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Hydrometallurgy 77 (2005) 219 225 www.elsevier.

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Extraction of titanium (IV) from acidic media by 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester
D. Fontana, P. Kulkarni, L. PietrelliT
ENEA, C.R. Casaccia, Via Anguillarese, 301. I-00060 Rome, Italy Received 25 February 2004; received in revised form 13 January 2005; accepted 20 January 2005

Abstract The extraction of titanium(IV) from sulphate, chloride and nitrate solutions has been investigated using 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (EHEHPA) in kerosene. The kinetics of extraction was slow, requiring 60 min for the complete extraction of titanium and was improved with the increase of the extractant concentration in the organic phase. When the acid concentration in the aqueous feed phase was varied from 0.5 M to 4 M, the distribution ratios of titanium showed minimal values at 12 M acid. The effect of the initial concentration of titanium on extraction was found to be negligible, indicating the presence of mononuclear species in the aqueous phase. The stripping of titanium was studied using H2SO4, H2SO4+H2O2 and Na2CO3. The kinetics of the stripping was very slow when sulphuric acid was used, but was improved with complex forming stripping agents (H2SO4+H2O2 and Na2CO3). The extraction and stripping of titanium were 100% using an aqueous nitrate medium and sodium carbonate strip. Hence, results generated would be applicable to separate titanium from secondary sources such as fly ash originated from incinerators of Municipal Solid Waste. D 2005 Elsevier B.V. All rights reserved.
Keywords: Titanium(IV); Sulphuric acid; Hydrochloric acid; Nitric acid; Solvent extraction; EHEHPA; Stripping

1. Introduction Titanium and its alloys, due to their excellent characteristics as industrial materials, are used for various purposes in industry. In particular, titanium has been widely used in the aerospace industry while titanium dioxide finds application as pigment in the paint industry. Moreover a larger-scale output
T Corresponding author. Tel.: +39 0630484362; fax: +39 0630483818. E-mail address: pietrelli@casaccia.enea.it (L. Pietrelli). 0304-386X/$ - see front matter D 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.hydromet.2005.01.003

of lower-cost titanium and titanium alloy products for use in automotive parts and buildings is increasing. The recovery of titanium from secondary sources such as fly ash generated from the Municipal Solid Waste (MSW) incineration could minimise landfill disposal and the waste of natural resources. Generally a medium size incineration plant (170 tons/ day of MSW) annually produce about 80 tons of fly ash which contain 700012 000 mg Ti/kg (Wiles, 1996; Pietrelli and Porzio, 2002). Fly ash can be effectively leached by H2SO4, HNO3, HCl

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and mixed acid solutions. A preliminary study shows that in terms of titanium yield, the best result was obtained by H2SO4+HNO3 (Giacco, 2003). The selective separation of titanium from fly ash is a tough task considering the presence of many metal ions and impurities such as Fe, Zn, Al, Mn, etc., at various concentrations. Many reagents have been tested for the extraction of titanium(IV) from aqueous solutions. It is recognised that neutral organo-phosphorous compounds are effective extractants for tetravalent metals, particularly for titanium(IV). Among these, tri-n -butyl phosphate (TBP), tri-octylphosphine oxide (TOPO) and Cyanex 923 (TRPO) have been used widely for the extraction of titanium(IV) from acidic chloride solutions (Allal et al., 1997; Sheng et al., 1983; John et al., 1999a). However, the use of TBP and TOPO leads to third phase formation when titanium(IV) is extracted from concentrated metal ion solutions (Allal et al., 1997). Quaternary amine extractants such as Aliquat 336 extract titanium efficiently at low acidity range from HCl solutions (Sundaramurthi and Shinde, 1989). Organo-phosphorous acid derivatives such as dodecyl phosphoric acid (Ritcey and Ashbrook, 1979), di-o -tolylphosphoric acid (Islam et al., 1985) and p -(1,1,3,3-tetramethylbutyl) phenyl phosphoric acid (Mellah and Bauer, 1995), di(2-ethylhexyl) phosphoric acid (D2EHPA) (Biswas and Begum, 1998, Biswas et al., 2002), have been used by several investigators but they are found to have very slow kinetics and to be less selective. Mixtures of extractants, seems to give faster kinetics (Kislik and Eyal, 1993a). Critical reviews of published data on titanium(IV) extraction appeared in 1993 (Kislik and Eyal, 1993b) and 1999 (Sole, 1999a). The review by Kislik and Eyal, in particular, showed that titanium extraction passes through a minimum, depending on the acidity of aqueous phase. Moreover, mono-2-ethylhexyl phosphate (MEHPA) was found to be better and more selective than its counter part D2EHPA, because of its strong chelating capability and less sterically hindered sites. Among the acidic organo-phosphoric compounds, EHEHPA (commercially known as PC88A or Ionquest 801 or P507), has been widely used for NiCo separation (Sarangi et al., 1999). Titanium extraction by EHEHPA has been studied

by Jayachandran and Dhadke (1998), John et al. (1999b, 2003) and by Sing and Dhadke (2002) in H2SO4, HCl and HClO4 solutions, respectively. In this paper the solvent extraction of titanium(IV) from HCl, HNO3, H2SO4 solutions by EHEHPA has been investigated to evaluate if the recovery of titanium from the fly ash produced by a MSW incineration plant could be carried out after leaching. Therefore, the extraction of titanium using sulphate, nitrate and chloride as medium was compared to determine the best extraction and stripping conditions for the effective recovery of titanium from other impurity elements.

2. Experimental 2.1. Reagents The extractant 2-ethylhexyl phosphonic acid mono2-ethylhexyl ester (EHEHPA) was supplied by Albright and Wilson (now Rhodia), and was used without further purification. As small amounts of diacid, such as 2-ethylhexyl phosphonic acid, are usually present in this commercial extractant, EHEHPA was titrated by KOH in a 70% (v/v) aqueous/acetone solution and its content was found to be 96.4%. Low odour kerosene (Aldrich) with a boiling fraction: 180 250 8C was used as a diluent due to the high extraction efficiency observed when kerosene was employed (Saji and Reddy, 2003). All other chemicals used were of analytical grade. Titanium(IV) stock solution was prepared by leaching titanium dioxide in concentrated H2SO4 (98%) and ammonium sulphate at 230 8C for about 120 min until the solution turned from yellow to colourless. The final stock solution contains 0.04 M Ti and b0.02 M H2SO4 as free acid, therefore the experimental tests were performed with solutions containing a maximum of additional H2SO4 of 0.01 M. It is necessary to note that the actual fly ash leach solution would be a mixed acid (H2SO4+HNO3) in order to produce a salt sludge that can be subsequently dissolved by an acid solution and give the best titanium yield. A typical MSW leaching solution contains Ti, Fe, Zn, Al and Pb; therefore three simulated solutions containing 0.5 g/L for each metal were

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prepared in HCl, H2SO4 and HNO3 medium to check the effect of competing ions on titanium extraction. 2.2. Procedure Extraction and stripping were determined by shaking equal volumes of aqueous and organic phases for 60 min in sealed bottles using a mechanical shaker at room temperature; phase separation occurred within 5 min. EHEHPA concentrations of 0.2 M and 0.5 M were used throughout the experiments. The titanium concentration was varied from 0.006 M to 0.02M, while the effect of acid concentration was examined within the 0.54 M range. The concentrations of the titanium in the aqueous feed and strip solutions were determined spectrophotometrically (Model: UVVIS DMS-200 Varian) by complexing with hydrogen peroxide in acidic medium (Vogel, 1961), as well as using an Atomic Absorption Spectrophotometer (Perkin Elmer Series 5100 ZL) for titanium and other metals. The error in analysis was within F3%.

effect of the extractant concentration on the kinetics. 3.2. Effect of titanium concentration 1 M aqueous solutions of H2SO4, HNO3 and HCl, but with different amounts of titanium (0.0060.02 M) were equilibrated separately with 0.5 M.EHEHPA in kerosene solution. The results show that the distribution coefficients in all the acidic media used are not influenced by the initial titanium concentration. The lack of dependence on the metal concentration and the horizontal plots having zero slope, clearly indicate the presence of mononuclear species in the acidic medium over the whole range of the experimental conditions. Biswas and Begum (1998) noticed similar behaviour for the extraction of titanium using D2EHPA. However, this statement can only be valid when the acidity and concentration of EHEHPA remain constant and when the extractant concentration is much higher than that of the metal ions. From these data, moreover, it can be seen that titanium extraction from a nitrate medium presents higher distribution coefficient values than sulphate and chloride media. It may be due to the difference in the activity of Ti(IV) and ion-pairing nature of these anions. 3.3. Effect of sulphuric acid concentration Sulphuric acid is mainly used for the leaching of titanium oxide and its ores (Sole, 1999b). It is important to study thoroughly the effect of sulphuric acid concentrations on the extraction of titanium. The log D vs. [H2SO4] plots for 0.01 M and 0.02 M Ti(IV) and 0.2 M. and 0.5 M.EHEHPA systems are given in Fig. 1. Higher distribution values are observed at 0.5 M. and 4 M.H2SO4; moreover the extraction increases with reagent concentration. Higher extraction at 0.5 M.H2SO4 depends upon a cation exchange mechanism, while at 4 M. it is due to a solvation mechanism with sulphate ions incorporated into the complex as reported elsewhere for D2EHPA (Sato and Nakamura, 1975) and EHEHPA (Jayachandran and Dhadke, 1998). The distribution ratios passed through a minimum at 1 M H2SO4 concentration. Amongst the four plots, the highest distribution curve is observed for 0.01 M.Ti(IV) and 0.5 M.EHEHPA.

3. Results and discussion 3.1. Kinetics of extraction Sole (1999a) in her review reports on the very slow kinetics for the extraction of titanium by organo-phosphorous extractants. Saji and Reddy (2003) observed that by using EHEHPA, extraction equilibrium was attained within 90 min in HCl, while Sing and Dhadke (2002) observed a short equilibrium time (3 min) in HClO4. Therefore, the evaluation of the extraction equilibriums of titanium from mixed acid solutions has been achieved. For the present investigation, 0.01 M Ti(IV) at 0.5 M acid (sulphuric, nitric and hydrochloric) as aqueous phase and 0.2 M.EHEHPA were used. The extraction rate of titanium from nitrate and chloride media requires 60 min to reach equilibrium, while the kinetics is much slower in the sulphate medium and required 120 min to attain equilibrium. Using 0.5 M.EHEHPA, it was found that the extraction of titanium from the nitrate and chloride media is achieved within 30 min, while from the sulphate medium it is achieved in 60 min showing a positive

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2,5

log D
2 1,5 1

0,5

0,01M Ti + 0,2M EHEHPA 0,01M Ti + 0,5M EHEHPA 0,02M Ti + 0,2M EHEHPA 0,02M Ti + 0,5M EHEHPA

0 0 1 2 3 4 5

[H2SO4], M
Fig. 1. Dependence of distribution coefficient on sulphuric acid concentration.

3.4. Effect of hydrochloric acid concentration Many authors studied extraction of titanium from acidic chloride solutions, where Ti(IV) forms a variety of complexes. John et al. (1999a) used a neutral extractant (Cyanex 923) for the extraction of titanium and found an increase in extraction with the increase in chloride ion concentration.

Fig. 2 shows a very slight minimum in the distribution values at 1 M HCl concentration. It indicates that extraction of titanium using EHEHPA is much less dependent on the hydrochloric acid concentration; probably because at b4 M HCl the dominating species is still TiO2+ and the cation exchange mechanism occurs as reported for D2EHPA (Biswas and Begum, 1998) and for EHEHPA (Saji and Reddy, 2003). It appears that Cl does not

log D

2,5

1,5

1 0,01M Ti + 0,2M EHEHPA 0,01M Ti + 0,5M EHEHPA 0,02M Ti + 0,2M EHEHPA 0,02M Ti + 0,5M EHEHPA 0 1 2 3 4 5

0,5

[HCl], M
Fig. 2. Dependence of distribution coefficient on hydrochloric acid concentration.

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participate in the extracted species TiO(HX2)2 (Saji and Reddy, 2003). 3.5. Effect of nitric acid concentration Iio et al. (1991) have studied the extraction of titanium from nitric acid solutions using D2EHPA and no further information is available on the extraction of titanium by EHEHPA in HNO3 medium. Therefore, the extraction of titanium with varying nitric acid concentrations was performed and the experimental curves are shown in Fig. 3. It was found that with the increase in acid concentration, the extraction increases up to 1 M. HNO3, but thereafter it passes through a minimum at 2 M acidinstead of 1 M as was the case when sulphuric and hydrochloric acid were used. The same behaviour was reported with perchloric acid (Sing and Dhadke, 2002). 3.6. Effect of associated metal ions Based on the percentage metal extraction obtained with synthetic leaching solutions, selective titanium separation can be done efficiently at 1 M acid concentration (Table 1). In particular aluminium and lead do not interfere in any of the acids, while zinc is slightly extracted: it is well known that zinc extraction by EHEHPA quantitatively occurs at pHN1 (Moreno and Garzia, 1999; John et al., 1999b). Iron(III) seems to be the most competitive ion, reaching 67%
2,5

Table 1 % Metals extraction from synthetic leaching solution (0.5 g/L metal ion, 0.5 M EHEHPA in kerosene, O/A=1, H+=1 M) Medium Sulphate Chloride Nitrate Ti 80.4% 90.1% 95.6% Fe 20.6% 51.1% 67.0% Zn 1.3% 1.1% 7.8% Al 0 0 0 Pb 0 0 0

extraction in nitric acid medium while the sulphuric medium seems offer the lowest iron extraction. The extent of titanium extraction decreases in the following order HNO3NHClNH2SO4. 3.7. Stripping evaluations The effect of stripping agents and their concentration on titanium recovery from a loaded organic phase consisting of 0.5 M EHEHPA and 0.01 M Ti(IV) has been investigated. A single stage experiment with 3 M sulphuric, hydrochloric and nitric acid shows that the titanium stripping kinetics is very slow (N180 min). The maximum percentage of stripping was found to be about 5% because of the strong Ti EHEHPA complex. Other stripping agents such as HClO4, tartaric acid, Na2S2O3 have been used (Sing and Dhadke, 2002). Jayachandran and Dhadke (1998) reported that a mixture of H2O2 and sulphuric acid produces quantitative stripping of titanium as Ti(OH)4(H2O2)SO4. This is probably much more stable than the extracted

log D

1,5

1 0,01M Ti + 0,2M EHEHPA 0,01M Ti + 0,5M EHEHPA 0,02M Ti + 0,2M EHEHPA 0,02M Ti + 0,5M EHEHPA 0 1 2 3 4 5

0,5

[HNO3], M
Fig. 3. Dependence of distribution coefficient on nitric acid concentration.

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% Ti recovery

100 90 80 70 60 50 40 30 20 10 0 0 20 40 60 80 100 120 140 160 180 200 Na2CO3 (1M) H2SO4 (3M)+3%H2O2 H2SO4 (3M)+1%H2O2 H2SO4 (3M)

Time (min)
Fig. 4. Rate of stripping of titanium from EHEHPA using different stripping agents.

complex. In our investigation we found that with the increase in concentration of H2O2, the stripping of titanium increases to 80% as shown in Fig. 4. A further interesting breakthrough was achieved when sodium carbonate was used as a stripping agent. The stripping of titanium was very fast and the yield was 100% (Fig. 4). The time required for the complete stripping was only 30 min. Probably, the carbonate complex is much more stable than the other complexes. The stripping of a loaded organic phase that also contained iron, using 1 M Na2CO3, gave a promising result because 97% Ti was recovered with an iron content below 9%. In this case the simulated aqueous solution had an equimolar Ti/Fe concentration, but in the actual leaching solution the Ti/Fe ratio is typically 1.9. However separation from co-extracted Fe(III) can be easily achieved, because iron can be stripped first by H2SO4 and subsequently titanium can be quantitatively stripped by 1 M Na2CO3.

4. Conclusions Liquidliquid extraction of titanium(IV) was investigated in order to examine the effect of different acid media, over the concentration range of 0.54 M on the recovery by using 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester. EHEHPA is shown to be a very effective extractant for titanium(IV) from acidic medium. However, the kinetics of extraction is very

slow, within 60120 min, according to the acidic media. The extraction of titanium is independent of the initial metal ion concentration indicating presence of mononuclear species up to 0.02 M Ti(IV). The highest distribution value is observed for 1 M nitric acid. The distribution values of titanium depend on the sulphuric and nitric acid concentration in the aqueous phase, while it is slightly dependent on the hydrochloric acid medium. However most extractants have poor efficiency with an acidity between 0.53 M, probably due to the strong hydration of the dominant [TiO]2+ species (Kislik and Eyal, 1993b). The extraction mechanism appears to change from cation exchange to solvation with an increase in the acid concentration. It is believed that the [TiO]2+ species are not strong enough to compete with H+; and that acid takes part as a neutral complexant at high acidity. The stripping of titanium by sulphuric acid is much more effective adding H2O2; but is more complete and faster when sodium carbonate is used. From the practical point of view, the results of this study suggest that the extraction of titanium can be performed using EHEHPA with each acidic solution. In particular an extraction scheme can be designed for titanium recovery from a sulphuric acid leach that is being considered for the fly ash. Regarding competition among impurity metal ions, iron(III) seems to be the most competitive ion with 2067% co-extracted, depending upon the acid medium.

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Acknowledgement Authors thank M.R. Montereali and S. Giacco for their help during the research work. Moreover one of the authors, Prashant Kulkarni, wishes to thank ENEA for the postdoctoral fellowship.

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