Recovery of Niobium and Tantalum from tin ores Manono-Kitotolo tin ores by alkaline

fusion using potassium hydroxide (KOH)

Muliangala Mbalaba Francis1, *, Chungu Mwana Mwamba Yannick1, Mbayo Kasha Igor1, Kabangu Ngoie Michael1*,
Kasambay Mutangala Francis1, Mulunda Kadjele Bruce1, Kongolo Bulof Georges1,2, Ngenda Banka Richard1,
Kipepe Awaka Odon1, Kongolo Kitala Pierre1

1
Department of Metallurgy and Materials, Polytechnics faculty, University of Lubumbashi
2
Laboratory of Extractive Metallurgy, Polytechnics faculty, University of Lubumbashi

Corresponding authors: Muliangala.mbalaba@unilu.ac.cd, Kabangu.ngoie@unilu.ac.cd

Abstract
Coltan (columbite-tantalite), a mineral containing two strategically important metals (Niobium
and Tantalum), continues to fuel technological advances as a result of its multiple applications,
most notably in microelectronics. This paper showed an alkaline fusion process that has been
developed from niobium and tantalum recovering in trace form from Manono-Kitotolo tin ores,
using potassium hydroxide (KOH). Following an orthogonal matrix L 25 (53) of the experimental
designs, alkaline fusion tests were carried out by varying several parameters. The Taguchi
methods and analysis variance were used to optimize conditions the experimental variables. This
analysis shows that temperature is the most important parameter whichparameter that
considerably influences the extraction of niobium and tantalum. The optimal conditions used are
as followed (500 ˚C, KOH/ore mass ratio 3, 30 minutes) for niobium, (500 ˚C, KOH/ore mass
ratio 3, 150 minutes) for tantalum and (650 ˚C, KOH/ore mass ratio 1.5, 150 minutes) for tin. On
these conditions, the predictive model extracted 88, 99 and 41 % respectively for niobium,
tantalum and tin.
Keywords: Coltan, alkaline fusion, niobium, tantalum, potassium hydroxide, tin ores.
I Introduction
The 20th century has been characterised by a drastic increase in global material extraction, and
this trend is far from any changes in the 21st century [1,2]. In the last decades, there we have has
bseen a sharp considerable increase in the demand on for certain metals, especially intended for
the manufacture of electric and electronic components [3]. Niobium and tantalum, with high
melting points, hasve been utilized widely in the steel, electronic and other high-tech industries
[4,5]. These two metals frequently occur together in various minerals and in combination with
oxide impurities that impede their metallurgical processing [6]. Ccolumbite, tantalite, columbite-
tantalite (Coltan), pyrochlore, and euxenite constitute the major primary sources for niobium and
tantalum and are located in Canada, Brazil, Nigeria, Democratic Republic of the Congo and
Russia [7]. Niobium and tantalum are known to occur with cassiterite deposits [8]. In fact, their
abundance in the earth’s crust is quite low, tantalum with its symbol Ta being found around 2
ppm [9,10] and niobium with its symbol Nb around 24 ppm [11,12].
Coltan mineral is the largest resource natural of Ta that is found in ore deposits with appreciable
reserves in central Africa, especially in Democratic Republic of the Congo [13,14,15]. A large
number of chemical treatment procedures for the breakdown of primary sources has been
developed. Some of these has been adopted for commercial production while others hasve been
tested on a fairly large scale [1][15]. All tThosehese processes can essentially be divided into a
reduction to metallic or compound frorm, chlorination, alkaline fusion and acid dissolution
(leaching) [16]. At present, Mmost minerals containing niobium and tantalum nowadays are
decomposed by concentrated hydrofluoric acid [16, 17]. However, this method such an approach
is only appropriate for high-grade niobium-tantalum ore [18, 19]. Hydrofluoric acid is not ideal
for the decomposition stage because the process is heldedaccompanied by the loss of about 6-
7% of HF due to volatilization [20], which is hazardous. Furthermore, a large amount of
wastewater containing fluoride is generated that needs to be treated [1] [21]. Ffor a low -grade
niobium-tantalum ore, a new process for the decomposition has been proposed by Zhou et al,
(2005) and Wang et al, (2009) using a highly concentrated caustic potash (KOH) solution under
atmospheric pressure and a KOH roast-water leach solution, respectively [18, 19]. In this
process, the ore is decomposed in concentrated KOH solution (sub-molten salt) at atmospheric
pressure, giving about 10% higher decomposition higher than that for the HF process [1]. Indeed,
a prolific large amount of KOH solution is required to be evaporated and recycled in this
process, thatwhich is very energy intensive. This process is therefore the future of Niobium and
tantalum metallurgy because not only being clean, but also suitable for recovering of low-grade
ores containing Coltan.
The objective of this work is to recover Niobium and tantalum traces form from tin ores. Its also
aims to evaluate the behavior of this ore in tin dissolution processes. For this purpose, an alkaline
fusion using potash caustic (KOH) followed water leaching has been developed and two
statistical analysis (Taguchi approach and Variance Analysis (ANOVA) tools were used. Based
on experimental designs, aA Ttaguchi approach facilitates the consideration of the effects of
uncontrollable factors by identifying the optimal of combination parameters, while vVariance
aAnalysis (ANOVA) allows the measurement of the main effects of each factor on the response
beyond experimental variability.
II Materials and Method
Materials
The sample chosen for this study came from Manono-Kitotolo deposits in Manono city located at
Tanganyika province in South-East of the Congo Democratic Republic. 30 kg of primary sample
consisting of large particles were received and crushed until obtaining particles of dimensions
less than two2 mm. after homogenization by the quartering technique, samples of 5 kg were
taken from the ores collected at deposits.
Chemical characterization was determined using inductively coupled plasma atomic emission
spectroscopy (ICP-OES, PerkinElmer, Optima 8300) at the mineral analysis laboratory of the
Congolese Control Office and the results are presented in table 1. The mineralogical composition
of the ore was characterized by X-Ray Diffraction (XRD, Bruker D2 PhaserPhase) and the X-ray
diffraction pattern of the ore is shown in figure 1. The XRD analysis show that cassiterite and
Colombo-tantalite (Coltan) were the major valuable minerals present in the ore sample. Besides
the valuable minerals, the gangue material was mainly constituted of quartz, feldspar, iron oxide,
mica and phyllite minerals.
The reagents used in the alkaline fusion and leaching tests were potassium hydroxide (KOH:
85%) provided by Bethel Trading Solutions (BTS) SARL and water (H2O).
Method
For study an influence of the different parameters on alkaline fusion efficiency of the ore studied,
we opted for a statistical method using taguchi approach and analysis of variance (ANOVA) and
the tests carried out following experimental procedure:
- The Nb2O5 to Ta2O5 mass ratio in the ore was adjusted to a specified value and mixed
homogeneously before decomposition with KOH in the reactor;
- Weight y grams of KOH in a mass ratio and make an ore-KOH mixture in stainless steel
crucible;
- Place the crucible in the furnace for the duration of the processing time and heat the
furnace to the set temperature;
- Run the chronometer when the set temperature is reached and remove the crucible from
the furnace when set time is reached
- The roast obtained is thus cooled, dissolved in 250 ml of water for one hour.
III Results
1. Chemical characterization and mineralogical composition of ore
 Chemical characterization
Chemical analysis of tin ore by Inductively Coupled Plasma-Optical Emission Spectroscopy
(ICP-OES, PerkinElmer, Optima 8300) at the mineral analysis laboratory of the Congolese
Control Office show the results contained in table 1.
Table 1. Chemical Analysis results of the niobium-tantalum ore simple (wt. %)

Elements Nb Ta Sn Mn Fe Si Al
% 0,58 0,496 22,81 1,35 3,77 32,39 4,26

These results show that niobium-tantalum are in low-grade in the ore sample. Therefore, this is a
coltan poor ore. its concentration by gravimetric, electrostatic, magnetic and flotation methods
prove important in the conventional treatment process.
 Mineralogical composition
The X-Ray diffraction patterns of the ore is shown in figure 1.
 2. Alkaline fusion tests and taguchi approach
At this stage, several parameters can influence the dissolution of niobium and tantalum, such as:
mass ratio, temperature, time, particle size, etc. for this work, a batch tests following a taguchi
approach has been developed by varying three parameters during this fusion are: temperature,
mass ratio KOH/ore and time. In fact, the Ttaguchi factorial design combining 3 factors at 5
levels is shown in table 2.
Table 2. different parameters (factors) and their levels

Parameters
Levels
Codes
Names 1 2 3 4 5

A Temperature [°C] 350 425 500 575 650

B Mass ratio KOH/ore 1 1,5 2 2,5 3
Decomposition time
C 30 60 90 120 150
[min]

An alkaline fusion tests of tin ores from Manono-Kitotolo deposits realised to combine with
water leaching were performed in the order established by the orthogonal matrix L 25 (5^3) and the
results are presented in table 3.
Table 3. Taguchi experimental designs and extraction yields

Temperatur Mass ratio Decomposition Yield [%]

N°
e [°C] KOH/Ore time [min] Nb Ta Sn
1 350 1 30 45,35 34,97 14,12
2 350 1,5 60 52,27 50,35 25,61
3 350 2 90 34,38 33,93 14,18
4 350 2,5 120 54,81 52,49 21,42
5 350 3 150 75,67 81,05 28,64
6 425 1 60 75,32 83,34 24,23
7 425 1,5 90 82,71 93,06 36,68
8 425 2 120 52,9 60,06 30,99
9 425 2,5 150 68,11 81,32 37,73
10 425 3 30 85,66 92,17 22,65
11 500 1 90 79,02 85,28 20,08
12 500 1,5 120 69,17 76,52 33,57
13 500 2 150 75,83 85,77 39,15
14 500 2,5 30 74,42 83,73 33,45
15 500 3 60 72,42 82,5 40,15
16 575 1 120 27 28,24 25,72
17 575 1,5 150 47,38 51,45 36,44
18 575 2 30 71,29 79,39 37,21
19 575 2,5 60 65,02 74,05 31,82
 20 575 3 90 43,73 48,25 27,55
21 650 1 150 56,53 61,66 31,06
22 650 1,5 30 56,5 61,77 35,68
23 650 2 60 8,63 8,07 31,09
-24 650 2,5 90 44,13 47,11 35,7
25 650 3 120 48,74 52,78 39,96
It appears from table 3 that the best solubilizations for niobium, tantalum and tin are retained
respectively on tests 10, 7 and 15. The extraction yields are 85,66 % for niobium and 93,06 %
for tantalum.
 Statistical analysis of results for niobium
We present here the results obtained for niobium extraction using a tTaguchi method which,
introducing the signal-to-noise (SN) ratios, analyzes the response (yield in this case) and the
corresponding variation. The means values were calculated to determine the optimal level and
the influence of each factor on the niobium extraction yield. The table 4 shown a statistical
analysis result for niobium.
Table 4. means values for Signal to Noise Ratios for niobium extraction

Parameters
Level
A B C
1 34,12 34,46 36,26
2 37,14 35,61 32,82
3 37,4 31,71 34,55
4 33,66 35,61 33,69
5 31,09 36 36,08
Signal to Noise Ratios for
A3=500 °C B5=3,0 C1=30 min
optimal conditions
Delta 6,30 4,29 3,45
Parameters intercation,
71,05-4,12y 53,61+1,69y 61,11-0,81y
linear adjustment

Statistical analysis of table 4 and figure 4, has enabled us to identify the parameters that optimise
the niobium extraction yield, highlighting the effects of the factors and the high values of the
signal/noise ratios.
 Main Effects Plot for SN ratios
Data Means
Temperature [°C] Mass ratio KOH/Ore Decomposition time [min]
38

37

Mean of SN ratios 36

35

34

33

32

31
350 425 500 575 650 1,0 1,5 2,0 2,5 3,0 30 60 90 120 150

Signal-to-noise: Larger is better

Figure 1. Main effects of controllable factors on SN ratios statistical performance on niobium extraction

Indeed, the combination of parameters to give optimum recovery is A3B5C1, the letters are the
factors and the indices in figures are the parameter levels (table 4). The temperature: 500°C, the
mass KOH/ore ratio:3.0 and decomposition time: 30 minutes. The predictive model gives 88.7%
(S/N 40.3 dB) as the extraction yield.
The influence of the parameters is given by the Δ (Delta) value, which allows the extent or size
of the effects on the response (yield) to be assessed. It’s a purely statistical concept used in
engineering, calculated as the difference between the maximum and minimum marginal values
of a factor. The larger value corresponds to a larger influence on the response. In fact, table 4
gives different values of Delta and these values show the influence of the various parameters
during the tests.
 Interaction Plot for Recovery of Nb [%]
Data Means
1,0 1,5 2,0 2,5 3,0 30 60 90 120 150

80 Temperature
350
425
500
Temperature 40 575
650

0
80 mass ratio
KOH/ore
1,0
1,5
mass ratio KOH/ore 40 2,0
2,5
3,0

decomposition time

 Statistical analysis of results for tantalum

The table 5 show the statistical analysis results for tantalum extraction. These results can to determine the optima
and each parameter influence.

Table 5. means values for Signal to Noise Ratios for Tantalum extraction

Parameters
Level
A B C
1 33,62 34,55 36,49
2 38,17 36,23 33,26
3 38,35 32,20 35,15
4 34,46 36,38 34,22
5 31,53 36,78 37,01
Signal to Noise Ratios for
A3=500 °C B5=3,0 C5=150 min
optimal conditions
Delta 6,82 4,59 3,75
Parameters intercation,
73,85-3,43y 55,6+2,64y 64,16-0,195y
linear adjustment
 Main Effects Plot for SN ratios
Data Means
Temperature [°C] mass ratio KOH/Ore Decomposition time [min]
39

38

37
Mean of SN ratios

36

35

34

33

32

31
350 425 500 575 650 1,0 1,5 2,0 2,5 3,0 30 60 90 120 150
Signal-to-noise: Larger is better

Interaction Plot for Recovery of Ta [%]

Data Means
1,0 1,5 2,0 2,5 3,0 30 60 90 120 150
100
Temperature
350
425
500
50
Temperature 575
650

0
100
mass ratio
KOH/ore
1,0
1,5
50
mass ratio KOH/ore 2,0
2,5
3,0

decomposition time

 Statistical analysis of results for tin

the statistical analysis results of tin extraction during alkaline fusion shows in the table 6. better dissolution of tin
would be beneficial because its separation from niobium and tantalum in solution is by simple evaporation.
 Table 6. means values for Signal to Noise Ratios for Tin extraction

Parameters
Level
A B C
1 25,99 26,96 28,61
2 29,49 30,45 29,57
3 30,2 29,2 28,05
4 29,94 29,95 29,44
5 30,77 29,83 30,72
Signal to Noise Ratios for
A5=650 °C B2=1,5 C3=150 min
optimal conditions
Delta 4,78 3,49 2,67
Parameters intercation,
21,46-2,91y 25,42+1,59y 26,68-1,17y
linear adjustment

Main Effects Plot for SN ratios

Data Means
Temperature [°C] Mass ratio KOH/Ore Decomposition time [min]
31

30
Mean of SN ratios

29

28

27

26

350 425 500 575 650 1,0 1,5 2,0 2,5 3,0 30 60 90 120 150

Signal-to-noise: Larger is better

 Interaction Plot for Recovery of Sn [%]
Data Means
1,0 1,5 2,0 2,5 3,0 30 60 90 120 150
40 Temperature
350
425
30 500
Temperature 575
650
20

40 mass ratio
KOH/ore
1,0
30 1,5
mass ratio KOH/ore 2,0
2,5
20 3,0

decomposition time

3. Analysis of Variance
Analysis of Variance (ANOVA) was used to examine the statistical significance of the
developed nonlinear general model. The comparison term used to determine the significance of a
factor is the residual variance. Indeed, the level of significance (first kind risk) of 5% is used in
all tests of homogeneity. If the factor F calculated is better than the F in the tables, the parameter
then considered is significant. It should be noted that the Fisher – Snedecor tables (tables of
critical values for the F distribution) give these values of F.
 Analysis of variance for niobium recovery
Table 7 give an analysis of variance results for niobium recovery
Table 7. Analysis of Variance for niobium extraction

Source DF Adj SS Adj MS F- P-Value Pure-S Contribution

Value
  Temperature [°C] 4 3955,9 989,0 4,32 0,022 3040,2 35,98
  Mass ratio KOH/ore 4 820,7 205,2 0,90 0,496 Very low <0,00001
  Decomposition time [min] 4 926,9 231,7 1,01 0,439 11,3 0,13
Error 12 2747,3 228,9     63,89
Total 24 8450,8       100,00
F (4, 12) α=0,05 3,2
6
the results of table 7 relating to the analysis of variance (ANOVA) for niobium recovering show
that the value F (4,32) calculated for the temperature is better than the critical value F (3,26) read
in the Fisher – Snedecor at a significance level of α = 0,05. These results show that temperature
is a significant parameter in the extraction of niobium. A result which is also confirmed by the
critical probability or P-Value which is lower. Its contribution is nearly 36% while the rest is
squarely attributed to uncontrollable factors. The other two parameters would contribute to the
results as an interaction.
 Analysis of variance for tantalum
The tantalum analysis of variance results is presented in the table 8
Table 8. Analysis of Variance for Tantalum recovery

Source DF Adj SS Adj MS F- P-Value Pure-S Contribution

Value
  Temperature [°C] 4 6145 1536,4 5,00 0,013 4915,4 40,74
  Mass ratio KOH/ore 4 1068 266,9 0,87 0,511 Very low <0,00001
  Decomposition time [min] 4 1164 291,0 0,95 0,471 Very low <0,00001
Error 12 3689 307,5     59,26
Total 24 12066       100,00
F (4, 12) α=0,05 3,2
6

The values obtained in the table 8 for the analysis of variance relating to the extraction of
tantalum show that the value F (5) calculated for the temperature is better than the critical value
F (3,26) read in the Fisher – Snedecor at a significance level of α = 0,05. As for niobium,
temperature is the most significant parameter also for the extraction of tantalum. A result which
is also confirmed by a low P-value and its contribution is 40%. The other parameters would act
in interaction.
 Analysis of variance for tin

Source DF Adj SS Adj MS F- P-Value Pure- Contribution

Value S
  Temperature [°C] 4 603,3 150,82 6,64 0,005 512,6 36,98
  Mass ratio KOH/ore 4 343,6 85,91 3,78 0,032 253 18,25
  Decomposition time [min] 4 166,8 41,69 1,84 0,187 75,9 5,48
Error 12 272,4 22,70     39,30
Total 24 1386,1       100,00
F (4, 12) α=0,05 3,2
6
The values obtained in table 9 for tin extraction show that the statistics F (6,64 and 3,79)
calculated for the temperature and mass ratio KOH/ore are better than the critical value F (3,26)
read in the Fisher – Snedecor. This highlights that for tin recovery, the temperature and mass
ratio KOH/ore are the most significant parameters.

IV Conclusion
Niobium and tantalum recovery was done in traces form from Manono-Kitotolo tin ores by
alkaline fusion using potash caustic (KOH) followed water leaching. After sample
characterisation by Inductively Coupled Plasma-Optical Emission Spectroscopy and X-Ray
Diffraction, several tests have been carried out in order to see the behavior of these ores in
niobium and tantalum extraction. A taguchi approach and analysis of variance (ANOVA) were
used during tests and, 3 factors (temperature, mass ratio KOH/ore, decomposition time) were
taken at 5 levels in sight to optimize experimental conditions and highlight the factor effects on
the response, which can be a variable in a process or the measurement of the quality of a product.
the optimal conditions for signal to noise ratio analysis retained after the alkaline fusion tests are:
(500 °C, mass ratio KOH/ore: 3.0 and 30 minutes) for niobium, (650 °C, mass ratio KOH/ore:3.0
and 150 minutes) for tantalum and (650 °C, mass ratio KOH/ore: 1.5 and 150 minutes) for tin. In
these conditions
Acknowledgements
The authors would like to thank the managers of the laboratories of the Congolese Control Office
and the polytechnics Faculty of the University of Lubumbashi for having agreed to use their
equipment for certain analyses to which their results seemed to give added value to this study.
Conflicts of Interest
The authors declare no conflicts of interest regarding the publication of this paper.

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