Hydrometallurgy 173 (2017) 1–8

Contents lists available at ScienceDirect

Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Reduction leaching of rare earth from ion-adsorption type rare earths ore: II. MARK
Compound leaching
Xiao Yanfeia,⁎, Lai Fuguoa, Huang Lic, Feng Zongyub, Long Zhiqib
a
School of Metallurgical and Chemical Engineering, Jiangxi University of Science and Technology, Jiangxi 341000, China
b
National Engineering Research Center for Rare Earth Materials, General Research Institute for Nonferrous Metals, Beijing 100088, China
c
Institute of Engineering & Research, Jiangxi University of Science and Technology, Jiangxi 341000, China

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

Keywords: The colloidal sediment phase rare earth was little leached even if the pH of leaching agent reached 1.00, but part
The ion-adsorption type rare earths ore of it could be reduction leaching by the ferrous ion. To solve the problems appeared in the FeSO4 leaching
Reduction process, a magnesium-ferrous compound leaching was put forward in this paper. It was demonstrated that lower
FeSO4 proportion of Mg/Fe and higher acidity of leaching agent, could result in a higher rare earth leaching efficiency
Compound leaching
and relative a bigger cerium partition in the leaching liquor. But the leaching performance of the magnesium-
Ascorbic acid
ferrous compound leaching system was unsatisfactory because of some problems. Therefore, another compound
leaching method using MgSO4 and ascorbic acid was proposed, taking advantage of the reducibility and the
ability to strengthening the leaching process of ascorbic acid. It was shown that about 50% rare earths colloid
sediment phase was dissolved into the leaching liquor when with 0.20 mol/L MgSO4 and 0.5 g/L ascorbic acid.
85.85% rare earth leaching efficiency and a low content of Fe and Al were achieved as well. Therefore, com-
pound leaching with MgSO4 and ascorbic acid was proposed to an excellent alternative leaching agent for further
studies, which may realize efficiency extraction, low consumption and be environmentally friendly.

1. Introduction can be expressed as Eq. (1). The reaction is an ion-exchangeable process

between the cations in the leaching agent and the rare earth absorbed
Rare earth elements (REEs) comprise of 15 lanthanides, scandium on the clay minerals (Chi and Tian, 2006).
and yttrium. They are usually divided into three categories except Pm
[Al 4 (Si 4 O10 )(OH)8 ]m ·nRE3 +(s) + 3nNH+4 (aq) ↔ [Al 4 (Si 4 O10 )(OH)8 ]m ·
and Sc (Xu, 2002), light rare earth elements (LREEs), middle rare earth
elements (MREEs) and heavy rare earth elements (HREEs). The MREEs 3nNH+4 (s) + nRE3 +(aq) Eq. (1)
and HREEs, which are of vital importance for the hi-tech industry be-
where: s and aq represent solid phase and aqueous phase, respectively.
cause of their unique properties, are high-priced and in low-supply
And m, n represent for Arabic numerals.
(Chen, 2011). The ion-adsorption type rare earths ore, first discovered
Although the (NH4)2SO4 leaching agent has been widely used in
at 1969, are mainly located in the seven provinces of South China. This
industrial production, there are still some problems as follows: (1)
kind of ore has many advantages, such as complete rare earth partition,
7–9 tons (NH4)2SO4 consumption was required for every tons of rare
low radioactivity, simple leaching process and rich in the middle and
earth concentrate, which could lead to a serious ammonia-nitrogen
heavy rare earth elements, which makes it a valuable strategic mineral
pollution (Xiao et al., 2015a). (2) (NH4)2SO4 could desorb most of rare
resource (Chi and Tian, 2006).
earth in the ion-exchangeable phase, but not the colloidal phase which
Rare earth in the ion-adsorption type rare earths ore exists in four
accounts for above 5% of whole-phase rare earth (Tian et al., 2013). For
phases (Chi et al., 2005): Water soluble phase, ion-exchangeable phase,
the first problem, an innovative magnesium salt leaching agent (Xiao
colloidal sediment phase and minerals phase. The ion-exchangeable
et al., 2015b) was proposed by our team to deal with the ion-adsorption
phase rare earth accounts for more than 80% of whole-phase rare earth
type rare earths ore. With the new leaching agent, the problem of
in general. It can be easily released when encountering the cations
ammonia nitrogen pollution could be solved. Moreover, the application
(such as NH4+, Mg2 +) (Tian et al., 2010). Nowadays, rare earth is
of magnesium salt leaching agent could maintain the soil nutrient so as
recovered with (NH4)2SO4 in the industry, and the leaching reaction
to reduce the dosage of calcium–magnesium fertilizer, and may realize

⁎
Corresponding author at: No. 156 Kejia St., Ganzhou, Jiangxi Province 341000, China.
E-mail address: [email protected] (X. Yanfei).

http://dx.doi.org/10.1016/j.hydromet.2017.07.006
Received 21 September 2016; Received in revised form 5 June 2017; Accepted 25 July 2017
Available online 25 July 2017
0304-386X/ © 2017 Elsevier B.V. All rights reserved.
X. Yanfei et al. Hydrometallurgy 173 (2017) 1–8

the ecological friendly leaching of the ion-adsorption type rare earths 30

RE partition (%) RE partition (%) RE partition (%) RE partition (%)

ore (Xiao et al., 2016a). Meanwhile, the reduction leaching of rare earth Minerals phase
from ion-adsorption type rare earths ore with FeSO4 was put forward to 20
solve the second problem (Xiao et al., 2016b). The column leaching
experiments of the ion-adsorption type rare earths ore were carried out 10

in the condition of 0.20 mol/L leaching agent, pH 2.00, a flow rate of

0.6 mL/min, 25 °C. It was shown that the rare earth leaching efficiency 0

with FeSO4 leaching agent was about 85.50%, and it was only 81.58% 60
Colloidal sediment phase
when with (NH4)2SO4 agent (The content of ion-exchangeable phase
40
rare earth was accounted for 83.33% of the whole-phase rare earth in
the experimental sample). Moreover, the study of the existing state of 20
rare earth in the leaching residues showed that part of colloidal sedi-
ment phase rare earth could be reduction leached by Fe2 + and the 0

leaching efficiency was about 50%. However, the use of FeSO4 may 30
Ion-exchangeable phase
bring environmental problems, increase the consumption of impurity
20
removal reagents and the precipitation agent, lead to high costs and low
product purity. 10
In view of the environmental friendly characteristics of MgSO4 and
the reduction properties of FeSO4, the magnesium-ferrous compound 0

leaching of rare earth from ion-adsorption type rare earths ore was put 30
Whole phase
forward, it had been taken into consideration to solve problems existed 20
in the FeSO4 leaching process, and to achieve none of ammonia-ni-
trogen emissions from the source. In this paper, the analysis on the 10
leaching of colloidal sediment phase rare earth was carried out, and the
0
influence of Mg/Fe proportion and pH values of compound leaching
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Y
agent on rare earths leaching were presented. Moreover, in view of the
reduction property and coordination capability with rare earth, the RE element
ascorbic acid was chosen as the addition agent, and the compound Fig. 2. Rare earth partition in different phases for LT ore sample.
leaching with MgSO4 and ascorbic acid was simply performed in this
paper. Hence, a feasible operation would be provided for the leaching
phase and 0.16‰ minerals phase. The rare earth partition of different
of colloidal sediment phase as well as for realizing efficiency extraction
phase from the LT ore had been determined by ICP-AES (PerkinElmer,
and environmental friendly.
Co., Ltd. Optima 8300) and shown in Fig. 2. Rare earth in this ore
contained 15 rare earth elements except Pm and Sc. It can be seen from
2. Experimental the rare earth partition of the ion-changeable phase in Fig. 2 that the
rare earth ore was the type of middle Y and rich Eu, shown in the.
2.1. The characterization of experimental ion-adsorption type rare earths
ore 2.2. Apparatus and experimental procedure

The experimental ion-adsorption type rare earths ore was from All chemicals used in the experiments, such as FeSO4, MgSO4 and
completely weathered layer, obtained from Liutang (LT) Rare Earth ascorbic acid, were of analytical grade. Unless specific stated, all the
Mine area located in the Chongzuo City. solutions were prepared with deionized distilled water and the ex-
The existing state of rare earth in the LT rare earths ore was de- periments were performed at ambient temperature (ca. 25 °C).
termined with the sequential fractionating extraction methods (Chi In the column leaching process, columns of 40 mm inner diameter
et al., 2005), the results were shown in Fig. 1. The content of ion-ex- were used as the leaching equipment, similar to that described with
changeable phase rare earth was 1.50‰, accounted for 83.33% of the other chromatographic experiments. Precision pumps (Baoding Longer
whole-phase rare earth. Moreover, there was 0.14‰ colloid sediment Precision Pump Co., Ltd., BT100-1F) were used to control the flow rate
of leaching agent to 0.60 mL/min. 300 g dried rare earth ore in a spe-
1.8 cific particle size, obtained by the method of quadrate, was packed into
the column and slightly tapped to make sure that the packed bed height
1.6
was of 20 cm in different experiments. The ore in the column was eluted
Rare earth content (‰, mass fraction)

1.4 with leaching agent in a certain pH. Leaching liquor was collected from
the bottom of column, and every 25 mL leaching liquor was collected as
1.2
one sample. Finally, there were a total of 10 samples and 250 mL
1.0 leaching liquor in the experiments. The existing state of rare earth in
the leaching residues was also determined with the sequential fractio-
0.8
nating extraction methods (Chi et al., 2005).
0.6 The concentration of rare earth elements, aluminum and iron in the
leaching liquor samples were analyzed by ICP-AES (PerkinElmer, Co.,
0.4
Ltd. Optima 8300). The pH of leaching liquor samples was tested by pH
0.2 meter (Mettler Toledo, Co., Ltd. M400). From the analysis results, the
rare earth leaching efficiency (η, %) and Ce partition (δ, %) in total
0.0
Whole-phase Water-soluble Ion-exchangeable Colloidal sediment Minerals 250 mL leaching liquor are calculated according to the following Eqs.
Phases (2) and (3):

Fig. 1. Rare earth content in different phases for LT ore sample. η = ε v ε0 Eq. (2)

2
X. Yanfei et al. Hydrometallurgy 173 (2017) 1–8

δ = Ce250 RE250 Eq. (3) 0.34

0.35 0.33
pH=1.00
where: εV (g) is the total amount of rare earth in total V (collected 0.31 0.31 pH=1.50

Rare earth content (‰, mass fraction)

volume) ml leaching liquor, and ε0 (g) is the total amount of whole- 0.30 pH=2.00
pH=3.00
phase rare earth in the original experiment ore sample. Ce250 (g) is the
total amount of Ce element (Calculated by CeO2) in total 250 mL 0.25
leaching liquor. RE250 (g) is the total amount of rare earths (Calculated
by REO) in total 250 mL leaching liquor. 0.20
0.16 0.16 0.16 0.16
0.14 0.14
0.15 0.13 0.13
3. Results and discussion
0.10
3.1. The analysis on the leaching of colloidal sediment phase rare earth
0.05 0.04
0.03
0.02 0.02
The colloidal sediment phase rare earth was divided into two parts
(Chi and Tian, 2006), the first part referred to the rare earth adsorbed 0.00
0.00 0.00 0.00 0.00

on Fe/Mn colloid by coordination (Chi et al., 2005, 1994), which could Whole-phase Water-soluble Ion-exchangeable Colloidal-sediment Minerals

be released by ions with stronger adsorption ability or very strong Phases

acidic conditions (Chi et al., 2000; Ran and Liu, 1993). The second part Fig. 4. Rare earth content in different phases for the leaching residues in single MgSO4
referred to the rare earth oxide or hydroxide bonded with or deposited leaching system.
on the mineral (Deng et al., 1996; Chi et al., 1999), mainly CeO2/Ce
(OH)4 (Chi et al., 2005). The cerium partition in the colloidal sediment
decrease with high acidity. Therefore, the colloidal sediment phase rare
phase was as high as 55.84%, shown in Fig. 2, which indirect demon-
earth was little leached even if the pH of leaching agent reached 1.00.
strated that most of colloidal sediment phase were the second part.
In the case, the rare earth leaching efficiency was only 83.27% and the
Cerium ions (IV) are very easy to hydrolysis to form cerium hy-
rare earth content in colloidal sediment phases for the leaching residues
droxide in the solution, and can be precipitated when the solution pH is
was 0.13‰.
0.8 (Chi and Tian, 2006). This is one of the important reasons which
It was shown that direct acid dissolution of CeO2 was very difficult.
lead to the Ce Loss Effect in the ion-exchangeable phase (Chi et al.,
However, it will become easier by adding H2O2 in the system (Xu,
2006; Nesbitt, 1979). Moreover, according to the Eh-pH diagram of
2002). CeO2/Ce(OH)4 would be reduction dissolved and Ce3 + could be
cerium (Zhang, 2000; Wang, 2004; Kim and Osseo-Asare, 2012), the
acquired when there was a reductive agent in the system. The reaction
solution pH should be less than 0.5 to obtain Ce4 + by acid dissolution
could happen as Eq. (4) (Zhang, 2000; Kim and Osseo-Asare, 2012; Li,
of CeO2/Ce(OH)4, consistent with the reported results (Chi et al., 2000;
1980). φ denoted the electrode potential. Therefore, hydroxylamine
Um and Hirato, 2013). It was also reported that CeO2/Ce(OH)4 was
hydrochloride (Chi and Tian, 2006), sodium sulfite (Chi et al., 2002)
very slowly dissolved in acid solutions, it took more than 48 h to dis-
and ferrous sulfate (Huang et al., 2014) was used to leaching the col-
solve 0.02 mol cerium dioxide powder in 8 mol/L sulfuric acid at 125 °C
loidal phase rare earth, especially the second part. Taking Fe2 + for
(Um and Hirato, 2012).
example, the potential was 0.769 V (Tianjin university, 2009) for the
In order to discuss whether the experimental acidity could leach the
oxidation of Fe2 +, which was shown in Eq. (5). According to the Eh-pH
colloidal sediment phase or not, the column leaching experiments was
diagram of cerium (Xiao et al., 2016b; Kim and Osseo-Asare, 2012),
carried out with magnesium sulfate leaching agent in different acidity.
when the pH of leaching system was less than 4.0, CeO2/Ce(OH)4
The results were shown in Figs. 3 and 4. With the decrease of pH, more
would be reduction leached by Fe2 + and Fe2 + was oxidized to Fe3 +.
ion-exchangeable phase rare earth was leached and the rare earth
The rare earth leaching efficiency were about 85.50% and about 50% of
leaching efficiency increases slightly (He et al., 2016; Xiao et al.,
the colloidal phase rare earth was extracted when with 0.20 mol/L
2015c). The Ce partition in the leaching liquor and the content of
FeSO4 leaching agent in pH 2.00. The mechanism of reduction leaching
colloidal sediment phase in the leaching residues had just a little
had been detailed explained with Eh-pH diagram of cerium in the paper
(Xiao et al., 2016b). But FeSO4 leaching agent may reveal environ-
90
RE leaching efficiency mental problems, would also increase the cost of production and reduce
Comprehensive Ce partition 6 the purity of the product.
85
Ce(OH)4 + 4H+ + e− ↔ Ce3 + + 4H2 O φ = 1.68 − 0.23∗pH (V)
RE leaching efficiency(%)

5 Eq. (4)
80
Fe2 + − e− ↔ Fe3 + φ = 0.769 (V)
Ce partition (%)

Eq. (5)
75 4

3.2. Leaching characteristics of magnesium-ferrous compound leaching

70
3
system with different proportion

65
In order to solve the problems appeared in the ferrous sulfate
2
leaching process, such as iron pollution, high costs for more raw ma-
terial consumption and low product purity, experiments were con-
60 ducted by changing the proportion of MgSO4 and FeSO4 in the mag-
1.0 1.5 2.0 2.5 3.0
nesium-ferrous compound leaching system. In the leaching process, the
pH of leaching agent
total concentration of leaching agent was 0.20 mol/L and the pH of
Fig. 3. RE leaching efficiency and Ce partition with different initial pH of leaching agent leaching agent was adjusted to be 2.00 by sulfuric acid, consistent with
in single MgSO4 leaching system. previous studies (Xiao et al., 2016a). In the reduction leaching process,
(The average particle size of rare earths ore 1.0 mm, leaching temperature 298 K, flow since the content of colloid sediment phase was only 0.14‰, a small
rate 0.60 mL/min, 0.2 mol/L MgSO4 leaching agent).
amount of ferrous ions were used to provide reductive surroundings

3
X. Yanfei et al. Hydrometallurgy 173 (2017) 1–8

90 Furthermore, the iron concentration elution curve and pH elution

83.33% curve in the leaching process were also developed under different Mg/
80 Fe proportion, shown in Figs. 7 and 8. Due to the consumption of iron
Rare earth leaching efficiency (%)

ions, iron concentration in leaching liquor was low in initial leaching

70 stage, then increased rapidly in the first 125 mL. The bigger the pro-
portion of Mg/Fe was, the lower the iron concentration in the leaching
60 liquor was. Meanwhile, in Fig. 8, the pH of leaching liquor was higher
MgSO4:FeSO4=0:100
than the initial pH of the leaching agent because of the buffer function
MgSO4:FeSO4=90:10
50 of clays, and it would reduce with the increase of collected volume
MgSO4:FeSO4=98:2
because the buffering capacity of clay minerals is gradually destroyed
MgSO4:FeSO4=99:1
40 (Xiao et al., 2015c). When the Mg/Fe proportion was 0:100, the pH of
MgSO4:FeSO4=99.5:0.5 leaching liquor was lower than other proportion because of the pre-
30 MgSO4:FeSO4=100:0 sence of a large number of iron ions and its strong hydrolysis in the
system.
20 The total amount of iron ions and aluminum ions in total 250 mL
0 50 100 150 200 250 300
leaching liquor were calculated and shown in Fig. 9. The content of iron
Collected volume (mL)
ions increased with the decrease of Mg/Fe proportion, and the content
Fig. 5. Rare earth leaching efficiency curve under different Mg/Fe proportion. of aluminum ions was always between 40 mg and 70 mg. When the
(The average particle size of rare earths ore 1.0 mm, leaching temperature 298 K, proportion of Mg/Fe was less than 99:1, the concentration of iron ions
leaching agent concentration 0.20 mol/L, flow rate 0.60 mL/min, pH = 2.00). was high enough, and the leaching liquor was easy to turn tawny and
turbid because of the oxidation of ferrous ions and the hydrolysis of
and to ensure stoichiometric excess. Hence, the Mg/Fe proportion was ferric ions. More importantly, the presence of iron ions, whether ferrous
chosen as 90:10, 98:2, 99:1, 99.5:0.5 in the experiments. In addition, or ferric, would increase costs by consuming impurity removal reagents
leaching characteristics of single FeSO4 and MgSO4 were also taken for and the precipitation agent in the extraction process, and even result in
comparison. low purity of rare earth enrichment and increase operating loads of the
Related rare earths leaching efficiency curves were shown in Fig. 5. follow-up separation process(Xiao et al., 2015d; Qiu et al., 2012). The
The rare earth leaching efficiency increased rapidly in the first 150 mL, more the iron ions were, the more serious the problems were. In view of
then slowed down as time went on, which indicated that rare earth these, 99:1 was chosen as a suitable Mg/Fe proportion for the following
leaching behavior was controlled by kinetics in the first 150 mL and experiments. With this condition, the rare earth leaching efficiency was
then approached to equilibrium. Data in Fig. 5 demonstrated that rare 83.50%, the Ce partition was 3.20%, and the content of colloidal se-
earth leaching efficiency slightly increased with the decrease of the Mg/ diment phases in the leaching residues was 0.12‰. Moreover, the
Fe proportion, it could increase to exceed 83.33% finally when the Mg/ content of Al and Fe in the total 250 mL leaching liquor was 40.88 mg
Fe proportion was smaller than 99.5:0.5. It was highest to be about and 1.33 mg, respectively.
85.50% when the Mg/Fe proportion was 0:100. Moreover, Ce partition
and the content of colloidal sediment phases in the leaching residues 3.3. Leaching characteristics of magnesium-ferrous compound leaching
under different Mg/Fe proportion were listed in Fig. 6. In the leaching system with different pH
system, the second part colloidal sediment phase rare earth, mainly
CeO2/Ce(OH)4, was leached by Fe2 +. With the decrease of the Mg/Fe The acidity of the leaching agent not only affected the leaching of
proportion, the reaction equilibrium of Eq. (4) would move to the right, ion-exchange phase rare earth, but also the colloidal phase rare earth.
so that the Ce partition increased and the content of colloidal sediment Therefore, the effects of the leaching agent acidity were studied in a
phases in the leaching residues decrease. For example, when the Mg/Fe Mg/Fe proportion of 99:1. Under the circumstances, the concentration
proportion was 90:10, the Ce partition was 4.08%, and the content of of iron in the leaching solution was 112.00 mg/L. The sulfuric acid was
colloidal sediment phases in the leaching residues was 0.10‰. used to adjust the acidity. Rare earth leaching efficiency curve with

0.18 6.50 Fig. 6. Ce partition in the leaching liquor and the content of colloidal
sediment phases in the leaching residues under different Mg/Fe
6.00 proportion.
The content of colloidal sediment phases (‰)

0.16
5.50

0.14 5.00
Ce partition (%)

4.50
0.12
4.00
0.10
3.50

0.08 3.00

2.50
0.06
2.00

0.04 1.50
0:100 0:10 98:2 99:1 99.5:0.5 100:0

MgSO4:FeSO4

4
X. Yanfei et al. Hydrometallurgy 173 (2017) 1–8

Fig. 7. Iron concentration elution curve of leaching liquor under

1000
different Mg/Fe proportion.

800 10000
Concentration of iron ions (mg/L)

Concentration of iron ions (mg/L)

MgSO4:FeSO4=0:100
600 MgSO4:FeSO4=90:10
MgSO4:FeSO4=98:2 8000
400
MgSO4:FeSO4=99:1
MgSO4:FeSO4=99.5:0.5
120 6000
100
80
60 4000
40
20
0
2000
0 50 100 150 200 250 300
Collected volume(mL)

5.0 90
MgSO4:FeSO4=0:100 83.33%
MgSO4:FeSO4=90:10 80
4.5 MgSO4:FeSO4=98:2 Rare earth leaching efficiency (%)
70
MgSO4:FeSO4=99:1
MgSO4:FeSO4=99.5:0.5
4.0 60
MgSO4:FeSO4=100:0

50
pH

3.5
40
pH=1.00
pH=1.50
30
3.0 pH=2.00
pH=3.00
20

2.5 10
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Collected volume(mL) Collected volume (mL)

Fig. 8. pH elution curve of leaching liquor under different Mg/Fe proportion. Fig. 10. Rare earth leaching efficiency curve with different initial pH of leaching agent.
(The average particle size of rare earths ore 1.0 mm, leaching temperature 298 K,
leaching agent concentration 0.20 mol/L, MgSO4:FeSO4 = 99:1, flow rate 0.60 mL/min).

Fig. 9. The content of main impurities in total 250 mL leaching li-

2400 90
quor under different Mg/Fe proportion.
2250 85

Fe 80
2100
Al 75
1950
70
The content of Fe (mg)

The content of Al(mg)

65

150 60
55

100 50

45

50 40

35

0 30

25
0:100 90:10 98:2 99:1 99.5:0.5 100:0

Proportion of MgSO4 and FeSO4

5
X. Yanfei et al. Hydrometallurgy 173 (2017) 1–8

Fig. 11. Ce partition in the leaching liquor and the content of col-
0.16 7.00
loidal sediment phases in the leaching residues with different initial
pH of leaching agent.
6.50
The content of colloidal sediment phases (‰)

0.14
6.00

Comprehensive Ce partition (%)

0.12 5.50

5.00
0.10
4.50
0.08
4.00

0.06 3.50

3.00
0.04
2.50

0.02 2.00
1.00 2.00 3.00
pH

different pH was presented in Fig. 10. With the decrease of the pH, the
rare earth leaching efficiency was slightly increased and was almost all 250
more than 83.33% when the collected volume was 250 mL finally. The Concentration of iron ions (mg/L)
Ce partition in the leaching liquor and the content of colloidal sediment
phases in the leaching residues with different initial pH of leaching 200
agent was shown in Fig. 11. With the decrease of pH, the redox reaction pH=1.00
between colloidal sediment phase rare earth and reductive ions became 150 pH=1.50
more intense, so that the Ce partition increased from 2.92% to 6.36% pH=2.00
and the content of colloidal sediment phases decrease from 0.14‰ to pH=3.00
0.06‰. It could be seen that the vast majority of the ion-exchangeable 100
phase was desorbed, and the slightly increase of rare earth leaching
efficiency with the decrease of pH was due to the leaching of colloidal
50
sediment phase rare earth.
Similarly, the pH elution curve and iron concentration elution curve
of leaching liquor were investigated and shown in Figs. 12 and 13. pH 0
of leaching liquor would reduce with the increase of collected volume, 0 50 100 150 200 250
shown in Fig. 12. It would slowly approach to the pH of the leaching Collected volume (mL)
agent when the buffering capacity of clays was destroyed (Breemen and Fig. 13. Iron concentration elution curve under different initial pH of leaching agent.
Wielemaker, 1974), the results were basically in accord with the de-
scription in the references (Xiao et al., 2015c). When the initial pH of
hydrolyzed and precipitated. They would all enter into the leaching
the leaching agent was 1.00, the pH of leaching liquor decreased from
liquor, resulting in higher concentration in the leaching liquor than it
1.50 to about 1.00. At this case, the iron in the mineral could been
was in leaching agent, shown in Fig. 13. When the initial pH of the
leached (Shi et al., 2011). And the added ferrous ions in the leaching
leaching agent was 1.50, the pH of leaching liquor decreased from 4.00
agent and the generated ferric ions by redox reaction would not be
to about 2.00 and the iron concentration in the leaching liquor in-
creased with the increase of collected volume. On this condition, the pH
4.5 of leaching liquor was about 4.00 at the beginning of leaching process
because of the buffering capacity of clay minerals, the generated ferric
4.0 ions would be hydrolyzed and remain in ore. With the decrease of pH,
the hydrolysis tendency became weaker, and the iron in the mineral
3.5
would be leached, then the iron concentration in the leaching liquor
could increase to a higher level than it was in leaching agent. When the
3.0
pH=1.00 initial pH of the leaching agent was larger than 2.00, the pH of leaching
pH=1.50
liquor was larger than 3.50 all the time. The iron concentration in the
pH

2.5 pH=2.00
pH=3.00 leaching liquor was basic consistent and kept at a lower levels because
2.0 of the hydrolysis of generated ferric iron.
Taking into account the negative impact of iron ions, the content of
1.5 main impurities in total 250 mL leaching liquor was performed in
Fig. 14. It could be seen that the trend of iron concentration with the
1.0
initial pH of leaching agent was consistent with that in Fig. 13. The iron
0 50 100 150 200 250 300 concentration was less than 5.00 mg when the initial pH of leaching
Collected volume (mL) agent was larger than 2.00. The iron concentration increased from
about 5.00 mg to 59.25 mg with the decrease of pH. Moreover, the
Fig. 12. pH elution curve of leaching liquor under different initial pH of leaching agent.

6
X. Yanfei et al. Hydrometallurgy 173 (2017) 1–8

200 NO.1 (0.16mol/L MgSO4+0.5g/L Ascorbic acid)

100
NO.2 (0.20mol/L MgSO4+0.5g/L Ascorbic acid)
NO.3 (0.20mol/L MgSO4) 85.85
180 81.88 82.08
Fe
Al 80
The content of main impurities (mg)

100

Numerical value
60
80
43.54
40.10
38.72
60 40

40
20
20
4.15 5.33 3.01
1.09 1.35 0.23
0 0
Fe content Al content RE leaching efficiency Ce partition
1.0 1.5 2.0 2.5 3.0 (mg) (mg) (%) (%)
Initial pH of leaching agent The results in exploratory experiment

Fig. 14. The content of main impurities in total 250 mL leaching liquor with different Fig. 15. The relevant conditions and results in exploratory experiment of magnesium-
initial pH of leaching agent. ascorbic acid compound leaching agent.
(The average particle size of rare earths ore 1.0 mm, leaching temperature 298 K,
pH = 2.00, flow rate 0.60 mL/min).
aluminum concentration increased greatly from 8.22 mg to 180.76 mg
with the increase of acidity, as shown in Fig. 11, this was because of the
dissolution of hydroxy-aluminum phase. Therefore, the leaching with a liquor were shown in Fig. 15. When the concentration of MgSO4 and
high acidity would lead to a large number of impurities and the de- ascorbic acid in leaching agent was 0.16 mol/L and 0.5 g/L, respec-
struction of mine environment. tively, 81.88% rare earth leaching efficiency was achieved, it had
After all, on the one hand, rare earth leaching efficiency and Ce reached the same level with 0.20 mol/L MgSO4 leaching agent, which
partition would have a considerable improvement with a low Mg/Fe could reduce the dosage of MgSO4. Moreover, 85.85% rare earth
proportion or a high acidity, but this would result in a large number of leaching efficiency and 5.33% Ce partition could be achieved with
aluminum ions and iron ions dissolved into the leaching liquor, caused 0.20 mol/L MgSO4 and 0.5 g/L ascorbic acid. More importantly, con-
a lot of problems. Moreover, the leaching agent with high acidity or a tent of Fe and Al in leaching liquor in the exploratory experiments was
low Mg/Fe proportion might have a great influence to the soil and all about 1.00 mg and 40.00 mg, kept at a low level, and had just a little
water-body. On the other hand, no significant increase of rare earths increased with the addition of ascorbic acid. The existing state of rare
leaching efficiency was observed with a high Mg/Fe proportion and an earth in the leaching residues was determined with the sequential
appropriate acidity, compared with 0.20 mol/L MgSO4 leaching pro- fractionating extraction methods by column leaching, shown in Fig. 16.
cess. For example, when the initial pH of leaching agent was 2.00, the The mineral phase in the leaching residues was almost the same and
rare earth leaching efficiency was only 83.50% when the Mg/Fe pro- was about 0.16‰ in the No.1-No.3. The contents of colloidal sediment
portion was 99:1, and it was 82.08% in 0.20 mol/L MgSO4 leaching phase in the No.1 and No.2 were 0.10‰ and 0.07‰, less than it in raw
process. But the iron content of iron and aluminum was 4.06 mg and ore. It was visible that ascorbic acid had a stronger reduction property
43.28 mg, bigger than it in MgSO4 leaching process. Therefore, to than Fe2 + when the pH was 2.00. So the addition of ascorbic acid could
evaluate the magnesium-ferrous compound leaching process, the var- leach part of colloidal sediment phase rare earth by reduction reaction
ious factors, such as the rare earth leaching efficiency, the cost of the (Eq. (6)), resulting in the increase of Ce partition in leaching liquor and
subsequent enrichment and the influence of iron on the environment the decreased of the colloidal sediment phase content in the leaching
should be taken into consideration. residues. When the concentration of MgSO4 and ascorbic acid in
leaching agent was 0.20 mol/L and 0.5 g/L, respectively, the leaching
efficiency of colloid sediment phase rare earth could reach to about
3.4. Exploratory experiment of magnesium-ascorbic acid compound
leaching 0.35
0.32 0.33

NO.1 (0.16mol/L MgSO4+0.5g/L Ascorbic acid)

It could be known that part of colloidal sediment phase rare earth, 0.30 NO.2 (0.20mol/L MgSO4+0.5g/L Ascorbic acid)
Rare earth content (‰, mass fraction)

namely Ce(OH)4/CeO2, could be reduction leached by reductive sub- 0.25 NO.3 (0.20mol/L MgSO4)
stance (Xiao et al., 2016b). However, the leaching performance of the 0.25
FeSO4 or magnesium-ferrous compound leaching system was un-
satisfactory. It was reported that ascorbic acid could form a stable co- 0.20
ordination with rare earth ions (Huang, 1997), therefore it can be used 0.16 0.16 0.16
as an assistant to strengthen the leaching process and reduce the dosage 0.15 0.14
of leaching agent (Xiao et al., 2016c). Moreover, ascorbic acid had a
0.10
stronger reduction properties than Fe2 +, its potential was about 0.28 at 0.10
pH 2.00 (Borsook and Keighley, 1933). It could leach the colloidal se- 0.07
0.06
diment phase rare earth better. Furthermore, it could be degraded and 0.05 0.03
absorbed by organisms had not side-effect on the follow-up process. In 0.02

view of these, ascorbic acid was an ideal choice to be introduced into 0.00
0 0 0
the leaching agent. Whole-phase Water-soluble Ion-exchangeable Colloidal-sediment Minerals
The exploratory experiments of magnesium-ascorbic acid com- Phases
pound leaching were conducted, the rare earth leaching efficiency, Ce
Fig. 16. Rare earth content in different phases for the leaching residues.
partition and the content of main impurities in total 250 mL leaching

7
X. Yanfei et al. Hydrometallurgy 173 (2017) 1–8

50%. Chi, R., Xu, J., He, P., 1994. Study on the extraction of colloidal phase rare earth from the
black weathered rare earth ore in southwest. Chin. Rare Earths 15 (3), 15–19 (in
Ce(OH)4 + 4H+ + [Ascorbic acid]reduced ↔ Ce3 + + 4H2 O Chinese).
Chi, R., Zhu, G., Zhang, P., et al., 1999. Chemical behavior of cerium element in rock
+ [Ascorbic acid]Oxidized Eq. (6) weathering system. Trans. Nonferrous Metals Soc. China 9 (1), 158–164.
Chi, R., Zhu, G., Tian, J., 2000. Leaching kinetics of rare earth from black weathering mud
Therefore, compound leaching with MgSO4 and ascorbic acid was with hydrochloric acid. Trans. Nonferrous Metals Soc. China 10 (4), 5314.
proposed to avoid the problems mentioned in the magnesium-ferrous Chi, R., Zhu, G., Xu, S., et al., 2002. Kinetics of manganese reduction leaching from
weathered rare-earth mud with sodium sulfite. Metall. Mater. Trans. B Process Metall.
compound leaching process. It would reduce the dosage of MgSO4 and Mater. Process. Sci. 33 (1), 41–46.
avoid the presence of a large number of impurities in the leaching li- Chi, R., Tian, J., Li, Z., et al., 2005. Existing state and partitioning of rare earth on
quor. It could realize the leaching of partial colloidal sediment phase weathered ores. J. Rare Earths 23 (6), 756–759.
Chi, R., Dai, Z., Xu, Z., et al., 2006. Correlation analysis on partition of rare earth in ion-
and strengthen the leaching of ion-exchangeable phase rare earth. The exchangeable phase from weathered crust ores. Trans. Nonferrous Metals Soc. China
technology and its follow-up effects of magnesium-ascorbic acid com- 16 (6), 1421–1425.
pound leaching agent would be detailed studied next. Deng, X., Chi, R., Shi, Z., 1996. Study on physicochemical properties and rare earth
distribution patterns in black weathered earth. Chin. Rare Earths 17 (2), 35–40 (in
Chinese).
4. Conclusions He, Z., Zhang, Z., Yu, J., et al., 2016. Kinetics of column leaching of rare earth and
aluminum from weathered crust elution-deposited rare earth ore with ammonium
salt solutions. Hydrometallurgy 163, 33–39.
The colloidal sediment phase rare earth was little leached even if the
Huang, C., 1997. Rare Earth Coordination Chemistry. Science Press, Beijing (in Chinese).
pH of leaching agent reached 1.00. But Ce(OH)4/CeO2, part of the Huang, X., Xiao, Y., Feng, Z., et al., 2014. A Kind of Leaching Agent and Leaching Method
colloidal sediment phase rare earth, could generate a redox reaction for the Ion-adsorption Type Rare Earths Ore. (China, 201410484417.X. in Chinese).
Kim, E., Osseo-Asare, K., 2012. Aqueous stability of thorium and rare earth metals in
with the ions with reduction properties. The leaching process with
monazite hydrometallurgy: Eh–pH diagrams for the systems Th–, Ce–, La–, Nd– (PO
FeSO4 could dissolve partial colloidal sediment phase rare earth, but it 4)–(SO4)–H2O at 25 °C. Hydrometallurgy 113–114, 67–78.
would lead to a lot of problems. Li, L., 1980. Air oxidation of cerium among rare earth hydroxide. Chin. Rare Earths 1,
A compound leaching agent with MgSO4 and FeSO4 was put forward 27–32 (in Chinese).
Nesbitt, H., 1979. Mobility and fractionation of rare earth elements during weathering of
to instead of FeSO4. The leaching efficiency of colloidal sediment phase a granodiorite. Nature 279 (5710), 206–210.
rare earth would have a considerable improvement with the decrease of Qiu, T., Wu, H., Li, X., 2012. The current situation and trends of the technology for
Mg/Fe proportion or the decrease of the pH. However, a low Mg/Fe impurity removal of weathering crust ion-absorbed type rare earths ore. Chin. Rare
Earths 33 (4), 81 (in Chinese).
proportion or a high acidity would result in a large number of im- Ran, Y., Liu, Z., 1993. Specific adsorption and its mechanisms of rare earth elements by
purities in the leaching liquor. The leaching performance of the mag- soils and oxides. Sci. Bull. 38 (9), 757–763.
nesium-ferrous compound leaching system was unsatisfactory. Shi, Z., Bonneville, S., Krom, M., et al., 2011. Iron dissolution kinetics of mineral dust at
low pH during simulated atmospheric processing. Atmos. Chem. Phys. 11 (3),
In view of the reducibility and the ability of strengthening the 995–1007.
leaching process for ascorbic acid, the magnesium-ascorbic acid com- Tian, J., Yin, J., Chi, R., et al., 2010. Kinetics on leaching rare earth from the weathered
pound leaching process was simply preformed. With 0.20 mol/L MgSO4 crust elution-deposited rare earth ores with ammonium sulfate solution.
Hydrometallurgy 01 (1), 166–169.
and 0.5 g/L ascorbic acid in leaching agent, 85.85% rare earth leaching
Tian, J., Tang, X., Yin, J., et al., 2013. Enhanced leaching process of a low-grade
efficiency and 5.33% Ce partition could be achieved, and the leaching weathered crust elution-deposited rare earth ore with carboxymethylsesbania gum.
efficiency of colloid sediment phase rare earth was about 50%. Hydrometallurgy 139, 124–131.
Tianjin university, 2009. Physical Chemistry. Higher Education Press, Beijing (in
Moreover, the content of Fe and Al in leaching liquor was only about
Chinese).
1.00 mg and 40.00 mg. Therefore, magnesium-ascorbic acid compound Um, N., Hirato, T., 2012. Precipitation of cerium sulfate converted from cerium oxide in
leaching would be a feasible operation for the leaching of colloidal sulfuric acid solutions and the conversion kinetics. Mater. Trans. 53 (11), 1986–1991.
sediment phase as well as for realizing efficiency extraction and en- Um, N., Hirato, T., 2013. Dissolution behavior of La2O3, Pr2O3, Nd2O3, CaO and Al2O3 in
sulfuric acid solutions and study of cerium recovery from rare earth polishing powder
vironmental friendly. waste via two-stage sulfuric acid leaching. Mater. Trans. 54 (5), 713–719.
Wang, Y., 2004. Preparation of Nano Cerium Oxide by Precipitation. Chengdu University
Acknowledgments of Technology, Chengdu (in Chinese).
Xiao, Y., Chen, Y., Feng, Z., Huang, X., et al., 2015a. Leaching characteristics ofion-ad-
sorption type rare earths ore with magnesium sulfate. Trans. Nonferrous Metals Soc.
The authors gratefully acknowledge the financial supports of China (11), 3784–3790.
National Science and Technology Support Program of China Xiao, Y., Feng, Z., Hu, G., Huang, L., et al., 2015b. The leaching and mass transfer
characteristics of elements from the ion-adsorption type rare earths ore. Rare Metals
(2015BAB16B01), Program of National Natural Science Foundation of 34 (5), 357–365.
China (51604128), Training program of major academic and technical Xiao, Y., Feng, Z., Huang, X., et al., 2015c. Recovery of rare earths from weathered crust
leaders in Jiangxi Province (20142BCB22005). elution-deposited rare earths ore without ammonia-nitrogen pollution: I. Leaching
with magnesium sulfate. Hydrometallurgy (153), 58–65.
Xiao, Y., Huang, X., Feng, Z., et al., 2015d. The environmental impact assessment and
References prospect for the ion-adsorption type rare earths ore leaching by magnesium salt. J.
Chin. Soc. Rare Earths 33 (1), 1–9 (in Chinese).
Xiao, Y., Xu, Z., Ni, Z., et al., 2016a. A Leaching Method of Cerium in Colloidal Phase
Borsook, H., Keighley, G., 1933. Oxidation-reduction potential of ascorbic acid (vitamin
From the Ion-adsorption Type Rare Earth Ore. (China, 201610188866.9 in Chinese).
C). PNAS 19 (9), 875–878.
Xiao, Y., Feng, Z., Huang, X., et al., 2016b. Recovery of rare earth from the ion-adsorption
Breemen, N., Wielemaker, W., 1974. Buffer intensities and equilibrium pH of minerals
type rare earths ore: II. Compound leaching. Hydrometallurgy (163), 83–90.
and soils: II. Theoretical and actual pH of minerals and soils1. Soil Sci. Soc. Am. J. 38
Xiao, Y., Feng, Z., Huang, L., et al., 2016c. Reduction leaching of rare earth from ion-
(1), 61–66.
adsorption type rare earths ore with ferrous sulfate. J. Rare Earths 34 (9), 917–923.
Chen, Z., 2011. Global rare earth resources and scenarios for future rare earth industry. J.
Xu, G., 2002. Rare Earth. Metallurgy Industry Press, Beijing (in Chinese).
Rare Earths 29 (1), 1–6.
Zhang, Y., 2000. Application of potential-pH figure. J. Shenyang Normal Univ. 5, 84–86.
Chi, R., Tian, J., 2006. Chemical and Metallurgy Process of Weathered Crust Rare Earths
Ore. Science Press, Beijing (in Chinese).