Hydrometallurgy 66 (2002) 77 – 83

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Tantalum (V) and niobium (V) extraction

by octanol
V.G. Mayorov, A.I. Nikolaev *
Institute of Chemistry and Technology of Rare Elements and Mineral Raw Materials, Kola Science Centre, Russian Academy of Sciences,
26a Fersman Str., Apatity, 184200, Murmansk region, Russia
Received 14 August 2001; accepted 7 June 2002

Abstract

The extraction, separation and purification of Ta and Nb by octyl alcohol from fluoride and fluoride – sulphuric acid
solutions have been studied. Processes have been developed for solvent extraction of Ta and Nb pure compounds as the result of
processing tantalite and columbite and a more depleted rare metal mineral—loparite.
D 2002 Elsevier Science B.V. All rights reserved.

Keywords: Tantalum; Niobium; Octanol

1. Introduction tion with the production of pure pentoxides of these

The solvent extraction method is widely applied in
technologies of rare element compounds. A promising
extractant for the extraction and purification of Ta and
Nb is octanol-1 (OCL) (He et al., 1998; Mayorov et
al., 1998). In previous work (He et al., 1998), the
efficiency of OCL is shown to be comparable with
methyl isobutyl ketone (MIBK) commonly used in the
industrial technologies of Ta and Nb (Babkin et al.,
1988). However, OCL is preferable since MIBK is
fire- and explosion-hazardous and readily soluble in
aqueous solutions.
This work presents the results of investigation into
the conditions of Ta and Nb separation and purifica-
*
Corresponding author.
elements.
2. Experimental
In the experiments OCL-octanol-1 (CH3(CH2)6
CH2OH) was used. OCL has water solubility of
0.05 w/o, specific mass 824 kg/m3, boiling temper-
ature 195 jC, flash point 81 jC, the main product
content f 98%. The equilibrium during the Ta and
Nb extraction by OCL is achieved after less than
5 min. All the extraction experiments were con-
ducted at ambient temperature (18 F 2 jC). By
preliminary studies it was found that OCL and
other octanol isomers—octanol-2 and 2-ethylhexa-
nol—have similar extracting parameters. These
organic solvents are industrially manufactured and
reasonably priced. The methods of conducting the
experiments are described in detail in the works of

0304-386X/02/$ - see front matter D 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 4 - 3 8 6 X ( 0 2 ) 0 0 0 9 1 - 9
78 V.G. Mayorov, A.I. Nikolaev / Hydrometallurgy 66 (2002) 77–83

Mayorov and Nikolaev (1996) and Mayorov et al.

(1999).

3. Results and discussion

3.1. Comparison of extracting abilities of OCL and

tributyl phosphate (TBP)

In Table 1 and Fig. 1, the extracting properties of

OCL and TBP, another neutral organic solvent, often
applied for solvent extraction of rare elements includ-
ing Ta and Nb, are compared (Babkin et al., 1988). The
comparison was made both for the systems with low
Ta and Nb contents (Table 1) realized, for instance, in
some variants of the loparite process (Babkin et al.,
1988), and with high Ta and Nb contents (Fig. 1)—in
tantalite and columbite processes. Free HF is an
arbitrarily calculated content of HF in excess of the
formation of HTaF6, HNbF6, H2TiOF4, H2SiF6 com- Fig. 1. Ta and Nb extraction by OCL (Vo/Vaq = 1.5:1) and TBP (Vo/
plexes (in the systems in question, as was noted earlier Vaq = 0.75:1) from a solution 0.45 M Ta, 0.75 M Nb and 6 M free
(Mayorov and Nikolaev, 1996; Mayorov et al., 1999)); HF.
the dominating complexes have the above composi-
tion); Vo/Vaq is the ratio of organic and aqueous phase
volumes during the extraction. at an H2SiF6 content higher than 4 M, the extracting
As was earlier established (Mayorov and Nikolaev, ability of the less basic OCL will be close to that of
1996; Mayorov et al., 1999), Ta and Nb are more TBP even at the same Vo/Vaq value. This is indicative of
easily extracted by TBP from hexafluorosilicic acid the fact that the character of the influence of acids—
H2SiF6 solutions than from sulphuric acid solutions H + suppliers—on fluorometallate acids HTaF6 and
(systems with high H2SiF6 contents are realized, for HNbF6 distribution (Babkin et al., 1988) depends not
instance, during the processing of some kinds of on the acid type only [tetrafluorooxotitanic, hexafluor-
tantalite and columbite). For OCL this effect not only osilicic, hexafluorostannic, sulphuric and hydrochloric
holds (Table 1) but is even better pronounced than in (Mayorov and Nikolaev, 1996; Mayorov et al., 1999)]
the case of extraction by TBP. It can be anticipated that but on the nature of the organic solvent as well.
In systems with high Ta and Nb concentrations, the
degrees of extraction for both extractants in the
Table 1 conditions selected are approximately equal (Fig. 1).
Comparison of Ta and Nb extraction by OCL and TBP from
solution (M): 0.005 Ta, 0.1 Nb, 3 HFfree at Vo/Vaq = 1:10
However, the latter is achieved by increasing the ratio
Vo/Vaq for OCL twofold, and in terms of moles of the
Concentration (M) Extractant Extraction (%)
substance (the molecular mass of OCL is 133 whereas
H2SO4 H2SiF6 Ta Nb that of TBP is 266) the OCL consumption is 3.5 times
2 – OCL 18.0 3.4 as high. It should be noted that higher H2SO4 con-
4 – OCL 38.3 21.7 centration affects the element extraction more pro-
– 2 OCL 32.4 8.8
– 4 OCL 79.0 61.8
foundly using OCL than TBP.
2 – TBP 93.9 14.1 Notwithstanding its much lower extracting ability,
4 – TBP 95.5 45.0 OCL has a number of advantages over TBP. An
– 2 TBP 95.4 31.1 important characteristic feature of an extractant is its
– 4 TBP 95.5 93.1 stability on prolonged contact with process solutions.
 V.G. Mayorov, A.I. Nikolaev / Hydrometallurgy 66 (2002) 77–83 79

It is found that when the time of contact of OCL with 4

M HF, 5 M H2SO4 solution (Vo/Vaq = 1:1) is increased
to 280 days, the extraction of HF and H2SO4 falls
gradually from 36% to 26% and from 15% to 10%,
respectively, while OCL remains applicable for
repeated use. Under the same conditions, during TBP
extraction, after 70 days a homogeneous solution was
formed, which determines the limit of stability of this
extracting agent. The products of TBP destruction
(hydrolysis) contaminate niobium and tantalum prod-
ucts with phosphorus and other impurities (Babkin et
al., 1988), which renders TBP virtually inapplicable
for the production of high-purity Ta and Nb com-
pounds. Another shortcoming of TBP is its high
specific mass, which reduces separation of emulsions
and brings about greater size and higher cost of
extracting equipment.

3.2. Extraction, separation and purification of Ta and

Nb

The results of experiments characterizing the Ta Fig. 2. The effect of H2SO4 on Ta and Nb extraction from a solution
and Nb extraction are collected in Table 2 and Fig. 2. of 0.45 M Ta, 0.75 M Nb, 0 M free HF (Vo/Vaq = 1:1).
During the extraction from solutions with high Ti
contents obtained, for instance, in one of the variants
of the loparite concentrate processes (Sklokin et al., varying the acid content and the Vo/Vaq ratio, it is
2000), sulphuric acid was not introduced since the possible to conduct both consecutive and collective
solution acidity needed was achieved due to the extraction of Ta and Nb. It should also be noted that the
presence of tetrafluorooxotitanic acid (H2TiOF4) in introduction of H2SO4 improves the extracting char-
the system (Mayorov and Nikolaev, 1996; Mayorov acteristics of a system with OCL considerably. It is
et al., 1999, 2000). It is easily seen (Table 2) that by best to separate Ta and Nb from solutions with a mini-
mum HF concentration and an H2SO4 content around
2 M (Fig. 2).
Table 2
Ta and Nb extraction by OCL The scrubbing regimes of Ta and Nb extracts have
Starting solution composition (M) Vo/Vaq Extraction (%)
also been studied. The cleaning of tantalum from
impurities was controlled by distribution of the hard-
Ta Nb Ti Free HF H2SO4 Ta Nb Ti
est-to-remove impurity from this element, i.e. nio-
0.45 0.75 – – 1.5 – 0.8:1 38.0 2.7 – bium, whereas niobium cleaning was controlled by
0.45 0.75 – 15 – 0.8:1 22.0 40.0 –
0.59 1.14 – – 1.3 – 2.5:1 70.0 4.3 –
titanium distribution (Babkin et al., 1988). During the
0.70 – – – 0.2 3.0 1.2:1 91.0 – – Ta stripping, good results were obtained when water
0.33 0.62 0.1 – 0.8 2.0 0.8:1 84.3 7.4 – was used (Vo/Vaq = 7:1; the degree of Nb scrubbing in
0.45 0.75 – 6.5 4.0 1.5:1 85.0 88.0 – one stage was f 70%, on Ta transition to the aqueous
0.0068 0.15 1.9 4.5 – 1:1 95.8 36.5 0.23 phase, f 10%), and in the case of a 2 M H2SO4
0.0068 0.15 3.1 4.5 – 2:1 > 97 71.3 23.8
0.0045 0.11 2.5 9.0 – 1:1 97.3 81.8 3.0
solution doped with HF to 0.5 M (Vo/Vaq = 4:1), the
0.016 0.40 3.2 1.9 – 1:15 79.6 4.8 0.17 degree of Nb and Ta scrubbing was, respectively, 87%
0.021 0.46 4.1 8.8 – 1:2 93.0 84.0 3.2 and not more than 25%).
0.024 0.53 4.8 3.1 – 1:2 95.6 90.0 5.1 Table 3 presents the data on Nb extract scrubbing.
0.033 0.80 6.3 3.8 – 1:3 92.0 80.0 3.4 As is known (Babkin et al., 1988), Nb is harder to
80 V.G. Mayorov, A.I. Nikolaev / Hydrometallurgy 66 (2002) 77–83

Table 3 variant is actually effected not by fluoride – sulphuric

Scrubbing of niobium extract of the composition (M): 0.15 – 0.45 acid solutions, but a mixture of HF, H2SO4 and Ta or
Nb, 0.003 Ti
Nb.
Scrub solution composition (M) Vo/Vaq Extraction (%)
a
HF Nb Nbb Ti 3.3. Production of pure Ta and Nb compounds
0 – 10:1 49 86
10 – 10:1 28 87 It is known that octanol is applied for the production
14 – 10:1 22 86
of pure Ta and Nb in the technology of tantalite and
20 – 10:1 13 68
10c – 3:1 17 70 columbite (He et al., 1998). We have developed a
5 0.45 6:1 71 73 method for the processing of tantalite from a Urals
10 0.45 6:1 91 75 deposit incorporating the isolation of Ta from a solution
5 0.90 6:1 108 99 of a 0 –0.5 M free HF, 1.5– 2 M H2SO4 followed by Nb
10 0.90 6:1 132 87
extraction from a 7 – 10 M free HF, 5– 6 M H2SO4
a
When washed with niobium solution it means free HF con- solution. After scrubbing the Ta extract by a f2 M
centration.
b
When washed with niobium solution it means the ratio of the
H2SO4 solution doped with HF and then water, and Nb
amount of niobium in the washed extract to the initial one, %. extract by a 7– 13 M HF, 4– 5 M H2SO4 solution and
c
The solution also contains 5 M H2SO4. water, the cleaned Ta and Nb are isolated by treating the
organic phases with water. This flowsheet was used to
produce in batch experiments Ta and Nb pentoxides
clean from impurities than Ta. Therefore, we tried to with the content of controlled impurities (mg/kg) in
wash the Nb extract with a fluoride solution of this Ta2O5 –Sn, Pb, V, Cr, Mn, Co, Ni < 3, Mg V 3, Cu, Al,
element. The reason is that OCL is a weakly basic Ti, Zr, Bi < 5, Nb < 20, Ca, Si, Mo, Fe < 30 and in
extractant and is characterized by relatively low Nb2O5 –Mn < 1, Mg, Al < 3, Cu, Sn, Pb, V, Cr, Fe,
capacity and extracting ability. Introducing Nb to the Co < Ni < 4, Ti, Bi < 5, Ca, Si, Zr, Mo < 10, Ta < 50. The
scrubbing solution should increase the Nb content in contents of most of the impurities are lower than the
the extracting system and, consequently, the passing sensitivity of the analytical method used, namely, spark
of impurities from the organic phase to the aqueous mass-spectrometry.
one. For instance, introducing one of the separated Tantalite and columbite are relatively clean nio-
components to the scrubbing solution is successfully bium – tantalum raw materials. It is of considerable
employed in cobalt and nickel technologies (Ritcey interest to isolate Ta and Nb from solutions with a high
and Ashbrook, 1979). Re-extracts can be used as content of impurities, for instance, those resulting in
scrubbing solutions (directly or after evaporation), or one of the flowsheets of loparite processing (Sklokin et
solutions obtained by pentoxide dissolution in HF. al., 2000)—a unique rare metal source (rare earth
The results given in Table 3 testify to the possibility of titanoniobate) located on the Kola peninsula (Russia)
good purification of Nb either by HF (14 M) solution in huge quantities (Kudrin et al., 1999). The compo-
or a mixture of HF and H2SO4, and, particularly, by an sition of loparite concentrate (%): 37.8 TiO2, 7.98
Nb solution (0.9 M). Nb2O5, 0.63 Ta2O5, 31.8 Ln2O3, 0.69 ThO2, 3.62
Preliminary attempts to scrub Ta and Nb extracts SrO, 1.0 Al2O3, 1.90 Fe2O3, 4.80 CaO, 7.01 Na2O,
obtained from batch experiments have shown that the 2.42 SiO2. The above solutions are characterized by
most effective cleaning from impurities is achieved if high contents of Ti (molar ratio Ti/Nb/Ta f 210:25:1),
the organic phases are sequentially treated by a diluted silicon and other impurities. The introduction of
Ta or Nb solution ( < 0.4 –0.7 M) and a mixture of HF H2SO4 in the extracting system is ruled out, since
and H2SO4 and water. However, in a continuous duty H2SO4 hinders pyrohydrolysis of Ti fluoride solution
process it is sufficient to carry out only two latter (raffinate after Ta and Nb extraction) with the produc-
operations. During scrubbing with water much of the tion of TiO2 and HF (Sklokin et al., 2000). Fig. 3
metal purified passes to the aqueous phase, and since shows a flowsheet of Ta and Nb extraction by OCL
the water used cannot be added to the solution of a from fluoride titanium solutions based on collective
mixture of HF and H2SO4, the scrubbing under this extraction of Ta and Nb followed by their separation at
 V.G. Mayorov, A.I. Nikolaev / Hydrometallurgy 66 (2002) 77–83 81

Fig. 3. Solvent extraction of Ta and Nb from loparite (n is the number of extraction stages).

the stage of re-extraction. The key process stages of the Ta and Nb extraction it is sufficient to have three to
flowsheet were carried out under laboratory conditions four extraction stages. Hence, it follows that if seven
either on an extractor or in batch processing and the stages are used, the process may run at a smaller OCL
main body of the experimental data is given below. flow, for instance, at Vo/Vaq = 1:3 and it is possible to
Collective extraction of Ta and Nb in a continuous
counterflow regime was tested on an extractor of the
Table 4
mixer-settler type with the capacity in terms of the Component contents in multistage contactor, M
starting aqueous solution 0.5 L/h. The extraction was
NNa stages Organic phase Aqueous phase
carried out at Vo/Vaq = 1:2.5 from a solution with the
composition (M): 0.027 – 0.034 Ta, 0.64 – 0.79 Nb, Ta Nb Ti Ta Nb
5.2 – 6.4 Ti and 3 – 9 free HF. The distribution of 1 < 0.00027 0.0090 1.68 0.000059 0.00012
components at extractor stages at steady state is shown 2 – – – 0.000068 0.00023
3 < 0.00027 0.043 1.86 – 0.00059
in Table 4. Ta and Nb, as one would expect, are ex- 4 – – – 0.000086 0.00067
tracted much better than Ti, and while they are passing 5 0.0054 0.059 1.81 0.00014 0.0011
to the organic phase, Ti is displaced; its content in the 6 – – – 0.0021 0.022
organic phase reduces by more than sevenfold. It is 7 0.058 1.35 0.22 0.013 0.058
a
also clear that in order to ensure practically complete Along the extractant flow.
82 V.G. Mayorov, A.I. Nikolaev / Hydrometallurgy 66 (2002) 77–83
obtain extracts more concentrated in target compo-
nents and minimally contaminated with Ti and other
impurities. During the trials the Ta and Nb extraction
was not less than 99.6% at Ti co-extraction of about
1.7%.
The most effective solution for the extract scrub-
bing proved to be a fluoride solution 0.09 – 0.11 M Ta,
2.3– 2.8 M Nb with the Nb to Ta ratio close to the ratio
of these elements in loparite: in a continuous counter-
flow system the TiO2 impurity in the sum of Ta and Nb
pentoxides was reduced to < 0.02% and the passing of
Ta and Nb to the aqueous phase was < 20%. The
scrubbing solution used was joined to the solution
flowing to Ta and Nb extraction (Fig. 3), which ruled
out rare metal losses.
The Ta and Nb solution washed free of impurities
is sent to Nb re-extraction by water. It was found that
at Vo/Vaq f 3:1, approximately 80% Nb and less than
20% Ta pass to the aqueous phase in one stage. In a
counterflow regime the Nb concentration achieved in
Fig. 4. The effect of Nb content in the starting solution on Ta and
Nb extraction at the ratios Vo/Vaq = 0.9:1 and 1.2:1 (molar ratio Ta/
Nb = 1:1660, free HF concentration f 0 M).
the re-extract was 2.3 – 2.6 times as high and higher.
The tantalum-containing organic phase was washed
from Nb impurity by water or a Ta fluoride solution.
When the organic phase with the composition 0.11 M,
0.0015 M Nb was washed by 0.45 M Ta solution, the
level of washing Nb in one stage (Vo/Vaq = 5.1) was
around 80%. Ta re-extraction was carried out by
water. In one treatment (Vo/Vaq = 2:1) over 80% Ta
passed to the aqueous phase.
We have also studied the Nb re-extract purification
from Ta impurity (Fig. 4). The best separation of Nb
and Ta is achieved from solutions with the content
2.0 –2.7 M Nb at Vo/Vaq>1.2:1. The purified Nb re-
extract is sent to produce compounds, and the organic
phase is cleaned from rare metals by water treatment.
Using the flowsheet presented in Fig. 1, from the
collective extract of Ta and Nb, Ta and Nb pentoxides
are obtained in batch processing with the content of
controlled impurities (Cu, Ca, Al, Si, Ti, Zr, Sn, Pb, V,
Cr, Mo, W, Mn, Fe, Co, Ni) V 0.01 w/o each. The
contents of Nb in Ta and Ta in Nb are V 0.01 w/o.
These are the data of spectral emission analysis. Addi-
tional research now underway suggests the possibility
of diminishing the impurity content to the values close
to those obtained during tantalite and columbite pro-
cessing. The flowsheet is applicable for technologies
of other kinds of raw materials with macro-contents of
impurities, for instance, for tin slag processing.
4. Conclusion
Our studies have demonstrated high performance
of octanol in the solvent extraction technology of Ta
and Nb. Octanol is stable on prolonged contact with
process solutions, and has a number of advantages
over such well-known extractants as methyl isobutyl
ketone and tributyl phosphate. Using octanol allows
the near complete separation of Ta and Nb and
extensive purification of these elements from impur-
ities.
There have also been developed flowsheets for the
production of pure Ta and Nb not only from niobium
and tantalum-containing raw materials, tantalite and
columbite, but from raw materials with the content of
impurities exceeding the Ta and Nb contents by an
order of magnitude, for instance, from rare earth
titanium niobate, i.e. loparite. Octanol may find appli-
 V.G. Mayorov, A.I. Nikolaev / Hydrometallurgy 66 (2002) 77–83
cation in solvent extraction technologies of other
elements as well.
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