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Article history:
Received 10 March 2016
Revised 6 September 2016
Accepted 23 September 2016
Keywords:
Red mud
Acid leaching
Metal recovery
Bauxite residue
Waste processing
a b s t r a c t
Red mud represents an environmental and economic liability for the alumina industry in the form of
wasted raw material. Although some leaching studies have been performed, there are deficiencies in
the current literature regarding the amounts of metals extracted relative to each other, and minimal
information regarding silicon contamination of extracts. There is also limited knowledge of extraction
efficiencies of different acids (particularly in the case of phosphoric acid) under the same experimental
conditions. This study focused on the leaching behaviour of the four most extractable elements present
within red mud (iron, titanium, aluminium and silicon). By varying the experimental conditions, acid
concentration, and type of acid, a comprehensive dataset of leaching trends was obtained. This allowed
for direct comparison of leaching efficiency for the four elements under the same conditions, which was
difficult previously due to the variation of experimental conditions and red mud composition between
studies. The patterns in recoveries were explained in terms of the reactivities of the mineral phases
within red mud and the interaction between the different acids and the reaction surfaces. Out of the four
acids studied (nitric, hydrochloric, sulfuric, and phosphoric) phosphoric and hydrochloric acids produced
some of the best recoveries for iron (7678%) and titanium (2324%), and phosphoric acid also produced
the highest recoveries for silicon (49%) and aluminium (50%). The differences observed between the acid
types and reaction conditions revealed potential for development of element selective extraction methods. Additionally, explaining leaching behaviour in terms of the mineral phases present allowed easier
prediction of expected leaching trends for these four elements, which made this study applicable to
red muds with a wide variety of compositions.
2016 Elsevier Ltd. All rights reserved.
1. Introduction
Metals present in industrial wastes represent significant losses
in raw material and are a significant environmental liability (Power
et al., 2011). Thus, development of practices to recover and reuse
metals from wastes or to treat industrial effluents is potentially
of great value. The alumina industry produces one of the largest
industrial waste streams in the form of red mud; for every tonne
of alumina extracted, between 1 and 1.5 tons of red mud is generated (Liu et al., 2009). Global red mud storage deposits are estimated at around 3 billion tons with an additional 120 million
tons produced per annum (Marcel Ct and Wilson, 2012). Due
to the highly caustic nature of the red mud slurry and the high proportion of heavy metals within it, disposal has been a major issue
(Power et al., 2011). Before 1970, disposal of red mud was achieved
Corresponding author.
E-mail address: graeme.millar@qut.edu.au (G.J. Millar).
http://dx.doi.org/10.1016/j.mineng.2016.09.012
0892-6875/ 2016 Elsevier Ltd. All rights reserved.
that unless side by side extractions are carried out, the leaching
patterns for multiple elements relative to each other cannot be
determined. To confirm this hypothesis it was necessary to assess
the effects that variation of experimental parameters such as reaction time, temperature and solid:solution ratio had on the final
amount of each element leached from red mud, what effect acid
concentration and type had on the extraction of these four elements, as well as if any elements were favoured over others under
certain conditions.
This paper has addressed these questions through a series of
leaching experiments, and through analysis of these results some
leaching trends have been established for the four elements studied. The results represent valuable insight of leaching trends for
four of the most extractable elements found in red mud, particularly in the case of silicon, which has been previously overlooked.
The importance of knowing the composition of red mud extracts
should not be underestimated, particularly in the context of possible tailored extraction methods or re-use of the extracts for metal
scavenging or recovery.
2. Material and methods
2.1. Materials
Red mud used in this study was obtained from an Australian
alumina refinery in the form of a slurry. The slurry was subsequently filtered to isolate the solid red mud, washed with deionised water until the filtrate was a neutral pH, dried at 80 C and
finally crushed. The crushed red mud was then sieved to obtain
particles smaller than 212 lm. AR grade hydrochloric (32 wt/v%),
nitric (70 wt/v%), sulfuric (98 wt/v%) and phosphoric (80 wt/v%)
acids were used, and required concentrations for testing purposes
were made from these concentrated stock solutions along with
MilliQ ultrapure water through serial dilutions.
2.2. Experimental procedure
Acid leaching of red mud was performed using hydrochloric,
nitric, sulfuric and phosphoric acids. The general procedure for
these experiments involved: adding the desired amount of red
mud and acid to 50 mL falcon tubes; allowing the digestion to proceed under specific conditions as described below; and then collecting the solid and liquid phases upon completion of each test.
Separation of the solids from the liquid samples was achieved via
centrifugation (3000 rpm for 10 min, Eppendorf 5702 centrifuge).
All liquid samples were syringe filtered prior to storage and solid
samples were washed with MilliQ water, dried in an oven at
80 C and crushed before storage. ORP and pH measurements were
taken of the liquid extracts using a Cole-Parmer Ag/AgCl electrode
and a TPS pH probe. All testing series explored in this study were
conducted at four different acid concentrations (0.01, 0.1, 1.0 and
5.0 M) to compare the leaching and metal recovery profiles. Particulars for each experimental test are as follows:
Temperature leaching trials: A solid:solution ratio of 0.005 and a
leaching time of 24 h were used for all tests. The digestions were
performed in a pre-heated bead bath using pre-heated acids with
manual agitation. Temperatures tested were 25, 40, 55, 70 and
80 C.
Time leaching trials: Reactions in this series were performed for
1, 4, 24, 48 and 168 h with a solid:solution ratio of 0.005 at room
temperature (approximately 25 C). A rotary stirrer was used to
ensure constant, gentle agitation.
Solid:solution ratio leaching trials: Reactions in this series were
performed at room temperature on a rotary stirrer to ensure constant, gentle agitation for a period of 24 h. The solid:solution ratios
that were tested were 0.00125, 0.0025, 0.005, 0.0125 and 0.025.
10
Fig. 1. X-ray diffraction pattern for red mud with corresponding reference patterns.
11
Chemical formula
Element
Quartz
Anatase
Rutile
Hematite
Calcite
Boehmite
Gibbsite
Sodalite
Kaolinite
Unidentified
SiO2
TiO2
TiO2
Fe2O3
CaCO3
c-AlOOH
Al(OH)3
Na8(Al6Si6O24)Cl2
Al2Si2O5(OH)4
1.95
3.16
1.96
26.85
0.69
8.00
2.51
4.63
2.02
48.23
0.370
0.067
0.022
0.456
0.038
0.133
0.065
0.218
0.161
0.634
Al
C
Ca
Cl
Fe
H
Na
O
Si
Ti
Unidentified
5.73
0.08
0.28
0.34
18.78
0.10
0.88
20.36
2.16
3.07
48.23
0.027
0.004
0.013
0.014
0.285
0.002
0.037
0.205
0.137
0.041
0.565
Fig. 2. Variations in Al recovery under different experimental conditions; the acids used were hydrochloric, nitric, sulfuric, and phosphoric.
12
Fig. 3. Variations in Si recovery under different experimental conditions; the acids used were hydrochloric, nitric, sulfuric, and phosphoric.
Fig. 4. Variations in Fe recovery under different experimental conditions; the acids used were hydrochloric, nitric, sulfuric, and phosphoric.
13
Fig. 5. Variations in Ti recovery under different experimental conditions; the acids used were hydrochloric, nitric, sulfuric, and phosphoric.
to expect that bauxite residues with a higher proportion of aluminosilicate materials will leach more aluminium under conditions
similar to those used in this study than those with a higher proportion of boehmite or gibbsite. Incomplete characterisation of different red muds and varied experimental conditions that are used
across studies different studies lead to problems when attempting
to directly compare the recoveries of metals from different leaching studies. This highlights the value of a comprehensive study that
allows direct comparison between different elements for a larger
range of experimental variables and acid types.
The type of acid used for the extraction had some effect on the
recovery of Al. Phosphoric acid performed better than other acids
at higher acid concentrations. When the concentration of acid
was 0.1 M and below, recoveries for the four acids were relatively
similar, which may be due to the initial leaching of only the most
easily digestible Al phases at lower acid concentrations (Liang
et al., 2014). The highest recoveries were for phosphoric acid followed by sulfuric, then hydrochloric and nitric acids which exhibited similar recovery patterns. The similar recovery profiles for
nitric and hydrochloric acids across the four variables tested may
indicate that dissolution of Al in these systems is driven by the
interaction of the Al-bearing materials with the protons released
by these acids. This hypothesis is also supported by the greater
recoveries of Al that were obtained using higher concentrations
of these acids, and also those that were obtained through use of
sulfuric acid. Being a diprotic acid, sulfuric acid donated more protons to the solution at the same concentration relative to both
nitric and hydrochloric acids. Phosphoric acid however would not
be fully dissociated under the conditions used in this study, since
the pKa value for the first dissociation event of phosphoric acid
is 2.14 (Stone et al., 2016). Despite the incomplete dissociation of
the phosphoric acid, the pH measurements of the leaching experiments were still low enough for Al leaching to occur from aluminosilicate phases such as sodalite and kaolinite (Yang and Steefel,
14
2H2 O
for all acids tested than those at 40 C. Despite this, the large fluctuations in the recoveries observed at different temperatures
means that temperature may not be a reliable measure for controlling Si recovery from red mud. The absence of a clear trend in Si
recovery with increasing temperature as was seen for Al in Fig. 2C
suggested that the observed recoveries were due to the stabilities
of Si complexes in solution, rather than a fluctuation in aluminosilicate dissolution. As stated above, silica solubility is highly dependent on other species that are also present in solution, and so the
observed fluctuation may be a result of slightly unfavourable solution conditions at different temperatures. For example, the concentrations of extracted elements varied quite widely across the
temperature tests (see Supporting information), although specific
conclusions about the exact complexes that were forming in these
systems is difficult owing to their complexity. Study into the specific elemental speciation and complex formation in these systems is
certainly a worthwhile endeavour, but is deemed to be outside the
scope of this work, which was primarily to offer a direct comparison in leaching trends and to study the leaching behaviour of understudied elements such as silicon.
The trends for Si extraction with changes in time and with RM:
acid ratio (Fig. 3D and B, respectively) closely resemble those of
aluminium, which supports the notion that these elements are leached predominantly from aluminosilicate materials in the red
mud. The slight increase in Si recovery at the 24 h mark before a
lower plateau is attributed to the stability of the soluble Si species
in the reactions over time. The plateau in Si recovery likely indicates that equilibrium has been reached in the system, and it
appeared that this equilibrium state corresponded with a lower
recovery of Si. Therefore, if Si is an element of interest for extraction from red mud, shorter reaction times may be of benefit.
The leaching trends observed with respect to silicon show that
Si is leached exclusively from aluminosilicate phases, while Sicontaining minerals such as quartz remain in the red mud. The
instability of Si in more acidic extracts may provide a pathway
for either eliminating or recovering silicon from extracts of red
mud, and could be exploited to design targeted leaching or recovery methods.
3.2.3. Iron
The leaching behaviour of iron from red mud differed substantially from those of Al and Si. Rather than a sharp initial increase in
recovery with rising acid concentration or reaction time, Fe recovery was initially low and increased steadily with longer reaction
times, temperatures and acid concentrations (Fig. 4). These clear
differences to Si and Al behaviour were attributed in part to the relative reactivities of aluminosilicates and iron containing phases
within the red mud. Hematite accounted for most of the iron present in the red mud sample, which agreed with the observed
trends in Fe recovery. Hematite and most other iron oxides require
pH conditions of less than 1 for complete dissolution at temperatures as high as 70 C (Cornell and Schwertmann, 2006), so it
was expected to record lower levels of recovery for less concentrated acids and lower temperatures.
Increased acid concentration and time promoted the greatest
improvement in Fe recovery; however, the order of most efficient
acids differed between these two variables. For extractions using
5 M acids the order of the most effective acid was phosphoric,
hydrochloric, sulfuric and nitric, while for the 7 day extractions,
the order was sulfuric, phosphoric, hydrochloric and nitric. These
differences suggested that the dissolution of hematite from red
mud was influenced by the availability of hydrogen ions, the types
of counter-ions that were present in solution, and the stability of
the released iron complexes in solution. The dependence of iron
extraction from red on reaction with protons can be seen both in
the enhanced recoveries at higher acid concentrations but also in
15
16
was not observed in the HCl digests, which were also in the ferrous
region. It is possible that the reaction conditions for hydrochloric
acid were too mild to efficiently dissolve the Fe-containing phases
(Cornell and Schwertmann, 2006), and that the complexation behaviour of chloride was not sufficient to overcome these thermodynamic barriers.
The conditions that favoured Fe dissolution in this study have
the disadvantage of also favouring the dissolution of other elements; which means that selective extraction of iron from red
mud may not be feasible without pre-treatment of the red mud
or treatment of the extract. This could involve enrichment of iron
containing phases in the red mud by a mild digestion, followed
by an extraction step to recover the iron from the red mud in a soluble and reactive from. The pre-treatment step also has the advantage of removing some species which may interfere with
downstream recovery of iron, such as aluminium or silicon
(Cornell et al., 1987). The leaching results also suggest that the
solution chemistry and stability of the leached Fe is a complex
and multi-faceted phenomenon, which would benefit from indepth study. Further study of the leaching behaviour may also help
to design better leaching methods that are more selective for iron.
3.2.4. Titanium
Leaching patterns of titanium from red mud may be found in
Fig. 5. Of the four acids studied, sulfuric acid was found to be the
most effective when leaching Ti, while phosphoric acid gave consistently lower recoveries with the exception of the 5 M digestion
(Fig. 5). These results were in contrast with those observed for the
other elements, for which phosphoric acid had consistently higher
metal recoveries.
Despite improved recoveries for Ti when sulfuric acid was used,
titanium recovery did not exceed 24% for any of the experiments.
XRD revealed the presence of anatase (3.16%) and rutile (1.96%),
both with the formula TiO2. The XRD analysis brought the total
TiO2 content to 5.12%, which differed from the value given by
XRF (6.88%) by 1.76%. This was a difference of 25.6%, which corresponded with the recoveries of Ti; suggesting that the recovery of
Ti was from the dissolution of amorphous Ti-containing phases.
XRD data collected after leaching showed that amorphous Ti was
leached preferentially over rutile and anatase, which were identified in the leached residues.
Both rutile and anatase tend to be more stable than other Fe and
Al containing minerals within red mud, with some studies resorting to the use of hydrofluoric acid (HF) to fully solubilise the anatase phase (Hanaor and Sorrell, 2011), although rutile remained
unreacted even after HF treatment. It has been previously reported
that amorphous metal oxides have better solubilities compared to
their crystalline counterparts (Schwertmann, 1991), so it is
expected that they would dissolve prior to any crystalline phases.
However, dissolution from predominantly amorphous phases presents a problem in terms of understanding the leaching mechanisms that are occurring, due to the nature of these amorphous
phases being largely unknown. It was likely that there are a number of amorphous phases that contributed to the overall amount of
leached Ti. These could include ilmenite or amorphous titania, both
of which have been observed in red muds before.
Unfortunately, due to the uncertainty regarding the nature of
amorphous phases that were responsible for the release of Ti for
the red mud sample, discussion of the leaching results in the context of reaction mechanisms is not feasible. Therefore, the general
trends that were observed in the data and the stability of the liberated Ti species will form the basis for the interpretation of the
leaching data.
Although the identities of the phases that contributed to Ti
release from red mud were unclear, it can be seen that the dissolution of these phases was promoted by increasing the concentration
17
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