Accepted Manuscript

Sulfuric acid leaching of Sm-Co alloy waste and separation of

samarium from cobalt

Kanggen Zhou, An Wang, Duchao Zhang, Xinwang Zhang,

Tianzu Yang

PII: S0304-386X(16)31001-5
DOI: doi:10.1016/j.hydromet.2017.09.014
Reference: HYDROM 4659
To appear in: Hydrometallurgy
Received date: 22 December 2016
Revised date: 1 August 2017
Accepted date: 21 September 2017

Please cite this article as: Kanggen Zhou, An Wang, Duchao Zhang, Xinwang Zhang,
Tianzu Yang , Sulfuric acid leaching of Sm-Co alloy waste and separation of samarium
from cobalt. The address for the corresponding author was captured as affiliation for all
authors. Please check if appropriate. Hydrom(2017), doi:10.1016/j.hydromet.2017.09.014

This is a PDF file of an unedited manuscript that has been accepted for publication. As
a service to our customers we are providing this early version of the manuscript. The
manuscript will undergo copyediting, typesetting, and review of the resulting proof before
it is published in its final form. Please note that during the production process errors may
be discovered which could affect the content, and all legal disclaimers that apply to the
journal pertain.
 ACCEPTED MANUSCRIPT

Sulfuric Acid Leaching of Sm-Co Alloy Waste and Separation of

Samarium from Cobalt
Kanggen Zhou, An Wang, Duchao Zhang*, Xinwang Zhang, Tianzu Yang

School of Metallurgy and Environment, Central South University, Changsha 410083, China

*Corresponding author.
E-mail address: zdc015@sina.com (D. Zhang).

PT
RI
SC
NU
MA
T ED
C EP
AC
 ACCEPTED MANUSCRIPT

Abstract
The Sm-Co alloy waste is considered to be one of the most valuable wastes for recycling, primarily due to the
value of the Co and Sm metals. The two metals were extracted from the Sm-Co alloy waste by sulfuric acid
leaching, and Sm(III) was separated by sodium sulfate as a precipitate of sodium samarium sulfate. It
was found that 99.9% of the Co and 24.1% of the Sm were extracted into the leach solution under the most
suitable conditions: liquid-solid ratio of 6:1, leaching temperature of 60 °C, leaching time of 75 min and
H2 SO4 concentration of 4 mol/L. A high fraction of 93.4% Sm was precipitated at 80 °C, and the Na2SO4 to
Sm molar ratio was 4:1 with 60 min of precipitation time. Thus, sulfuric acid leaching followed by sodium
sulfate precipitation is feasible for recovering Co and Sm from the Sm-Co alloy waste.

PT
Keywords: Sm-Co alloy waste; Sulfuric acid; Leaching; Sodium sulfate; Double salt precipitation

RI
SC
NU
MA
T ED
C EP
AC
 ACCEPTED MANUSCRIPT

1. Introduction
The Sm-Co alloy is a rare earth magnet material with excellent permanent magnet properties, and it has
been comprehensively researched and widely used in many fields, such as communication technology,
electrical engineering, computing technology, automation technology, transportation, magnetic technology,
medical treatment and national defense (Yi et al., 2003; Talijan, 2006; Feng et al., 2016). This alloy may
contain small amounts of nickel, copper, iron and other rare earth metals according to the required properties
of materials. Both Sm and Co are scarce resources; thus it is necessary to separate and recover Sm and Co
from waste Sm-Co material (Binnemans et al., 2013).
Generally, the recovery of valuable metals from the Sm-Co alloy waste is conducted via a
hydrometallurgical process (Ellis et al., 1994; Bounds, 1994), including acid leaching followed by solvent

PT
extraction or chemical precipitation (Murase et al., 1995). The common leaching agents are hydrochloric acid,
sulfuric acid and nitric acid (Wang et al., 2015; Walawalkar et al., 2016). Different extractants, such as

RI
D2 EHPA (Rabie, 2007; Wang et al., 2010; Yadav et al., 2013), D2 EHPA/Cyanex 301 (Torkaman et al., 2013;
Torkaman et al., 2014), HEH/EHP (Miranda and Zinner, 1997), Cyanex 923 (El-Nadi, 2010), and TEHDGA

SC
(Mowafy and Mohamed, 2015) have been proposed by researchers. In this process, Sm(III) can be extracted
into the organic phase, whereas Co(II) is still present in the leach liquor. Although solvent extraction has a
good separation selectivity, its high production cost limits its wide application. The chemical precipitation
NU
method has advantages due to its low cost and mild operation conditions. The leached Sm(III) can be
precipitated from solution by adjusting the pH with sodium hydroxide, sodium carbonate, oxalic acid,
ammonium oxalate and phosphoric acid as the precipitator (Xu and Peng, 2009; Xu et al., 2010; Onoda and
MA

Kurioka, 2015; Onoda and Kurioka, 2016). However, it is inevitable to produce a small amount of Co(II)
precipitates because of the high Co concentration (He et al., 2011). In addition, the excessive consumption of
the precipitator will lead to the burden of effluent treatment.
Sodium sulfate is also one of the commonly used precipitators for rare earth elements in acid solutions
ED

(Pietrelli et al., 2002); however, it has been rarely reported for precipitating Sm(III) from solutions containing
a mixture of the sulfates of Sm(III) and Co(II). Based on the differences in solubility of samarium sulfate and
cobalt sulfate in sulfuric acid solution, the Sm-Co alloy can be initially treated under sulfuric acid leach to
T

acquire a liquor containing Sm(III) and Co(II) and a residue with a certain amount of Sm. Then, by adding
EP

sodium sulfate into the resultant leach liquor, the partially leached Sm(III) can be precipitated in the form of
an insoluble double sulfate. This work investigated the influences of sulfuric acid concentration, liquid-solid
ratio, temperature, and reaction time on extraction. Additionally, the precipitation of Sm(III) from the leach
C

liquor was studied at different Na2SO4 concentrations, temperatures, and reaction times.
2. Experimental
AC

2.1. Materials and analysis

The Sm-Co alloy material used in the experiments was an unqualified product from a factory in Sichuan
Province. Table 1 shows the chemical composition of the alloy material. All other chemical reagents used in
the experiments were of analytical grade and were supplied by Sinopharm Chemical Reagent Co., Ltd. They
were used without further purification. The water used in all experimental work was ultrapure water
(conductivity of <0.2μS/cm) unless otherwise specified.
Table 1 Chemical composition of the alloy material (mass fraction, %).
Sm Co Ni Fe
32.83 65.86 0.01 0.02
 ACCEPTED MANUSCRIPT

The phases of the material sample and residue samples were examined using a D/Max-2550 X-ray
diffractometer (Rigaku, Japan) with CuKα radiation in the range of 10° to 80°. Elemental analysis of all of the
residue samples and the filtered leach liquor was conducted using an iCAP 7000 Series ICP-OES. The
extraction of Sm and Co with sulfuric acid can be calculated using the following equation:
v1  c1
Me  100% , (1)
m1  w1
where  Me is the extraction of the metal, m1 is the mass of the alloy sample, w1 is the metal content of the
alloy sample, v1 is the volume of the leach solution, and c1 is the mass concentration of the metal in the leach
solution. Then, the precipitation percentage of Sm(III) from the leach solution was calculated using the
following equation:

PT
v2  c2  v3  c 3
Sm  100% , (2)
v2  c2

RI
where Sm is the precipitation percentage of Sm(III), v2 and v3 are the volume of the leach solution and the
filtrate, respectively, and c2 and c3 are the mass concentrations of Sm(III) in the leach solution and in the

SC
filtrate, respectively.
2.2. Experimental procedures
The simplified flowsheet of waste Sm-Co alloy processing is shown in Fig. 1. After the Sm-Co alloy
NU
waste was crushed and milled, Co and a smaller amount of Sm were leached in the sulfuric acid solution, and
most of the Sm was left in the leach residue. Then, a specified amount of Na2 SO4 was added to the leach
solution to produce the double salt precipitate of NaSm(SO4)2·nH2 O to separate Sm(III) from Co(II) in the
MA

leach solution. The obtained solution containing Co(II) and the precipitate containing Sm(III) can be used to
produce the corresponding products.

Sm-Co alloy waste

ED

Crushing and milling

H 2SO4 Acid leaching

T
EP

Filtration

Solution
C

Residue
AC

Na2SO 4 Double salt precipitation Sm recovery

Filtration

Solution Residue

Co recovery Sm recovery

: Procedure described in this paper

Fig. 1. Proposed flowsheet for recovering Sm and Co from Sm-Co alloy waste
 ACCEPTED MANUSCRIPT

3. Results and discussions

3.1 Reactions
The phase structure of the alloy material was determined via XRD and the XRD pattern is depicted in
Fig. 2. The XRD pattern of the alloy material is almost identical to that of Co5Sm.

PT
RI
SC
NU
Fig. 2. XRD pattern of the alloy material
MA

The two metals can react with sulfuric acid according to the standard reduction potentials, which are
o +
lower than the E H /H2 value of 0 V (Dean, J.A., 2003):
Sm3++3e = Sm Eº = -2.30V (3)
2+
Co +2e = Co Eº = -0.277V (4)
ED

The main reaction equations are listed as follows:

2Sm+3H2 SO4 = Sm2 (SO4 )3 +3H2 ↑ (5)
Co+H2 SO4 = CoSO4 +H2 ↑ (6)
T

As shown in Table 2 (Wei et al., 1989), because of the low solubility of samarium sulfate, most Sm(III)
EP

will be precipitated. The Sm(III) existing in the sulfuric acid solution and added sodium sulfate can precipitate
as the double salt. The reaction equation can be expressed as follows:
Sm2 (SO4 )3 + Na2 SO4 +2H2 O =2NaSm(SO4 )2 ·H2 O↓ (7)
C

Although very few data have been reported on the solubilities of sodium rare-earth double sulphate salts,
the limited information available indicates that the solubility increases with increasing atomic weight of the
AC

rare earths (Lokshin et al., 2007). The atomic weight of Sm is between those of Nd and Ga, and the solubility
products of NaNd(SO4)2·H2O and NaGa(SO4)2·H2 O are 7.84×10-8 and 3.09×10-6 at 20 °C, respectively. Thus,
the solubility product of NaSm(SO4)2·H2 O should be below 3.09×10-6 and above 7.84×10-8.
Table 2 Solubility products (Ksp) of Sm2(SO4)3 at different temperatures.
Temperature (°C) Ksp
0 9.75×10-6
20 2.11×10-6
40 5.36×10-7
-7
60 1.98×10
80 8.38×10-8

3.2 Sulfuric acid leaching

 ACCEPTED MANUSCRIPT

The effects that the liquid-solid ratio, leaching temperature, leaching time and sulfuric acid concentration
have on the metal extraction from the Sm-Co alloy waste were studied, and the results are shown in Fig. 3.

PT
RI
(a) (b)

SC
NU
MA
ED

(c) (d)
T
C EP

Fig. 3. (a) Effect of the liquid-solid ratio on the metal extraction (CH2SO4, 5 mol/L; T, 80 oC; Time, 90 min). (b) Effect of leaching
AC

temperature on the metal extraction (CH2SO4, 5 mol/L; Liquid/ solid, 6 mL/g; T, 80 oC; Time, 90 min,). (c) Effect of leaching
time on the metal extraction (CH2SO4, 5 mol/L; Liquid/ solid, 6 mL/g; T, 60 oC). (d) Effect of H2SO4 concentration on the metal
extraction (Liquid/ solid, 6 mL/g; T, 60 oC; Time, 75 min).

The liquid-solid ratio has little effect on the Sm extraction of approximately 23% (Fig. 3a). However, the
Co extraction changes with an increase in the liquid-solid ratio, and when the liquid-solid ratio increased from
3:1 to 6:1, the extraction of Co increased from 90.6% to approximately 100%. Thus, the high liquid-solid ratio
is conducive to complete dissolution of Co in the Sm-Co alloy. Compared with the liquid-solid ratio, the
influence of temperature on the metal extraction is more obvious (Fig. 3b). The temperature has a negative
effect on Sm extraction, which varies from 21.1% to 18.1% as the temperature increases from 20 °C to 90 °C.
This may be because the solubility of samarium sulfate decreases with increasing temperature, as shown in
 ACCEPTED MANUSCRIPT

Table 2 (Wei et al., 1989; William et al., 1975). With an increase in temperature, Co extraction increases
significantly between 20 °C and 60 °C and then remains constant. The Co extraction can reach 99.9% as the
temperature increases to 60 °C, indicating that almost all the Co dissolves into the solution. The leaching time
has different effects on the extractions of Sm and Co (Fig. 3c). With increase in reaction time, the extraction of
Sm does not undergo a significant increase and remains approximately at 20%. Meanwhile, it shows a
positive effect on Co extraction, which varies from 79.2% to nearly 100% as the reaction time increases from
15 min to 75 min, indicating that almost all of the Co dissolves after 75 min. The increase in H2SO4
concentration improves the leaching of Co and suppresses the leaching of Sm (Fig. 3d). Then, 34.3% of Sm is
leached with a H2SO4 concentration of 2 mol/L. When the H2SO4 concentration reaches 6 mol/L, the
extraction of Sm decreases to 14.6%. This phenomenon could be explained by the following equation:

PT
2Sm3++ 3SO4 2- +8H2 O = Sm2 (SO4 )3 ·8H2 O↓ (8)
In contrast, the extraction of Co increases with an increase in acid concentration in the solution. Almost all of

RI
Co is dissolved by a leach solution of 4 mol/L H2 SO4 with a Co extraction of 99.9%.
Based on the results determined in the previous tests, the most suitable conditions were determined as
follows: liquid-solid ratio of 6:1, leaching temperature of 60 ℃, leaching time of 75 min and H2SO4

SC
concentration of 4 mol/L. Under these conditions, the extractions of Co and Sm were 99.9% and 24.1%,
respectively. Simultaneously, the remaining contents of Sm and Co in the residue after leaching were 47.9%
NU
and 0.2%, respectively. The acid leach residue was also characterized via XRD, and the result is shown in Fig.
5a. Thus, the main phases present in the residue are Sm2(SO4)3·8H2O and Sm.
3.3 Sodium samarium sulfate precipitation
MA

The effects of temperature, Na2SO4 to Sm molar ratio and time on the Sm(III) precipitation percentage
from the H2SO4 leach solution are presented in Fig. 4. An increase in temperature promoted the precipitation
reaction. The Sm(III) precipitation percentage increased from 67.2% to 93.3% by increasing the temperature
from 25 °C to 80 °C. Compared to the precipitation temperature, the Na2SO4 to Sm molar ratio, i.e., the
ED

addition amount of Na2SO4, plays a more significant role in Sm(III) precipitation when the reaction
temperature and time were fixed at 80 °C and 60 min, respectively. When the Na2SO4 to Sm molar ratio
increased from 0.5:1 to 4:1, the Sm(III) precipitation increased from 24.8% to 93.5%. The further addition of
T

Na2SO4 made no difference for Sm(III) precipitation. The effect of time on Sm(III) precipitation showed that
EP

the precipitation reaction was fast and that 81.7% of Sm(III) precipitated in the initial 15 min. After 60 min of
reaction, the Sm(III) precipitation increased to approximately 93%.
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
SC
NU
Fig. 4. Effects of temperature, Na2SO4 to Sm molar ratio and time on the Sm precipitation
According to the above results, the most suitable conditions can be summarized as follows: temperature
of 80 °C, molar ratio of Na2SO4 to Sm of 4:1, and reaction time of 60 min. The Sm(III) precipitation
MA

efficiency was 93.4% under these conditions.

By analyzing the XRD pattern of the precipitate in Fig. 5b, the main phase was determined to be
NaSm(SO4)2·H2 O. The contents of Sm and Na were 39.2% and 5.9%, which agree with the theoretical values
of 39.2% and 6%, respectively. Additionally, Fig. 5 also clearly shows the phase change of samarium in this
ED

study.
T
C EP
AC

Fig. 5. XRD patterns of the acid leach residue (a) and the precipitate (b) formed with Na2SO 4
4. Conclusions
1) Sulfuric acid leaching followed by sodium sulfate precipitation was selected as the process to recover
Co and Sm from the Sm-Co alloy waste.
 ACCEPTED MANUSCRIPT

2) The sulfuric acid leaching process could extract 99.9% Co and 24.1% Sm from the Sm-Co alloy
waste. The most suitable conditions were determined as follows: a liquid-solid ratio of 6:1, leaching
temperature of 60 °C, leaching time of 75 min and H2SO4 concentration of 4 mol/L.
3) Sm was precipitated from the sulfuric acid leach solution by sodium sulfate, and its precipitation
efficiency reached 93.4% under the following conditions: precipitation temperature of 80 °C, Na2SO4 to Sm
molar ratio of 4:1 and precipitation time of 60 min.
Acknowledgement
This study was financially supported by the 2011 Joint Innovation Center – “clean and effective
utilization of strategic mineral resources”.

PT
RI
SC
NU
MA
T ED
C EP
AC
 ACCEPTED MANUSCRIPT

References
Yi, J., Peng, Y., 2004. Review of Research on 2:17 Type SmCo Rare Earth Permanent Magnets. Rare Metal Materials and
Engineering 33 (04), 337-342. (in Chinese)
Talijan, N., 2006. Magnetic properties of sintered high energy Sm-Co and Nd-Fe-B magnets. Science of Sintering 38(1), 73-82.
Feng, D.Y., Zhao, L.Z., Liu, Z.W., 2016. Magnetic-field-induced irreversible antiferromagnetic–ferromagnetic phase transition
around room temperature in as-cast Sm–Co based SmCo7−xSix alloys. Physica B: Condensed Matter 487, 25-30.
Binnemans, K., Jones, P.T., Blanpain, B., Van Gerven, T., Yang, Y., Walton, A., Buchert, M., 2013. Recycling of rare earths: a
critical review. Journal of Cleaner Production 51, 1-22.
Ellis, T.W., Schmidt, F.A., Jones, L.L., 1994. Methods and opportunities in the recycling of rare earth based materials. In: Liddell,
K.C., Bautista, R.G., Orth, R.J. (Eds.), Symposium on Metals and Materials Waste Reduction, Recovery and Remediation, at

PT
the 1994 Materials Week Meeting Location: Rosemont, IL Date: October 03-06, 1994. The Minerals, Metals & Materials
Society, Warrendale,Pennsylvania, pp. 199-2006.

RI
Bounds, C.O., 1994. The recycle of sintered magnet swarf. In: Liddell, K.C., Bautista, R.G., Orth, R.J. (Eds.), Symposium on
Metals and Materials Waste Reduction, Recovery and Remediation, at the 1994 Materials Week Meeting Location:

SC
Rosemont, IL, October 03-06, 1994. The Minerals, Metals & Materials Society, Warrendale, Pennsylvania, pp. 173-186.
Murase, K., Machida, K.I., Adachi, G.Y., 1995. Recovery of rare metals from scrap of rare earth intermetallic material by chemical
vapour transport. Journal of Alloys and Compounds 217, 218-225.
NU
Wang, J., Ma, Y., Xu, T., Zhang, G., Wang, D., 2015. Research on the Comprehensive Utilization processes of Waste Samarium-
Cobalt Magnet. Chinese Rare Earths 36(5), 66-70. (in Chinese)
Walawalkar, M., Nichol, C.K., Azimi, G., 2016. Process investigation of the acid leaching of rare earth elements from
MA

phosphogypsum using HCl, HNO3, and H2SO4. Hydrometallurgy 166, 195-204.

Rabie, K.A., 2007. A group separation and purification of Sm, Eu and Gd from Egyptian beach monazite mineral using solvent
extraction. Hydrometallurgy 85, 81-86.
Wang, L., Long, Z., Huang, X., Yu, Y., Cui, D., Zhang, G., 2010. Recovery of rare earths from wet-process phosphoric acid.
ED

Hydrometallurgy 101, 41-47.

Yadav, K.K., Singh, D.K., Anitha, M., Varshney, L., Singh, H., 2013. Studies on separation of rare earths from aqueous media by
polyethersulfone beads containing D2EHPA as extractant. Separation and Purification Technology 118, 350-358.
T

Torkaman, R., Moosavian, M.A., Torab-Mostaedi, M., Safdari, J., 2013. Solvent extraction of samarium from aqueous nitrate
EP

solution by Cyanex301 and D2EHPA. Hydrometallurgy 137, 101-107.

Torkaman, R., Safdari, J., Torab-Mostaedi, M., Moosavian, M.A., 2014. A kinetic study on solvent extraction of samarium from
nitrate solution with D2EHPA and Cyanex 301 by the single drop technique. Hydrometallurgy 150, 123-129.
C

Miranda, P., Zinner, L.B., 1997. Separation of samarium and gadolinium solutions by solvent extraction. Journal of Alloys and
Compounds 249, 116-118.
AC

El-Nadi, Y.A., 2010. Effect of diluents on the extraction of praseodymium and samarium by Cyanex 923 from acidic nitrate
medium. Journal of Rare Earths 28(2), 215-220.
Mowafy, E.A., Mohamed, D., 2015. Extraction and separation of Nd(III), Sm(III), Dy(III), Fe(III), Ni(II), and Cs(I) from
concentrated chloride solutions with N,N,N′,N′-tetra(2-ethylhexyl) diglycolamide as new extractant. Journal of Rare Earths
33(4), 432-438.
Xu, T., Peng, H., 2009. Formation cause, composition analysis and comprehensive utilization of rare earth solid wastes. Journal of
Rare Earths 27(6), 1096-1102.
Xu, T., Zhang, X., Lin, Z., Lü, B., Ma, C., Gao, X., 2010. Recovery of rare earth and cobalt from Co-based magnetic scraps.
Journal of Rare Earths 28, 485-488.
Onoda, H., Kurioka, Y., 2015. Recovery of samarium from cobalt–samarium solution using phosphoric acid. Journal of
Environmental Chemical Engineering 3(4), 2825-2828.
 ACCEPTED MANUSCRIPT

Onoda, H., Kurioka, Y., 2016. Selective removal and recovery of samarium from mixed transition metal solution using phosphoric
acid. Journal of Environmental Chemical Engineering 4(4), 4536-4539.
He, X., Ye, H., Xu, K., Chen, Y., Deng, W., Zhou, J., Kuai, Q., Hounslow, M., 2011. Simulation on evolution of solution system in
precipitation of cobalt oxalate. The Chinese Journal of Nonferrous Metals 21(9), 2298-2303. (in Chinese)
Pietrelli, L., Bellomo, B., Fontana, D., Montereali, M.R., 2002. Rare earths recovery from NiMH spent batteries. Hydrometallurgy
66(1-3), 135-139.
Dean, J.A., 2003. Lang’s Handbook of Chemistry, fifteenth edition. Science Press. (in Chinese)
Wei, Y., Sato, N., Nanjo, M., 1989. Fundamental study on the recycling of rare earth magnet. The solubility of Sm2(SO4)3and
Nd2(SO4)3in sulfate solutions. Shigen-to-Sozai 105(12), 965-970.
Lokshin, E. P., Tareeva, O. A., Kashulina, T. G., 2007. A study of the solubility of yttrium, praseodymium, neodymium, and

PT
gadolinium sulfates in the presence of sodium and potassium in sulfuric-phosphoric acid solutions at 20 °C . Russian Journal
of Applied Chemistry 80(8), 1275-1280.

RI
William, L., Marshall, Rush S. 1975. Solubility and thermodynamic function for a 3-2 salt, samarium sulfate, in water and sulfuric
acid solutions at temperatures to 350 ℃. Journal of inorganic & Nuclear chemistry, 37(10), 2171-2176.

SC
NU
MA
T ED
C EP
AC
 ACCEPTED MANUSCRIPT

Highlights

 Sm-Co alloy waste was processed via sulfuric acid leaching followed by NaSm(SO4)2
precipitation.

 In total, 99.9% of the Co and 24.1% of the Sm were leached by H2SO4.

 In total, 93.4% of the Sm from the leach liquor could be precipitated in the form of
double sulfate.

PT
RI
SC
NU
MA
T ED
C EP
AC