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1

Solvent extraction of zinc(II) from ammonia leaching solution by LIX 54-100, LIX 84 i and TOA

Wejman-Gibas K., Pilsniak-Rabiega M., Ochromowicz K.

Physicochemical Problems of Mineral Processing

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2017

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Vol. 53, iss. 1

202--211

EN

Commercial extractants LIX 54 -100, LIX 84 I and TOA were used to recover zinc(II) from ammonia solutions. The effect of extractant and ammonia concentration, contact time and reextraction were studied. It was found that extraction of zinc depended on the ammonia, ammonium sulphate and extractant concentration but did not depend on the contact time. The McCabe-Thiele distribution isotherm for LIX 54-100 showed that 95% of zinc(II) ions can be recovered in four stages of extraction. Reextraction of Zn(II) ions from the loaded organic phase showed that the metal can be removed almost completely using sulphuric acid.

2

Solvent extraction of zinc(II) ions from chloride media by 4-pyridylketoximes

Parus A.

Chemistry, Environment, Biotechnology

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2016

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Vol. 19

93--100

EN

Three homologues of 4-pyridylketoximes were synthesized and used as potential ligands for zinc(II). Their solvent extraction behaviors for zinc(II) in chloride solutions were investigated using CHCl3 as the diluent. The effect of different variables on the extraction of zinc(II) ions, such as the pH of aqueous phase, metal and chloride ions as well as the type of oxime, has been investigated. Results indicated that 4-pyridylketoximes could extract zinc(II) ions from chloride solutions and the extraction depended on the concentrations of the ligand, chloride ions and hydrochloride acid. Slope analysis confirmed that the 4-pyridylketoximes ligands form a 1:2 complex with zinc(II) in both chloride/nitrate and chloride/perchlorate solutions. After extraction, zinc(II) could be easily stripped from organic phase with water.

3

Wydzielanie cynku(II) z roztworów odpadowych powstających w przemyśle metalurgicznym

Gajda B., Skrzypczak A., Bogacki M. B.

Rudy i Metale Nieżelazne Recykling

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2015

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R. 60, nr 1

23--29

PL

Celem pracy było zbadanie możliwości selektywnego wydzielenia jonów cynku(II) z polimetalicznych odpadowych roztworów chlorkowych zawierających kationy takich metali, jak: niklu(II), kobaltu(II), kadmu(II) z zastosowaniem polimerowych membran inkluzyjnych. Jako przenośnik jonów w membranie zaproponowany został 1-decyloimidazol. Uzyskane wyniki pozwoliły zauważyć znaczący wpływ stężenia anionów chlorkowych na proces separacji jonów metali. Stwierdzono również, że jony cynku(II) najefektywniej wydzielić można z roztworu o stężeniu 1M anionów chlorkowych. Z roztworu takiego odzyskuje się ok. 88-90 % Zn(II). Zdolność do wydzielenia pozostałych jonów kształtuje się w szeregu: Cd(II) ≥ Co(II) > Ni(II).

EN

The aim of the work was investigation of possibility of selective releasing of zinc(II) ions from polymetalic discarded chloride solutions containing metal cations like: nickel(II), cobalt(II) and cadmium(II) by applying polymer inclusion membranes. As a carrier of metal ions in membrane, the 1-decylimidazole was used. Based on obtained results, significant influence of chloride anions on separation process was observed. It was found that zinc(II) ions were transported fastest from solution containing 1M of chloride anions. In this case, it was possible to release about 88-90 % of Zn(II). The membrane ability to releasing rest of ions change in series: Cd(II) ≥ Co(II) > Ni(II).

4

Wpływ sposobu mieszania fazy zasilającej i odbierającej na transport cynku(II) przez polimerowe membrany inkluzyjne

Plackowski R., Nowak P., Idkowiak J., Pernak P., Bogacki M.

Przemysł Chemiczny

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2015

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T. 94, nr 11

1945-1948

PL

Przedstawiono wyniki badań wpływu sposobu mieszania faz na transport kationów cynku(II) przez polimerowe membrany inkluzyjne. Zastosowano trzy sposoby mieszania faz: mieszanie mechaniczne, mieszanie za pomocą ultradźwięków i mieszanie mechaniczne wspomagane ultradźwiękami. Każdy z eksperymentów prowadzono w temp. 20, 30, 40, 50 oraz 60°C. Na podstawie otrzymanych wyników scharakteryzowano proces transportu przez wyznaczenie parametrów charakterystycznych dla polimerowych membran inkluzyjnych, takich jak stała szybkości, strumień początkowy i współczynnik przepuszczalności. Badania w różnych temperaturach pozwoliły również na określenie wartości energii aktywacji dla poszczególnych procesów.

EN

Zn cations were transported through polymer inclusion membrane in an app. consisting of 2 interconnected glass vessels, sepd. with a 17.8 mm thick membrane made of cellulose triacetate, 1-decyl-1,2,4-triazole and (BuO)₃PO₄. Each vessel was equipped with connector pipes to introduce a mech. stirrer and a sampler. Optionally, the app. was placed in an ultrasound bath (160 W, 40 kHz). In one of the vessels, the supply phase (1 mol/L) of an aq. soln. of ZnCl₂ was placed, and the const. Cl (2 mol/L) concn. was maintained by addn. of NaCl. The mech., ultrasound or mech. supported with ultrasounds mixing was carried out at 20–60°C. The Zn concn. in the receiving phase was detd. each 1 h by titration. The increase of the process temp. from 20°C to 60°C resulted in an increase of Zn recovery from 27.35% to 48.54% for the mech. mixing, from 29.87% to 58.14% for ultrasound mixing, and from 47.02% to 99.90% for ultrasound – supported mech. stirring.

5

The use of the steric effect of the carrier molecule in the polymer inclusion membranes for the separation of cobalt(II), nickel(II), copper(II), and zinc(II) ions

Radzyminska-Lenarcik E., Ulewicz M.

Polish Journal of Chemical Technology

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2015

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Vol. 17, nr 2

51--56

EN

In this study, palladium-modified nickel foam substrate was applied to examine ethanol oxidation reaction (EOR) in 0.1 The transport of cobalt(II), nickel(II), copper(II), and zinc(II) ions from chloride solutions across polymer inclusion membranes (PIMs), which 1-heptylimidazole (1̲) or 1-heptyl-2-methylimidazole (2̲) or 1-heptyl-4-methylimidazole (3̲) as the ion carrier was reported. The steric effect for carriers 2̲&enspand 3̲&enspdecreases the transport of all ions except Cu(II). The initial fluxes of metal ions transport across PIMs with the 1̲- 2̲&enspdecrease in the sequence: Cu(II) > Zn(II) > Co(II) > Ni(II), whereas for 3 they were Cu(II) > Zn(II) > Ni(II) > Co(II). The highest recovery values were obtained for Cu(II), this being 99 and 85% for carrier 1̲&enspand 2̲, respectively. In both membranes the degree of deposition of the Zn(II) ions was comparable. Zn(II), Co(II) and Cd(II) ions, which form complexes with coordination numbers 4 and 6, are more easily recovered with the use of carriers 2̲&enspand 3̲. Ni(II) ions, which form complexes with coordination number 6 only, practically remain in the feeding phase. PIMs with alkylimidazoles were characterized by non-contact atomic force microscopy.

6

Application of polymer inclusion membranes doped with 1-hexyl-4-methylimidazole for pertraction of zinc(II) and other transition metal ions

Ulewicz M., Radzyminska-Lenarcik E.

Physicochemical Problems of Mineral Processing

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2015

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Vol. 51, iss. 2

447--460

EN

Transport of Zn(II) from unary aqueous chloride solutions and from solutions which contain mixtures of Cd(II), Co(II) and Ni(II) ions in source phases (cMe = 0.001 mol/dm3, pH = 6.0) across polymer inclusion membranes (PIMs) doped with 1-hexyl-4-methylimidazole as ion carrier was studied. The use of 1-hexyl-4-methylimidazole enables the separation of 98.5% Zn(II) from a unary solution and 96.9% from a quaternary solution of Zn(II)-Cd(II)-Co(II)-Ni(II) after running the process for 24 hours. Using that ion carrier, the metals are transported in the following order: Zn(II) > Cd(II) > Ni(II) > Co(II), and the selectivity coefficients of Zn(II)/Cd(II), Zn(II)/Ni(II), and Zn(II)/Co(II) are 12.9, 23.4 and 40.8, respectively. Findings of atomic force microscopy (AFM) examinations as well as thermograms of a polymer inclusion membrane containing 1-hexyl-4-methylimidazole are also presented. A membrane with 1.0 mol/dm3 of carrier has a porosity of 15.8%, and roughness of 6.6 nm. The membranes remain thermally stable at temperatures up to 200oC. The findings were compared with earlier-reported results for 1-hexylimidazole.

7

The use of 1-alkylimidzoles for selective separation of zinc ions in the transport process across a polymeric inclusion membrane

Radzyminska-Lenarcik E., Ulewicz M.

Physicochemical Problems of Mineral Processing

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2014

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Vol. 50, iss. 1

131--142

EN

The transport of Zn(II) ions from different aqueous nitrate(V) source feeding phases (cMe = 0.001 mol/dm3, pH 6.0) across polymer inclusion membranes (PIMs) doped with 1-alkylimidazole as an ion carrier was reported. Alkyl substituents in position 1 of imidazole ring have an effect on hydrophobic properties of the carriers and the initial flux of the transported metal ions. The membranes were characterized by an atomic force microscopy (AFM). The results show that the Zn(II) ions could effectively be separated from other transition metal cations such as Co(II) and Ni(II) from different equimolar ion mixtures. Also, the thermal stability of PIM doped with 1-decylimidazole was studied in replicate experiments. The highest separation coefficients for the Zn(II)/Co(II) and Zn(II)/Ni(II) systems, equal to 9.4 and 11.9 were recorded for the equimolar Zn(II)-Co(II)-Ni(II) mixture for 1-hexylimidazole as a carrier, while using 1-decylimidazole resulted in the highest values of initial flux of the Zn(II) ions transport across the polymeric membrane.

8

Lead(II) removal from aqueous solutions by solvent extraction with tetracarboxylresorcin[4]arene

Konczyk J., Kozlowski C., Walkowiak W.

Physicochemical Problems of Mineral Processing

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2013

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Vol. 49, iss. 1

213--222

EN

A novel tetracarboxylresorcin[4]arene was synthesized and its selective complexing ability towards Pb(II) ions was examined. The influence of several parameters such as pH of aqueous phase, agitation time, extractant and modifier concentrations on solvent extraction of Pb(II) ions from the aque-ous nitrate phase into chloroform organic phase was studied. The stoichiometry of the formed metal-ligand complexes was established by slope analysis. Pb(II) ions were quantitatively extracted in the form of 2:1 Pb(II)-resorcin[4]arene complex from aqueous solutions of pH 5.5 to the solution of ligand in chloroform. Competitive solvent extraction experiments in the presence of Zn(II) and Cd(II) ions were also carried out and high selectivity of the extractant towards Pb(II) over Zn(II) and Cd(II) was found. The selectivity order was: Pb(II) >> Cd(II) > Zn(II).

9

Badanie szybkości ekstrakcji cynku(ll) i żelaza(III) czwartorzędową solą fosfoniową Cyphos®IL 101 z układów chlorkowych

Marszałkowska B., Wiśniewski M.

Przemysł Chemiczny

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2012

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T. 91, nr 7

1374-1377

PL

Przedstawiono wyniki badań równowagi i kinetyki ekstrakcji cynku(II) i żelaza(III) z kwaśnych układów chlorkowych przy użyciu czwartorzędowej soli fosfoniowej chlorku triheksylo(tetradecylo)fosfoniowego (Cyphos®IL 101). Do badania kinetyki zastosowano dwie techniki eksperymentalne: mieszalnik ze stałą powierzchnią kontaktu faz i metodę pojedynczej kropli. Na podstawie uzyskanych wyników stwierdzono, że ekstrakcja Zn(II) i Fe(III) zachodzi wg mechanizmu wymiany anionowej, a skład kompleksu ekstrahent-anion ZnCl²⁻₄ lub FeCl⁻₄ wynosi odpowiednio 2:1 i 1:1. Na podstawie teorii warstewek granicznych wyznaczono strumienie oraz współczynniki transportu masy. W przypadku ekstrakcji Zn(II) ekstrahentem Cyphos®IL 101 oszacowano, że rzędowość reakcji w stosunku do metalu oraz ekstrahenta jest równa 1, a średnia wartość stałej szybkości ekstrakcji wynosi kśr.= 3745 ± 77 dm³/(mol·s). W przypadku ekstrakcji Fe(III) stała szybkości wynosi 74900 ±7300 dm³/(mol·s).

EN

Zn(II) and Fe(III) extn. equil. and extn. rate were examd. in systems contg. trihexyl(tetradecyl)phosphonium chloride by using Lewis cell and single drop method. The Zn and Fe complexes were transferred into the org. phase. Mass fluxes and mass-transfer coeffs. were detd. by using the boundary layer theory. The reactions were first order with respect to the metals. The extn. rate consts. were 3745 and 74900 L/(mol·s), resp.

10

Application of supported and polymer membrane with 1 decyl-2-methylimidazole for separation of transition metal ions

Ulewicz M., Radzyminska-Lenarcik E.

Physicochemical Problems of Mineral Processing

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2012

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Vol. 48, iss. 1

91-102

EN

The facilitated transport of Cu(II), Zn(II), Co(II), and Ni(II) ions from different aqueous nitrate source phases (cMe = 0.001M, pH 6.0) across polymer inclusion membranes (PIMs) consisting of cellulose triacetate (support) and 2-nitrophenylpentyl ether (plasticizer) doped with 1-decyl-2-methylimidazol as ion carrier was reported. The membrane is characterised by atomic force microscopy (AFM) and thermal analysis (DTA and TG) techniques. The results show that Cu2+ can be separated very effectively from other transition metal cations as Zn2+, Co2+, and Ni2+ from different equimolar mixtures of these ions. The recovery factor of Cu2+ ions during transport across PIM from different mixture is equal to 92-95.1%. The comparative transport of Cu(II), Zn(II), Co(II), and Ni(II) ions from aqueous nitrate source phase across supported (SLMs) containing 1-decyl-2-methylimidazol as ion carrier was reported.

11

The application of polymer inclusive membranes for removal of heavy metal ions from waste solutions

Gajda B., Bogacki M. B.

Journal of Achievements in Materials and Manufacturing Engineering

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2012

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Vol. 55, nr 2

673--678

EN

Purpose: The aim of the conducted studies was to determine the possibility of selective separation and precipitation of metal ions from polimetalic solution containing nickel(II), cobalt(II), cadmium(II) and zinc(II) cations using polymer inclusive membranes. 1-decylimidazole was used in membrane as a carrier of ions. The influence of chloride anions concentration on the process has also been investigated. Design/methodology/approach: Polymer inclusive membranes (PIM) containing cellulose acetate as a matrix, orto-nitrophenyl octyl ether (ONPOE) as a plasticizer and 1-decylimidazole as a carrier were used in investigations. The membrane processes were carried out in a membrane module for 24 hours. Findings: The results obtained point out a significant influence of chloride anions concentration on separation process of certain metal ions. It was observed that zinc(II) ions are isolated most effectively from the solution containing 2M of chloride anions. About 88% of Zn(II), 5.5% of Co(II), 6.5% of Cd(II) and below 1% of Ni(II) were separated from such a solution. Research limitations/implications: The obtained results show that it is possibility of the selective extraction of heavy metal ions from polymetallic chloride solutions in membrane processes. The aqueous solution containing 2M of chloride ions was used in the investigation. Practical implications: The results show that Zn(II) can be effectively recovered from solutions containing Co(II), Cd(II) and Ni(II). This process would allow the utilization of waste solutions containing the heavy metal ions. The results of the study presented in the paper can be used in the utilization process of the spent batteries and accumulators. Originality/value: The innovative issue shown in this paper concerns the usage of 1-decylimidazole in selective separation of nickel(II), cobalt(II), cadmium(II) and zinc(II) ions in membrane process using PIM.

12

Transport of metal ions across polymer inclusion membrane with 1-alkylimidazole

Ulewicz M., Radzymińska-Lenarcik E.

Physicochemical Problems of Mineral Processing

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2011

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Vol. 46

119-130

EN

The facilitated transport of copper(II), zinc(II), cobalt(II), and nickel(II) ions across polymer inclusion membranes (PIMs), which consist of cellulose triacetate as polymeric support, o-nitrophenyl pentyl ether as plasticizer and 1-alkylimidazole as ion carrier was reported. PIM was characterized by using atomic force microscopy (AFM) technique. The results show that Cu2+ can be separated very effectively from others heavy and transition metal cations as Zn2+, Co2+, and Ni2+ (at concentration of 10-3 M each). Alkyl substituents in position 1 of imidazole ring have an effect on hydrophobic properties and the initial flux of the transported metal ions. Also, the influence of the chloride ions concentration on the separation process was investigated. To explain the mechanism of membrane transport the diffusion of metal ions complexes with 1-alkylimidazole was also measured.

PL

Zbadano selektywność transportu jonów Cu(II), Zn(II), Co(II) i Ni(II) (cMe=0,001M, każdy) przez polimerowe membrany inkluzyjne składające się z trójoctanu celulozy (suportu), eteru o-nitrofenylooktylu (plastyfikatora) i przenośnika jonów (1 alkiloimidazole). Polimerowa membrana została scharakteryzowana przy pomocy mikroskopii sił atomowych (AFM). Wykazano, że podstawnik alkilowy w pozycji 1 pierścienia imidazolu zmieniając własności hydrofobowe przenośnika wpływa na strumień początkowy transportu jonów metali. Wartości strumienia początkowego transportu jonów przy użyciu przenośnika 1 i 2 maleją w szeregu: Cu(II) > Zn(II) > Co(II) > Ni(II), natomiast dla 3 - 5 w szeregu: Cu(II) > Zn(II) > Ni(II), Co(II). Strumień transportu Cu(II) wzrasta w szeregu użytych przenośników: 1 < 2 < 3 < 4 ɝ, osiągając najwyższą wartość 6,36 µµmol/m2 · s (dla 5). Na selektywność transportu wpływ również stężenie jonów chlorkowych w fazie zasilającej. Czynnikiem limitującym szybkości transportu Cu2+ przez PIM jest współczynnik dyfuzji kompleksu przenoszonego kationu przez membranę.

13

Separation of cobalt(II), nickel(II), zinc(II) and cadmium(II) ions from chloride solution

Gajda B., Skrzypczak A., Bogacki M. B.

Physicochemical Problems of Mineral Processing

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2011

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Vol. 46

289-294

EN

Selective distribution of cobalt(II), nickel(II), zinc(II) and cadmium(II) ions from chloride solutions through polymer inclusion membranes (PIM) has been studied. The carrier was 1-decylimidazole. The effect of chloride ion concentration on the ion permeation was analysed. The results suggest that some of metal ions change for the worse selectivity of separation process. Especially zinc(II) and cadmium(II) ions decreased five-fold selectivity of ion separation process.

PL

W pracy przedstawiono wyniki badań selektywnego rozdziału jonów kobaltu(II), niklu(II), cynku(II) i kadmu(II) z roztworów chlorkowych w procesie selektywnego ich rozdziału w procesie membranowym przez polimerowe membrany inkluzyjne (PIM). Jako przenośnik zastosowano 1-decyloimidazol. Uzyskane wyniki wskazują, że obecność jonów niektórych metali pogarszać może selektywność rozdziału. Szczególne znaczenie mają tutaj jony cynku(II) oraz kadmu(II), które prawie 5-krotnie pogarszają selektywność rozdziału jonów niklu(II) od kobaltu(II).

14

Quaternary phosphonium salts as effective extractants of zinc(II) and iron(III) ions from acidic pickling solutions

Marszałkowska B., Regel-Rosocka M., Nowak Ł., Wiśniewski M.

Polish Journal of Chemical Technology

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2010

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Vol. 12, nr 4

1-5

EN

Extraction of zinc(II) and iron(III) from hydrochloric acid solutions using quaternary phosphonium salts, CyphosŽ IL 101, CyphosŽ IL 104, CyphosŽ IL109 and CyphosŽ IL 111 in mixtures with toluene, was studied. Trihexyl(tetradecyl)phosphonium chloride (CyphosŽ IL 101) and trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate (CyphosŽ IL 104) showed the best zinc(II) and iron(III) extraction abilities. After three stages of zinc(II) extraction with CyphosŽ IL 101 and CyphosŽ IL 104 the efficiencies were 100 and 93.6%, respectively. Total iron(III) transport to the organic phase was achieved after two separation stages and amounted to 82.1 and 100% for CyphosŽ IL 101 and CyphosŽ IL 104, respectively. Zinc(II) and iron(III) could be effectively stripped from the loaded organic phases with 0.5 mol dm-3 sulfuric acid. The more hydrophobic the character of the anion type of phosphonium salts, the lower the efficiency of extraction.

15

Metallo-Supramolecular Assemblies Incorporating 1,3- and 1,4-Aryl Linked Bis-beta-Diketones - Some Recent Studies

Clegg J. K., Jolliffe K. A., Lindoy L. F., Meehan G. V.

Polish Journal of Chemistry

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2008

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Vol. 82, nr 6

1131-1144

EN

A review of recent work in the authors laboratories in volving the interaction of 1,3- and 1,4-aryl linked bis-beta-diketone derivatives with divalent and trivalent metal ions is presented. In some in stances, bifunctional bridging ligands have been employed to extend the resulting structures from two to three dimensions. Examples of metallosupra molecular dinuclear 'platforms', tetranuclear cofacial dimers, dinuclear helicates, trinuclear triangles, stepped metallo-polymers, a prismatic columnar polymer and large cavity-containing, tetranuclear tetrahedra are all discussed.

16

Application of Macrocyclic Compounds to the Transport of Zn(II), Cd(II), and Pb(II) Ions Across the Polymer Inclusion Membrane (PIM)

Ulewicz M.

Polish Journal of Chemistry

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2008

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Vol. 82, nr 6

1237-1244

EN

The applications of macrocyclic ligands for the transport of Zn(II), Cd(II) and Pb(II) ions across PIMs are revisited. As macrocyclic compounds, such chemical substances, as non-ionizable crown ethers, ionizable crown ethers (lar iat ethers), acyclic polyesters, cyclodextrins and calix[4]arenes were used. Literature data, as well as our own recentre search data on the removal and separation of these metal ions are reported. The review has shown that the transport phenomena are dependent on the membrane characteristics, as well as on the physico chemical properties of the source and the receiving aqueous solutions.

17

Methods of regeneration of spent pickling solutions from steel treatment plants

Regel-Rosocka M., Cieszyńska A., Wiśniewski M.

Polish Journal of Chemical Technology

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2007

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Vol. 9, nr 2

42-45

EN

Facing the still growing demand for metals, particularly for zinc, the recovery of metals from secondary sources should be considered. Spent pickling solutions can be the source of valuable products such as hydrochloric acid, zinc or iron salts or even metallic zinc. The selection of an efficient, selective and economical method for the regeneration of such solutions is a key issue for hot dip galvanizing plants, especially in reference to strict environmental protection regulations.

18

Selective transport of Pb(II) across polymer inclusion membrane using imidazole azocrown ethers as carriers

Ulewicz M., Sadowska K., Biernat J. F.

Physicochemical Problems of Mineral Processing

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2007

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Vol. 41

133-143

EN

Transport of Pb(II) ions from equimolar aqueous solutions of Zn(II), Cd(II), and Pb(II) as well as from solutions containing only Pb(II) ions source phase (cMe = 0.001 M) through polymer inclusion membranes (PIMs) containing imidazole azocrown ethers as carriers has been investigated. The polymer membranes consisting of cellulose triacetate (support), o-nitrophenyl pentyl ether (plasticizer) and imidazole crown ether derivatives (as ion carriers) were investigated. The influence of lipophilicity of macrocycles on the selectivity and efficiency of Pb(II) transport with azocrown 3 are higher than 1, accordingly with the hydrophile-lipophile balance of imidazole azocrown ethers. The highest transport recovery for Pb(II) ions was observed for 3 (91.6%). The transport selectivity of the polymer inclusion membrane with 3 was: Pb(II) > Zn(II) > Cd(II) and the selectivity coefficient Pb(II)/Cd(II) and Pb(II)/Zn(II) equals 40.1 and 13.4, respectively. The stability of PIM with imidazole azocrown derivatives was confirmed by replicate experiments.

PL

Zbadano selektywność transportu jonów ołowiu(II) z równomolowych roztworów jonów Zn(II), Cd(II) i Pb(II) oraz z roztworów zawierających jony Pb(II) przez polimerowe membrany inkluzyjne (PIM) zawierające imidazolowe etery azokoronowe. Badania prowadzono dla azotanowych roztworów Pb(II) o stężeniu 0,001 M oraz dla roztworów zawierających równomolową mieszaninę jonów Pb(II), Cd(II) i Zn(II) (cMe= 0,001 M każdego). Badane azokorony różniły się miejscem podstawienia imidazolu i rodzajem dołączonej do niego grupy (-H, -CH3, -C6H5). Polimerowe membrany inkluzyjne otrzymywano z trójoctanu celulozy (nośnik), eteru o-nitrofenylopentylowego (pastyfikator) i jednego z eterów koronowych 1 ÷ 3 (przenośnik jonów); stężenie przenośnika jonów w przeliczeniu na objętość plastyfikatora wynosiło 0,05 M. Wykazano, że początkowe wartości strumienia transportu jonów ołowiu(II) maleją ze wzrostem balansu hydrofilowo-hydrofobowego (HLB) eteru koronowego, tj. 3 > 1. Ponadto stwierdzono, że strumienie początkowe transportu jonów przy użyciu eterów 2 i 3 maleją w szeregu: Pb(II) > Zn(II) > Cd(II). Współczynniki separacji Pb(II)/Cd(II) i Pb(II)/Zn(II) przez PIM przy użyciu eteru 2 z 0,01M roztworu mieszaniny jonów wynosiły 11,3 i 53,6 natomiast z roztworów o stężeniu 0,001 M odpowiednio 16,3 i 46,0. Ponadto wykazano, że polimerowe membrany inkluzyjne z imidazolowymi azokoronami wykazują dużą stabilność, zależną w dużym stopniu od rodzaju jonoforu.

19

Selective removal of Cu(II), Co(II), Zn(II), and Ni(II) with ionizable dibenzo-16-crown-5 and dibenzo-19-crown-6 lariat ethers as ion carriers in polymer inclusion membrane transport

Kozłowski C. A., Walkowiak W.

Ars Separatoria Acta

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2007

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No. 5

19-26

EN

A selective removal of transition metal cations, i.e. Cu(II), Co(II), Zn(II), and Ni(II), with ionizable dibenzo-16-crown-5 and dibenzo-19-crown-6 lariat ethers as ionic carriers in transport across polymer inclusion membrane has been presented. The competitive transport from aqueous nitrate solutions containing metal ions at concentrations of 0.0010 M at pH 4.0 and 7.0 through the cellulose triacetate membrane with 0.5 M lariat ether 1 and 2 (based on a plasticizer) as the ion carrier and o-nitrophenyl pentyl ether (ONPPE) as the plasticizer into 0.5 M hydrochloric solution was performed. For pH = 4.0 and 7.0 of source aqueous phases the selectivity orders were as follows: Cu(II) > Co(II) > Zn(II) > Ni(II), and Cu(II) > Zn(II), Ni(II), Co(II), respectively. The semi-empirical equation was used for calculations of enthalpy formation for complexes of lariat ethers studied with transition metal cations. The two possibilities of metal cation-lariat ether coordination were assumed, i.e. via the crown ether cavity or ionizable carboxylic group. We found that for the both lariat ethers studied at pH 4.0 of source phase the transport rate linearly decreases with the enthalpy of formation increase. This correlation confirms that the observed behavior is connected with the stability of complexes formed by interaction of the lariat ether ring and the transition metal cations studied.

20

Removal of Zn(II), Cd(II) and Pb(II) using polymer inclusion membrane transport with proton ionizable DB-16-C-5 crown ethers

Ulewicz M., Walkowiak W.

Physicochemical Problems of Mineral Processing

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2006

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Vol. 40

185-194

EN

Competitive transport of Zn(II), Cd(II), and Pb(II) ions from aqueous nitrate source phase (Cme = 0.001 M) through polymer inclusion membranes (PIMs) containing cellulose triacetate (as support), o-nitrophenyl pentyl ether (as plasticizer) and proton ionizable lariat ether derivatives (as ion carriers) has been investigated. The influence of varying the lipophilicity of sym(R)(hydroxy)dibenzo-16-crown-5 macrocycles with R groups such as hydrogen (in 1), decyl (in 2) and phenyl (in 3) on the selectivity and efficiency of Zn(II), Cd(II), and Pb(II) transport through polymer inclusion membranes is studied. The influence of HLB (hydrophile-lipophile balance) and Vx (molecular volumes) on the transport selectivity of metal ions was investigated. Relationship between the cation size and initial fluxes transport of metal cation was shown. The selectivity coefficients of Pb(II)/Zn(II) and Cd(II)/Zn(II) decrease with increase of carrier concentration in inclusion membrane.

PL

Zbadano selektywność wydzielania jonów cynku(II), kadmu(II) i ołowiu(II) z wodnych roztworów azotanowych zawierających równomolową mieszaninę metali (cMe= 0,001 M) w procesie transportu przez polimerowe membrany inkluzyjne (PIM) przy użyciu w roli przenośników jonów jonizowalnych eterów koronowych o koronie DB-16-C-5. Badane etery różniły się rodzajem grupy dołączanej do korony ( -H, -C10H21, -C6H5). Polimerowe membrany inkluzyjne syntezowano z trójoctanu celulozy (nośnik), eteru o-nitrofenylopentylowego (pastyfikator) i jednego z eterów koronowych 1 ÷ 3 (przenośnik jonów); stężenie przenośnika jonów w przeliczeniu na plastyfikator zmieniano w granicach 0,3 - 1,0 M. Współczynniki separacji Pb(II)/Cd(II) i Pb(II)/Zn(II) przez PIM przy użyciu eteru 2 były nieznacznie wyższe niż przy użyciu eteru 3 i 1. Dla badanych eterów o stężeniu 0,5 M w membranie współczynniki separacji Pb(II)/Cd(II) i Pb(II)/Zn(II) wynosiły odpowiednio 1,4 i 1,8; 1,5 i 3,1 oraz 1,6 i 3,4 dla eterów 1, 2, i 3. Wykazano, że początkowe wartości strumienia transportu badanych jonów rosną ze wzrostem objętości molowej eteru koronowego, natomiast maleją ze wzrostem bilansu hydrofilowo-hydrofobowego (HLB) eteru koronowego. Ponadto stwierdzono, że niezależnie od zastosowanego eteru lariatowego o koronie DB-16-C-5 najlepiej transportowane są kationy o największej średnicy.