Materials Transactions, Vol. 53, No. 11 (2012) pp. 2034 to 2037
© 2012 The Japan Institute of Metals
EXPRESS REGULAR ARTICLE
Recovery of Rhenium and Molybdenum from Molybdenite Roasting Dust
Leaching Solution by Ion Exchange Resins
Sung-Ho Joo1,2, Young-Uk Kim1, Jin-Gu Kang2, J. Rajesh Kumar1,2,
Ho-Sung Yoon2, P. K. Parhi2 and Shun Myung Shin1,2,+
1
Department of Resource Recycling, University of Science & Technology (UST), Daejeon 305-350, Korea
Extractive Metallurgy Department, Mineral Resources Research Division, Korea Institute of Geoscience
& Mineral Resources (KIGAM), Daejeon 305-350, Korea
2
Ion exchange separation of rhenium using Purolite A-170 and Purolite A-172 was carried out from the dust leach solution of molybdenite
concentrate. Different parameters such as effect of contact time, equilibrium pH, and solid liquid ratio were investigated. The optimum
absorption condition for Purolite A-172 resin was determined, and the absorption efficiency of Re and Mo were obtained to be about 90 and 0%,
respectively. From results, it was evident that, the performance of Purolite A-172 resin was more effective than Purolite A-170 resin, towards the
selective recovery of Re from the molybdenite dust leach solution. [doi:10.2320/matertrans.M2012208]
(Received June 11, 2012; Accepted August 27, 2012; Published October 11, 2012)
Keywords: rhenium, ion exchange, molybdenite roasting dust, anion resin
1.
Introduction
Rhenium (Re) is a rare metal with a high melting point and
often being used in making super alloys to improve the
characteristic feature such as creep strength. It is also used as
a catalyst in petroleum refining industries for making of leadfree, high-octane gasoline. The wide industrial applications
of rhenium and its low availability relative to demand, makes
it expensive. Hexabutyltriamide of phosphoric acid dissolved
in kerosene used as promising extractant for extraction of
Re(VII) and Mo(VI) from mineral acids such as sulfuric,
hydrochloric and nitric acid solutions were reported. And the
reports consists fundamental experimental parameters like
time effect, temperature effect and extractant concentration
influence on title metal ions and found that, 5 min time is
more than enough for extraction equilibrium.1,2) The possible
separation of Rh and Mo by using Amberlite IRA-400
(ClO4¹) was studied by Meloche and Preuss.3) Thus a small
quantity of rhenium can be obtained as a by-product during
roasting molybdenites. Hydrometallurgical methods have
been adopted to recover rhenium in order to meet the
increasing industrial demand. The flowsheet developed
for Re recovery by precipitation methodology followed
by decomposition and final product formed as crude
NH4ReO4.4,5) Resin-in-pulp process established for Re
separation from molybdenite calcine and they successfully
leached 95% Re with selectivity of Mo.5) The chemical
leaching of rhenium using different acids namely sulfuric
acid or nitric acid provides an economic and efficient
process.6) On the other hand, bioleaching can also be another
aspect where microorganisms play an important role to
solubilize rhenium into the solution phase.7) Hydrometallurgical methods such as precipitation, chlorination, adsorption
on activated carbon, solvent extraction (liquid-liquid extraction) and ion exchange are used for selective rhenium
extraction from these solutions.8­10) Fisher and Meloche
(year 1952) reported11) on the separation of rhenium from
+
Corresponding author, E-mail: [email protected]
molybdenum in the form of perrhenate by using Amberlite
IRA-400 and used 2.5 N sodium hydroxide and 7 N hydrochloric acid solutions, for removal of the molybdate
and perrhenate, respectively. In more recent work rhenium
concentration and molybdenum separation from sulfuric
and nitric-sulfuric acid solutions were accomplished using
weak base anion exchangers.12)
In the present study ion exchange behavior of rhenium and
molybdenum were conducted using Purolite A-170 and
Purolite A-172. The complete investigation includes the
adsorption of metals in bench scale method followed by
elution process. The key parameters such as effect of
contact time, equilibrium pH and solid liquid (S/L) ratio
are examined. The performance for loading of title metals
(molybdenum and rhenium) for both of the ion exchange
resins i.e., Purolite A-170 and Purolite A-172 were
compared.
The optimum conditions for each resins (Purolite A-170
and Purolite A-172), were established by investigating the
effects of various parameters namely equilibrium pH (E. pH),
solid liquid (S/L) ratio and contact time. In the elution study,
different elution agents were introduced for observing
stripping behavior of Re.
2.
Experimental Procedure
2.1 Preparation sample
After precipitating the major amount of molybdenum from
molybdenite dust leaching solution, the remaining filtrate
containing 109 mg/dm3 Re, 63 mg/dm3 Mo, 16 mg/dm3 Cu
and 3.1 mg/dm3 Ca was used for adsorption of Re by ion
exchange resins.
2.2 Procedures and analysis
The resins viz. Purolite A-170 and Purolite A-172 used in
the experimental study were subjected to the pretreatment
using H2SO4. Weighed amount of resins were kept with
2 kmol/m3 H2SO4 for 48 h and subsequently leads to the
swelling of resin. Thereafter, the treated resins were filtered
Adsorption efficiency(%)
Recovery of Rhenium and Molybdenum from Molybdenite Roasting Dust Leaching Solution by Ion Exchange Resins
100
90
80
70
60
50
40
30
20
10
0
(a)
(a)
Re
600
2035
1200
1800
2400
Mo
3000
3600
Adsorption efficiency(%)
Time, t/s
100
90
80
70
60
50
40
30
20
10
0
(b)
Re
Mo
600
1200
1800
2400
3000
(b)
3600
Time, t/s
Fig. 1 Adsorption efficiency of Re and Mo by contact time with Purolite
A-170 (a) and Purolite A-172 (b). (Solid/Liquid ratio: 40 kg/m3, Temp.:
298 K, agitation speed: 130 rpm, pH: 2.5).
followed by washing with deionized water till a constant
value of pH was achieved and later were dried by a oven at
323 « 1 K duration next 24 h. Desired quantity of resin was
introduced to a conical flask (100 cm3) containing molybdenide dust leached solution and then it was placed in
horizontal shaker for a definite time period. A sample of
5 cm3 was withdrawn in a regular time interval and the resin
separated from the slurry and was returned to the original
slurry. The loaded resin was separated from the slurry, which
was later washed and eluted. The concentration of the metal
remaining in the slurry and in elute were analyzed by ICPAES (JOBIN-YVON JY 38). Prior to the elution study the
metal loaded resin was washed with deionized water and
dried. A desired quantity of loaded resin was treated with the
specific reagents in a 50 cm3 conical flask for elution of the
respective metal ions from the resin phase.
3.
Results and Discussions
3.1 Effect of time
The effect of contact time was investigated in the range of
600 to 3,600 s in the following experimental conditions: solid
liquid (S/L) ratio, 40 kg/m3; temp., 298 K; shaking speed,
130 rpm. The results show that the adsorption equilibrium
was achieved just after 2,400 s of the reaction time and there
after the percentage of metal adsorption remained constant.
The maximum adsorption efficiency of Re and Mo with
Purolite A-170 was obtained to be ³99 and 95%,
respectively (Fig. 1(a)). Whereas with Purolite A-172
adsorption of Re was not significantly affected with increase
in the time and just after 1200 s of reaction time the
Fig. 2 Adsorption efficiency of Re and Mo by equilibrium pH with
Purolite A-170 (a) and Purolite A-172 (b). (Solid/Liquid ratio: 40 kg/m3,
Temp.: 298 K, agitation speed: 130 rpm, contact time: 2,400 s for Purolite
A-170 and 1,200 s for Purolite A-172).
adsorption rate remained the same. On the other hand the
adsorption efficiency of Mo was found to be increasing from
8 to 35% during 600 to 3000 s and remained constant on
further increase in the contact time (up to 3600 s). From the
results, the optimum contact time for selective adsorption
Re was 1200 s and the adsorption efficiency of Re and Mo
were found to be 99 and 20%, respectively (Fig. 1(b)).
3.2 Effect of pH
In case of Purolite A-170, the adsorption behavior of Re
and Mo were examined as the function of E. pH. The other
conditions adopted in this test were: S/L ratio 40 kg/m3,
298 K, 130 rpm and contact time 2400 s. As shown in
Fig. 2(a), about 95% of Re was adsorbed at E. pH 7 and
thereafter, a quick decrease in the Re adsorption is observed
on further increase in the E. pH value up to 10. On the other
hand, the adsorption efficiency of Mo was increased to ³95%
up to E. pH of 4.0 and then sharply decreased to zero with an
increase in the E. pH of 9.0. From the results it was observed
that pH 0 is the most suitable condition for selective
separation of Re in order to obtain the absorption efficiency
of Re (95%) and Mo (10%). The preferential adsorption of
Re with respect to Mo is due to the abundant existence of
cationic form of Mo and anionic form of Re at the solution
E. pH 0.
S.-H. Joo et al.
100
90
80
70
60
50
40
30
20
10
0
(a)
Elution concentration(mg/dm3)
Adsorption efficiency(%)
2036
Re
Mo
13
23
33
43
110
100
90
80
70
60
50
40
30
20
10
0
Mo-NH4OH
Re-NaCl
Mo-NaCl
Re-HNO3
Mo-HNO3
Re
Mo
13
2
3
4
5
Concentration, C/mol·dm-3
(b)
Elution concentration(mg/dm3)
Extraction efficiency(%)
Re-NH4OH
1
Solid/liquid ratio (g·dm-3)
100
90
80
70
60
50
40
30
20
10
0
(a)
23
33
Solid/liquid ratio
43
(g·dm-3)
Fig. 3 Adsorption efficiency of Re and Mo by solid/liquid ratio with
Purolite A-170 (a) and Purolite A-172 (b). (Temp.: 298 K, agitation speed:
130 rpm, pH: 0 and contact time: 40 min for Purolite A-170 and 1,200 s
for Purolite A-172).
The Purolite A-172 adsorption process pH effect was
shown in Fig. 2(b). It is found that over 95% adsorption is
taking place at the solution E. pH 8, and later being decrease
on further increase of the E. pH (up to 10.0). Meanwhile,
the adsorption efficiency of Mo was reached to about 50%
between E. pH of 4 and a sharp decrease of the Re adsorption
is observed on further increase of the pH value up to 10.0.
At E. pH 0, the adsorption efficiency of Re and Mo were 95
and 3%, respectively.
3.3 Effect of solid liquid (S/L) ratio
The absorption behavior of Re and Mo were examined as
function of solid liquid (S/L) ratio. The other experimental
conditions were adopted viz. temperature 298 K, shaking
speed 130 rpm, contact time 2400 s for Purolite A-170
whereas 1200 s for Purolite A-172 and initial pH 0 were
kept constant for both resins. From Fig. 3(a), it is seen that
adsorption efficiency of both the metals were steadily
increased with an increase in the Solid liquid ratio. The
maximum adsorption efficiency of Re and Mo at Solid
liquid ratio 40 is about 90 and 20%, respectively with
Purolite A-170. The adsorption percentage of Re was
increased from 38 to 90% with an increase in the solid
liquid ratio from 13 to 40 kg/m3 and the adsorption of
Mo was not observed at the studied solid liquid ratio range
by Purolite A-172 (Fig. 3(b)).
110
100
90
80
70
60
50
40
30
20
10
0
(b)
Re-NH4OH
Mo-NH4OH
Re-NaCl
Mo-NaCl
Re-HNO3
Mo-HNO3
1
2
3
4
5
Concentration, C/mol·dm-3
Fig. 4 Elution efficiency of Re and Mo by concentration of elution solution
from Purolite A-170 (a) and Purolite A-172 (b). (Solid/Liquid ratio:
40 kg/m3, Temp.: 298 K, agitation speed: 130 rpm, and contact time:
2,400 s for Purolite A-170 and 1,200 s for Purolite A-172).
3.4
Elution behavior of Re and Mo from Purolite A-170
and Purolite A-172
Various reagents such as ammonium hydroxide, sodium
chloride, nitric acid were used as elution process and the
elution profile for Re and Mo above said reagents was
presented in Fig. 4(a) for Purolite A-170 and Fig. 4(b) for
Purolite A-172 resins. The loaded Purolite A-170 resin
having 100.6 mg/dm3 of Re and 17 mg/dm3 of Mo, whereas
in case of second resin Purolite A-172 having 84 mg/dm3 of
Re and 1 mg/dm3 of Mo. The conditions like solid liquid
(S/L) ratio 40 kg/m3, temp. 298 K shaking speed 130 rpm
and contact time 2400 s are kept fixed during experimental
study. In case of loaded Purolite A-170 resin, it was cleared
that almost all Re adsorbed in the loaded resin was eluted
at all label concentration of NH4OH, but at the same time
the elution of Mo was found to be very low (<10 mg/dm3)
which showed a selective separation of Re from Mo from the
metal loaded resin phase. On the other hand in case of second
metal loaded resin i.e., Purolite A-172 the obtained results
clearly demonstrates that, elution amount of Re was
increased while increasing the NH4OH concentration from
1 to 5 whereas nitric acid was eluted the Re 30 to 45 mg/dm3
(Fig. 4(b)).
Recovery of Rhenium and Molybdenum from Molybdenite Roasting Dust Leaching Solution by Ion Exchange Resins
4.
Conclusions
The investigation for the recovery of rhenium was carried
out using two types of anion exchange resins Purolite A170 and Purolite A-172. In case of Purolite A-170 resin,
the absorption efficiency of Re and Mo were about 90 and
20% at E. pH 0, contact time 40 min, Solid liquid ratio
40 g/m3, 298 K, whereas the absorption efficiency of Re
and Mo were about 90 and 0%, respectively using Purolite
A-172 resin. Although the adsorption performance for both
type of resins found to be similar with respect to adsorption
metal Re, however, Purolite A-172 was found to be
effective for selective adsorption of Re. Among the eluting
reagents, NH4OH showed a best reagent for quantitative
elution of Re. Elution amount of 100.6 mg/dm3 Re and
5 mg/dm3 Mo obtained using 1 to 5 mol/dm3 NH4OH.
On the other hand, the elution amount of Re and Mo were
obtained to be 50 and 1 mg/dm3, respectively, for the case
of Purolite A-172. Among the both of the resins, the
overall the adsorption behaviour of Purolite A-172 was
found to be significant in terms of the selective as well as
effective separation of Re from the molybdenite dust leach
solution.
2037
Acknowledgments
This research was supported by the Basic Research Project
(12-3111-1) of the Korea Institute of Geoscience and Mineral
Resources (KIGAM) funded by the Ministry of Knowledge
Economy of Korea.
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