Research Note

pubs.acs.org/IECR

Removal of Mo and Fe from the Cobalt Chloride Solution by Ion

Exchange during the Recovery Process from Spent
Hydrodesulfurization Catalysts
Thi Hong Nguyen,† Seong Ho Sohn,‡ and Man Seung Lee*,†
†
Department of Advanced Material Science and Engineering, Institute of Rare Metal, Mokpo National University, Chonnam 534-729,
Republic of Korea
‡
Incheon Technology Service Centre, Korea Institute of Industrial Technology, 7-47, Songdodong, Incheon, 406-840, Republic of
Korea

ABSTRACT: During the recovery of cobalt from the chloride leaching solutions of spent hydrodesulfurization catalysts by
solvent extraction with amine, a cobalt chloride solution of ∼98% purity was obtained by stripping of the loaded amine with HCl
solution. The major impurity elements in this cobalt chloride solution were molybdenum and iron, whose concentration was <10
ppm. In order to remove these impurities from the solution, ion exchange experiments have been performed. For this purpose,
strong cationic (Diphonix) and anionic exchange resins (AG1-x8) were tested in the pH range from zero to 4. Our results
indicated that Mo and Fe were removed simultaneously by ion exchange with Diphonix from the solution with pH 1. The
loading capacity of Diphonix for Mo and Fe at this pH was found to be 90 and 40 mg/g of resin. Column experiments verified
that pure cobalt chloride solution with 99.97% purity was obtained by ion exchange with Diphonix.

1. INTRODUCTION Table 1. Composition of the Leaching Liquor Obtained

Nowadays, demand for pure cobalt has increased steadily, under the Optimum Leaching Conditions
because of its promising usage in superalloys, catalysts, colors/ element amount (mg/L)
pigments, hard materials carbides/diamond tooling, chemical Mo 3900
applications, and batteries.1 Catalysts used in petroleum Co 1175
refining industries become contaminated with impurities and Al 18900
deactivated after certain period of catalytic processing. Since the Fe 5
environmental concern and the price of some metals Ni 8
(particularly cobalt) have been rising, spent catalysts have Si 8
been recognized as a secondary source for the recovery of
valuable metals such as molybdenum, cobalt, vanadium, and
nickel.
Many works have been conducted for the recovery of cobalt During the stripping of cobalt from the loaded amine by HCl
from acid leaching solution of spent catalysts in the presence of solution, most of the cobalt, together with a small amount of
other metals by precipitation,2 ion exchange,3 and solvent molybdenum and iron, was stripped to the HCl solution. The
extraction.1,4−8 Among these methods, solvent extraction has concentration of molybdenum and iron was <10 ppm in the
higher separation efficiency and loading capacity in the recovery stripping solution, and the purity of cobalt in this solution was
of cobalt from spent catalysts. However, a small amount of ∼98%. The optimum conditions for the separation of
impurities such as copper, iron, nickel, and aluminum are molybdenum and cobalt from the real leaching solution of
stripped together with cobalt during the stripping of the loaded spent HDS catalysts are shown in Figure 1.
extractants. Recently, we reported a process for the recovery of Comparing solvent extraction and ion exchange as a
cobalt and molybdenum and the regeneration of acid from the separation process in hydrometallurgy, each process has its
leaching solution of spent hydrodesulfurization (HDS) catalysts advantages and disadvantages over the other. When the
by solvent extraction.9 According to this process, the spent concentration of impurity metals in a solution is low, ion
HDS catalysts containing Mo (8.1 wt %), Co (2.5 wt %), Ni exchange seems to be more efficient than solvent extraction,
(0.02 wt %), Fe (0.03 wt %), Si (0.01 wt %), and Al (44.5 wt %) with regard to removing these impurities from the solution.
were leached by HCl solution without any pretreatment. Most Although ion exchange resins are expensive and the loading
of the Mo, Co, and Al was dissolved under the following capacity of resins for metals is low, continuous operation of ion
conditions: 3 M HCl, 90 °C, 250 μm particle size, 5% (w/v) exchange is simple and easy to run. Besides, unlike solvent
solid-to-liquid ratio, and 60 min of reaction time. The
composition of the leaching liquor is shown in Table 1. Mo Received: April 9, 2013
was separated from the leaching solution by solvent extraction Revised: July 3, 2013
with TBP at 3 M HCl. Then, cobalt was separated from the Accepted: July 7, 2013
raffinate via solvent extraction with amine (Alamine 308). Published: July 8, 2013

© 2013 American Chemical Society 10028 dx.doi.org/10.1021/ie401123h | Ind. Eng. Chem. Res. 2013, 52, 10028−10032
Industrial & Engineering Chemistry Research Research Note

Figure 1. The recovery process of cobalt solution from real leach liquor.

extraction, ion exchange results in a clean aqueous solution Table 2. Physico-chemical Characteristics of AG1-x8 and
without any organics. Diphonix Used in This Studya
It has been reported that the ferric ion (Fe3+) has a strong
capacity
tendency to form complexes with the chloride ion (Cl−) and dry mesh bead size (mequiv/ density
the distribution of Fe(III) depends on the concentration of Cl− resin ionic form size (μm) mL) (g/mL)
ion.10 In the case of Mo, diverse species exist in chloride AG1-x8 chloride 200−400 45−106 1.2 0.75
solution and the distribution of Mo in acidic solution is very Diphonix hydrogen 100−200 74−150 1.1 1.05
complex. Ion exchange experiments of Mo from strong acidic a
Data taken from ref 15.
solution revealed that Mo can be loaded into both strong
cationic and anionic exchange resins.11 When the concentration concentration of metals in the feed and filtrate was determined
of Cl− ion is moderate, Fe(III) can be easily loaded into strong by inductively coupled plasma−optical emission spectroscopy
cationic resins.12 (ICP-OES) (Spectro Arcos). The concentration of metals
Some works have reported on the removal of impurities from loaded into the resin was obtained by mass balance.
cobalt sulfate solution by ion exchange.12−14 However, little Loading capacity experiments were conducted by contacting
research has been performed on the removal of Mo and Fe 0.2 g Diphonix with 80 mL of fresh solution several times until
from a cobalt chloride solution by ion exchange. In this study, the amount of metal in the resin became constant. In these
ion exchange experiments have been performed to remove Mo experiments, the concentration of molybdenum and iron was
and Fe from the cobalt chloride solution. For this purpose, kept at 200 ppm and solution pH was adjusted to 1.0. Each
strong acidic (Diphonix) and anionic (AG1-x8) resins were sample was shaken for 24 h at room temperature. The
employed. The loading behavior of Co, Mo, and Fe was cumulative amount of the metal loaded into the resin was
investigated by varying the acidity of aqueous solution. An calculated by the difference in the concentration of metal in the
optimum condition to remove both Mo and Fe from the cobalt solution after each stage of contact.
solution was obtained. The loading capacity for Mo and Fe at In column experiments, a glass column (250 mm × 10 mm)
the optimum condition was determined. The applicability of was used, where 0.25 g of resin was poured. The operation was
this ion exchange process for the production of pure cobalt performed at a constant flow rate of 1.5 mL/min. In our
chloride solution was verified by column experiments. experiments, the flow rate was controlled by using a pump
(Fluid Metering, Inc. (FMI), Model QG20). The effluent was
2. EXPERIMENTAL SECTION fractionated into portions of desired volume as resin volume in
2.1. Materials and Reagents. A synthetic solution column. The concentration of metals in each fraction was
containing Co, Mo, and Fe was prepared by dissolving measured by ICP-OES (Spectro Arcos). The change of metal
CoCl2·6H2O (Junsei), Na2MoO4 (Sigma), and FeCl3·6H2O concentration in the effluent was represented using a
(Kanto) in distilled water. The concentration of Co, Mo, and concentration fraction that was defined as
Fe was kept at 888, 10, and 2 ppm, respectively. The acidity of concentration fraction
the synthetic solution was adjusted by adding HCl solution concentration of metal in the effluent
(Duksan). =
concentration of metal in the feed (1)
AG1-x8 (Bio-Rad) is a strongly anionic exchanger with
quaternary ammonium functional groups attached to the
sryrene divinylbenzene copolymer lattice. Diphonix (Ei- 3. RESULTS AND DISCUSSION
Chrom), which is a strongly cation exchanger, is comprised 3.1. Effect of pH Value. In our previous results,9 HCl
of a polymeric support which has been functionalized with solution of pH 1 was used to strip the cobalt from the loaded
diphosphonic and sulfonic acid groups. The physical and Alamine 308 phase. Since the distribution of Mo and Fe species
chemical characteristics of these resins are listed in Table 2.15 In in chloride solution depends on solution pH, the synthetic
this experiment, AG1-x8 and Diphonix resin were used as solutions with varying pH value from zero to 4 were employed
received without any treatment. in the experiments. Within this pH range, the loading behavior
2.2. General Ion Exchange Procedure. Batch experi- of the three metals was investigated by contacting 10 mL of the
ments were carried out in a shaking incubator (HB-201SF, synthetic solution with 0.5 g/L of Diphonix or AG1-x8 and the
Hanbeak Scientific Co.), using a 100-mL screwed-cap bottle. results are shown in Figures 2 and 3.
The temperature of the shaking incubator was controlled at These figures indicated that the pH value of the synthetic
room temperature (25 °C). After putting resin with 10 mL of solution had a significant influence on the loading of Mo with
synthetic solution, it was bottle-rolled for 24 h. The aqueous AG1-x8 and that of both Mo and Fe with Diphonix. As shown
solution was collected by filtering the resin after loading. The in Figure 2, the loading behavior of molybdenum was under
10029 dx.doi.org/10.1021/ie401123h | Ind. Eng. Chem. Res. 2013, 52, 10028−10032
Industrial & Engineering Chemistry Research Research Note

related to the formation of Mo cationic species.15 According to

the distribution diagram of Mo, the mole fraction of anionic
Mo species increases with increase of solution pH. Especially,
the predominant anionic species of Mo, Mo7O21(OH)33−,
begins to form at pH 2. According to the results on the
separation of Mo and V by ion exchange with Diphonix, it was
found that the loading percentage of Mo decreased with
increase of solution pH from 2 to 4.15 However, our data shows
that the loading percentage of Mo with Diphonix increased
linearly with the increase of solution pH, when the value of
solution pH was >2.
To investigate the increase in the loading percentage of Mo
in the pH range of 2−4, Diphonix was pretreated by FeCl3
solution of 2 ppm. The loading behavior of Mo from pure Mo
solution of 10 ppm then was compared in the pH range from 0
to 4 between fresh Diphonix and Diphonix, which had been
pretreated with an iron solution. Figure 4 shows that the

Figure 2. Effect of pH on the loading of metals from HCl solution

with AG1-x8 at room temperature (resin: 0.5 g/L).

10% in the pH range from 0 to 1.0 and increased rapidly to

90% at pH 2.0 and was constant with the further increases in
solution pH, while that of Co and Fe was approximately zero
under the same conditions. The loading behavior of Mo by
AG1-x8 may be ascribed to the variation in the distribution of
Mo species with solution pH. According to the distribution
diagram reported in the literature,16 the anionic species of Mo,
such as Mo7O21(OH)33−, Mo7O23(OH)5−, Mo7O22(OH)124−,
and MoO42− are only predominant when solution pH is higher
than 1.0. Since the loading percentage of Co and Fe was nearly
zero in our experimental range, it may be stated that no anionic
complexes of Co and Fe with the Cl− ion is formed in the
solution pH from 0 to 4.
Figure 3 shows that most of the Fe was loaded into the Figure 4. Effect of pH on the loading of Mo with Diphonix and Fe-
Diphonix at pH >1, while the loading percentage of cobalt into Diphonix at room temperature (resin: 0.5 g/L, [Mo] = 10 ppm).
Diphonix was negligible in any pH range. The loading
percentage of Mo increased steadily from 10% to 70% with
the increase of pH value from 0 to 4. The loading behavior of loading percentage of Mo with pretreated Diphonix (Fe-
molybdenum with Diphonix in the pH range from 0 to 2.0 was Diphonix) was higher than that with fresh Diphonix in any pH
range. These data indicates that the loading of Mo was
enhanced by ion exchange with Diphonix, which had been
pretreated by iron. The results of Figure 3 can be explained as
follows. First, the loading of Fe(III) with Diphonix may be
represented as
3RH resin + Fe3 + = FeR3resin + 3H+ (2)
where RH represents Diphonix.
Some of the iron loaded into the Diphonix can become
protonated as follows:17
3FeR3resin + H+ = FeR3H+resin (3)
The above protonated iron can load anionic Mo species via the
following equation:17
3FeR3H+resin + Mo7O21(OH)33 −
= 3(FeR3H)Mo7O21(OH)3resin (4)
Thus, both anionic and cationic complexes of Mo in the
Figure 3. Effect of pH on the loading of metals from HCl solution solution could be loaded simultaneously by pretreated
with Diphonix at room temperature (resin: 0.5 g/L). Diphonix and fresh Diphonix. This is the reason why the
10030 dx.doi.org/10.1021/ie401123h | Ind. Eng. Chem. Res. 2013, 52, 10028−10032
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loading percentage of Mo with Diphonix in Figure 3 increased

as the solution pH increased in the range of 2−4.
The reaction between cationic Mo species and fresh
Diphonix is represented in eqs 5 and 6:
RH resin + H3MoO4 + = RH3MoO4resin + H+ (5)

2RH + H6Mo2O82 + = R 2H6Mo2O8resin + 2H+ (6)

Figures 2 and 3 indicated that, within our experimental range,
cobalt was not loaded into both Diphonix and AG1-x8. From
these results, it might be inferred that cobalt exists as electrically
neutral species in the pH range from 0 to 4. AG1-x8 can absorb
only molybdenum from cobalt solution in the presence of iron
when solution pH was >1.0. However, not only Mo but also Fe
was loaded into Diphonix when the solution pH was >0.5.
According to the previous results on the stripping of cobalt
from the loaded Alamine 308,9 most of cobalt in the loaded
Alamine 308 was stripped by HCl solution with solution pH 1. Figure 6. Variation in the concentration fraction of Mo, Co, and Fe in
Therefore, Diphonix is found to be better than AG1-x8 in the the effluent during continuous column experiments (mass of resin =
removal of Mo and Fe from the cobalt solution, because there is 0.25 g, flow rate of feed = 1.5 mL/min, 1 BV = 0.23 mL).
no need to adjust the solution pH of the stripping solution and
Mo and Fe can be removed simultaneously. increase of bed volume, which means that most of Fe was
3.2. Loading Capacity Experiments. Loading capacity loaded into Diphonix. Molybdenum was loaded into Diphonix
experiments for molybdenum and iron from individual chloride until 400 BV and the breakthrough of molybdenum occurred at
solution at pH 1.0 was carried out to determine the applicability 3000 BV, where molybdenum concentration in the effluent was
of Diphonix in continuous operation. The results are shown in the same as that in the feed. In the case of cobalt, the
Figure 5. The cumulative loading of molybdenum increased as concentration fraction of cobalt was nearly unity, indicating that
most of cobalt remained in the effluent. From the obtained
results, it might be concluded that both Mo and Fe could be
separated completely from cobalt solution at pH 1.0 when 92
mL of solution (400 BV) was passed to 0.25 g of Diphonix in
the column experiments. The composition of the effluent was
Co (888 ppm), Mo (0.2 ppm), and Fe (0.04 ppm). The purity
of cobalt in the resulting solution after the column experiments
was ∼99.97%.
3.4. Regeneration of the Resin. In purification of metal
solutions by ion exchange, the regeneration of resin is very
important. Therefore, in the current study, the regeneration of
Diphonix was tested using acid solutions including hydro-
chloric, nitric, and sulfuric acid solutions. For this purpose, the
loaded Diphonix was prepared by contacting 80 mL of solution
containing 200 and 40 ppm of Mo and Fe, respectively, with 1 g
of resin. The concentration of the acid solutions was controlled
to 1.5, 2, and 2.5 M and the concentration of loaded resin was
kept at 1 g/L. The results are presented in Table 3. The elution
Figure 5. Loading capacity of Diphonix for Mo and Fe from chloride efficiency of Diphonix was significantly increased as the acid
acid solution with pH 1. concentration increased from 1.5 M to 2.5 M. Among the acid
solutions tested in this study, HCl solution had the best
efficiency for the elution of both Mo and Fe from loaded
the number of contacting stages increased and became constant Diphonix. In order to get optimum condition to regenerate
after three stages; however, there was no change in the case of Diphonix using 2.5 M HCl solution, experiments were carried
iron in our experimental range. The loading capacity for
molybdenum and iron from individual chloride solution was Table 3. Regeneration Efficiency of Diphonix Using HNO3,
found to be 90 and 40 mg per g of resin. Since the H2SO4, and HCl Solutions at Different Concentrations
concentration of molybdenum and iron in the stripping (Loaded Resin = 1 g/L)
solution was 10 and 2 ppm, respectively, 1 g of Diphonix can
treat at least 9 L of the stripping solution. Elution (%)
3.3. Continuous Experiment. In column experiments, the HNO3 H2SO4 HCl
aqueous solution containing Co (888 ppm), Mo (10 ppm), and
[acid concentration] (M) Mo Fe Mo Fe Mo Fe
Fe (2 ppm) was passed through a column of Diphonix (0.25 g
of resin). The obtained results are shown in Figure 6. It is seen 1.5 88.6 6.9 96.2 24.6 96.2 20.4
that the fraction concentration of Fe was approximately zero 2.0 90.6 10.3 88.4 33.2 89.5 34.0
until 4500 BV and increased slightly to 0.2 with the further 2.5 91.0 16.1 87.5 39 89.0 48.3

10031 dx.doi.org/10.1021/ie401123h | Ind. Eng. Chem. Res. 2013, 52, 10028−10032

Industrial & Engineering Chemistry Research

■
Research Note

out by varying the mass of loaded resin in a given volume of REFERENCES

eluent. Table 4 shows that most of Mo in the loaded resin was (1) Swain, B.; Jeong, J.; Lee, J.; Lee, G. H. Development of process
low sheet for recovery of high pure cobalt from sulfate leach liquor of
Table 4. Regeneration Efficiency of Diphonix with the Mass LIB industry waste: A mathematical model correlation to predict
of Loaded Resin in a Given Volume of Eluent (Eluent: 2.5 M optimum operational conditions. Sep. Purif. Technol. 2008, 63, 360.
HCl) (2) Valverde, I. M., Jr.; Paulino, J. F.; Afonso, J. C. Hydro-
metallurgical route to recover molybdenum, nickel, cobalt and
Elution (%) aluminum from spent hydrotreating catalysts in sulphuric acid
[loaded resin] (g/L) Mo Fe medium. J. Hazard. Mater. 2008, 160, 310.
(3) Zeng, L.; Cheng, C. Y. Recovery of molybdenum and vanadium
0.2 100 100
from synthetic sulphuric acid leach solutions of spent hydro-
0.4 100 78.4 desulphurization catalysts using solvent extraction. Hydrometallurgy
0.5 100 70.7 2010, 101, 141.
0.8 100 60.8 (4) Parhi, P. K.; Panigrahi, S.; Sarangi, K.; Nathsarma, K. C.
1.0 89 48.3 Separation of cobalt and nickel from ammonical sulphate solution
using Cyanex 272. Sep. Purif. Technol. 2008, 59, 310.
(5) Kumbasar, R. A. Selective extraction and concentration of cobalt
from acidic leach solution containing cobalt and nickel through
eluted in our conditions, while the elution of Fe was only emulsion liquid membrane using PC-88A as extractant. Sep. Purif.
quantitative when the concentration of loaded resin was 0.2 g/ Technol. 2009, 64, 273.
(6) Zhu, Z.; Zhang, W.; Pranolo, Y.; Cheng, C. Y. Separation and
L. It means that the concentration of loaded resin in eluent
recovery of copper, nickel, cobalt and zine in chloride solutions by
solution should be adjusted to 0.2 g/L for the complete synergistic extraction. Hydrometallurgy 2012, 127−128, 1.
regeneration of Diphonix using 2.5 M HCl as an eluent. (7) Banda, R.; Sohn, S. H.; Lee, M. S. Process development for the
separation and recovery of Mo and Co from chloride leach liquors of
4. CONCLUSIONS petroleum refining catalyst by solvent extraction. J. Hazard. Mater.
2012, 213-214, 1.
Ion exchange experiments have been conducted to remove a (8) Banda, R.; Sohn, S. H.; Lee, M. S. Solvent extraction separation of
small amount of Mo and Fe from cobalt chloride solution Mo and Co from chloride solution containing Al. Mater. Trans. 2013,
during the process of recovering cobalt from spent hydro- 54 (No. 1), 61.
desulfurization catalysts. Loading behavior of Mo, Fe, and Co (9) Banda, R.; Nguyen, T. H.; Sohn, S. H.; Lee, M. S. Recovery of
was tested in the pH range value from 0 to 4 using cationic valuable metals and regeneration of acid from the leaching solution of
(Diphonix) and anionic resins (AG1-x8). Our results showed spent HDS catalysts by solvent extraction. Hydrometallurgy 2013, 133,
that Diphonix was more effective than AG1-x8 in removing 161.
both Mo and Fe from the cobalt solution without any loss of (10) Biswas, R. K.; Begum, D. A. Solvent extraction of Fe3+ from
cobalt. The loading capacity of Diphonix for Mo and Fe was chloride solution by D2EHPA in kerosene. Hydrometallurgy 1998, 50,
153.
obtained from the cumulative loading curve and was found to (11) Lee, M. S.; Sohn, S. H.; Lee, M. H. Ionic Equilibria and Ion
be 90 and 40 mg/g of resin, respectively, when the pH of Exchange of Molybdenum(VI) from Strong Acid Solution. Korean
hydrochloride acid solution was 1. The column experiments Chem. Soc. 2011, 32, No. 10.
indicated that the removal of molybdenum and iron from (12) Lee, M. S.; Nicol, M. J. Removal of iron from cobalt sulfate
cobalt solution was complete using Diphonix. A cobalt chloride solutions by ion exchange with Diphonix resin and enhancement of
solution with high purity (>99.97%) was obtained from the iron elution with titanium (III). Hydrometallurgy 2007, 86, 6.
column experiments. The Mo and Fe loaded into the resin can (13) Sadanandam, R.; Fonseca, M. F.; Srikant, K.; Sharma, A. K.;
be eluted completely with 2.5 M hydrochloride acid solution Tangri, S. K.; Suri, A. K. Production of high purity of cobalt oxalate
and the Diphonix was successfully regenerated. from spent ammonia cracker catalyst. Hydrometallurgy 2008, 91, 28.
The industrial importance of our work lies in the fact that (14) Wen, J. J.; Zhang, Q. X.; Zhang, G. Q.; Cao, Z. Y. Deep removal
of copper from cobalt sulfate electrolyte by ion exchange. Trans.
cobalt chloride solution with purity higher than 99.9% can be Nonferrous Met. Soc. 2010, 20, 1534.
obtained from the leaching solution of the spent catalysts by (15) Nguyen, T. H.; Lee, M. S. Separation of molybdenum and
ion exchange with negligible loss of cobalt. vanadium from acid solutions by ion exchange. Hydrometallurgy 2013,

■ AUTHOR INFORMATION
Corresponding Author
136, 65−70.
(16) Zeng, L.; Cheng, C. Y. A literature review of the recovery of
molybdenum and vanadium from spent hydrodesulphurization
catalysts. Part II: Separation and purification. Hydrometallurgy 2009,
*Tel.: 82 61 450 2492. Fax: 82 61 450 2498. E-mail: mslee@ 98, 10.
mokpo.ac.kr. (17) Dodbiba, G.; Fujita, T.; Kikuchi, T.; Manjanna, J.; Matsuo, S.;
Takahashi, H.; Tohji, K. Synthesis of iron-based adsorbents and their
Notes
application in the adsorption of molybdenum ions in nitric solution.
The authors declare no competing financial interest. Chem. Eng. J. 2011, 166, 496.

■ ACKNOWLEDGMENTS
This work was supported by a grant from the fundamental
R&D Program for Core Technology of Materials funded by the
Ministry of Knowledge Economy, Republic of Korea. The
authors would like to thank for the financial support. We
gratefully thank the Gwangju branch of the Korea Basic Science
(KBSI) for ICP data.
10032 dx.doi.org/10.1021/ie401123h | Ind. Eng. Chem. Res. 2013, 52, 10028−10032