Hydrometallurgy 61 Ž2001.

81–87
www.elsevier.nlrlocaterhydromet

Liquid–liquid extraction separation of iron žIII/ from titania wastes

using TBP–MIBK mixed solvent system
J. Saji, M.L.P. Reddy )
Inorganic and Analytical Chemistry Unit, Regional Research Laboratory (CSIR), TriÕandrum-695 019, India

Received 5 June 2000; received in revised form 10 January 2001; accepted 10 January 2001

Abstract

The extraction of ironŽIII. from hydrochloric acid solutions has been investigated using a mixed solvent system
consisting of tributyl phosphate ŽTBP. and methyl isobutyl ketone ŽMIBK.. The results demonstrate that ironŽIII. is extracted
as HFeCl 4 with 2 mol of the solvent. Extraction and stripping isotherms were obtained using the solvent mixture consisting
of 70 vol.% TBP and 30 vol.% MIBK with a typical solution containing 1 M of ironŽIII. and 2 M of hydrochloric acid. The
potential of the mixed solvent system for the recovery of high purity ironŽIII. chloride from waste chloride liquors of
titanium minerals processing industry has been assessed. q 2001 Elsevier Science B.V. All rights reserved.

Keywords: Liquid–liquid extraction; Separation; IronŽIII.; Titania wastes

1. Introduction not recovered. Nowadays, the liquid–liquid extrac-

The management of the waste acidic chloride
liquors from the titania industry containing heavy
metals represents a major environmental issue, af-
fecting every industrialised country in the world.
Although the most frequently employed techniques
for the disposal of the spent acid residues involves
either the neutralisation–precipitation–discharge se-
quence or the pyrohydrolysis of the waste liquors to
recover hydrochloric acid, these practices are in-
creasingly being questioned because of the environ-
mental consequences related to stocking of toxic
solid waste. Further, many valuable metal species are
)
Corresponding author.
E-mail address: reddy@csrrltrd.ren.nic.in ŽM.L.P. Reddy..
tion technique has been increasingly employed to
combat the iron control problem in many hydromet-
allurgical industries w1x. The extractability of ironŽIII.
with the acidic organophosphorus compounds and
carboxylic acids is the highest and it requires high
acid concentration for stripping of ironŽIII.. Several
attempts have been made to improve the stripping of
ironŽIII. from pregnant acidic extractants using mixed
solvent systems w2,3x. However, some problems such
as phase disengagement and stripping of ironŽIII. in
a cost-effective fashion, associated with the iron
purification remain unsolved. The present paper at-
tempts to study the influence of a mixed solvent
system containing TBP and MIBK, on the extraction
as well as stripping of ironŽIII. from concentrated
solutions. Further, the potential of the mixed solvent
system has been explored for the recovery of high

0304-386Xr01r$ - see front matter q 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 4 - 3 8 6 X Ž 0 1 . 0 0 1 4 6 - 3
82 J. Saji, M.L.P. Reddy r Hydrometallurgy 61 (2001) 81–87
purity ironŽIII. chloride from waste chloride liquors
of titanium minerals processing industry.
2. Experimental
Tributyl phosphate and methylisobutyl ketone,
supplied by Aldrich Chemical, USA were used with-
out further purification. Distilled kerosene Žboiling
range 160–2008C; composed of aliphatic hydrocar-
bons. was used as a diluent. All other reagents and
chemicals used were of analytical reagent grade. A
Hitachi 220 double beam microprocessor controlled
spectrophotometer was used for measuring ab-
sorbances. ICP-AES ŽLabtam, Australia. was used
for elemental analysis of the feed and product solu-
tions of the waste liquors of titania industry. An
Orion, USA, ion analyser was used for the pH
measurements.
Solvent extraction and stripping experiments were
carried out in separatory funnels of suitable volume
at 303 " 1 K. Preliminary experiments showed that
the extraction equilibrium was attained within 5 min.
After phase separation, the ironŽIII. content in the
aqueous phase was determined by the standard SnCl 2
reduction–K 2 Cr2 O 7 titration method w4x or spec-
trophotometrically by 1,10-phenanthroline method
Žwhenever the concentrations were low. w5x. The
concentration of the metal ion in the organic phase
was then obtained from material balance. The distri-
bution ratio, D, was taken as the ratio of the concen-
tration of metal ion in the organic phase to that
present in the aqueous phase.
3. Results and discussion
3.1. Iron(III) extraction with TBP, MIBK and TBP q
MIBK mixtures
As is well known, ironŽIII. extraction with MIBK
is lower than that of TBP at any given acid concen-
tration. Very high concentration of HCl Ž) 6 M. is
required to achieve complete extraction of ironŽIII.
with MIBK w6x. On the other hand, the use of TBP
leads to third-phase formation. Hence, a modifier has
to be introduced in the organic phase along with the
diluent. Further, it requires considerable time for
clear phase separation after extraction w7x. In order to
overcome the above problems with respect to TBP
and MIBK, Reddy and Bhaskara Sarma w8x have
suggested the use of a mixed solvent system consist-
ing of TBP and MIBK for the extraction of ironŽIII..
However, these authors have not utilised this mixed
solvent system for the separation of ironŽIII. from
waste chloride liquors of titania industry. Hence, in
the present study, an attempt has been made to
investigate the extraction behaviour of ironŽIII. from
hydrochloric acid solutions using a mixture of TBP
and MIBK as a solvent and also the potential of this
mixed solvent system has been explored for the
separation of ironŽIII. chloride from waste chloride
liquors. The extraction of ironŽIII. from solutions
containing 1 M ironŽIII. and 2 M hydrochloric acid
using TBP, MIBK and their mixtures has been inves-
tigated and the results are shown in Fig. 1. IronŽIII.
extraction increases with increasing TBP concentra-
tion in kerosene in the organic phase. Here, isode-
canol Ž20 vol.%. has been used as a modifier in the
organic phase. On the other hand, it was found that
the extraction of ironŽIII. with MIBK alone was
negligible up to 40 vol.% concentration. However,
with the mixtures of MIBKq TBP, a small synergis-
tic enhancement in the extraction of ironŽIII. has
been observed. It is clear from these experiments that
a mixed solvent system Ž70 vol.% TBP and 30 vol.%
MIBK. can extract ironŽIII. chloride more effec-
tively from lower acid concentrations as compared to
TBP or MIBK alone Žat 2 M HCl D with TBP s
0.87; D with MIBKs negligible; D with TBP q
MIBKs 1.18.. Further, the phase disengagement is
also fast Žwithin a couple of minutes. as compared to
individual extractants Ž15–20 min.. The log–log plots
for TBP and TBP q MIBK mixtures are straight
lines with slope values of 1.9, indicating the associa-
tion of 2 mol of solvent in the extracted complexes.
The existence of similar species in the organic phase
was reported by earlier investigators for the extrac-
tion of ironŽIII. with TBP from HCl solutions
w2,9,10x. On the other hand, Reddy and Bhaskara
Sarma w8x have reported the extracted complexes as
HFeCl 4 P 3TBP from hydrochloric acid solutions with
TBP. A solvent mixture consisting of 70 vol.% TBP
and 30 vol.% MIBK was used in the subsequent
experiments for the optimisation of extraction and
stripping conditions.
 J. Saji, M.L.P. Reddy r Hydrometallurgy 61 (2001) 81–87 83

Fig. 1. Effect of TBP concentration on the extraction of ironŽIII.. Ža. TBP–isodecanol–kerosene system. Žb. TBP q MIBK system. Aq.
phase: wFe 3q x s 1 M, wHClx s 2 M.

3.2. Effect of hydrochloric acid concentration
The effect of hydrochloric acid concentration Ž1–3
M. on the extraction of ironŽIII. Ž1 M. has been
studied using a mixed solvent system consisting of
70 vol.% TBP and 30 vol.% MIBK. The extraction
of ironŽIII. was found to increase with the increase
in acid concentration. The effect of hydrogen and
chloride ion concentrations by employing HCl q
NaCl mixtures on the extraction of ironŽIII. has been

Fig. 2. Ža. Effect of hydrogen ion concentration on the extraction of ironŽIII. at constant Cly concentration. wFe 3q x s 1 M, wClyx s 5 M. Žb.
Effect of chloride ion concentration on the extraction of ironŽIII. at constant Hq concentration. wFe 3q x s 1 M, wHqx s 2 M.
84 J. Saji, M.L.P. Reddy r Hydrometallurgy 61 (2001) 81–87

Fig. 3. McCabe–Thiele plot for ironŽIII. extraction. wFe 3q x s 55.85 g Ly1 , wHClx s 2 M.

investigated using the mixed solvent system and the tem consisting of 70 vol.% TBP and 30 vol.% MIBK
results are presented in Fig. 2. The log wClyx versus can be represented as
log D plot is a straight line with a slope of 3.9, 3q
Fe aq q Hq y
aqq 4Cl aqq 2S org z HFeCl 4 P 2S org Ž 1.
indicating the association of four chloride ions with
iron in the extracting species. The log wHqx versus where S represents solvent molecule.
log D plot gave a straight line with a slope of unity The above extraction equilibrium is in good
indicating the extracting species as HFeCl 4 . agreement with the earlier reports for the extraction
Based on the preceding studies, the extraction of ironŽIII. from HCl solutions using TBP as an
equilibrium for ironŽIII. using a mixed solvent sys- extractant w2,9,10x.

Fig. 4. McCabe–Thiele plot for ironŽIII. stripping. wFe 3q xorg s 27.92 g Ly1 .
 J. Saji, M.L.P. Reddy r Hydrometallurgy 61 (2001) 81–87 85

Table 1 3.3. Extraction and stripping isotherms

Typical composition of waste chloride liquor from titania industry
ŽKerala Minerals and Metals, India.
Constituent g Ly1
A solvent mixture consisting of 70 vol.% TBP
and 30 vol.% MIBK was used to generate an extrac-
FeCl 2 170–210
FeCl 3 40–60
tion isotherm for ironŽIII. from 2 M hydrochloric
MgCl 2 15–16 acid solutions. The McCabe–Thiele plot for a feed
MnCl 2 7–8 solution containing 55.85 g Ly1 ironŽIII. showed
AlCl 3 2.5–6 that almost quantitative extraction of iron was possi-
TiOCl 2 2.5–3.2 ble in two counter-current stages at an AqrOrg ratio
CrCl 3 3–7
VOCl 3 2.5–3.5
of 1:2 ŽFig. 3.. The loaded organic phases obtained
HCl 30–40 from these experiments were used to carry out strip-
ping studies using distilled water. A McCabe–Thiele

Fig. 5. Schematic flow diagram for the solvent extraction process.

86 J. Saji, M.L.P. Reddy r Hydrometallurgy 61 (2001) 81–87

Table 2 stages of counter-current extraction Žaqrorgs 1:2.

Extraction of ironŽIII. chloride from waste liquors of titanium using the mixed solvent system consisting of 70
minerals processing industry using 70 vol.% TBPq30 vol.%
MIBK mixed–solvent system
vol.% TBP and 30 vol.% MIBK, and Ž3. stripping of
the loaded organic phase using distilled water in
Constituent Feed Raffinate Strip solution
Žg Ly1 . Žg Ly1 . Žg Ly1 . three stages Žaqrorgs 3:2. to recover high purity
ironŽIII. chloride. The schematic diagram of the
FeCl 3 162.240 0.090 162.150
TiOCl 2 0.110 0.107 - 0.003 process adopted is shown in Fig. 5. Typical results of
MgCl 2 6.705 6.532 0.173 the process are given in Table 2. The present investi-
MnCl 2 2.980 2.975 0.005 gations revealed that the mixed solvent system can
AlCl 3 6.679 6.674 - 0.005 be used as a selective solvent for the recovery of
VOCl 3 0.579 0.576 - 0.003
high purity ironŽIII. chloride Ž99.9%. with a yield of
CrCl 3 0.396 0.393 - 0.003
ZrCl 4 0.026 0.024 - 0.002 ) 99.9% from a multivalent metal chloride feed,
HCl 72.9 34 38.9 present in the waste chloride liquors of titanium
minerals processing industry. By converting ferric
Purity of ironŽIII. chlorides99.9%, product yields99.94%. chloride into iron oxide of various purities by the
known methodologies, it has applications in paint,
pigment and electronic industries.
plot for a loaded organic phase containing 27.92 g
Ly1 ironŽIII. showed that quantitative stripping of
iron is possible in three counter-current stages with 4. Conclusion
an AqrOrg ratio of 3:2 ŽFig. 4..
The present investigations clearly highlight that
3.4. Extraction of iron(III) from waste chloride high purity ironŽIII. chloride can be selectively re-
liquors of titania industry covered from titania waste chloride liquors through a
solvent extraction process using a mixed solvent
The developed solvent extraction procedure using system consisting of 70 vol.% TBP and 30 vol.%
the mixed solvent system consisting of 70 vol.% MIBK. Further, the problems associated with the
TBP and 30 vol.% MIBK was applied for the recov- TBP and MIBK when used individually for the
ery of high purity ironŽIII. chloride from the waste extraction of ironŽIII. could be overcome by using
liquors of titanium minerals processing industry. The the mixed solvent system.
typical composition of waste chloride liquor contain-
ing multivalent metal chlorides is given in Table 1.
As it is well known that ferrous iron is less ex-
Acknowledgements
tractable than ferric iron when extracted with solvat-
ing extractants, in the present study, the waste chlo-
ride liquor was chlorinated to convert ferrous to This work was supported by Science, Technology
ferric iron by passing chlorine gas Žin a stoichiomet- and Environment Department, Government of Ker-
ric amount to the divalent iron ions.. ala. The authors wish to thank Dr. G.D. Surender,
Head, Minerals Process Engineering Division and
2FeCl 2 q Cl 2 Ž g . ™ 2FeCl 3 Ž 2. Dr. G. Vijay Nair, Director, Regional Research Lab-
Batch type counter-current extraction and strip- oratory, Trivandrum for their constant encourage-
ping studies were made at laboratory scale using ment.
separatory funnels at 303 q 1 K. The extraction pro-
cess for the recovery of ironŽIII. chloride from the
waste liquor comprises the steps of Ž1. chlorination References
of waste chloride liquor and adjustment of acidity in
the feed, Ž2. selective extraction of ironŽIII. chloride w1x D.S. Flett, A.J. Monhemius, Solvent extraction for iron
from the chlorinated waste chloride liquor in three control in hydrometallurgy, in: J.E. Dutrizac, G.B. Harris
 J. Saji, M.L.P. Reddy r Hydrometallurgy 61 (2001) 81–87
ŽEds.., Proceedings of the International Symposium on Iron
Control in Hydrometallurgy, Canadian Institute of Mining
Metallurgy and Petroleum, Canada, 1996, p. 331.
w2x K.K. Sahu, R.P. Das, Metall. Trans. B 28B Ž1997. 181.
w3x T. Hirato, Z.C. Wu, Y. Yamada, H. Majima, Hydrometal-
lurgy 28 Ž1992. 81.
w4x A.I. Vogel, A Textbook of Quantitative Chemical Analysis,
5th edn., ELBS Longman, UK, 1989, p. 376.
w5x A.I. Vogel, A Textbook of Quantitative Chemical Analysis,
5th edn., ELBS Longman, UK, 1989, p. 691.
87
w6x A. Chiba, O. Kimura, in: C.M. Srivastava, M.J. Patni ŽEds..,
Proceedings of 5th International Conference on FerritesŽICF-
5., vol. 1, Oxford and IBH Publishing, New Delhi, 1989, p.
35.
w7x P.R. Vasudeva Rao, R. Damodaran, T.G. Srinivasan, C.K.
Mathews, Solvent Extr. Ion Exch. 11 Ž4. Ž1993. 645.
w8x B.R. Reddy, P.V.R. Bhaskara Sarma, Hydrometallurgy 43
Ž1996. 299.
w9x H. Specker, M. Cremer, Z. Anal. Chem. 167 Ž1959. 110.
w10x S.K. Majumdar, A.K. De, Talanta 7 Ž1960. 1.