfactory, with 2 d strength of 35 MPa and 28 d

strength of about 55 MPa (Figure 2).

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 Figure 2: Strengths of mortars.

FTIR results of the IP pastes showed an increase in the intensity of the band at 850-1200 cm-1

compared to the slag, and a reduction of the bands located between 1200-1500 cm-1, which can

be interpreted as a partial transformation of BO3 towards BO4 units in the IP and thus

incorporation in the binder (Figure S2). However, a definitive interpretation is difficult as addition

of the silicate activator produces a simultaneous increase in the Si-O band and overlap in this

area.

About 95 mg/L of B was detected from the paste specimen in the leach solutions after the

hydrolytic stability test. This result was also in line with EPMA-WDX analyses conducted on the

IPs, in which lower B contents were determined in the binder compared to the slag (Figure 3).

The samples thus released boron and sodium, but did not disintegrate.

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Figure 3: EPMA-WDX maps of the IP sample. The intensity of B2O3 is given as the background

was not considered in mapping analysis, which is important for quantification, particularly for

boron due to peak shifting compared to the standard.

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During the leaching test, white precipitates were observed in the leachate. After drying, XRD

analysis revealed the formation of tincalconite (Na2(B4O7)·5H2O) (Figure S3), the dehydration

product of borax (Na2(B4O5)(OH)4·8H2O), most likely formed from released Na and tetraborate

ions.

In contrast to previous works [5,6], the results demonstrated that boron was not, or at least not

fully, incorporated in the IP. Williams et al. [6] also detected the formation of hydrated borax as

a reaction product that might dissolve in contact with water and leach out. Additional research

on the mix design of the IP is needed: different dosage and type of activator may lead to

incorporation of B in the IP.

Apart from IP, other options for use of the slag, and an integrated near-zero-waste process,

exist. For instance, as the content of B and other fluxing elements is relatively high, the slag

could be used as flux in metallurgical processes, including the one herein. The slag is also a

potential raw material for glass ceramics. The migration of water soluble salts (efflorescence) to

the surface upon drying will produce a glazed outer surface upon firing, a process known as

self-glazing or salt glazing [12]. Finally, the IPs produced herein could also lead to glazed glass-

ceramics upon firing, in a process resembling the one described elsewhere [13].

4. Conclusion

This study presented an integrated process in which Fe recovery was followed by valorisation of

the remaining residue towards an inorganic polymer. A blend consisting of 75 wt% of the

residue combined with C, B2O3 and SiO2 was melted 1250 °C and then water-quenched.

Approximately 22 wt% of Fe, i.e. a recovery rate of 92 % Fe, and 78 wt% of almost fully vitrified

slag were obtained. Inorganic polymers with 28 d strengths exceeding 50 MPa were reached.

However, boron was not fully incorporated in the binder.

Acknowledgments

The research leading to these results has received funding from the European Community’s

Horizon 2020 Programme ([H2020/2014-2019]) under Grant Agreement no. 636876 (MSCA-

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ETN REDMUD). This publication reflects only the authors' views, exempting the Community

from any liability. Project website: http://www.etn.redmud.org.

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An integrated process for iron recovery and

binder production from bauxite residue (red mud)

10
Tobias Hertel*, Amy Van den Bulck, Bart Blanpain, Yiannis Pontikes

KU Leuven, Department of Materials Engineering, Kasteelpark Arenberg 44, 3001 Leuven,

Belgium

*Corresponding author: Tobias.Hertel@kuleuven.be

Highlights

- Integrated valorisation process for bauxite residue using boron oxide as flux

- Fe extraction in a first stage

- Valorisation of the remaining slag towards alkali-activated binders

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