Separation of copper(II), cobalt(II) and nickel(II) from chloride solutions by polymer inclusion membranes

doi:10.1016/j.seppur.2006.07.005

Separation and Purification Technology

Volume 57, Issue 3, 15 November 2007, Pages 461-465

https://doi.org/10.1016/j.seppur.2006.07.005 Get rights and content

Abstract

The separation of copper(II), cobalt(II) and nickel(II) from aqueous chloride solutions by polymer inclusion membranes is presented. The tertiary amines, i.e. tri-n-octylamine (TOA) and triisooctylamine (TIOA) have been applied as the ion carriers in membrane. The source phase was an aqueous HCl solution containing Cu(II), Co(II) and Ni(II). The selective transport of Cu(II), Co(II) and Ni(II) from aqueous chloride source phase through PIM containing cellulose triacatate (CTA) as the support, o-nitrophenyl pentyl ether (ONPPE) as the plasticizer and amines (TOA and TIOA) has been studied. Cu(II) and Co(II) ions were effectively removed from the source phase by transport through PIMs with TOA and TIOA as the ionic carriers into 0.1 M NaOH as the receiving phase. The initial fluxes of Cu(II) and Co(II) were higher with TIOA than with TOA. Ni(II) was not detected in the receiving phase. The effect of chloride ions concentration on the transport of Cu(II), Co(II) and Ni(II) has been investigated. Transport of Cu(II) and Co(II) increases with increasing of chloride ions concentration in the source phase. The metal ions fluxes decrease in the order Cu(II) > Co(II) > Ni(II).

Introduction

The transport of Cu(II), Co(II) and Ni(II) from chloride solution of the composition similar to aqueous solutions after leaching of polymetallic nodules was studied. The nodules, which are located at the bottom of the world's oceans, constitute a major and strategic resource and reservoir of cobalt, copper and nickel [1], [2], [3].

After leaching of deep-sea nodules in hydrochloric acid, iron(III) is present in leach solutions and its elimination is a major operational problem in hydrometallurgy. The recovery of iron(III) from such aqueous solutions is usually carried out by precipitation as jarosite, goethite or hematite [4], [5]. Though the iron removal is mainly achieved by precipitation techniques, the use of solvent extraction is also important for iron(III) removal from acidic aqueous solutions [6], [7], [8], [9], [10], [11], [12], [13].

The separation of copper(II), cobalt(II) and nickel(II) from aqueous solutions is frequently required in hydrometallurgical processing. The applications of liquid membranes offer a potentially attractive alternative to solvent extraction process and combine the process of extraction and stripping in a single unit operation. Solvent extraction is performed in order to evaluate the best conditions for operation of the membrane separation systems. For example, Juang and Kao [14] were studied extraction separation of Co(II)/Ni(II) from concentrated HCl solutions in rotating disccontactor (RDC) and hollow-fiber membrane contactor (HFMC). Batch experiments were first performed to select optimal conditions for effective separation including the type of the extractant. Finally, mass transfer rates of solvent extraction operations in a rotating disc contactor and newly developed hollow-fiber membrane contactor were compared. The hydrometallurgical process for the separation and recovery of Co(II), Ni(II) and Cd(II) from chloride leach liquors was investigated by Reddy et al. They used Cyanex 923 and Cyanex 272 as the extractants. Selectivity studies for cobalt–nickel separation indicated Cyanex 272 as the best extractant [15].

However, the liquid membranes containing an ion carrier have been used for the concentration and separation of metal ions. The application of liquid surfactant membranes (LSMs) for cobalt–nickel separation from a sulfuric liquor was investigated by Ribeiro et al. [16]. The membrane phase was composed of the carrier, the surfactant ECA 4360 and the diluent Escaid 110, while, as internal phase, a 0.5 mol/l solution of sulfuric acid. Cyanex 302 (bis(2,4,4-trimethylpentyl) monothiophosphinic acid) was used as the ionic carrier. Triisooctylamine (TIOA) has been studied by Li et al. [17] as an mobile carrier in the emulsion liquid membrane (ELM) for separation of metal ions. They investigated the transport mechanism of Cu(II), Co(II), Ni(II), Cd(II), Zn(II), Al(III), Mn(II) and Fe(II) across the emulsion liquid membrane from aqueous chloride solutions.

Development of polymer inclusion membranes (PIMs) containing specific metal ion carriers reached significant importance for use in separation and purification of metal ions in areas such as hydrometallurgy and water treatment. For example, Kozlowski et al. were investigated the transport of Cu(II), Co(II), Ni(II) and Zn(II) from aqueous solutions into distilled water through plasticized immobilized membranes. The hydrophobic β-cyclodextrin (β-CD) polymers have been used as the macrocyclic ion carriers. With the use of β-CD polymer as an ionic carrier in the competitive transport of metal ions shows the preferential selectivity order: Cu(II) > Co(II) > Ni(II) > Zn(II) [18].

The separation of Cu(II), Co(II) and Ni(II) can be achieved using the organophosphorous acids, i.e. di-(2-ethylhexyl) phosphoric acid D2EHPA [19], as well as amines [20], [21]. The Aliquat 336, immobilised in a polymer matrix, poly(vinyl chloride) (PVC), were used successfully in the transport of copper(II) from hydrochloric acid solutions [22].

A number of researchers utilized CTA membranes for carrier-mediated transport of metal ions from aqueous solutions. Kozlowski et al. have studied the transport of toxic metal ions, i.e. Cr(VI), Cd(II) and Zn(II) from acidic chloride aqueous solutions [23]. Transport of silver(I) and copper(II) ions through a plasticized cellulose triacetate membrane (CTA) containing macrocylic polyethers as carrier and 2-nitro phenyl octyl ether (ONPOE) as plasticizer has been investigated by Arous et al. [24]. In this work, the competitive transport of copper(II), cobalt(II) and nickel(II) ions from chloride acidic aqueous solutions through polymer inclusion membranes has been studied. As the ionic carriers tri-n-octylamine (TOA) and triisooctylamine (TIOA) were applied.

Section snippets

Reagents

Inorganic chemicals, i.e. nickel(II), cobalt(II) and copper(II) chlorides, sodium chloride and hydrochloric acid were of analytical grade and were purchased from POCh (Gliwice, Poland).Organic reagents, i.e.cellulose triacetate (CTA), o-nitrophenyl pentyl ether (ONPPE), trioctylamine (TOA), triisooctylamine (TIOA) and dichloromethane were of analytical reagent grade (Fluka) and used without further purification. The density of plasticizer, i.e. ONPPE, was 1.085 g cm⁻³. Aqueous solutions were

Results and discussion

The competitive transport of copper, cobalt and nickel through PIM with TOA and TIOA as the ion carriers and ONPPE as the plasticizer has been investigated. The kinetics of metal ions transported are shown in Fig. 1, Fig. 2. The source phase was composed of 0.01 M Cu(II), 0.002 M Co(II), 0.02 M Ni(II), 1.0 M HCl and 4.0 M NaCl. The initial fluxes and recovery factors for competitive transport of Cu(II) and Co(II) are presented in Table 1. Ni(II) was not detected in the receiving phase. The metal

Conclusion

Copper(II) and cobalt(II) can be effectively separated from aqueous solutions containing nickel(II) by polymer inclusion membranes transport with TOA and TIOA as the ion carriers. The highest fluxes of Cu(II) and Co(II) were obtained using membrane containing TIOA as the ion carrier.

The initial fluxes of these metal ions depend strongly on the hydrochloric acid concentration in the source phase. It was found that the fluxes of Cu(II) and Co(II) are the highest at 2.0 M HCl in the source solution

Acknowledgment

Financial support of this work was provided by Polish Science Foundation Grants—grant no. 3 T09C 019 26.

References (24)

M.R.C. Ismael et al.
Iron recovery from sulphate leach liquors in zinc hydrometallurgy
Min. Eng.
(2003)
J.E. Dutrizac
The effect of seeding on the rate of precipitation of ammonium jarosite and sodium jarosite
Hydrometallurgy
(1996)
C. Lupi et al.
Reductive stripping in vacuum of Fe(III) from D2EHPA
Hydrometallurgy
(2000)
R.K. Biswas et al.
Solvent extraction of Fe³⁺ from chloride solution by D2EHPA in kerosene
Hydrometallurgy
(1998)
R.K. Biswas et al.
Study of kinetics of forward extraction of Fe(III) from chloride medium by di-2-ethylhexylphophoric acid in kerosene using the single drop technique
Hydrometallurgy
(1999)
R.K. Biswas et al.
Kinetics of stripping of Fe³⁺—D2EHPA complexes from D2EHPA-kerosene phase by aqueous HCl–Cl⁻ phase using the single drop technique
Hydrometallurgy
(2001)
J. Jayachandran et al.
Liquid–liquid extraction separation of iron(III) with 2-ethyl hexyl phosphonic acid mono 2-ethyl hexyl ester
Talanta
(1997)
J. Saji et al.
Liquid–liquid extraction separation of iron(III) from titania wastes using TBP–MIBK mixed solvent system
Hydrometallurgy
(2001)
J. Saji et al.
Extraction of iron(III) from acidic chloride solutions by Cyanex 923
Hydrometallurgy
(1998)
B. Gupta et al.
Recovery of cobalt, nickel, and copper from sea nodules by their extraction with alkylphosphines
Hydrometallurgy
(2003)

R.-S. Juang et al.

Extraction separation of Co(II)/Ni(II) from concentrated HCl solutions in rotating disc and hollow-fiber membrane contactors

Sep. Purif. Technol.

(2005)

B.R. Reddy et al.

Solvent extraction and separation of Cd(II), Ni(II) and Co(II) from chloride leach liquor of spent Ni–Cd batteries using commercial organo-phosphorus extractants

Hydrometallurgy

(2005)

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Separation of copper(II), cobalt(II) and nickel(II) from chloride solutions by polymer inclusion membranes

Abstract

Introduction

Section snippets

Reagents

Results and discussion

Conclusion

Acknowledgment

Min. Eng.

Hydrometallurgy

Hydrometallurgy

Hydrometallurgy

Hydrometallurgy

Hydrometallurgy

Talanta

Hydrometallurgy

Hydrometallurgy

Hydrometallurgy

Sep. Purif. Technol.

Hydrometallurgy