Minerals Engineering 178 (2022) 107401

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

A novel process for recovery of scandium, rare earth and niobium from
Bayan Obo tailings: NaCl-Ca(OH)2-coal roasting and acid leaching
Bo Zhang a, b, c, Xiangxin Xue b, c, He Yang b, c, *
a
State Key Laboratory of Baiyunobo Rare Earth Resource Researches and Comprehensive Utilization, Baotou 014030, PR China
b
School of Metallurgy, Northeastern University, Shenyang 110819, PR China
c
Liaoning Key Laboratory of Recycling Science for Metallurgical Resources, Shenyang 110819, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: Bayan Obo tailings from Baotou Steel were discharged into tailings pond. The advantages of symbiotic resources
Activated roasting have not been fully played. A large number of accumulated tailings also have a great impact on the surrounding
Sc-Fe-bearing silicate environment. Comprehensive utilization of valuable elements in tailings becomes key measure to solve the above
CaTiO3-type compounds
problems. Extraction of valuable elements, such as scandium, rare earth and niobium could be achieved by
Phase transition
Leaching rate
roasting Bayan Obo tailings in NaCl-Ca(OH)2-coal, followed by hydrochloric acid and sulfuric acid leaching. The
phase transitions of main minerals were investigated. In the roasting process, niobium minerals were converted
to CaTiO3-type compounds. The original rare earth minerals turned into rare earth oxide or rare earth silicate.
Iron in Sc-Fe-bearing silicate migrated to CaFeSiO4, FeSiO3 and Fe3O4. Meanwhile, the structure of silicate was
destroyed completely, which facilitated for leaching scandium. In the acid leaching process, newly generated
niobium minerals were dissolved in sulfuric acid as niobium sulfate or niobic acid. For Bayan Obo tailings, under
the optimal roasting and leaching conditions determined in this research, 97.6% Sc2O3, 97.18% REO and 40.1%
Nb2O5 entered hydrochloric acid. 51.67% Nb2O5 was leached by concentrated sulfuric acid. Sc2O3 and REO were
enriched in hydrochloric acid.

1. Introduction 10 times of that in raw ore. From the perspective of environmental

protection, some heavy metal ions in tailings pond will pollute
Bayan Obo deposit is well known as a large-scale polymetallic de­ groundwater with the infiltration of waste water into ground. In addi­
posit associated with iron, rare earth and niobium. The proven reserves tion, a small amount of radioactive thorium will bring radiation damage.
of iron ore in the deposit are 1.4 billion tons (Li, 2003). Rare earth (REO) No matter in terms of valuable element reserves or environmental re­
reserves are about 35 million tons. Prospective reserves of niobium quirements, it is worthy of further study for improving utilization rate of
(Nb2O5) are 6.6 million tons, ranking second in the world. The total associated resources in Bayan Obo tailings.
reserves of scandium (Sc2O3) are about 115,000 tons (Lin et al., 2007), Currently, sulfuric acid roasting method has become industrial
and thorium (ThO2) resource reserves of Bayan Obo mine are 221,000 approach for decomposing Bayan Obo rare earth minerals (Li, 2011).
tons (Xu, 2005). However, comprehensive utilization rate of niobium, The summary of previous works on recovering niobium from niobium
scandium and some other elements in Bayan Obo ore is very low. So far, minerals are listed in Table 1. Nearly all kinds of niobium minerals could
an industrial production process has not been established, and almost all be processed by H2SO4-NH4+ leaching, H2SO4-HF leaching or pressure
kinds of valuable elements have entered tailings pond. The reserves of dissolution with sulfuric acid (Guo and Wang, 2009; Ribagnac et al.,
iron, rare earth oxides, niobium oxide and thorium oxide in tailings 2017; Yang et al., 2014, 2018). At the decomposition process, consid­
pond can reach up to 31.3 million tons, 13.82 million tons, 272 thousand erable amount of hydrofluoric acid or NH4+ would enter the atmosphere
tons and 90 thousand tons, respectively (Wang et al., 2009). Nearly 70% or water body and cause environmental problems. Conventional method
of scandium in Bayan Obo ore was thrown into tailings pond (Zhang for decomposing niobium minerals in sub-molten salt system is accom­
et al., 2010). It is worth noting that scandium content in tailings is about panied by discharge of alkaline wastewater (Zhou et al., 2005). It also

* Corresponding author at: School of Metallurgy, Northeastern University, Shenyang 110819, PR China; Liaoning Key Laboratory of Recycling Science for
Metallurgical Resources, Shenyang 110819, PR China.
E-mail address: neuyanghe@163.com (H. Yang).

https://doi.org/10.1016/j.mineng.2022.107401
Received 1 April 2021; Received in revised form 16 December 2021; Accepted 7 January 2022
Available online 26 January 2022
0892-6875/© 2022 Elsevier Ltd. All rights reserved.
B. Zhang et al. Minerals Engineering 178 (2022) 107401

Table 1 2. Experimental
Summary of previous works on recovering niobium from niobium minerals.
Methods Advantages Disadvantages References 2.1. Materials
H2SO4-NH4+ Increasing leaching Generation of NH4+ Yang et al.
solution rate of niobium in containing wastewater (2018) Calcium hydroxide and sodium chloride are of laboratory reagent
leaching H2SO4 grade. Analytically pure sulfuric acid (98 wt%), hydrochloric acid (36.5
H2SO4-HF (1) Decrease of Pollution of volatile Guo and wt%) and deionized water were used in the leaching procedures. Pul­
solution solution boiling point. hydrofluoric acid Wang verized coal is the power of semi-coke with a fixed carbon content of
leaching (2) Reduction of HF (2009)
dosage.(3) Price
83.66%.
advantage of sulfuric Niobium concentrate (2.80 wt%Nb2O5) and silicate minerals used in
acid the experiment were supplied by Baotou Research Institute of Rare
HF solution Formation of (1) High volatility and Guo et al. Earths. Raw material containing scandium, rare earth and niobium was
leaching precipitate with corrosion to (2014)
the tailings of dressing rare earth minerals, iron oxides and fluorite from
impurity elements equipment.(2)
Treatment of fluorine Bayan Obo ore. Table 3 shows the chemical composition of Bayan Obo
wastewater tailings. The elements with high content are mainly Ca, Si and Fe.
Molten or sub- Elimination of fluorine (1) Discharge of Zhou et al. Compared with Bayan Obo oxide ores, scandium and niobium enrich
molten pollution at the source alkaline wastewater. (2005) more than three times in tailings (Zhang et al., 2019). Mineral compo­
alkali (2) High alkali
roasting- consumption
sition of the tailings in Table 4 indicates that main rare earth minerals in
water Bayan Obo tailings are bastnasite and monazite. Niobium mainly exists
leaching in ilmenorutile, aeschynite, niobite and pyrochlore (Lin et al., 2007).
Carbon Chlorination products Formation of poisonous Wang et al. Silicates account for 44.81% of the tailings. According to previous
chloride with different boiling Cl2 (2008)
research, niobium existing in niobium minerals takes 75% of the total
method point for separation
niobium. About 70% of scandium distributes in silicates as isomorphism
(Zhang et al., 2019). Therefore, these minerals mentioned above should
requires equipment within high corrosion resistance. Up until now, be taken into consideration for recovering valuable elements. Dolomite,
much work has been done to recovery scandium from silicate minerals, calcite and hematite naturally become main impurity minerals for the
too. The previous works on recovering scandium from Sc-bearing min­ recovery process. Actually, as thermal decomposed products of dolomite
erals are summarized in Table 2. Carbon chloride method was demon­ and calcite, CaO will play a role of activation agent in the roasting
strated to be effective for extracting scandium from Bayan Obo tailings process (Peng and Wang, 2001). Furthermore, hematite can be reduced
(Bao et al., 2015). However, formation of poisonous chlorine severely to magnetite which is easy to be separated at the reducing atmosphere.
restricts the popularization and application of this process. Besides that,
researchers also studied to recovery scandium from silicate minerals 2.2. Experimental procedures
with a combination process of activated roasting-hydrometallurgy
(Wang et al., 2011). NaKCO3, NaHCO3, CaCl2 and NaOH have been Niobium concentrate with a grade of 2.80% was further purified to
successfully applied in pretreatment as activation reagent. Due to mul­ meet the requirement of experiment. Due to density difference, low-
tiple options of harmless activation reagents, this combination process is density dolomite and calcite were first separated from niobium min­
considered to be environment friendly. erals in CH2I2 (Zhou, 2007). And then the high-density part was treated
Based on above analysis, a novel combination process was proposed by magnetic separator. Magnetite, hematite, iron-bearing silicate and
for extracting rare earth, niobium and scandium. NaCl-Ca(OH)2-coal rare earth minerals were separated from niobium mineral through
was determined as roasting system in this research paper. Calcium hy­ adjusting exciting current gradually. With the methods of heavy liquid
droxide was selected as clean activator for activated roasting process. separation and magnetic separation, niobium concentrate grade was
Sodium chloride was added together to accelerate the mass transfer of increased to 42.33%.
reactant by providing liquid phase at low temperature. Addition of Bayan Obo tailings containing niobium and scandium were mixed
pulverized coal will promote iron transfer to recyclable magnetite. with NaCl-Ca(OH)2-coal in certain proportions. Then the mixture was
Moreover, hydrochloric acid and sulfuric acid were considered to be put in crucible and roasted at predefined roasting temperature in muffle
used in fractional leaching process. Application of cheaper Ca(OH)2 and furnace for a given time. When the holding time was up, the crucible was
NaCl not only reduces process costs, but also avoids the generation of taken out from furnace and cooled down naturally. The roasted ore was
poisonous gas and alkaline wastewater. leached in hydrochloric acid solution under stirring. And the leaching
liquid was separated from leaching residue by filtering. After repeated
washing and drying, the residue was further leached in concentrated
sulfuric acid for intensified leaching. The experimental apparatus for
leaching experiment is shown in Fig. 1. And Fig. 2 is flowchart of the
Table 2 whole process described above.
Summary of previous works on recovering scandium from Sc-containing The roasting and sulfuric acid leaching process for niobium
minerals. concentrate is the same as the process mentioned above. The difference
Methods Advantages Disadvantages References is that leaching solution of niobium concentrate was directly crystallized
H2SO4 pressure low cost High pressure Li and Li for further research.
leaching resistance (2014) The determination of objective elements in solid or liquid samples
requirement to was carried out by using ICP-OES (Inductively Coupled Plasma Optical
equipment
Emission Spectrometer). Based on ICP analysis data of residue and
Chlorination Higher conversion Low leaching rate Wang et al.
roasting-HCl of niobium minerals (2008) leachate from each leaching stage, element leaching efficiency was
leaching to chloride calculated. The calculation method is according to Eq. (1).
CaCl2-C roasting- High leaching rate Generation of Cl2 and Bao et al.
HCl leaching HCl (2015) C×V
Leaching efficiency = × 100% (1)
Molten NaOH Low reaction Generation of alkaline Li (2011) w×m
roasting temperature wastewater

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B. Zhang et al. Minerals Engineering 178 (2022) 107401

Table 3
Chemical composition of Bayan Obo tailings (wt%).
Na2O K2O MgO CaO BaO MnO2 SiO2 TiO2 ThO2 Al2O3 FeO

2.25 0.93 5.14 11.68 3.15 1.50 33.26 1.08 0.021 2.24 2.38
Sc2O3 REO P2O5 Nb2O5 F S TFe Magnetic Iron Burning loss
0.030 2.14 0.87 0.36 3.14 2.15 15.74 <0.50 7.81

Table 4
Mineral composition of Bayan Obo tailings (wt%).
Magnetite Hematite Siderite Ilmentite Pyrite Rutile Ilmenorutile

0.61 13.56 0.01 0.26 3.13 0.27 0.42

Bastnasite Monazite Epidote Aeschynite Fergusonite Pyrochlore Niobite
0.97 0.49 0.16 0.24 0.02 0.11 0.01
Pyrolusite Fluorite Apatite Barite Wollastonite Feldspar Amphibole
0.14 1.93 1.26 2.71 0.31 5.77 15.04
Pyromicite Mica Serpentine Chlorite Quartz Dolomite Calcite
16.38 7.62 0.32 0.40 9.37 13.16 3.87

where C is the element concentration of leaching liquid, g/L; V is the

volume of leaching liquid, L; w is the mass fraction of element, %; m is
the mass of roasted ore or hydrochloric acid leaching residue, g.

3. Results and discussion

3.1. Phase transition of niobium in the activated roasting process

Owing to low-content niobium of Bayan Obo tailings, it is difficult to

study phase transition mechanism of niobium through analyzing roasted
Bayan Obo tailings. In this section, the interaction law between niobium
concentrate and NaCl-Ca(OH)2-coal will be comprehensively investi­
gated. To provide sufficient activator for activated reactions of niobium
minerals, Ca(OH)2 amount is determined by the chemical reaction in Eq.
(2), in which consumption of Nb2O5 to Ca(OH)2 is the largest. Moreover,
coal consumption also reaches the peak if the hematite in Bayan Obo
tailings is reduced into metallic iron completely as Eq. (3). In order to
simulate this reducing atmosphere, the mass ratio of coal-ore is deter­
Fig. 1. Experimental apparatus for leaching experiment. mined as 5:100. The direct purpose of adding NaCl is to accelerate re­
action rate through providing liquid phase at 800 ◦ C. However, previous
exploration experiments had indicated that the roasted products will
appear agglomeration phenomenon which goes against the elements
leaching at a NaCl-ore mass ratio higher than 10:100. In that case, NaCl,
Ca(OH)2, coal and niobium concentrate should be mixed with a mass
ratio of 10:20:5:100.

Nb2O5 + 2Ca(OH)2 = Ca2Nb2O7 + 2H2O(g) (2)

Fe2O3 + 3C = 2Fe + 3CO(g) (3)

3.1.1. Thermal analysis of niobium concentrate-NaCl-Ca(OH)2-coal

Fig. 3 shows TG-DSC curves of the mixture (mass ratio of niobium
concentrate-NaCl-Ca(OH)2-coal as 100:10:20:5). Four endothermic
peaks can be observed in the DSC curve during the heating process. The
temperature of the first endothermic peak is 418.9 ◦ C, and the mass of
reaction system decreases significantly near this temperature. The mass
loss at this stage may be caused by water volatilization and thermal
decomposition of calcium hydroxide in the mixture. The temperature of
the second endothermic peak is 616.9 ◦ C. The slight mass loss of 1.22%
may be caused by endothermic reaction between niobium concentrate
and calcium hydroxide. The temperature of the third endothermic peak
is 888.3 ◦ C. The sharp mass decrease around 888.3 ◦ C results from phase
Fig. 2. Flowchart of the new process. reconstruction of niobium minerals under the joint action of molten
sodium chloride and calcium hydroxide. The initial temperature of this
reaction is about 800 ◦ C. The temperature of the fourth endothermic

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Ti0.8Fe0.1Nb0.1O2 also became weaker at 800 ◦ C. After roasting at

800 ◦ C, Nb-containing perovskite and residual aeschynite, rutile, bro­
centite in roasted products can be dissolved in hot concentrated sulfuric
acid (Zhang, 2012). Niobium minerals tended to completely decompose
as the roasting temperature increased.
The roasted products at 800 ◦ C were characterized by SEM-EDS. Its
elemental mapping images are shown in Fig. 5. As can be seen, Fe dis­
tributes relatively uniformly at the whole scanning area, and the dis­
tribution areas of Na and Cl are consistent. The distribution indicates
that Na and Cl are still present as sodium chloride in the newly formed
niobium minerals. Sodium chloride did not significantly participate in
the reconstruction proccess of niobium phase. It only played a role of
accelerating mass transfer as expectations. The distribution areas of Ca,
Nb and Ti are overlapping to a large extent, indicating that Ca, Nb and Ti
are tightly bound. Fig. 6 shows SEM image and EDS spectra of roasted
products. It can be seen from Fig. 6(a) that the boundaries of the mineral
particles are clear, and the sintering behavior among niobium minerals
and other reactants is not observed. As shown in Fig. 6(b), the niobium-
Fig. 3. TG-DSC analysis of niobium concentrate-NaCl-Ca(OH)2-coal. containing minerals in the roasted products are mainly composed of Nb,
Ca, Ti, O and rare earth elements. Based on researches above, it can be
judged that the niobium in concentrate migrates to niobium-containing
peak is 1064.7 ◦ C. The mass loss around 1064.7 ◦ C may be caused by
perovskite. This conclusion is consistent with XRD analysis.
reduction reaction of a small amount of iron oxide in niobium
concentrate.
3.1.3. Phase transition law of niobium minerals with Ca(OH)2 amount and
roasting time
3.1.2. Phase transition law of niobium minerals at different roasting
Effect of Ca(OH)2 amount on phase transition of niobium minerals
temperatures
was investigated under the following conditions: niobium concentrate,
Based on the TG-DSC results, roasting experiments were carried out
sodium chloride, coal at a mixing ratio of 100:10:5, 800 ◦ C for roasting
at 600 ◦ C, 700 ◦ C and 800 ◦ C. Other experimental parameters are as
temperature. Fig. 7 shows XRD patterns of products after roasting
follows: niobium concentrate, sodium chloride, calcium hydroxide and
niobium concentrate with different Ca(OH)2 amounts. It can be seen that
coal at a mixing ratio of 100:10:20:5, roasting time of 2 h. Fig. 4 shows
diffraction peaks intensity of natural niobium minerals such as
XRD patterns of products at different temperatures.
Ti0.8Fe0.1Nb0.1O2 and CeTiNbO6 were gradually weakened with the in­
It can be seen that the niobium phases have changed significantly
crease of Ca(OH)2 amount. With Ca(OH)2 amount less than 10%, newly
after calcination. Newly generated niobium phases mainly include
formed niobium minerals were mainly (Na0.5Ce0.3Ca0.2)(Ti0.8Nb0.2)O3.
(Na0.5Ce0.3Ca0.2)(Ti0.8Nb0.2)O3 and (Ca0.7Na0.3)(Ti0.7Nb0.3)O3, indi­
At Ca(OH)2 amount higher than 10%, (Ca0.7Na0.3)(Ti0.7Nb0.3)O3 and
cating that calcium hydroxide obviously participated in the mineral
(Ca,Na)(Nb,Ti,Fe)O3 were first detected in the roasted products. As
phase reconstruction of niobium minerals. Appearance of new niobium
shown in Fig. 7, with the increase of Ca(OH)2 amount, diffraction peaks
phases diffraction peaks reveals that the transformation of natural
intensity of Ti0.8Fe0.1Nb0.1O2 and CeTiNbO6 gradually decreased while
niobium minerals to Nb-containing perovskite had occurred at 600 ◦ C.
the diffraction peaks intensity of newly generated Nb-containing
However, diffraction peaks of natural niobium minerals such as rutile
perovskite gradually increased.
(Ti0.8Fe0.1Nb0.1O2) and aeschynite (NdTiNbO6) were still observed
At 800 ◦ C, phase transition law of niobium minerals with roasting
clearly due to insufficient decomposition of niobium minerals at 600 ◦ C.
time is shown in Fig. 8. (Na0.5Ce0.3Ca0.2)(Ti0.8Nb0.2)O3 and (Ca0.7Na0.3)
Increasing roasting temperature to 700 ◦ C and 800 ◦ C, diffraction peaks
(Ti0.7Nb0.3)O3 successively appeared in the roasted products at 0.5 h and
intensity of new niobium phases were significantly strengthened
1 h. Extending roasting time, diffraction peaks intensity of these two
compared with that at 600 ◦ C. Diffraction peaks intensity of

Fig. 4. XRD patterns of products at different temperatures.

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B. Zhang et al. Minerals Engineering 178 (2022) 107401

Fig. 5. SEM image and elemental mapping images of roasted products.

Fig. 6. (a) SEM image and (b) EDS spectra of roasted products of niobium concentrate.

phenomenon of niobium in aeschynite has been confirmed in the

research report of Wang and Zhao (2007). Because of crystals damage
and quasi-crystallization of CeNbO4, diffraction peaks only appeared at
the XRD pattern after heating and recrystallization (Ma et al., 1981), and
then became weaker with niobium transfer.

3.2. Activated roasting of silicate mineral in NaCl-Ca(OH)2-coal

As main Fe-Sc associated silicate mineral in Bayan Obo tailings,

thermal decomposition of acmite in NaCl-Ca(OH)2-coal system was
studied in this section. According to reaction between NaFeSi2O6 and Ca
(OH)2 shown in Eq. (4), the mass ratio of NaFeSi2O6-Ca(OH)2 should be
100:48. To investigate iron phase type in the decomposition process, Ca
(OH)2 amount needs to be controlled lower than the theoretical amount.
Fig. 7. XRD patterns of products under different Ca(OH)2 amounts.
The determination principle of NaCl amount and Ca(OH)2 amount are as
same as that in Section 3.1. In this investigation, NaFeSi2O6, NaCl, Ca
minerals kept increasing while diffraction peaks intensity of (OH)2 and coal were mixed with a mass ratio of 100:10:20:5. Fig. 9
Ti0.8Fe0.1Nb0.1O2 and NdTiNbO6 showed a trend from ascent to descen. shows the TG-DSC analysis of NaFeSi2O6-NaCl-Ca(OH)2-coal. Mass loss
This trend resulted from enrichment of niobium towards rutile, of the mixture in heating process could be divided into three stages. The
aeschynite and migration to Nb-containing perovskite. Concentration temperature range of the first stage is 420.8–458.6 ◦ C, in which the mass

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B. Zhang et al. Minerals Engineering 178 (2022) 107401

Fig. 8. XRD patterns of products at different roasting time.

Fig. 9. TG-DSC analysis of NaFeSi2O6-NaCl-Ca(OH)2-coal.

loss and heat absorption were caused by decomposition reaction of Ca

Fig. 10. XRD pattern of the roasted products of NaFeSi2O6-NaCl-Ca(OH)2-coal.
(OH)2. The temperature range of the second stage is 660.8–714.5 ◦ C.
Main reaction in this stage may be decomposition reaction between
niobium minerals and Ca(OH)2. The third stage is within a temperature
range of 1000–1100 ◦ C, the endothermic reaction may be the reduction FeSiO3 + CaO = CaFeSiO4 (7)
reaction of iron-containing minerals. According to analysis above, it can
be inferred that decomposition temperature of acmite is around
702.9 ◦ C, which is much lower than the melting temperature of NaCl.
Therefore, decomposition reaction of acmite in NaCl-Ca(OH)2-coal 3.3. Activated roasting of Bayan Obo tailings
should be controlled around 801 ◦ C (melting point of sodium chloride).
The mixture of NaFeSi2O6, NaCl, Ca(OH)2 and coal was roasted at The Bayan Obo tailings were roasted under the optimum roasting
800 ◦ C for 2 h. XRD pattern of the roasted products is shown in Fig. 10. condition determined by the leaching experiments in Section 3.4. XRD
Diffraction peaks of iron-containing minerals indicate that Fe3O4, pattern of the roasted products is shown in Fig. 11. It can be seen that the
CaFeSiO4 and FeSiO3 had become carrier minerals of iron in roasted iron-containing phases in the roasted ore mainly contain Fe3O4, FeSi2
silicate. Part of iron in NaFeSi2O6 was successfully reduced to ferro­ and Fe2SiO4. Iron in hemaite could be separated from roasted ore by
magnetic at 800 ◦ C. In the roasting process, decomposition products of weak magnetic separation. The rare earth in roasted ore mainly exists as
NaFeSi2O6 was reduced to hematite. Then the freshly formed hematite rare earth oxides (Ce2O3) and rare earth silicates (Nd4Si3O12) which can
was partially reduced into FeO, which further transformed to CaFeSiO4 be recovered through acid leaching.
or FeSiO3 through chemical reaction. Activated roasting reaction of
NaFeSi2O6 can be described with Eqs. (4)–(7). 3.4. Mechanism of leaching niobium with sulfuric acid

2NaFeSi2O6 + 3Ca(OH)2 = Fe2O3 + Na2SiO3 + 3CaSiO3 + 3H2O(g) (4) The roasted products of niobium concentrate was subjected to sul­
3Fe2O3 + CO = 2Fe3O4 + CO2 (5) furic acid leaching. The leaching conditions are as follows: 98%
concentrated sulfuric acid, acid-ore ratio of 8:1 (ml/g), leaching tem­
Fe3O4 + CO = 3FeO + CO2 (6) perature of 300 ◦ C, leaching time of 1 h. Leaching solution and residue

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B. Zhang et al. Minerals Engineering 178 (2022) 107401

at the points 1 and 2 are niobium sulfate. Existence of niobium sulfate in

crystals also proves that the roasted niobium minerals are soluble in
sulfuric acid. The formation reactions of niobium sulfate are shown in
Eqs. (11) and (12).

(Ca0.7Na0.3)(Ti0.7Nb0.3)O3 + 1.85H2SO4 = 0.15Na2SO4 + 0.7TiOSO4 +

0.15Nb2O3(SO4)2 + 0.7CaSO4 + 1.85H2O(g) (11)

(Na0.5Ce0.3Ca0.2)(Ti0.8Nb0.2)O3 + 1.9H2SO4 = 0.3CeNa(SO4)2 + 0.1Na2SO4

+ 0.8TiOSO4 + 0.1Nb2O3(SO4)2 + 0.2CaSO4 + 1.9H2O(g) (12)

3.5. Roasting-leaching of elements in Bayan Obo tailings

3.5.1. Effect of sodium chloride amount on leaching

Bayan Obo tailings were mixed with NaCl-Ca(OH)2-coal (mass ratio
of Ca(OH)2, coal and tailings equal to 50:5:100) and roasted at 800 ◦ C
for 2 h. Then the roasted products was leached in hydrochloric acid
Fig. 11. XRD pattern of roasted products of fluorite tailings-NaCl-Ca solution (6 mol/L) at 90 ◦ C for 2 h. The leaching residue was dried and
(OH)2-coal. continually leached in concentrated sulfuric acid (18 mol/L) at 300 ◦ C
for 1 h. Acid-ore ratios for hydrochloric acid leaching and sulfuric acid
were dried for removing residual acid. Then the drying materials were leaching are 8:1 (ml/g) and 4:1 (ml/g), respectively.
analyzed by X-ray diffraction. Result in Fig. 12 shows that Nb-containing Effects of NaCl amount on the leaching rates of elements in hydro­
mineral in residue and crystals is mainly Nb2O5. The mineral phase chloric acid and sulfuric acid are shown in Fig. 14. It can be seen from
analysis has proved non-existence of Nb2O5 in the roasted niobium Fig. 14 that the leaching rates of scandium, rare earth increased with the
concentrate. Hence, Nb2O5 comes from the crystallization of leaching increase of NaCl amount. The leaching rate of niobium first increased
solution. The presence of Nb2O5 in crystals reveals that roasted niobium and then decreased with increase of sodium chloride amount. Analyzing
minerals have dissolved in sulfuric acid. Related reactions of sulfuric the leaching laws of elements in sulfuric acid, it can be found that the
acid leaching and crystallization can be described as Eqs. (8)–(10). leaching rates of the three elements in sulfuric acid showed a downward
trend. Generally, increase of NaCl amount has little effect on the total
(Ca0.7Na0.3)(Ti0.7Nb0.3)O3 + 1.55H2SO4 = 0.15Na2SO4 + 0.7TiOSO4 +
leaching rates of scandium and rare earth. Unlike scandium and rare
0.3Nb(OH)5 + 0.7CaSO4 + 0.8H2O(g) (8)
earth, total leaching rates of niobium decreased steadily with increasing
(Na0.5Ce0.3Ca0.2)(Ti0.8Nb0.2)O3 + 1.7H2SO4 = 0.3NaCe(SO4)2 + 0.1Na2SO4 NaCl amount. The suitable NaCl amount is 10%.
+ 0.8TiOSO4 + 0.2Nb(OH)5 + 0.2CaSO4 + 1.2H2O(g) (9)
3.5.2. Effect of Ca(OH)2 amount on leaching
2Nb(OH)5 = Nb2O5(s) + 5H2O(g) (10) To optimize Ca(OH)2 amount, various amounts of Ca(OH)2 were
According to relevant reports, there should be a certain amount of studied while kept sodium chloride amount at 10%. Other process pa­
niobium sulfate (Nb2O3(SO4)2) existing in the crystals (He et al., 2018; rameters were constant with that in Section 3.5.1. Fig. 15 respectively
Zhang et al., 2014). Due to the lack of powder diffraction card of show the influence of Ca(OH)2 amount on the leaching rates of elements
Nb2O3(SO4)2, Nb2O3(SO4)2 cannot be detected by X-ray diffraction. The in hydrochloric acid and sulfuric acid.
leaching residue and crystals were analyzed by SEM-EDS. EDS results In this series of experiments, the increase of Ca(OH)2 amount has no
and elemental mapping images of related areas are shown in Fig. 13. It significant effect on the leaching of scandium and rare earth in hydro­
can be seen from EDS spectra that the main elements of points 1 and 2 chloric acid. And the leaching rate of niobium decreased dramatically
are O, S, Ca, Ti, Fe and Nb. According to the elemental mapping images with further increasing Ca(OH)2 amount. That may be due to con­
of the box area in SEM image, the distribution areas of S and O obviously sumption of excessive Ca(OH)2 to hydrochloric acid. The leaching rate
cover the distribution area of Nb, which indicates that Nb is combined of niobium in sulfuric acid shown in Fig. 15 tended to increase with
with O and S in this area. It can be inferred that Nb-containing material raising Ca(OH)2 amount, but the total leaching rate of niobium in the
two-step acid leaching process did not change significantly. The result
indicates that the roasted niobium minerals had been fully dissolved in
sulfuric acid solution at Ca(OH)2 amount of 20%. It also reflects that
amount of hydrochloric acid has an impact on the distribution of
niobium in different acid.

3.5.3. Effect of sulfuric acid ratio on leaching

According to experiment result of Section 3.5.2, the total leaching
rates of scandium and rare earth were all closer to 95% while the highest
total leaching rate of niobium failed to reach 90%. In this section, sul­
furic acid leaching condition will be optimized to improve leaching rate
of niobium. Five groups of roasted ore numbered as 1–5 were leached by
hydrochloric acid. Then the corresponding leaching residues were
leached in sulfuric acid successively with acid-residue ratio varying from
2:1 to 10:1 (ml/g). Amounts of NaCl and Ca(OH)2 were respectively kept
as 10% and 20%. Other experimental conditions were consistent with
that in Section 3.5.1. The leaching rates of each element in hydrochloric
acid and sulfuric acid are shown in Table 5 and Fig. 16.
Fig. 12. XRD pattern of residue and crystals . It can be seen from Table 5 that scandium and rare earth in roasted

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B. Zhang et al. Minerals Engineering 178 (2022) 107401

Fig. 13. SEM-EDS analysis and elemental mapping images of the dried products.

ore can be effectively leached by hydrochloric acid. And the leaching hydrochloric acid shown in Fig. 17 is due to the lack of acid. Moreover,
rate of niobium in hydrochloric acid fluctuated within a small range the scandium and rare earth also had low leaching rates in sulfuric acid.
between 15% and 20%, which is due to uneven distribution of niobium Part of scandium or rare earth may combine into double salt in Na-
minerals. As observed in Fig. 16, the leaching rate of scandium in sul­ containing sulfuric acid solution. That led to low leaching rates of
furic acid maintained at about 6% and the total leaching rate of scan­ scandium and rare earth in sulfuric acid. Increasing the ratio of hydro­
dium was about 98%. The leaching rate of niobium gradually increased chloric acid-roasted ore, the leaching rates of elements in hydrochloric
with the increase of acid-residue ratio. Increasing the acid-residue ratio acid enhanced significantly. The total leaching rates of each element in
higher than 8:1, the leaching rate of niobium had no significant change. this condition also increased obviously. More importantly, scandium
Optimal acid-residue ratio in the sulfuric acid leaching process should be and rare earth began to concentrate in hydrochloric acid under an acid-
8:1. roasted ore of 6:1. This distribution characteristic is conducive to the
further extraction and separation of the three target elements.
3.5.4. Effect of hydrochloric acid ratio on leaching Continuing to increase the ratio of hydrochloric acid-roasted ore, scan­
The roasted ore was leached in hydrochloric acid while varying the dium and rare earth became more concentrated in hydrochloric acid
hydrochloric acid-ore ratio from 2:1 to 10:1 (ml/g). Then the leaching solution. As the ratio of hydrochloric acid-roasted ore increased to 10:1,
residues were numbered as 1–5 and leached in sulfuric acid in turn. In the leaching rates of scandium, rare earth and niobium in hydrochloric
this section, amounts of NaCl and Ca(OH)2, sulfuric acid-residue ratio acid reached to 97.46%, 97.18% and 40.41%, respectively. In this
were all kept at optimum conditions. Other process conditions are the condition, the leaching rates of scandium, rare earth and niobium in
same as that in Section 3.5.1. Fig. 17 shows the leaching rates of each sulfuric acid were 0.56%, 0.86% and 51.67%, respectively. Therefore,
element in hydrochloric acid under different acid-ore ratios. The 10:1 (ml/g) was selected as the best hydrochloric acid-roasted ore ratio.
leaching rates of each element in sulfuric acid are shown in Table 6.
Low leaching rates of scandium, rare earth and niobium in

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B. Zhang et al. Minerals Engineering 178 (2022) 107401

Fig. 14. Influence of NaCl amount on elements leaching. Fig. 16. Influence of sulfuric acid-residue ratio on sulfuric acid leaching.

Fig. 17. Influence of hydrochloric acid-roasted ore ratio on leaching.

Fig. 15. Influence of Ca(OH)2 amount on elements leaching.

Table 6
Table 5
Leaching rates of each element in sulfuric acid.
Leaching rates of elements in hydrochloric acid for each group of experiment.
HCl leaching residue Leaching rates of elements/%
Roasted ore Leaching rates of elements/%
Sc2O3 REO Nb2O5
Sc2O3 REO Nb2O5
1 84.32 77.34 91.81
1 92.86 98.19 22.55
2 39.32 28.59 74.38
2 91.65 97.92 21.38
3 6.67 1.69 42.26
3 92.30 98.25 17.34
4 6.95 1.41 49.21
4 91.85 98.11 18.36
5 0.56 0.86 51.67
5 91.90 98.04 16.16

(1) In the system of NaCl-Ca(OH)2-coal, niobium concentrate un­

4. Conclusions
dergoes phase transformation in the roasting process. The newly
generated minerals are mainly (Na0.5Ce0.3Ca0.2)(Ti0.8Nb0.2)O3
A novel activated roasting-leaching process was developed to recycle
and (Ca0.7Na0.3)(Ti0.7Nb0.3)O3. In the activated roasting process,
valuable elements from Bayan Obo tailings comprehensively. The re­
the diffraction peaks of (Na0.5Ce0.3Ca0.2)(Ti0.8Nb0.2)O3 and
action mechanism of objective minerals which own independent min­
(Ca0.7Na0.3)(Ti0.7Nb0.3)O3 appear in the XRD patterns of the
erals in the roasting-leaching process were investigated. The influence of
roasted products successively with the increase of Ca(OH)2
roasting and leaching conditions on the leaching results of valuable el­
amount. Niobium in minerals first enriches in aeschynite and
ements in Bayan Obo tailings was analyzed. The main conclusions of this
rutile, and then migrates to (Na0.5Ce0.3Ca0.2)(Ti0.8Nb0.2)O3 and
research are as follows:
(Ca0.7Na0.3)(Ti0.7Nb0.3)O3. The research on sulfuric acid leaching

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B. Zhang et al. Minerals Engineering 178 (2022) 107401

of the roasted ore shows that (Na0.5Ce0.3Ca0.2)(Ti0.8Nb0.2)O3 and Development Program of China (No. 2012CBA01205).
(Ca0.7Na0.3)(Ti0.7Nb0.3)O3 could be dissolved in sulfuric acid.
(2) The roasting experiment of natural acmite shows that acmite References
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Acknowledgments

This work is supported by the Major State Basic Research

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