Hydrometallurgy 80 (2005) 90 97 www.elsevier.

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Solvent extraction of aluminium in the presence of cobalt, nickel and magnesium from sulphate solutions by Cyanex 272
P.E. Tsakiridis *, S. Agatzini-Leonardou
National Technical University of Athens, Department of Mining and Metallurgical Engineering, Laboratory of Metallurgy, 9, Iroon Polytechniou Street, 157 80 Zografou, Athens, Greece Received 12 May 2004; received in revised form 5 July 2005; accepted 6 July 2005 Available online 10 August 2005

Abstract The extraction and separation of aluminium from cobalt, nickel and magnesium sulphate solutions have been carried out using the organo-phosphinic extractant Cyanex 272. Statistical design and analysis of experiments were used in order to determine the main effects and interactions of extraction pH at equilibrium, temperature, extractant concentration and organic to aqueous phase ratio. A statistically designed experiment was also carried out in order to study the stripping of the aluminium loaded Cyanex 272 organic phase by sulphuric acid solution. The number of stages required for both extraction and stripping processes of aluminium was also evaluated. The results of the continuous counter current, mini plant tests demonstrated the recovery of aluminium from cobalt, nickel and magnesium sulphate solution. D 2005 Elsevier B.V. All rights reserved.
Keywords: Cyanex 272; Solvent extraction; Aluminium; Cobalt; Nickel; Magnesium

1. Introduction The Laboratory of Metallurgy of the National Technical University of Athens has developed and patented a novel integrated hydrometallurgical method, suitable to treat low-grade nickel oxide ores efficiently and economically. It involves heap leaching of the ore by dilute sulphuric acid at ambient temperature, purification of the leach liquors and
* Corresponding author. Tel.: +30 210 7722179; fax: +30 210 7722218. E-mail address: ptsakiri@central.ntua.gr (P.E. Tsakiridis). 0304-386X/$ - see front matter D 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.hydromet.2005.07.002

recovery of nickel and cobalt (Agatzini and Dimaki, 1991, 2000; Tsakiridis and Agatzini, 2004a,b). A typical composition of the pregnant solution produced from heap leaching of Greek low-grade nickeliferous laterites with sulphuric acid is the following (Agatzini and Dimaki, 1991): Ni2+ = 4.0 g/L, Co2+ = 0.6 g/L, Fe2+=22.0 g/L, Al3+=6.0 g/L, Cr3+ = 1.0 g/L, Mg2+ = 5 g/L. Iron can be removed by oxidation and precipitation as jarosite in the pH range 2.53.0 at 95 8C. In this pH range, a small quantity of aluminium can be co-precipitated (Agatzini et al., 1999), but most remains to be subsequently removed by precipitation at pH N3.0 or by solvent extraction.

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Whilst the solvent extraction of Fe(III) has received much attention, relatively little work has been carried out on the solvent extraction of Al(III) from such liquors. The present paper gives the results of a fundamental study on the solvent extraction of aluminium using the organo-phosphinic extractant Cyanex 272, in the presence of cobalt, nickel and magnesium, but in the absence of iron which would otherwise co-extract and interfere. A synthetic sulphate solution was used with concentrations similar to those of a real leach liquor. The solvent extraction technique is one of the most versatile methods used for the removal, separation and concentration of metallic species from aqueous media and Cyanex 272 has been widely used in the extraction of cobalt, in the presence of nickel from sulphate solutions (Rickelton et al., 1984; Preston, 1982; Tait, 1993; Preston and Du Preez, 1988). The recovery of aluminium by solvent extraction has been studied by several researchers. Preston (1985) has examined the solvent extraction behavior of solutions of Versatic 10, naphthenic 2-bromodecanoic and 3,5-di-isopropyl-salicylic acids in xylene towards a large number of metal cations. With regard to aluminium, cobalt and nickel extraction by Versatic 10, the order of metal extraction decreases through the series Al3+ N Ni2+ N Co2+. The pH0.5 values proposed are Al 3.53, Ni 6.34 and Co 6.55. Toth et al. (1990) studied the extraction of Ga3+ and Al3+ with the liquid cation-exchangers di-n-butyldithiophosphoric acid (DBTPA) and di-(2-ethylhexyl) dithiophosphoric acid (DETPA) in kerosene, in the presence and absence of alcohols and tri-n-butyl phosphate (TBP). Both Ga3+ and Al3+ could be extracted in the form of a neutral complex, MA3. Mishra and Dhadke (1998) examined Cyanex 921, a neutral extractant, for the separation of beryllium (II) and aluminium (III). Cyanex 921 diluted in cyclohexane extracted beryllium (II) in the pH range 8.010.0 and aluminium (III) between 4.5 and 5.5. The extracted beryllium (II) was stripped with 0.5 M NaOH without any significant loss, whilst loaded aluminium (III) was stripped with 2 M HCl. Zhang et al. (1997) demonstrated a new solvent extraction process using the 2ethylhexyl ester of 2-ethylhexyl phosphonic acid (PC88 A), for efficient separation and recovery of rare metals, such as molybdenum, vanadium, aluminium, cobalt and nickel from an aqueous sulphuric acid

solution derived from spent hydrodesulphurization catalysts. In this process, preferential extraction and separation of molybdenum and vanadium over aluminium was achieved at low pH based on the differences in equilibria and kinetics of extraction. Phalke et al. (1996) studied the extraction and the separation of beryllium (II) and aluminium (III) from an aqueous sulphate solution with bis-2 ethylhexyl phosphoric acid (HDEHP) in toluene. They showed that the extraction of Be (II) was quantitative in the pH range 2.55.5, whereas in the case of Al (III) it was quantitative in the pH range 3.255.0. The present research work is aimed at the solvent extraction of aluminium by organo-phosphinic acid Cyanex 272, in the presence of cobalt, nickel and magnesium, from sulphate solutions. Factorial design of experiments and statistical analysis of the data were used to determine the main effects and interactions of the chosen factors and select the optimum conditions. The factors studied were equilibrium pH, temperature, extractant concentration and aqueous/organic phase ratio. Stripping of the loaded Cyanex 272 organic phase was also studied using sulphuric acid solution. Aluminium isotherms were constructed, for both the extraction and stripping processes, and the number of stages required under optimum conditions was predicted. Extraction and stripping processes were further studied in a continuous counter-current laboratory solvent extraction unit.

2. Experimental 2.1. Reagents Cyanex 272 was kindly supplied by Cytec, Holland. The active component is bis (2,4,4-trimethylpentyl) phosphinic acid (M.W 290; density 0.95 g/ cm3) having the following structure (Cyanex 272Technical Brochure, 1989):

R P R

O OH

CH3 CH3

CH3

where: R= CH3 C CH2 CH CH2

The extractant was used without further purification The organic diluent, Exxsol D-80 was obtained

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100

Extraction

Al3+ 80

Mg2+

Co2+

Ni 2+

2+

%Al , Co , Ni , Mg

60

2+ 3+ 2+

40

20

0 1 2 3 4 5 6 7

pH Extarction
Fig. 1. Aluminium, cobalt, nickel and magnesium extraction from sulphate solution by Cyanex 272. Organic phase: 20% Cyanex 272 in Exxsol D-80 with 5% TBP, T: 40 8C, Aqueous phase: 5.85 g/L Al3+, 0.63 g/L Co2+, 3.8 g/L Ni2+ and 5.75 g/L Mg2+.

from Exxon Chemical Holland. In all cases, the organic phases were modified with 5% TBP. 2.2. Procedure The initial aqueous phase was a synthetic solution with 5.85 g/L Al3+, 0.63 g/L Co2+, 3.80 g/L Ni2+ and 5.75 g/L Mg2+, similar in concentration to those of a real heap leach liquor. All batch experiments were conducted in a 500-mL five-necked, round bottomed split reactor, which was fitted with a glass stirrer, a vapor condenser, a thermometer and a pH electrode. The two phases were contacted by rapid stirring and the pH was controlled by small additions of 5 N NaOH, using an automatic titration device (Metrohm-Dosimat/Impulsomat). Heating was provided by an electrical mantle and the temperature of the liquid was controlled by a Fisons Scientific Apparatus monitor. Stripping of the loaded Cyanex 272 organic phase was carried out by diluted sulphuric acid. Continuous tests were carried out in a laboratory solvent extraction unit (Bell Engineering Model 282; effective volume 185 mL for each mixer and 364 mL for the settler). Aluminium, nickel, cobalt and magnesium in the aqueous phases were analyzed by atomic absorption spectrophotometry.

3. Results and discussions 3.1. Effect of pH on the extraction Extraction tests were carried out at various equilibrium pH values and the results in Fig. 1 show that Cyanex 272 can efficiently selectively extract aluminium in the pH range 2.53.0, whereas cobalt, nickel and magnesium are extracted at a pH above 3.0. 3.2. Statistical study of the extraction process Factorial design and analysis of experiments were used in order to determine the main effects and interactions of the solvent extraction factors.
Table 1 Aluminium extraction by Cyanex 272minimum and maximum levels of variables Factor A B C D Variables Extraction pH (pH) Temperature (T) Extractant concentration (C) O/A ratio (R) Low level 2.5 25 10 1/2 High level 3.0 40 20 1/1 Units measured pH units 8C % v/v

P.E. Tsakiridis, S. Agatzini-Leonardou / Hydrometallurgy 80 (2005) 9097 Table 2 Aluminium extraction from cobalt, nickel and magnesium solutions by Cyanex 272 Treatment code (1) a b ab c ac bc abc d ad bd abd cd acd bcd abcd Aluminium concentration (mg/l) Before extraction 5850 5850 5850 5850 5850 5850 5850 5850 5850 5850 5850 5850 5850 5850 5850 5850 After extraction 486 503 503 521 380 365 389 269 246 257 170 193 140 117 59 35 % Al3+ extraction 91.7 91.4 91.4 91.1 93.5 93.8 93.4 95.4 95.8 95.6 97.1 96.7 97.6 98.0 99.0 99.4

93

The factors studied and their levels are shown in Table 1. The parameters which were kept constant during experimentation were as follows: stirring speed = 1200 rpm; [Al] = 5.85 g/L; [Co] = 0.63 g/L; [Ni] = 3.80 g/L; [Mg] = 5.75 g/L. The main response under investigation was the percentage of aluminium extracted in the organic phase as given in Table 2.

As can be seen in Table 2, in all runs of the factorial design, high percentages of aluminium extraction were obtained demonstrating the application of Cyanex 272 for the extraction of Al3+ from sulphate solutions in the presence of Co2+, Ni2+ and Mg2+. Magnesium and cobalt co-extraction did not exceed 0.5%, under the present experimental conditions, and nickel was not extracted. Cobalt and magnesium could be easily scrubbed out, as shown below. To study the main effects and interactions of the factors on aluminium extraction, a Yatess analysis and an analysis of variance were carried out on the percentages of Al3+ extracted in the organic phase according to standard statistical analysis (Box et al., 1978). The results in Table 3 show the main effects B, C, D, and the two-factor interactions AC and BD were found to be statistically significant at a = 0.01 and positive. In the range of variables studied, the phase ratio O/A (D) and the extractant concentration (C) had the largest effects, with a wide gap separating them from the remaining contrasts. It should be stressed, however, that because of statistically significant interactions, the main effects should not be individually interpreted but the interacting variables should be considered jointly. The nature of the interactions BD and AC is indicated by the two-way tables (Fig. 2), obtained by averaging over levels of the other variables. The

Table 3 Yates analysis and analysis of varianceresponse: % Al3+ extraction by Cyanex 272 Treatment code Response Al3+ extraction (%) F 0.2 91.7 91.4 91.4 91.1 93.5 93.8 93.6 95.4 95.8 95.6 97.1 96.7 97.6 98.0 99.0 99.4 Yates analysis 1 183 182 187 189 191 194 196 198 0.3 0.3 0.3 2.1 0.2 0.4 0.4 0.4 2 366 376 385 394 0.6 2.3 0.6 0.8 0.6 1.5 2.4 2.8 0.0 1.8 0.2 0.0 3 742 779 1.7 0.2 0.9 5.2 1.8 0.2 10.4 8.8 2.9 1.4 2.1 0.4 1.8 0.2 4 1521 1.9 6.1 1.6 19.2 4.3 2.5 2.0 37.6 1.5 4.3 2.0 1.6 1.5 1.7 1.6 Divisor 16 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 Effects F 0.12 95.1 0.2 0.8 0.2 2.4 0.5 0.3 0.3 4.7 0.2 0.5 0.2 0.2 0.2 0.2 0.2 Identification Average A B AB C AC BC ABC D AD BD ABD CD ACD BCD ABCD Analysis of variance t = eff/S e t 0.01 (U = 16) 2.92 2.92 2.92 2.92 2.92 2.92 2.92 2.92 2.92 2.92 2.92 2.92 2.92 2.92 2.92 Significance at a = 0.01 NS S NS S S NS NS S NS S NS NS NS NS NS

(1) a b ab c ac bc abc d ad bd abd cd acd bcd abcd

1.98 6.33 1.67 20.02 4.48 2.58 2.08 39.15 1.56 4.50 2.08 1.69 1.56 1.75 1.67

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93.7
(+)
Extraction pH

96.6

92.8
(+)
Temperature

97.4

(A)

(B)

(-)

(C)
Extractant Concentration

(+)

(-)

(D)
O/A Ratio

(+)

94.0

95.9

92.6

96.8

(a)

(b)

Fig. 2. Two-way tables showing the interaction AC (a) and BD (b).

interaction AC, for example, occurs because at the low extractant concentration an increase in pH reduces aluminium extraction, whereas an increase in pH, at a higher extractant concentration, increases its extraction. The existence of statistically significant interactions meant that a model, based on the main effects only, would not be suitable and that the response surface was curved in the particular region of the present design. Based on the above, the suggested bbestQ fitted model for aluminium extraction, strictly in the ranges of variables studied and under the present conditions of experimentation, is: Y 95:1 0:40X2 1:20X3 2:35X4 0:25X1 X3 0:25X2 X4 1 where Y is the predicted value of the percentage of aluminium extracted by Cyanex 272 and X 1, X 2, X 3 and X 4 are coded variables, related to the natural variables by the following equations: X1 pH 2:75=0:25; X3 C 15=5; X2 T 32:5=7:5; X4 R 0:75=0:25:

acidified water at pH = 2.8, O/A= 4:1, T = 40 8C, agitation speed = 1200 rpm for 5 min. It was found that the cobalt and magnesium co-extracted with aluminium in the organic phase could be effectively scrubbed out, with final co-extraction not exceeding 0.1%. No nickel extraction and scrubbing was detected in the pH range 2.53.0. 3.4. Statistical study of the stripping process On the basis of conclusions drawn from preliminary experiments, the following variables and levels were chosen in order to study the stripping of aluminium from the organic phase by diluted sulphuric acid: [H2SO4] = 2 M and 3 M; O/A ratio = 1:1 and 2:1. Parameters with constant values throughout the design were as follows: organic phase [Al3+]org = 5.81 g/L; T = 40 8C; stirring speed 1200 rpm. The response under investigation was the percentage of aluminium stripped from the loaded Cyanex 272, as given in Table 4. As the table shows, high percentages of Al3+ were stripped from the organic phase demonstrating the strippability of Cyanex 272 by diluted sulphuric

Based on the statistical analysis of the results, the optimum conditions determined for the aluminium extraction from a sulphate solution, in the presence of cobalt, nickel and magnesium, by Cyanex 272, were as follows: pH = 3.0, T = 40 8C, extractant concentration = 20% and O/A phase ratio = 1:1. 3.3. Scrubbing of loaded organic phases The aluminium loaded Cyanex 272, resulting from the extraction tests, was subjected to scrubbing with

Table 4 Results of aluminium stripping from Cyanex 272 by 2 M sulphuric acid Treatment code (1) a b ab [Al3+]org concentration (mg/l) Before stripping 5810 5810 5810 5810 After stripping 85 72 61 26 % Al3+ recovery 98.5 98.8 99.0 99.6

P.E. Tsakiridis, S. Agatzini-Leonardou / Hydrometallurgy 80 (2005) 9097 Table 5 Yates analysis and analysis of varianceresponse: % Al3+ recovery from loaded Cyanex 272 Treatment code Response Co2+ extraction (%) F0.4 98.5 98.8 99.0 99.6 Yates analysis 1 197 198 0.22 0.6 2 396 0.82 1.2 0.38 Divisor 4 2 2 2 Effect F 0.4 98.95 0.41 0.60 0.19 Identification Average A B AB Analysis of variance t = eff/s e t 0.01 (U = 4) 4.6 4.6 4.6

95

Significance at a = 0.01 NS NS NS

(1) a b ab

1.03 1.50 0.48

acid. The Yatess analysis and the analysis of variance carried out on the data showed (Table 5) that none of the factors was found statistically significant. This practically means that the results differ only because of experimental error and that stripping could be conducted under any combinations of the factors values, within the ranges studied. Thus the optimum stripping conditions were determined at H2SO4 concentration = 2 M and phase ratio O/ A= 2:1 at 40 8C. 3.5. Construction of Al3+ extractionstripping isotherms using Cyanex 272 As Cyanex 272 proved to be an efficient extractant for aluminium from sulphate solutions, a McCabeThiele diagram was constructed for Al3+

and the number of counter-current stages required was predicted. The aluminium extraction isotherm was determined under the following conditions, optimised by the preceding statistical analysis: Cyanex 272 = 20% (v/v), diluent = Exxsol D-80, pH = 3.0 and T = 40 8C. The McCabeThiele diagrams indicated two stages for aluminium extraction at a phase ratio A/O = 2.5 (Fig. 3), and three stages for aluminium stripping from the loaded organic phase (Fig. 4) at H2SO4 = 2 M, temperature = 40 8C, phase ratio O/A= 2. 3.6. Continuous counter-current test Continuous tests were carried out in a laboratory solvent extraction unit set up with 2 extraction and 3 stripping stages using the above optimum operating

Concentration in the Organic Phase (g/l)

60

50

40

30

20

10

A/O=2.5 [Al3+]INITIAL= 5.85 g/l

Al

3+

0 0 1
3+

Al Concentration in the Aqueous Phase (g/l)

Fig. 3. McCabeThiele diagrams for Al3+ extraction by Cyanex 272 at 40 8C.

96
Al Concentration in the Aqueous Phase (g/l)

P.E. Tsakiridis, S. Agatzini-Leonardou / Hydrometallurgy 80 (2005) 9097

60 50 40 30 20
O/A=2

10
[Al3+]ORG=14.55 g/l

3+

10

12

14

16

Al

3+

Concentration in the Organic Phase (g/l)

Fig. 4. McCabeThiele diagram for Al3+ stripping from the loaded Cyanex 272 organic phase by H2SO4 at 40 8C.

conditions for the extraction and stripping of aluminium from cobalt, nickel and magnesium sulphate solution. The flow rate of aqueous feed = 20.57 mL/ min; solvent feed = 8.23 mL/min; strip feed = 4.12 mL/ min. Under these conditions, aluminium extraction reached 99.7% (giving 14.55 g/L Al3+ in the loaded solvent); whilst aluminium stripping by 2 M H2SO4 reached 99.8% (giving 28.95 g/L of Al3+ in the strip liquor).

Al recovery which could be totally stripped out in three stages at a phase ratio O/A= 2.

Acknowledgements The study was conducted in the framework of the Research Project BRE2-CT94-1020, entitled bA new approach to the metallurgical treatment of nickeliferrous lateritesQ, funded by the European Union.

4. Conclusions References The results obtained in the present work showed that Cyanex 272 can be used as a reagent to extract aluminium from cobalt, nickel and magnesium sulphate solutions. 20% v/v Cyanex 272 diluted in Exxsol D-80 with 5% TBP could extract 99.5% aluminium in one stage at pH = 3.0, T = 40 8C and phase ratio A/O = 1:1. After scrubbing with water at pH = 2.8, cobalt and magnesium co-extraction in the loaded Cyanex 272 was determined at 0.1%, whereas no nickel extraction occurred. Aluminium stripping from the loaded organic phase by 2 M H2SO4 was 99.6% in one stage at T = 40 8C and phase ratio O/ A= 2:1. Aluminium extraction isotherms from cobalt, nickel and magnesium sulphate solutions were constructed and demonstrated in continuous counter-current tests. Under optimum conditions, 2 stages of extraction at a phase ratio A/O = 2.5 achieved 99.7%
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