XXV International Mineral Processing Congress (IMPC 2010),

Brisbane, Australia

Stripping of Fe (III) from D2EHPA Using Different Reagents

Maryam Akhlaghi, Fereshteh Rashchi and Ehsan Vahidi

Fereshteh Rashchi
Associate professor of university of Tehran
School of Metallurgy and Materials Engineering, University of Tehran, Tehran, Iran
+9821 88012999
+9821 88006076
+989122024498

[email protected]

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 Stripping of Fe (III) from D2EHPA Using Different Reagents

Maryam Akhlaghi1, Fereshteh Rashchi2 and Ehsan Vahidi3

1
MSc, School of Metallurgy and Materials Engineering, University of Tehran, Tehran, Iran,
[email protected]
2
Associate professor, School of Metallurgy and Materials Engineering, University of Tehran, Tehran, Iran
[email protected]
3
MSc, School of Metallurgy and Materials Engineering, University of Tehran, Tehran, Iran,
[email protected]

2
 ABSTRACT
The common way to extract Fe(III) from an organic solvent is by using concentrated acidic solutions. The
stripping of Fe(III) from organic solvent Di-2-ethylhexyl phosphoric acid (D2EHPA) by hydrochloric acid (HCl)
solutions has been found to increase with increasing the acid concentration. However, the use of a
concentrated acidic solution such as 6 M HCl can degrade the organic molecules. In this research, to
increase the efficiency of Fe(III) stripping from D2EHPA, effect of some acids, salts and buffer solutions was
studied. Influence of Tri-butyl phosphate (TBP) as modifier on the Fe(III) stripping operation was also
investigated. According to the results, the best Fe stripping recovery was achieved in the presence of low
acid concentration and the salts which was 72.4 per cent oxalic acid, 70 per cent ammonium oxalate and 75
per cent buffer of oxalic acid and ammonium oxalate. The results also showed a better recovery in the
presence of the buffer rather than the salt. Finally, increasing the concentration of TBP, HCl and H 2SO4
resulted in a higher stripping efficiency of Fe(III). However, in the presence of oxalic acid and its salts
increasing the reagent concentration did not increase the stripping efficiency and at this condition, the
recovery of iron remained constant.

Keywords: D2EHPA, Iron stripping, Oxalic acid, Ammonium oxalate, Tri-butyl phosphate.

INTRODUCTION
In common way, to strip metal-loaded D2EHPA, acids are used in the stripping stage of a solvent extraction
process (Singh et al., 2005; Ismael et al., 2002). During the last two decades, a large number of researches
have been reported on the extraction of Fe (III) from different aqueous media by organo-phosphorus
extractants (Agrawal et al., 2007; Yadav et al.,1994; Jayachandran et al., 1997; O`Keefe et al., 2002). In the
extraction process of different elements, such as Zn and U from leaching solutions, organic solvents like
D2EHPA are used. In the leaching process, there are some impurities that can be also extracted by the
organic solvent, decreasing the selectivity. Fe (III) is one of these elements that can be extracted by
D2EHPA at the same condition as Zn ions. This will reduce the efficient sites of D2EHPA. Back extraction
of Fe(III) from organic phase was found to be very difficult even with concentrated H2SO4 (Musadaidzwa et
al., 2009; Sato et al., 1985; Lupi et al., 2000; Ambikadevi et al., 2000; Bonney et al., 1994). The difficulty in
stripping iron could be attributed to the possible formation of some stable complexes of iron with D2EHPA
(H2A2), such as Fe(OH)A2(HA)2 and Fe(HA2)3 (Shuqiu et al., 1989).

Various concepts have been developed in order to find the best methods to recover expensive solvents like
D2EHPA and different conditions and solution have been suggested. Different parameters have an effect on
performance of solvent D2EHPA.

The stripping of Fe (III) by HCl solutions has been found to increase with increasing acid concentration;
however, the use of a concentrated acidic solution such as 6 M HCl can degrade the organic phase. A high
concentration of H2SO4 is also required to strip iron from D2EHPA (Pospiech et al., 2010; Hirato et al., 1992;
Sahu et al., 1997; Shuqiu et al., 1989). Compared to sulfuric acid, nitric acid is a less efficient stripping
agent. The difference is attributed to the relatively weak ability of Fe (III) to undergo aqueous complex
formation with the nitrate anion (Weert et al., 1998).

To overcome the above difficulty, it is therefore suggested to examine effect of reagents such as oxalic acid
(Worthington et al., 1984), reductive materials which are more well-known (Roux et al., 2006; Change et al.,
2000), different acids and buffer compositions which are some new efforts in order to improve old methods
(Zielinski et al., 1998). As amount of loaded Fe ions (2 gr/Lit) is considerable in some processes, stripping
can make a major rule at system efficiency.

In this research effect of different acids and new buffer compositions on the stripping of iron ions from Fe
(III)-loaded D2EHPA are studied. Different kinds of acids with different concentrations are investigated and
effect of parameters such as time, temperature and phase ratio A/O are kept constant. Influence of TBP in
increasing the stripping efficiency is also investigated.

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 MATERIALS AND METHODS

Materials
Industrial grade Di-2-ethylhexyl phosphoric acid (D2EHPA), 97 per cent pure was obtained from Bayer,
Germany. Kerosene (#260), mostly aliphatic in nature, obtained from Tehran Oil Refining Company, Iran,
was used as diluent. Tri-butyl phosphate (TBP), 98 per cent was used as modifier, provided by Merck. Ferric
sulfate (Fe2(SO4)3), reagent grade, 73 per cent, from Rasayan Laboratory, India was used as the source of
iron. Sulfuric acid (H2SO4), 95-97 per cent pure was used as pH modifier. Hydrochloric acid (HCl), 32 per
cent pure, nitric acid (HNO3), 65 per cent, oxalic acid (C2O4H2), 90 per cent, ammonium and sodium oxalate,
95 per cent and ammonia, 25 per cent were all provided by Merck .

Aqueous / Organic solutions

The aqueous ferric ion solution (2 g/L) was prepared by dissolving ferric sulfate in distilled water. The
organic solution was prepared by mixing 4 per cent TBP and 20 per cent D2EHPA with kerosene. The
Fe(III)-loaded D2EHPA was prepared by contacting the organic solution with the aqueous ferric solution.
Then, sulfuric acid was used to adjust pH of the mixture to ca. 1. The pH of the mixed solution was
measured using a Sartorius pH meter, model PB11 made in Germany, with a special electrode for organic
phase. In the stripping tests, pH was kept constant by adding sulfuric acid (100 g/L) to the solution. The
aqueous phase used to strip iron was prepared from different reagents at different concentrations, such as,
sulfuric acid (H2SO4), Hydrochloric acid (HCl), nitric acid (HNO3), oxalic acid (C2O4H2) and some buffer
solutions.

Stripping set-up and procedure

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A plexi glass rectangular cell (10×10×15 mm ) was used for mixing the organic and aqueous solutions using
overhead stirrer. The cell was immersed in a temperature-controlled thermostatic bath.

Stripping experiments were carried out by mixing the two phases, 50 mL of the Fe(III) - loaded D2EHPA and
50 mL of the aqueous strip solution at organic to aqueous phase ratio (O/A) of 1:1 for 10 minutes (Mansur et
al., 2002; Pereira et al., 2007). After each test, the two phases were transferred to a decanter. Then the
aqueous phase was separated and analysed for Fe (III). The extraction tests were performed at room
temperature and the stripping tests at 40 ˚C.

RESULTS AND DISCUSSION

Effect of acid concentration

Figure1 illustrates the effect of H2SO4, HNO3 and HCl with various concentrations on the stripping efficiency
of Fe (III). It is obvious that the stripping efficiency increased with increasing the acid concentration and the
maximum Fe (III) recovery of 48 per cent was achieved at 6M HCl. The interaction between hydrochloric
acid with Fe (III) is more stable than the ones with sulfuric and nitric acid. Therefore, the iron ions would not
return to the sites on D2EHPA. Since the interaction between HNO3 and Fe (III) is relatively weak, the
stripping efficiency is low. It is also evident from Figure 1 that the increase in H2SO4 concentration increases
the stripping percentage of Fe (III) from loaded D2EHPA.

Effect of oxalic acid /oxalate salt

Figure 2 shows the effect of oxalic acid, oxalate salts (sodium and ammonium oxalate) and buffers ((sodium
oxalate + oxalic acid) and (ammonium oxalate + oxalic acid)) on the stripping efficiency of Fe (III). The Fe
(III) recovery enhances even with low concentrations of acids and salts and the best condition was obtained
using oxalic acid and ammonium oxalate with the efficiency of 75 per cent. Sodium oxalate shows a very low
efficiency compared to other reagents. This is probably due to the low solubility of sodium oxalate at the
experimental temperature applied (40 ˚C). According to Weast, (1998) 0.04 gr/mL of sodium oxalate is
soluble in water at 40 ˚C and at this condition the solubility of ammonium oxalate is twice, resulting in a
better efficiency. The efficiency of stripping can be attributed to the concentration of oxalate ions available in
the solution. As it can be seen ammonium oxalate and oxalic acid show close stripping efficiency especially
at high concentrations.

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This figure also shows improvement in the stripping efficiency by using buffers as the stripping solution. It is
interesting to note that sodium oxalate alone gives the lowest Fe (III) recovery; however, its buffer (sodium
oxalate + oxalic acid) results in almost the highest recovery among the reagents used. Table 1 summarizes
the results obtained from Figures 1 and 2.

Effect of acid/salt ratio on buffer performance

From previous experiments, the stripping efficiency in the presence of the buffer of oxalic acid and
ammonium oxalate was the best. To investigate the influence of acid/salt ratio on the stripping efficiency
different oxalic acid to ammonium oxalate ratios of 1/4, 2/3, 1/1, 3/2 and 4/1 were studied. Figure 3 illustrates
the results. As it can be seen increasing the acid concentration increases the stripping efficiency, except for
the ratio of 1/1 which requires more investigation. The figure also shows that the stripping efficiency
enhances to about 14 per cent by changing the acid/ salt ratio from 1/4 to 4/1. This confirms the previous
results in Figure 2, oxalic acid performing better than ammonium oxalate.

Effect of TBP concentration

HCl as the strip solution
Figure 4 shows the effect of TBP concentration (added to the solution at the extraction stage) on the
stripping efficiency using HCl as the strip solution. As it is shown increasing the TBP concentration,
enhanced the stripping efficiency significantly. In other words, in the presence of 4 per cent and 6 per cent
TBP, ca. 22 per cent and 40 per cent increase in the Fe (III) recovery, respectively, was obtained. During the
extraction process, TBP absorbs Fe (III) from aqueous phase by forming complex. Thus, a better recovery in
the presence of inorganic acids that are unable to form strong complexes with Fe (III) occurs. TBP is used as
modifier in the solvent extraction, as a result, enhances the effect of the organic solvent, D2EHPA (Jackson,
1986).

H2SO4 as the strip solution

Figure 5 shows the Fe (III) recovery using H2SO4 at different TBP concentration. At this condition, the same
trend as for HCl was observed and maximum recovery of ca. 48 per cent was obtained in the presence of 6
per cent TBP (i.e., ca. 23 per cent increase in the Fe (III) recovery as compared to the results in the absence
of TBP). It can also be concluded that HCl is more affected by TBP as compared to H2SO4.

Oxalic acid as the strip solution

Figure 6 shows the percentage of Fe (III) recovery as a function of different concentrations of oxalic acid and
in the presence of 4 per cent TBP. For two points, Effect of 0 per cent and 6 per cent TBP has also tested.
According to Figure 6, oxalic acid itself reveals a good performance (ca. 58 per cent recovery in the absence
of TBP) and the results are not influenced significantly by TBP; as in the case of HCl and H2SO4. This was
attributed to the ability of TBP to form a stable complex with iron. In other words, a pentagonal is formed
between two oxygen and two carbon atoms from oxalic acid and the iron ion. Therefore, there is a tendency
for iron ion to leave D2EHPA and take part in the structure of such a stable complex with TBP. On the other
hand, the hydrogen ions released from oxalic acid bind with D2EHPA to form the neutral form of the
molecule.

Oxalate buffer as the strip solution

Figures 7 and 8 show the results of stripping in the presence of ammonium oxalate and the buffer
(ammonium oxalate + oxalic acid), respectively. Same discussion as for oxalic acid can be given here, i.e.,
oxalate ions are able to form complexes with iron ions. As it can be seen in Figure 8 this is more
pronounced in the case of the buffer. According to this figure, the stripping efficiency improves slightly by
adding 6 per cent TBP in the extraction stage. In fact, a good efficiency even without adding TBP was
observed. Figure 7 shows a lower recovery of iron ion in the presence of ammonium oxalate and a higher
influence of TBP in the system. It can be concluded that the buffer performs better in the system studied
than the salt alone.

CONCLUSION
At the extraction stage, the Fe (III) ions as well as the desire metal ions can be extracted by D2EHPA at pH
range of 2.5-3.5. Stripping of the iron ions can be a difficult process.

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Adding inorganic acids at the stripping stage improved the efficiency. HCl resulted in a better efficiency as
compared to H2SO4 and HNO3.

Using weak organic acids such as oxalic acid even at a low concentration improved the stripping efficiency
more than the inorganic acids and the buffers (instead of acids) performed much better. Moreover,
increasing the acid/salt ratio in the buffer (from 1/4 to 4/1) resulted in a better iron ion recovery.

TBP acts as a modifier in the extraction stage and affects the Fe (III) recovery process:
TBP enhanced the stripping efficiency in the presence of inorganic acids, HCl and H2SO4.
TBP did not affect the stripping efficiency significantly, while oxalic acid and its sodium and ammonium salt
was added to the system.

The best Fe (III) recovery obtained using the buffer ammonium oxalate + oxalic acid.

REFERENCES
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pickle liquor of a steel industry by solvent extraction route, Hydrometallurgy, 88, pp 58–66.

Ambikadevi, V., Lalithambika, M, 2000. Effect of organic acids on ferric iron removal from iron-stained
kaolinite. Appl. Clay Sci. 16, pp 133–145.

Bonney, C.F., 1994. Removal of iron from kaolin and quartz: dissolution with organic acids. Proc. Int. Symp.
Hydrom. London, pp 313–323.

Change, C., Gu, H. and O'Keefe, T., 2000. Review of the galvanic stripping process for use in treating
oxidized metal wastes. Dep. Metal. Eng., Missouri-Rolla.

Chien Chang, C., Ming Chiu, T., Chu Hoh, Y. and Wang, W., 2003. Separation of iron from zirconium in
concentrated hydrochloric acid Solutions by extraction. Ins. Nuclear energy,Taiwan.

Cole, P.M. and Sole, K.C., 2002. Solvent extraction in the primary and secondary processing of zinc, The
Journal of The South African Institute of Mining and Metallurgy, pp 451–456.

Hirato, T., Wu, Z., Yamada , Y., 1992. Improvement of the stripping characteristics of Fe(III) utilizing a
mixture of di(2-ethyl) phosphoric acid and tri-n-butyl phosphate. Hydrometallurgy 28, pp 81–93.

Ismael, M., Carvalho, J., 2002. Iron recovery from sulphate leach liquors in zinc hydrometallurgy. Dep.
Eng. Quimica, Portugal.

Jackson, E., 1986, Hydrometallurgical Extraction and Reclamation, Ellis Horwood, Chichester, UK.

Jayachandran, J., Dhadke, P., 1997. Liquid-liquid extraction separation of iron(III) with 2-ethyl hexyl
phosphonic acid mono 2-ethyl hexyl ester, Talanta 44 , pp1285-1290.

Lupi, C., Pilone, D., 2000. Reductive stripping in vacuum of Fe(III) from D2EHPA, Hydrometallurgy, 57, pp
201–207.

Musadaidzwa, J.M., Tshiningayamwe, E.I., 2009. Skorpion zinc solvent extraction: The upset conditions, The
Southern African Institute of Mining and Metallurgy, Base Metals Conference, pp 245-259.

Pospiech, B., Walkowiak, W., 2010. Studies on iron(III) removal from chloride aqueous solutions by solvent
extraction and transport through polymer inclusion membranes with D2EHPA, Physicochemical Problems of
Mineral Processing, 44, pp 195-204.

Roux, E.A., Sechemene, M.J., and Holzhausen, S., 2006. “Iron Removal in the Skorpion Process”, Iron
Control technologies, J.E. Dutrizac and P.A. Riveros, Eds., Canadian institute of Mining, Metallurgy and
Petroleum, Montreal, pp. 491-500.

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Sahu, K., Das, R., 1997. Synergistic extraction of iron(III) at higher concentrations in D2EHPA–TBP mixed
solvent systems. Metall. Mater. Trans. B 28B, pp181–189.

Sato, T., Nakamura, T., 1985. The extraction of iron(III) from aqueous acid solutions by di(2-
ethylhexyl)phosphoric acid, Hydrometallurgy, 15 ,pp 209.

Shuqiu, Yu., Chen, 1989. Stripping of Fe(III) extracted by di-2-ethylhexyl phosphoric acid from sulfate
solution with sulphuric acid. Hydrometallurgy , 22, pp 267–272.

Singh, D., Mishra, S., Singh, H., 2006. Stripping of Iron(III) from the D2EHPA + TBP extract produced during
uranium recovery from phosphoric acid by oxalic acid, Hydrometallurgy, 81 ,pp 214-218.

Sun, J., O`Keefe, T.J., 2002. An evaluation of steel scrap as a reducing agent in the galvanic stripping of
iron from D2EHPA. Min. Eng. 15, pp 177–185.

Weast, R.C., 1998, Hand Book of Chemistry and Physics. CRC. Press.

Weert, G.V., Sandwijk, T. P, 1998. Solvent extraction of ferric iron from zinc sulfate solutions with DEHPA
investigation of nitric acid as stripping agent, in: B. Mishra (Ed), Extraction and Processing Division
Congress, TMS, Warrendale (PA), pp. 245–266.

Worthington R.E., Magdics A, 1984, Process for stripping uranium from an alkyl pyrophosphoric acid, US
Patent, 4,490,336.

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elements using Cyanex 925: application to zinc ores. Hydrometallurgy, 36, pp 53.

Zielinski, S., Buca, M., Famulski, M., 1998. Precipitation-Stripping Processes for Heavy Metals. Wroclaw Uni,
Poland.

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FIGURE CAPTIONS
Fig. 1. Effect of H2SO4, HNO3 and HCl concentration on Fe (III) recovery as a function of
concentration in the presence of 4 per cent TBP.
Fig. 2. Effect of oxalic acid, ammonium oxalate, sodium oxalate and buffers on Fe (III)
recovery as a function of concentration in the presence of 4 per cent TBP .
Fig.3. Effect of acid/ salt ratio (buffer) on the stripping efficiency (oxalic acid + ammonium
oxalate) in the presence of 4 per cent TBP.
Fig.4. Effect of TBP concentration on the stripping efficiency of HCl.
Fig. 5. Effect of TBP concentration on the stripping efficiency of H 2SO4 .
Fig. 6. Effect of TBP concentration on efficiency of oxalic acid.
Fig. 7. Effect of TBP concentration on efficiency of ammonium oxalate.
Fig.8. Effect of TBP concentration on efficiency of oxalic acid + ammonium oxalate.

TABLE CAPTION
Table1
The best recovery efficiencies for various compositions in special concentrations in the
presence of 4 per cent TBP.

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Fig. 1. Effect of H2SO4, HNO3 and HCl concentration on Fe (III) recovery as a function of
concentration in the presence of 4 per cent TBP.

Fig. 2. Effect of oxalic acid, ammonium oxalate, sodium oxalate and buffers on Fe (III)
recovery as a function of concentration in the presence of 4 per cent TBP.

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 80

70
70
61.7
60 57.25
53.85

50 46.9
Recovery (%)

40

30

20

10

0
"1/4" "2/3" "1/1" "3/2" "4/1"

Acid / Salt

Fig.3. Effect of acid/ salt ratio (buffer) on the stripping efficiency (oxalic acid + ammonium
oxalate) in the presence of 4 per cent TBP.

Fig.4. Effect of TBP concentration on the stripping efficiency of HCl.

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Fig. 5. Effect of TBP concentration on the stripping efficiency of H2SO4 .

Fig. 6. Effect of TBP concentration on efficiency of oxalic acid.

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Fig. 7. Effect of TBP concentration on efficiency of ammonium oxalate.

Fig.8. Effect of TBP concentration on efficiency of oxalic acid + ammonium oxalate.

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Table1
The best recovery efficiencies for various compositions in special concentrations in the
presence of 4 per cent TBP.

Stripping
Reagent Concentration (M)
(per cent) of iron
HNO3 6 1.8
H2SO4 6 32.5
HCl 6 48.2

oxalic acid 0.95 72.4

sodium oxalate 0.4 12.2

ammonium oxalate 0.8 65

sodium + oxalate 0.4 50

oxalic acid +
0.95 75
ammonium oxalate

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