minerals

Article
Optimizing Conditions for Scandium Extraction from
Bauxite Residue Using Taguchi Methodology
Theopisti Lymperopoulou *, Paraskevas Georgiou * , Lamprini-Areti Tsakanika,
Konstantinos Hatzilyberis and Maria Ochsenkuehn-Petropoulou
School of Chemical Engineering (Chem Eng.), National Technical University of Athens (NTUA),
9 Iroon Polytechniou St., 15780 Athens, Greece; [email protected] (L.-A.T.); [email protected] (K.H.);
[email protected] (M.O.-P.)
* Correspondence: [email protected] (T.L.); [email protected] (P.G.);
Tel.: +30-2107723073 or +30-697400304 (T.L.); +30-6947301800 (P.G.)




Received: 14 March 2019; Accepted: 15 April 2019; Published: 17 April 2019


Abstract: Bauxite residue is the voluminous by-product of alumina production after Bayer process.
Its high alkalinity causes disposal problems and harmful environmental impacts. However, the residue
contains significant amounts of valuable elements, such as rare earth elements, including scandium.
Greek bauxite residue contains a high amount of scandium close to its main resources. Taking into
account scandium’s limited availability coupled with its high demand in modern technology,
bauxite residue could be considered as a potential resource for scandium recovery. In this study,
the optimization of scandium extraction from bauxite residue with sulfuric acid is investigated
using Taguchi methodology. Based on previous studies, acid molarity, leaching time, solid/liquid
ratio, and reaction temperature were selected as control parameters for the selective Sc recovery.
Method optimization targeted the highest concentration of scandium combined with the lowest
concentration of iron without taking into account application constraints. Maximization of scandium
concentration can be achieved only by reduced selectivity. The predicted values resulted from the
Taguchi methodology were affirmed by a confirmation experiment conducted at optimal conditions.
Regression analysis provided the respective equations to be applied on several conditions, depending
on different applications.

Keywords: Taguchi method; experimental design; optimization; scandium; extraction; sulfuric acid

1. Introduction
Bauxite residue (BR) or red mud (RM) is the by-product generated in alumina production after
Bayer process. About 1–1.5 tons of BR are generated per ton of alumina produced [1], raising its
annual output up to almost 120 million tons and its accumulation up to 2.7 billion tons globally [2].
Its disposal is problematic, requiring large land areas and overloading the alumina’s production cost [3].
During the years, many investigations have been performed aiming for a low cost and environmental
friendly treatment and utilization of BR in numerous uses [4–6], such as an agent in building and
constructing materials [7–10], an agent in the ceramic and glass industry [11–13], as an adsorbent for
pollutant removal from water and wastewater or in pigments [14–19], as a coagulant for waste and
water treatment [20–22], an absorbent of waste acidic gases [23–25], an agent for neutralizing acidic
waste and raw materials of low cost for the recovery of valuable elements [26–38], in catalysts [39,40],
and as an agent for soil remediation [41–44].
All these applications could be potential and beneficial routes for BR consumption and its
introduction in the economic cycle. BR is a complex material enriched in numerous metals.
Depending on bauxite origin and Bayer process conditions, it mainly consists of Fe, Al, Ca, Na,

Minerals 2019, 9, 236; doi:10.3390/min9040236 www.mdpi.com/journal/minerals

Minerals 2019, 9, 236 2 of 13

Si, Ti oxides, and salts, and significant amounts of minor and trace elements, such as V, Cr, Zn, Ga,
Nb, Zr, and Ta as well as rare earths (REEs) (Sc, Y, lanthanides) [45–48]. It was found that Greek
BR—produced by Mytilineos S.A. (formerly Aluminum of Greece, the largest Greek alumina and
aluminum producer)—contains ~1kg REEs/t of dry BR with a Sc content of about 120g/t of dry BR
(0.02% Sc2 O3 ), close to Sc main resources [45–48]. Scandium is the most valuable of rare earth elements
in BR [47] and is classified by the European Commission as a Critical Raw Material (CRM) due to its
high economic importance, resulting from the growing market demand in advanced technologies in
combination with its low availability [49,50].
Scandium extraction from its main minerals is difficult due to its rarity, as well as its
low concentration in natural deposits (1–800 mg/kg), in addition to the presence of radioactive
elements [51–53]. Different methods have been investigated for the recovery of REEs and Sc from
BR, such as hydrometallurgical treatment, ion liquid leaching, bioleaching, or pyrometallurgical
pretreatment of the residue before the leaching process. Pyrometallurgy, although energy consuming,
may result in an overall cost reduction due to major removal of main elements, thus having an
important impact on the cost of the subsequent Sc purification [54]. Furthermore, leaching with
ionic liquids falls short due to their cost and lower Sc recoveries, while bioleaching is not thoroughly
investigated [55–57]. Hydrometallurgy technique is performed for Sc and REE recovery, since it is
usually of low cost at ambient conditions [26]. Several solutions (acidic, alkaline) have been tested as
solvents. Mineral acids were found to be more suitable, resulting in higher Sc recovery and favoring
following processes, e.g., ion exchange and solvent extraction. Method yield and selectivity highly
depend on the type of mineral acid used, as well as the leaching parameters [28,58,59].
A large number of experiments are needed in order to study the effect of each parameter in
addition to all possible interactions between them on the response variable. The Taguchi experimental
design can be employed instead. The Taguchi Method uses orthogonal arrays to conduct a set of a
limited number of experiments. It involves the description of the control factors in order to obtain the
optimum results of the process. The relative importance of each parameter is determined with ANOVA
statistical method. The results of the experiments are evaluated in order to predict the optimum
outcome [60–62].
In this study, the optimization of the scandium selective leaching process from BR with sulfuric
acid is investigated using Taguchi methodology. Sulfuric acid was preferred for its mild environmental
impact compared to other mineral acids of the same molarity. Method performance was assessed by Sc
concentration in the leachate solution. Method selectivity was estimated in respect to iron content, since
it is the major element of BR, and therefore its removal becomes problematic in subsequent processes of
scandium isolation. Taguchi experimental design was used in order to evaluate the contribution of each
parameter and define the optimal conditions for maximization of concentration. Application limitations,
such as scale–up of the process and feed requirements of a subsequent ion exchange procedure for
scandium purification, were not taken into account in this study. The scope of this study was to
evaluate the interaction of different parameters. Previous studies assess the effect of each parameter,
either on specific leaching condition or by taking into account the combined effect of the maximum of
two parameters. The key point of the present work is to estimate the synergy effect of all leaching
variables, which has not been previously presented. Acid molarity, leaching time, solid-to-liquid ratio,
and reaction temperature were indicated as control parameters for Sc concentration in the leachate
solution and its selective recovery in respect to iron [63]. Signal-to-noise (S/N) ratio and analysis of
variance (ANOVA) statistical approach was employed for the calculation of percentage contribution
of each parameter and optimization of leaching conditions. Equations for Sc and iron concentration
were produced by applying regression analysis. A confirmation experiment was conducted under the
optimal conditions and the results were in good agreement with the predicated values.
Minerals 2019, 9, 236 3 of 13

2. Materials and Methods

2.1. Sample Collection and Characterization

Bauxite residue used in this study was obtained from Mytilineos S.A., formerly Aluminum of
Greece, in the form of ferroalumina. Ferroalumina is a cake with 26% humidity produced from a BR
slurry, which is washed and filtered under pressure. The BR sample was very fine, having a particle
size of D80 = 25 µm. The initial pH of the BR slurry was 11.3 (5 g of BR stirred with 100 mL of deionized
water for 30 min). The sample used in all tests was dried at 105 ◦ C and crushed prior to leaching.
As mentioned elsewhere [63], the chemical composition of BR is Fe2 O3 (43.5%), Al2 O3 (19%), SiO2
(7.3%), TiO2 (5.6%), Na2 O (3%), and CaO (9.4%). Mineralogical analysis of BR revealed phases of
iron (hematite, goethite), alumina (gibbsite, diaspore, aluminium oxide) titania (rutile), silica (quartz),
calcium (calcite), and aluminosilicates (kaolinite, anorthite, cancrinite, montmorilonite). Scandium
rises up to an average of 100 mg/kg and is almost constant over 20 years.

2.2. Preliminary Tests

Several different acids had been tested previously [45,46,64]. It was proven that the type of acid
used in the leaching procedure was critical for the recovery of all metals studied. Extraction of Sc is
mainly influenced by the protons produced by the acids. The acid counter ion severely influences iron,
with HCl resulting in the highest recovery [45]. Chloride ions compared to sulfate more easily replace
the hydroxyl groups of hematite, and iron is readily released in the solution [58]. Thorough studying
of the processes and mechanisms taking place is beyond the scope of this study.
The “one-factor-at-a-time” approach was used in order to evaluate the effect of several parameters,
such as solid-to-liquid ratio (S/L), acid concentration (M), time, temperature, final pH, and type of
agitation [63].
The results obtained indicated four parameters being the most important control factors for
Sc recovery and concentration: Acid (H2 SO4 ) molarity, Temperature, Solid-to-Liquid ratio (S/L),
and Leaching time. In order to study the effect of these parameters on the proposed process,
and identify their optimized values, a matrix experiment is set up by appropriately changing their
values over a specified range [65,66]. According to the findings of the previous phase and following a
symmetric as well as a rational resources’ use approach, each parameter is chosen to vary among three
values: minimum, middle, and maximum, as shown in Table 1.

Table 1. Parameters and their values at each level to be set and studied in experiments.

Level
Factor Parameter Unit
1 (Minimum) 2 (Middle) 3 (Maximum)
A H2 SO4 molarity M 2 4 6
B Temperature ◦C 25 55 85
C Solid-to-Liquid ratio % 10 20 30
D Leaching time h 1 4 7

2.3. Experimental Procedure

The experimental procedure as well as instrumentation and reagents used are reported in details
elsewhere [63]. All experiments investigated in this study were conducted using sulfuric acid at three
different acid concentrations (2, 4, and 6 M), as designed by Taguchi’s experimental methodology
(Table 1). The different solid-to-liquid ratios were obtained by mixing a specific amount of BR with
200 mL of sulfuric acid of a certain molarity.
The solution was magnetically stirred at 600 rpm in all cases on a magnetic stirring plate. Agitation
rate was not involved in the parameters tested, since it is of lesser importance [63].
The leaching process was allowed to proceed for the different time intervals (1, 4, and 7 h).
After each experimental run, the pH of the slurry was measured. Temperature leaching tests were
Minerals 2019, 9, 236 4 of 13

performed under reflux in a pre-heated water bath using pre-heated acids with magnetic agitation.
Temperatures tested are also listed in Table 1.
Separation of liquid from solid residue was performed after completion of each test,
via centrifugation (3000 rpm for 10 min, Eppendorf 5702 centrifuge). All liquid samples were filtered
under vacuum with 0.45 µm cellulose nitrate membranes supplied by Whatman plc (GE Healthcare
Life Sciences, Little Chalfont, UK) prior to storage and analysis.
All solutions were analyzed with an Optima 7000 DV, Perkin Elmer Inductively Coupled Plasma
Optical Emission Spectrometer (ICP-OES) instrument. External calibration method was applied using
multi-element stock solutions (High Purity Standards, Charleston, USA). The wavelengths used (nm)
were Sc (361.383 nm) and Fe (259.939 nm), while method accuracy and precision was checked using
BX-N Certified Reference Material, as reported elsewhere [48].

2.4. Taguchi Method

In the case of four parameters with values of three different levels, a traditional experimental
design—to satisfy all possible combinations (34 )—would require the realization of 81 individual
experiments. Considering that each experiment has to be repeated 2–3 times (requirements of
repeatability), a significant analytical measurement load arises, lasting a long time and also having
a high cost due to the extensive consumption of resources and man-hours. To avoid this fully
combinatorial pattern, a fractional experimental plan is proposed based on the Taguchi method [67].
The Taguchi method sets the norms for performing experiments in order to test the sensitivity
of a set of response variables (dependent variables) under the effect of a set of control parameters
(independent variables) by considering experiments in “orthogonal array”, thus aiming to attain the
optimum setting of the control parameters [68]. The fundamental advantage of Taguchi method lies in
using “orthogonal array” distribution. It allows a much-reduced set of experiments to be done in order
to find the optimum settings of involved control factors, at a minimum cost of resources but in a robust
way, achieving high rates of reproducibility [62,66,69].
The Taguchi method is applied through (a) the design phase of the experiment, (b) the calculation of
factor effects, (c) the selection of optimum factor levels, and finally at (d) the validation of experimental
results stage [66].
In our study (four factors at three levels), the appropriate orthogonal array is LA (BC ),
which distributes the factors (parameters) in a balanced manner, is L9 (34 ). A = 9 is the requisite number
of experiments to be conducted, indicating the significant economy of the experimental procedure
(materials and man-hours) under the Taguchi design, as the traditional design of 81 experiments is
reduced by a square root. B = 3 denotes the number of levels and C = 4 corresponds to the factors
involved in the experiment. Table 2 presents the L9 orthogonal matrix experiment plan with the
resulting combinations among factors and their levels to be considered in order to study the effect of Sc
leaching parameters.

Table 2. L9 (34 ) orthogonal matrix experimental plan.

Factors/Parameters
Experiment No.
A (H2 SO4 Molarity) B (Temperature) C (Solid/Liquid) D (Time)
1 2 25 10 1
2 2 55 20 4
3 2 85 30 7
4 4 25 20 7
5 4 55 30 1
6 4 85 10 4
7 6 25 30 4
8 6 55 10 7
9 6 85 20 1
Minerals 2019, 9, 236 5 of 13

As reported above, iron concentration in leachate was chosen to be monitored for selectivity
assessment, since it is co-extracted in large quantities, and therefore its subsequent removal is a
strenuous task. The focus is on Sc, aiming for the maximum concentration possible, in contrast to
Fe, where the lowest content is considered as optimal. Both element concentrations act as response
variables under the Taguchi method. Table 3 shows the results for Sc and Fe throughout all nine
experiments, where each measurement was repeated thrice, accompanied with the arithmetic average of
each triplet of experiments. It has to be noted that in the Taguchi method, the experiment corresponding
to optimum conditions for Sc extraction from BR might not exist within the designed orthogonal matrix
experimental plan [70].

Table 3. Measurements of Sc and Fe concentrations for the corresponding factor combinations of the
L9 (34 ) experimental plan.

Concentration (mg/L)
Exp. Factors
No. Combination Sc Fe
CSc 1 CSc 2 CSc 3 CSc avg CFe 1 CFe 2 CFe 3 CFe avg
1 A1 B1 C1 D1 3.72 3.57 3.69 3.66 1263 1255 1294 1271
2 A1 B2 C2 D2 9.36 8.89 8.96 9.07 22806 21815 22698 22440
3 A1 B3 C3 D3 13.77 14.58 14.31 14.22 50260 51389 52072 51240
4 A2 B1 C2 D3 7.80 7.65 7.68 7.71 15075 15133 14855 15021
5 A2 B2 C3 D1 13.16 13.94 13.48 13.53 25684 25594 25459 25579
6 A2 B3 C1 D2 8.90 9.66 9.41 9.32 36225 39154 37358 37579
7 A3 B1 C3 D2 11.88 10.93 12.71 11.84 19588 19111 20814 19838
8 A3 B2 C1 D3 8.14 7.99 8.91 8.34 31388 32697 32685 32257
9 A3 B3 C2 D1 12.57 14.29 13.22 13.36 43741 41526 41370 42212

According to the Taguchi method, the metric of signal-to-noise (S/N) ratio is employed to find
the optimum conditions of BR’s H2 SO4 leaching process. Sc and Fe concentrations follow exactly the
opposite direction for this particular expression of “objective function” to be optimized, meaning that
for Sc, the higher the concentration, the better the performance characteristics, while for Fe it applies
exactly the opposite—the smaller the concentration, the better the performance is [62,65,71,72]. As for
the case of Sc (the larger-the-better type), the form of S/N ratio is expressed as:
 
n
S  1 X 1 
 
= −10 · log · (1)

N n Sc 2 
 
CSc

avg i=1 Cavg i

While for the case of main elements, in specific Fe (the smaller-the-better type), the form of S/N
ratio is as follows:
n 
 
S  1 X
  2 
Fe
= −10 · log ·
 Cavg  

i
(2)
N CFe
avg
n
i=1

In both cases n = 9, meaning the number of experiments done for an experimental combination
and CSc i or CFe i is the performance value for the corresponding ith experiment.

Yi = µ + Xi + ei (3)

where µ is the overall mean of performance value, Xi the fixed effect of the parameter level combination
used in ith experiment, and ei the random error in ith experiment [70,71,73].

2.5. Analysis of Experimental Data

Analysis of Variance (ANOVA) is used to evaluate the experimental data of Table 3, and to identify
the relative influence of each factor on the variation of results of Sc and Fe concentrations, respectively.
Minerals 2019, 9, 236 6 of 13

Furthermore, a regression analysis is performed in order to extract an equation correlating the four
independent variables with the dependent variable of Sc and Fe concentrations. This step will provide
the necessary tool to predict the response in Sc/Fe concentrations for a larger variety of the four factors
combinations outside the norms of the orthogonal array distribution and their set levels. As in the
design of the experimental plan, Minitab Statistical Software is used to calculate the effects of leaching
process parameters with a 95% confidence level, as well as the regression model and its coefficients.

3. Results and Discussion

According to ANOVA results, for Sc, the prioritization of four factors’ contribution is as shown in
Table 4. The most significant factor is S/L with a contribution of 58.95%, followed by Temperature with
33.32%, while the other two factors have a much lower contribution to BR leaching process, and thus
to Sc concentration. H2 SO4 molarity presents a percentage of 7.71%, while Leaching time seems to
have an almost negligible effect at 0.02%.

Table 4. ANOVA results for Sc.

Degree of Sequential Sums Contribution Adjusted Sums Adjusted Mean

Factor F-Value P-Value
Freedom of Squares (%) of Squares Squares
A 2 2.2742 7.71 7.2742 3.6371 * *
B 2 31.4224 33.32 31.4224 15.7112 * *
C 2 55.5981 58.95 55.5981 27.7991 * *
D 2 0.0187 0.02 0.0187 0.0094 * *
Error 0 * * * *
Total 8 94.3135 100.00

Regression analysis for Sc concentration produced the following best-fit equation with an R2 = 1
(Equation (4)):

CSc = −3.017 − 0.758 · A + 0.112 · B + 0.262 · C − 0.067 · D

(4)
−0.026 · A2 − 0.328 · 10−3 · B2 + 1.066 · 10−3 · C2 + 6.469 · 10−3 · D2

As for Fe concentration, the corresponding findings of ANOVA are emphatically different

compared to those for Sc. As reported in Table 5, the largest contribution by far belongs to Temperature,
with 81.89%. This result is very reasonable as Fe is fully coupled with temperature, meaning that
increased temperatures favor Fe dissolution [74,75]. Unlike Sc, S/L effect is significantly lower for Fe,
with a 6.14% weight. Leaching time has a contribution share of 8.06%, while H2 SO4 molarity remains
at the same order of magnitude at 3.90% as that of Sc.

Table 5. ANOVA results for Fe.

Factor Degree of Sequential Sums Contribution Adjusted Sums Adjusted Mean F-Value P-Value
Freedom of Squares (%) of Squares Squares
A 2 7.169 × 107 3.90 7.169 × 107 3.584 × 107 * *
B 2 150.350 × 107 81.89 150.350 × 107 75.175 × 107 * *
C 2 11.274 × 107 6.14 11.274 × 107 5.637 × 107 * *
D 2 14.805 × 107 8.06 14.805 × 107 7.403 × 107 * *
Error 0 * * * *
Total 8 183.597 × 107 100.00%

Regression analysis for Fe concentration produced the following best-fit equation with an R2 = 1
(Equation (5)):
CFe = −6751 − 2687 · A + 392.5 · B − 135.3 · C + 470.9 · D
(5)
+537.5 · A2 + 1.224 · B2 + 14.03 · C2 + 145.7 · D2
The effects of each parameter associated with their levels on Sc and Fe concentration are graphically
presented in Figures 1 and 2.
 C Fe = -6751 − 2687 ⋅ A +? 92.5 ⋅ B − 135.3 ⋅ C + 470.9 ⋅ D
(5)
+537.5 ⋅ A 2 + 1.224 ⋅ B 2 + ? 4.03 ⋅ C 2 + ? 45.7 ⋅ D 2
The effects of each parameter associated with their levels on Sc and Fe concentration7 ofare
Minerals 2019, 9, 236 13
graphically presented in Figures 1 and 3.
Since higher S/N ratio is better for obtaining higher Sc concentration, the optimum leaching
Since higher
conditions for Sc canS/Nbe ratio
drawnis better
from for obtaining
Figure 2, where higher Sc concentration,
the numerical value of the the optimum
maximumleachingpoint at
conditions
each factor corresponds to the optimized value of Sc concentration according to experimental at
for Sc can be drawn from Figure 3, where the numerical value of the maximum point each
design
factor corresponds
[62]. Concerning to the
factor A optimized value the
(Acid molarity), of Sc concentration
maximum according
S/N ratio (20.80)toisexperimental
obtained at 6 design
M (level[62].
3).
Concerning
Similarly, forfactor A (Acid(Factor
Temperature molarity), theS/L
B) and maximum S/N ratio
ratio (Factor C) the(20.80)
maximum is obtained
values of at S/N
6 M ratio
(levelalso
3).
Similarly, for Temperature (Factor B) and S/L ratio (Factor C) the
appear at level 3, meaning 21.65 corresponding to 85 °C and 22.38 corresponding to 30%, maximum values of S/N ratio also
appear at levelThe
3, meaning 21.65 ◦ C and 22.38 corresponding to 30%, respectively.
respectively. maximum S/Ncorresponding
ratio output for to 85
Leaching time (Factor D) appears at level 2 with
The maximum S/N ratio output for Leaching time (Factor
20.00, being related to 4 hours. Therefore, the parameterization giving D) appears at levelthe 2 with 20.00, being
optimum related
BR leaching
to 4 h. Therefore,
conditions for Sc the parameterization
concentration is A3B3giving
C3D2 (6M,the optimum
85 C, 30%,
o BR4h).
leaching conditions for Sc concentration
is A3 B 3 C3 D2 (6M,
Scandium 85 ◦ C, 30%, 4h).
concentration in this case is predicted to be 16.4mg/L, while iron is estimated as
51,472Scandium
mg/L. Itconcentration
is clear that in thethis case is predicted
maximization of Sc to be 16.4mg/L,can
concentration whilebe iron is estimated
achieved with high as
51,472 mg/L.ofItiron
dissolution is clear thatexpense
at the the maximization of Sc
of selectivity. concentration
This is in agreementcan be achieved
with studieswith high dissolution
reporting that most
of iron at the expense
the scandium contentof selectivity.
is trapped in Thistheishematite
in agreementphasewith
[76]. studies
The optimumreporting that mostforofiron
conditions the
scandium content is trapped in the hematite phase [76]. The optimum
extraction can be deduced from the respective S/N plot (Figure 4), although in this case maximum conditions for iron extraction
can
S/N be deduced
values depictfromthethe respective
minimum S/N plot (Figure
concentration of iron,4), as
although
definedinbythis thecase maximum S/N model.
smaller-the-better values
depict the minimum concentration of iron, as defined by the smaller-the-better
The optimum BR leaching conditions for Fe are A1B1C1D1, corresponding to leaching for 1 hour at model. The optimum
BR leaching conditions for Fe are10%
A1 Bsolid-to-liquid ◦ C using 2M
25 °C using 2M sulfuric acid and 1 C1 D1 , corresponding
ratio. Irontoconcentration
leaching for 1inhthis at 25case is identical
sulfuric acid and 10%
to the measured valuesolid-to-liquid
for experiment ratio.No.1
Iron concentration
(see Table 3),inbeing this case
1271 is identical
mg/L, and to the measured
scandium is
value for
3.66 mg/L. experiment No.1 (see Table 3), being 1271 mg/L, and scandium is 3.66 mg/L.
It should be noted that the proposed optimal conditions refer only to the maximization of Sc
concentration.
concentration. Any Anyapplication
application parameters,
parameters, suchsuch
as costasanalysis for large-scale
cost analysis extraction or
for large-scale restrictions
extraction or
resulting
restrictionsfrom subsequent
resulting from purification
subsequent process, wereprocess,
purification not included in the
were not design of
included in the
the present
design ofstudy.
the
Instead,
present regression
study. Instead,analysis equationsanalysis
regression are suggested
equationsfor anyarerecommended
suggested for application conditions.
any recommended
In any case, the
application leaching In
conditions. behavior
any case, highly
thedepends
leachingon the chemical
behavior highlyand mineralogical
depends on thecomposition
chemical and of
the bauxite residue
mineralogical utilized.of the bauxite residue utilized.
composition

Main Effects Plot for Means

Data Means
molarity temperature S/L time
14
Sc Concentration (Mean of Means)

13

12

11

10

2 4 6 25 55 85 10 20 30 1 4 7

1. Effects
Figure 1. Effectsofofeach
eachparameter
parameter ((A)
((A) Acid
Acid molarity,
molarity, (B) Temperature,
(B) Temperature, (C) Solid-to-Liquid
(C) Solid-to-Liquid ratio
ratio (S/L),
(S/L), and (D) Leaching time) associated with their levels on Sc concentration.
and (D) Leaching time) associated with their levels on Sc concentration.
 2 4 6 25 55 85 10 20 30 1 4 7

SN(
Signal-to-noise: Larger is better

Figure 2. Effects of each parameter ((A) Acid molarity, (B) Temperature, (C) Solid-to-Liquid ratio
(S/L),
Minerals and
2019, (D) Leaching time) associated with their levels on the statistical performance of S/N ratio8 of 13
9, 236
for Sc.

Main Effects Plot for Means

Data Means
molarity temperature S/L time
45000
Fe Concentration (Mean of Means)

40000

35000

30000

25000

20000

15000

10000
2 4 6 25 55 85 10 20 30 1 4 7

Figure 2.
3. Effects
Effectsofofeach
eachparameter
parameter ((A)
((A) Acid
Acid molarity,
molarity, (B) (B) Temperature,
Temperature, (C) Solid-to-Liquid
(C) Solid-to-Liquid ratio
ratio (S/L),
(S/L),
Minerals
and and
2019,
(D) x(D)
FORLeaching
9,Leaching
PEER time) associated
REVIEW
time) associated withlevels
with their their levels on Fe concentration.
on Fe concentration. 8 of 13

Main Effects Plot for SN ratios

Data Means
SN(CSc)=-10*log(1/n*Σ(1/y^2)) (Mean of SN ratios)

molarity temperature S/L time

23

22

21

20

19

18

17

16
2 4 6 25 55 85 10 20 30 1 4 7

Signal-to-noise: Larger is better

Figure 3.
2. Effects
Effectsofofeach
eachparameter
parameter ((A)
((A) Acid
Acid molarity,
molarity, (B) (B) Temperature,
Temperature, (C) Solid-to-Liquid
(C) Solid-to-Liquid ratio
ratio (S/L),
(S/L), and (D) Leaching time) associated with their levels on the statistical performance of S/N
and (D) Leaching time) associated with their levels on the statistical performance of S/N ratio for Sc. ratio
for Sc.

Main Effects Plot for Means

Data Means
molarity temperature S/L time
45000
Minerals 2019, 9, 236 9 of 13
Minerals 2019, 9, x FOR PEER REVIEW 9 of 13

Main Effects Plot for SN ratios

Data Means
SN(CFe)=-10*log(1/n*Σ(y^2)) (Mean of SN ratios)

molarity temperature S/L time

-75

-80

-85

-90

-95
2 4 6 25 55 85 10 20 30 1 4 7

Signal-to-noise: Smaller is better

Figure 4.4. Effects

Effectsofofeach
eachparameter
parameter ((A)
((A) Acid
Acid molarity,
molarity, (B) Temperature,
(B) Temperature, (C) Solid-to-Liquid
(C) Solid-to-Liquid ratio
ratio (S/L),
(S/L),(D)
and and (D) Leaching
Leaching time) associated
time) associated withlevels
with their theiron
levels on the statistical
the statistical performance
performance of S/N
of S/N ratio forratio
Fe.
for Fe.
As seen from the above optimized conditions, for Sc the experiment-combination linked to
the optimum
As seen fromleaching acid conditions
the above optimizedisconditions,
not included for in
Scthe
theLexperiment-combination
9 orthogonal matrix experiment
linked toplan
the
(see Table leaching
optimum 2), while acid
in the case of Feisthe
conditions notoptimized
included conditions correspond
in the L9 orthogonal to experiment
matrix experiment No.1 under
plan (see
the Taguchi
Table design
2), while [62].
in the case of Fe the optimized conditions correspond to experiment No.1 under the
In order
Taguchi design to[62].
verify that the optimal conditions resulting from Taguchi method are indeed the
best match
In orderfortothe above
verify thatpredicted performance
the optimal conditionsfor Sc concentration,
resulting confirmation
from Taguchi method areexperiments
indeed thewere
best
conducted
match for theunder the predicted
above specific conditions [77]. for
performance Sc Sc
concentration
concentration,wasconfirmation
predicted to experiments
be 16.4 mg/Lwereand
measured
conductedasunder
16.6 mg/L, while Fe
the specific concentration
conditions forconcentration
[77]. Sc the same conditions was predicted
was predicted as 51,472
to be 16.4 mg/Lmg/L
and
and measured as 55,289 mg/L. The results are very satisfactory, since the percent deviation
measured as 16.6 mg/L, while Fe concentration for the same conditions was predicted as 51,472 mg/L is 1.2% for
Sc
andand 7.4% foras
measured Fe.55,289 mg/L. The results are very satisfactory, since the percent deviation is 1.2%
for Sc and 7.4% for Fe.
4. Conclusions
4. Conclusions
Recovery of scandium and iron from bauxite residue by sulfuric acid leaching depends significantly
on the conditions
Recovery of used.
scandium The and
applied
ironTaguchi experimental
from bauxite residuedesign clearly acid
by sulfuric showed that scandium
leaching depends
concentration in the leachate solution is enhanced with high acid concentrations,
significantly on the conditions used. The applied Taguchi experimental design clearly showed elevated reaction
that
temperatures, and high solid-to-liquid
scandium concentration in the leachate ratios.
solution The most influential
is enhanced with highfactor
acidis concentrations,
the solid-to-liquid ratio
elevated
(58.95%),
reaction followed by temperature
temperatures, and high(33.32%). Iron shows
solid-to-liquid similar
ratios. The leaching
most behavior,
influentialbeing influenced
factor is the
mainly by temperature (81.89%), and secondarily by all the other factors.
solid-to-liquid ratio (58.95%), followed by temperature (33.32%). Iron shows similar leaching The optimal conditions
predicted ◦ C, solid/liquid 30%, 4h; and for Fe: 2M
behavior, from
beingthe Taguchi design
influenced mainlyareby for Sc: 6M of H
temperature 2 SO4 , 85and
(81.89%), secondarily by all the other factors.
of H2optimal ◦
SO4 , 25 C, solid/liquid 10%, 1h.from
Therefore, the maximization of Sc
The conditions predicted the Taguchi design are forconcentration
Sc: 6M of H can
2SObe4, reached
85 °C,
along with an30%,
solid/liquid increased dissolution
4h; and for Fe:of 2M
iron,ofat the
H2SO expense
4, 25 °C,of leaching selectivity.
solid/liquid 10%, The1h.predicted
Therefore, values
the
were experimentally confirmed. Regression equations resulted from the statistical
maximization of Sc concentration can be reached along with an increased dissolution of iron, at the evaluation of the
obtained
expense of results can be
leaching applied on
selectivity. The leaching
predictedconditions
values weredepending on the requirements
experimentally confirmed. of different
Regression
applications. The optimal
equations resulted from the conditions
statisticalderived in this
evaluation of study are indicative
the obtained results of thebeleaching
can appliedbehavior
on leachingfor
bauxite residues of similar mineralogical and chemical composition.
conditions depending on the requirements of different applications. The optimal conditions derived
in this study are indicative of the leaching behavior for bauxite residues of similar mineralogical and
chemical composition.
Minerals 2019, 9, 236 10 of 13

Author Contributions: This work has been performed by the members of NTUA School of Chemical Engineering.
L.-A.T., T.L. performed the experiments and integrated ICP-OES measurements. P.G. and T.L. evaluated the data.
P.G., T.L. and L.-A.T. wrote the draft paper. K.H. corrected the draft paper. M.O.-P supervised the whole work,
and reviewed and corrected the paper.
Acknowledgments: The research leading to these results has been performed within the SCALE project and
received funding from the European Community’s Horizon 2020 Program (H2020/2014-2020), under Grant
Agreement no. 730105. The companies II-VI Inc. (Saxonburg, PA, USA) and MYTILINEOS S.A., formerly
Aluminum of Greece S.A. (AoG) are also gratefully acknowledged for their fruitful collaboration and cooperation
in the context of SCALE, as well as in previous joint projects.
Conflicts of Interest: The authors declare no conflict of interest. The results of this work have been derived in
the context of the SCALE project (Grant Agreement No. 730105) and the publication is in accordance with its
terms. The funding sponsors (EU/EASME) had no role in the design of the study, in the collection, analyses,
or interpretation of data, and in the writing of the manuscript.

References
1. Kumar, S.; Kumar, R.; Bandopadhyay, A. Innovative methodologies for the utilisation of wastes from
metallurgical and allied industries. Resour. Conserv. Recycl. 2006, 48, 301–314. [CrossRef]
2. Power, G.; Gräfe, M.; Klauber, C. Bauxite residue issues: I. Current management, disposal and storage
practices. Hydrometallurgy 2011, 108, 33–45. [CrossRef]
3. Liu, X.; Zhang, N. Utilization of red mud in cement production: A review. Waste Manag. Res. 2011, 29,
1053–1063. [CrossRef]
4. Sutar, H.; Mishra, S.C.; Sahoo, S.K.; Chakraverty, A.P.; Maharana, H.S. Progress of red mud utilization:
An overview. Am. Chem. Sci. J. 2014, 4, 255–279. [CrossRef]
5. Mishra, B.; Gostu, S. Materials sustainability for environment: Red-mud treatment. Front. Chem. Sci. Eng.
2017, 11, 483–496. [CrossRef]
6. Samal, S.; Ray, A.K.; Bandopadhyay, A. Proposal for resources, utilization and processes of red mud in
india—A review. Int. J. Miner. Process. 2013, 118, 43–55. [CrossRef]
7. Dodoo-Arhin, D.; Nuamah, R.A.; Agyei-Tuffour, B.; Obada, D.O.; Yaya, A. Awaso bauxite red mud-cement
based composites: Characterisation for pavement applications. Case Stud. Constr. Mater. 2017, 7, 45–55.
[CrossRef]
8. Yang, X.; Zhao, J.; Li, H.; Zhao, P.; Chen, Q. Recycling red mud from the production of aluminium as a red
cement-based mortar. Waste Manag. Res. 2017, 35, 500–507. [CrossRef]
9. Dodoo-Arhin, D.; Konadu, D.S.; Annan, E.; Buabeng, F.P.; Yaya, A.; Agyei-Tuffour, B. Fabrication and
characterisation of ghanaian bauxite red mud-clay composite bricks for construction applications. Am. J.
Mater. Sci. 2013, 3, 110–119.
10. Lavanya, P.M.; Kumar, K.S. Characterization of red mud as a construction material using bioremediation.
Int. J. Res. Sci. Adv. Eng. 2017, 2, 132–139.
11. Liao, C.Z.; Shih, K. Chapter 20—Thermal behavior of red mud and its beneficial use in glass-ceramic
production. In Environmental Materials and Waste; Prasad, M.N.V., Shih, K., Eds.; Academic Press: Cambridge,
MA, USA, 2016; pp. 525–542.
12. Kim, Y.; Kim, M.; Sohn, J.; Park, H. Applicability of gold tailings, waste limestone, red mud, and ferronickel
slag for producing glass fibers. J. Clean. Prod. 2018, 203, 957–965. [CrossRef]
13. Ascensão, G.; Seabra, M.P.; Aguiar, J.B.; Labrincha, J.A. Red mud-based geopolymers with tailored alkali
diffusion properties and ph buffering ability. J. Clean. Prod. 2017, 148, 23–30. [CrossRef]
14. Ma, M.; Lu, Y.; Chen, R.; Ma, L.; Wang, Y. Hexavalent chromium removal from water using heat-acid
activated red mud. Open J. Appl. Sci. 2014, 4, 275–284. [CrossRef]
15. Pepper, R.A.; Couperthwaite, S.J.; Millar, G.J. Re-use of waste red mud: Production of a functional iron oxide
adsorbent for removal of phosphorous. J. Water Process Eng. 2018, 25, 138–148. [CrossRef]
16. Alighardashi, A.; Gharibi, H.R.; Raygan, S.; Akbarzadeh, A. Study of novel mechano-chemical activation
process of red mud to optimize nitrate removal from water. Water Sci. Technol. 2015, 73, 899–908. [CrossRef]
17. Guo, T.; Yang, H.; Liu, Q.; Gu, H.; Wang, N.; Yu, W.; Dai, Y. Adsorptive removal of phosphate from aqueous
solutions using different types of red mud. Water Sci. Technol. 2018, 2017, 570–577. [CrossRef] [PubMed]
Minerals 2019, 9, 236 11 of 13

18. Li, J.; Xu, L.; Sun, P.; Zhai, P.; Chen, X.; Zhang, H.; Zhang, Z.; Zhu, W. Novel application of red mud:
Facile hydrothermal-thermal conversion synthesis of hierarchical porous Alooh and Al2 O3 microspheres as
adsorbents for dye removal. Chem. Eng. J. 2017, 321, 622–634. [CrossRef]
19. Oliveira, E.H.C.; Mendonça, É.T.R.; Barauna, O.S.; Ferreira, J.M.; Motta Sobrinho, M.A. Study of variables for
optimization of the dye indosol adsorption process using red mud and clay as adsorbents. Adsorption 2016,
22, 59–69. [CrossRef]
20. Wang, X.; Zhang, Y.; Lu, R.; Zhou, F.; An, Q.; Meng, Z.; Fei, B.; Lv, F. Novel multiple coagulant from bayer
red mud for oily sewage treatment. Desalin. Water Treat. 2015, 54, 690–698. [CrossRef]
21. Kulishenko, A.E.; Klimenko, N.A.; Grechanik, S.V.; Kravchenko, T.B.; Kostyuk, V.A.; Avramenko, L.P.;
Kosogina, I.V. The use of products of recycling waste of aluminum manufacturing as a coagulant when
purifying highly colored natural water. J. Water Chem. Technol. 2018, 40, 265–271. [CrossRef]
22. Ni, F.; He, J.; Wang, Y.; Luan, Z. Preparation and characterization of a cost-effective red mud/polyaluminum
chloride composite coagulant for enhanced phosphate removal from aqueous solutions. J. Water Process Eng.
2015, 6, 158–165. [CrossRef]
23. Tao, L.; Wu, H.; Wang, J.; Li, B.; Wang, X.-Q.; Ning, P. Removal of SO2 from flue gas using bayer red mud:
Influence factors and mechanism. J. Cent. South Univ. 2019, 26, 467–478. [CrossRef]
24. Thang, N.H.; Quyen, P.V.T.H.; Nhung, L.T.; Phong, D.T.; Tuyen, N.N.K. Utilization of red mud and bagasse
for production of gas absorption materials. Aip Conf. Proc. 2018, 1954, 040010. [CrossRef]
25. Thang, N.H.; Ngoc, N.H.L.; Uyen, V.T.N.; Kien, P.T. Novel materials synthesized from red mud, bagasse,
and bentonite for gas treatment by CO2 absorption. Matec Web Conf. 2018, 207, 03005. [CrossRef]
26. Liu, Z.; Li, H. Metallurgical process for valuable elements recovery from red mud—A review. Hydrometallurgy
2015, 155, 29–43. [CrossRef]
27. Borra, C.R.; Blanpain, B.; Pontikes, Y.; Binnemans, K.; Van Gerven, T. Recovery of rare earths and other
valuable metals from bauxite residue (red mud): A review. J. Sustain. Metall. 2016, 2, 365–386. [CrossRef]
28. Borra, C.R.; Pontikes, Y.; Binnemans, K.; Van Gerven, T. Leaching of rare earths from bauxite residue
(red mud). Miner. Eng. 2015, 76, 20–27. [CrossRef]
29. Liu, Y.; Naidu, R. Hidden values in bauxite residue (red mud): Recovery of metals. Waste Manag. 2014, 34,
2662–2673. [CrossRef] [PubMed]
30. Yang, Y.; Wang, X.; Wang, M.; Wang, H.; Xian, P. Recovery of iron from red mud by selective leach with oxalic
acid. Hydrometallurgy 2015, 157, 239–245. [CrossRef]
31. Urík, M.; Bujdoš, M.; Milová-Žiaková, B.; Mikušová, P.; Slovák, M.; Matúš, P. Aluminium leaching from red
mud by filamentous fungi. J. Inorg. Biochem. 2015, 152, 154–159. [CrossRef]
32. Samouhos, M.; Taxiarchou, M.; Tsakiridis, P.E.; Potiriadis, K. Greek “red mud” residue: A study of microwave
reductive roasting followed by magnetic separation for a metallic iron recovery process. J. Hazard. Mater.
2013, 254–255, 193–205. [CrossRef] [PubMed]
33. Kaußen, F.; Friedrich, B. Reductive smelting of red mud for iron recovery. Chem. Ing. Tech. 2015, 87,
1535–1542. [CrossRef]
34. Zhu, X.-f.; Zhang, T.-a.; Wang, Y.-X.; Lü, G.-z.; Zhang, W.-g. Recovery of alkali and alumina from bayer red
mud by the calcification–carbonation method. Int. J. Miner. Metall. Mater. 2016, 23, 257–268. [CrossRef]
35. Alkan, G.; Xakalashe, B.; Yagmurlu, B.; Kaußen, F.; Friedrich, B. Conditioning of red mud for subsequent
titanium and scandium recovery—a conceptual design study. World Metall.-Erzmetall 2017, 70, 5–12.
36. Agatzini-Leonardou, S.; Oustadakis, P.; Tsakiridis, P.E.; Markopoulos, C. Titanium leaching from red mud by
diluted sulfuric acid at atmospheric pressure. J. Hazard. Mater. 2008, 157, 579–586. [CrossRef]
37. Ochsenkühn-Petropoulou, M.; Hatzilyberis, K.S.; Mendrinos, L.N.; Salmas, C.E. Pilot-plant investigation of
the leaching process for the recovery of scandium from red mud. Ind. Eng. Chem. Res. 2002, 41, 5794–5801.
[CrossRef]
38. Ochsenkühn-Petropulu, M.; Lyberopulu, T.; Ochsenkühn, K.M.; Parissakis, G. Recovery of lanthanides and
yttrium from red mud by selective leaching. Anal. Chim. Acta 1996, 319, 249–254. [CrossRef]
39. Feng, Y.; Wu, D.; Liao, C.; Deng, Y.; Zhang, T.; Shih, K. Red mud powders as low-cost and efficient catalysts
for persulfate activation: Pathways and reusability of mineralizing sulfadiazine. Sep. Purif. Technol. 2016,
167, 136–145. [CrossRef]
40. Wu, J.; Gong, Z.; Lu, C.; Niu, S.; Ding, K.; Xu, L.; Zhang, K. Preparation and performance of modified red
mud-based catalysts for selective catalytic reduction of NOX with NH3 . Catalysts 2018, 8, 35. [CrossRef]
Minerals 2019, 9, 236 12 of 13

41. Zou, Q.; An, W.; Wu, C.; Li, W.; Fu, A.; Xiao, R.; Chen, H.; Xue, S. Red mud-modified biochar reduces soil
arsenic availability and changes bacterial composition. Environ. Chem. Lett. 2018, 16, 615–622. [CrossRef]
42. Wang, Y.; Li, F.; Song, J.; Xiao, R.; Luo, L.; Yang, Z.; Chai, L. Stabilization of cd-, pb-, cu- and zn-contaminated
calcareous agricultural soil using red mud: A field experiment. Environ. Geochem. Health 2018, 40, 2143–2153.
[CrossRef] [PubMed]
43. Shin, W.; Kim, Y.-K. Stabilization of heavy metal contaminated marine sediments with red mud and apatite
composite. J. Soils Sediments 2016, 16, 726–735. [CrossRef]
44. Luo, H.L.; Zhu, Q.; Zhou, Y.; Liu, Z.L.; Ou, W.Q. Stabilization of cd in ore soil using modified red mud
materials. Adv. Mater. Res. 2017, 1142, 296–299. [CrossRef]
45. Lymperopoulou, T. Determination and Recovery of Rare Earths from Bauxites and Red Mud. Ph.D. Thesis,
National Technical University of Athens, Athens, Greece, 1996.
46. Tsakanika, L.-A. Separation and Recovery of Lanthanides from Red Mud by Use of Selective Extraction and
Chromatographic Techniques. Ph.D. Thesis, National Technical University of Athens, Athens, Greece, 2013.
47. Ochsenkühn-Petropoulou, M.; Tsakanika, L.-A.; Lymperopoulou, T. Process Control of an Innovative
Method for the Recovery and Separation of rare Earths from Red Mud by Different analytical Techniques.
In Proceedings of the 1st European Rare Earth Resources Conference (ERES 2014), Milos Island, Greece,
4–7 September 2014; pp. 28–29.
48. Ochsenkühn-Petropulu, M.; Lyberopulu, T.; Parissakis, G. Direct determination of landthanides, yttrium
and scandium in bauxites and red mud from alumina production. Anal. Chim. Acta 1994, 296, 305–313.
[CrossRef]
49. European Commission. Critical Raw Materials. Third List of Critical Raw Materials for the EU of 2017.
Available online: https://ec.europa.eu/growth/sectors/raw-materials/specific-interest/critical_en (accessed on
28 February 2019).
50. SCANDIUM Investing News. Why Scandium Could be a Huge Opportunity. Available online:
http://investingnews.com/daily/resource-investing/critical-metalsinvesting/scandiuminvesting/scandium-
production-the-problem-and-the-opportunity/ (accessed on 28 February 2019).
51. Williams-Jones, A.E.; Vasyukova, O.V. The economic geology of scandium, the runt of the rare earth element
litter. Econ. Geol. 2018, 113, 973–988. [CrossRef]
52. Samson, I.M.; Chassé, M. Scandium. In Encyclopedia of Geochemistry: A Comprehensive Reference Source on the
Chemistry of the Earth; White, W.M., Ed.; Springer International Publishing: Cham, Switzerland, 2016; pp. 1–5.
53. Krishnamurthy, N.; Gupta, C.K. Extractive Metallurgy of Rare Earths, 2nd ed.; Taylor & Francis: Didcot,
UK, 2015.
54. Rivera, R.M.; Xakalashe, B.; Ounoughene, G.; Binnemans, K.; Friedrich, B.; Van Gerven, T. Selective rare
earth element extraction using high-pressure acid leaching of slags arising from the smelting of bauxite
residue. Hydrometallurgy 2019, 184, 162–174. [CrossRef]
55. Bonomi, C.; Giannopoulou, I.; Panias, D. Correlation of scandium and titanium during leaching of bauxite
residue (red mud) by an imidazolium ionic liquid. In Proceedings of the 2nd conference on European Rare
Earth Resources (ERES2017), Santorini Island, Greece, 26 May 2017; pp. 199–201.
56. Davris, P.; Balomenos, E.; Panias, D.; Paspaliaris, I. Selective leaching of rare earth elements from bauxite
residue (red mud), using a functionalized hydrophobic ionic liquid. Hydrometallurgy 2016, 164, 125–135.
[CrossRef]
57. Qu, Y.; Lian, B. Bioleaching of rare earth and radioactive elements from red mud using penicillium tricolor
rm-10. Bioresour. Technol. 2013, 136, 16–23. [CrossRef]
58. Pepper, R.A.; Couperthwaite, S.J.; Millar, G.J. Comprehensive examination of acid leaching behaviour of
mineral phases from red mud: Recovery of Fe, Al, Ti, and Si. Miner. Eng. 2016, 99, 8–18. [CrossRef]
59. Hatzilyberis, K.; Lymperopoulou, T.; Tsakanika, L.-A.; Ochsenkühn, K.-M.; Georgiou, P.; Defteraios, N.;
Tsopelas, F.; Ochsenkühn-Petropoulou, M. Process design aspects for scandium-selective leaching of bauxite
residue with sulfuric acid. Minerals 2018, 8, 79. [CrossRef]
60. Taguchi, G.; Konishi, S. Taguchi Methods, Orthogonal Arrays and Linear Graphs, Tools for Quality Engineering;
American Supplier Institute: Dearborn, MI, USA, 1987.
61. Copur, M.; Kizilca, M.; Kocakerim, M.M. Determination of the optimum conditions for copper leaching from
chalcopyrite concentrate ore using taguchi method. Chem. Eng. Commun. 2015, 202, 927–935. [CrossRef]
Minerals 2019, 9, 236 13 of 13

62. Mbuya, B.I.; Kime, M.B.; Tshimombo, A.M.D. Comparative study of approaches based on the taguchi and
anova for optimising the leaching of copper–cobalt flotation tailings. Chem. Eng. Commun. 2017, 204, 512–521.
[CrossRef]
63. Ochsenkuehn-Petropoulou, M.; Tsakanika, L.-A.; Lymperopoulou, T.; Ochsenkuehn, K.-M.; Hatzilyberis, K.;
Georgiou, P.; Stergiopoulos, C.; Serifi, O.; Tsopelas, F. Efficiency of sulfuric acid on selective scandium
leachability from bauxite residue. Metals 2018, 8, 915. [CrossRef]
64. Lymperopoulou, T.; Tsakanika, L.A.; Ochsenkühn, K.M.; Ochsenkühn-Petropoulou, M. Optimization of
mineral acids leaching process for the recovery of rare earth elements from Greek red mud. In Proceedings
of the 2nd conference on European Rare Earth Resources (ERES2017), Santorini Island, Greece, 28–31 May
2017; pp. 182–184.
65. Phadke, M.S. Quality Engineering Using Robust Design; Prentice Hall: Upper Saddle River, NJ, USA, 1989.
66. Rai, S.; Wasewar, K.L.; Lataye, D.H.; Mishra, R.S.; Puttewar, S.P.; Chaddha, M.J.; Mahindiran, P.;
Mukhopadhyay, J. Neutralization of red mud with pickling waste liquor using taguchi’s design of
experimental methodology. Waste Manag. Res. 2012, 30, 922–930. [CrossRef]
67. Peace, G.S. Taguchi Methods: A Hands-on Approach; Addison-Wesley: Boston, MA, USA, 1993.
68. De, A. Design for Reliability and Quality; Indian Institute of Technology: Bombay, India, 2012; pp. 1–25.
69. Rai, S.; Wasewar, K.L.; Lataye, D.H.; Mukhopadhyay, J.; Yoo, C.K. Feasibility of red mud neutralization with
seawater using taguchi’s methodology. Int. J. Environ. Sci. Technol. 2013, 10, 305–314. [CrossRef]
70. Copur, M.; Özmetin, C.; Özmetin, E.; Kocakerim, M.M. Optimization study of the leaching of roasted zinc
sulphide concentrate with sulphuric acid solutions. Chem. Eng. Process. Process Intensif. 2004, 43, 1007–1014.
[CrossRef]
71. Bayca, S.U.; Kisik, H. Optimization of leaching parameters of aluminum hydroxide extraction from bauxite
waste using the taguchi method. Environ. Prog. Sustain. Energy 2018, 37, 196–202. [CrossRef]
72. Taguchi, G.; Chowdhury, S.; Wu, Y. Taguchi’s Quality Engineering Handbook; John Wiley & Sons, Inc.: Hoboken,
NJ, USA, 2005.
73. Phadke, M.S.; Kackar, R.N.; Speeney, D.V.; Grieco, M.J. Off-line quality control in integrated circuit fabrication
using experimental design. Bell Syst. Tech. J. 1983, 62, 1273–1309. [CrossRef]
74. EL Bar, D.; Barket, D. Leaching of metals from hydrometallurgical residue by sulfuric acid. Asp. Min.
Miner. Sci. 2018, 1. [CrossRef]
75. Liu, Z.-R.; Zeng, K.; Zhao, W.; Li, Y. Effect of temperature on iron leaching from bauxite residue by sulfuric
acid. Bull. Environ. Contam. Toxicol. 2009, 82, 55–58. [CrossRef]
76. Vind, J.; Malfliet, A.; Bonomi, C.; Paiste, P.; Sajó, I.E.; Blanpain, B.; Tkaczyk, A.H.; Vassiliadou, V.; Panias, D.
Modes of occurrences of scandium in greek bauxite and bauxite residue. Miner. Eng. 2018, 123, 35–48.
[CrossRef]
77. Roy, R.K. A Primer on the Taguchi Method, 2nd ed.; Society of Manufacturing Engineers: Dearborn, MI,
USA, 2010.

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