**22. References**


Alexandratos, S.D. (2007) New polymer-supported ion-complexing agents: Design, preparation and metal ion affinities of immobilized ligands, *Journal of Hazardous Materials*, Vol. 139, pp. 467–470

230 Ion Exchange Technologies

**21. Conclusions** 

waters and wastewaters.

Zbigniew Hubicki and Dorota Kołodyńska *Maria Curie-Skłodowska University, Poland* 

**Author details** 

**22. References** 

375, pp. 293-298.

Diphonix Resin®, respectively.

complexes with IDS and MGDA on Dowex M 4195 and Diphonix Resin®. They are equal to 121.58 mg/g and 97.64 mg/g on Dowex M 4195 and 112.37 mg/g and 100.20 mg/g on

For the studied systems regeneration tests were conducted using HCl, HNO3, H2SO4 and NaCl at 1M and 2M concentrations. Based on the series of five experiments using known amounts of Cu(II) complexes with IDS and MGDA sorbed, it was established that the overall recoveries of Cu(II) eluted from Dowex M 4195 and Diphonix Resin® by 2M HCl

The presence of biodegradable complexing agents of a new generation that is IDS and MGDA affects the sorption process of Cu(II), Zn(II), Cd(II) and Pb(II) ions on Dowex M4195 and Diphonix Resin®. The effectiveness of sorption depends on the type of complexes and their stability that facilitates their decomposition in the resin phase. The batch equilibrium was relatively fast and reached equilibrium after about 10-20 min of the contact. The experimental data have been analyzed using the Langmuir and Freundlich models. The sorption of studied metal ions in the presence of IDS and MGDA Dowex M 4195 and Diphonix Resin® followed the pseudo second order kinetics. As follows from the experiment pH does not have a significant effect on the sorption of Cu(II), Zn(II), Cd(II) and Pb(II) ions in the presence of IDS and MGDA on the chelating ion exchanger under consideration. The affinity of the above analyzed heavy metal complexes with IDS and MGDA Dowex M 4195 and Diphonix Resin® were found to be as follows: Pb(II) > Cd(II) > Cu(II) > Zn(II) for IDS and MGDA. The studied complexing agents can be proposed as alternative chelating agents to EDTA or NTA for the removal of heavy metal ions from

Abollino, O., Aceto, M., Bruzzoniti, M.C., Mentasti, E., Sarzanini, C. (1998) Determination of metals in highly saline matrices by solid-phase extraction and slurry-sampling inductively coupled plasma-atomic emission spectrometry, *Analytica Chimica Acta*, Vol.

Abrams, I.M., Milk, J.R. (1997) A history of the origin and development of macroporous ion-

Ahuja, M., Rai, A.K., Mathur P.N. (1999) Adsorption behaviour of metal ions on

exchange resins, *Reactive and Functional Polymers*, Vol. 35, 7-22.

hydroximate resins, *Talanta*, Vol. 43, pp. 1955-1963.

and H2SO4 were above 98 %, suggesting that the recovery is quantitative.


Dybczyński R., Hubicki Z., Kulisa K. (1988) Ion exchange behaviour of 23 elements and amphoteric properties of chelating resin Duolite ES 346 containing amidoxime groups, *Solvent Extraction and Ion Exchange*, Vol. 6, 699-724.

232 Ion Exchange Technologies

70.

107.

217-222.

pp. 793-807.

*Chemosphere*, Vol. 56, pp. 91-106.

*and Technology*, Vol. 43, pp. 2343-2362.

*Hydrometallurgy*, Vol. 78, pp. 147-155.

*Macromolekulare Chemie*, Vol. 200, pp. 27-36.

Corella, M.B., Siggia, S., Barnes, R.M. (1984) Synthesis and characterization of a poly(acryloamidoxime) metal chelating resin, *Analytical Chemistry*, Vol. 56, pp. 967-972. Dambies, L., Salinaro, R., Alexandratos, S.D. (2004) Immobilized N-methyl-D-glucamine as an arsenate-selective resin, *Environmental Science and Technology*, Vol. 38, pp. 6139-6146. Dąbrowski, A., Hubicki, Z., Podkościelny, P., Robens, E. (2004) Selective removal of the heavy metal ions from waters and industrial wastewaters by ion-exchange method,

De Dardel, F., Arden, T.V. (2001) *Ion exchangers*. Principles and applications, Ullmann's Encyclopaedia of Industrial Chemistry, Sixth Edition, Wiley-VCH Verlag GmbH, pp. 1-

Deepatana A., Valix M. (2006) Recovery of nickel and cobalt from organic acid complexes: Adsorption mechanisms of metal-organic complexes onto aminophosphonate chelating

Dimick, P.D., Kney, A., Tavakoli, J., Mylon, S.E., Zhao, D. (2008) A comparison of metalloaded DOW3N ion exchanger for removal of perchlorate from water, *Separation Science* 

Ding, X., Mou, S.F., Liu, K., Yan, Y. (2000) Improved scheme of chelation ion chromatography with a mixed eluent for the simultaneous analysis of transition metals

Ding, X., Mou, S. (2001) Retention behavior of transition metals on a bifunctional ionexchange column with oxalic acid as eluent, *Journal of Chromatography,* Vol. 920, pp. 101-

Diniz, C.V., Doyle, F.M., Martins A.H. (2000) Uptake of heavy metals by chelating resins from acidic manganese chloride solution, *Minerals Metallurgy Processing,* Vol. 17, pp.

Diniz, C.V., Doyle, F.M., Ciminelli, V.S.T. (2002) Effect of pH on the adsorption of selected heavy metal ions from concentrated chloride solutions by the chelating resin Dowex M-

Diniz, C.V., Ciminelli, V.S.T., Doyle, F.M. (2005) The use of the chelating resin Dowex M-4195 in the adsorption of selected heavy metal ions from manganese solutions,

Drăgan, S., Grigoriu, G. (1992) Ion exchangers, I. Anion exchanges with tertiary amine groups on poly(acrylonitrile-co-divinylbenzene) network, *Die Angewandte* 

Du, W., Pan, B., Jiang, P., Zhang, Q., Zhang, W., Pan, B., Zhang, Q., Zhang, Q. (2008) Selective sorption and preconcentration of tartaric acid using a copper(II)-bound

Dybczyński, R. (1987) Selective separation of zinc from other elements on the amphoteric resin Retardion 11A8 and its use for the determination of zinc in biological materials by

polymeric ligand exchanger, *Chemical Engineering Journal,* Vol. 139, pp. 63-68. Duffus, J.H. (2002) "Heavy metals" – a meaningless term? *Pure Applied Chemistry,* Vol. 74,

resin, *Journal of Hazardous Materials*, Vol. 137, pp. 925-933.

at mg l-1 levels, *Journal of Chromatography,* Vol. 883, pp. 127-136.

4195, *Separation Science and Technology,* Vol. 37, pp. 3169-3185.

neutron activation analysis, *Analyst,* Vol. 112, pp. 449-453


Kabay, N., Demircioğlu, M., Yayl, S., Günay, E., Yüksel, M., Sağlam, M., Streat, M. (1998a) Recovery of uranium from phosphoric acid solutions using chelating ion-exchange resins, *Industrial and Engineering Chemistry Research*, Vol. 37, pp. 1983-1990.

234 Ion Exchange Technologies

pp. 943-966.

*Thermochimica Acta*, Vol. 139, pp. 327-332.

ion exchangers, US Patent 5281631.

*Polymers*, Vol. 66, pp. 1539-1545.

ion exchange resins. US Patent 5449462.

Helfferich F. (1962) Ion Exchange Resins, Mc-Grow Hill:New York.

complex ion-exchanger, *Analytica Chimica Acta*, Vol. 334, pp. 1-4

Hajiev, S.N., Kertman, S.V., Leykin, U.A., Amelin, A.N. (1989) Thermochemical study of ion echange processess. V. Sorption of copper ions in complex-forming resins,

Hirayama, N., Umehara, W. (1996) Novel separation of inorganic anions using a charged

Horwitz, E.P., Chiarizia, R., Diamond, H., Gatrone, R.C., Alexandratos, S.D., Trochimczuk, A.Q., Crick, D.W. (1993) Uptake of metal ions by a new chelating ion-exchange resin. Part 1. Acid dependencies of actinide ions, *Solvent Extraction and Ion Exchange*, Vol. 11,

Horwitz, E.P., Alexandratos, S.D., Gatrone, R.C., Chiarizia, R. (1994) Phosphonic acid based

Horwitz, E.P., Alexandratos, S.D., Gatrone, R.C., Chiarizia, R. (1995) Phosphonic acid based

Hosseini, M.S., Raissi, H., Madarshahian, S. (2006) Synthesis and application of a new chelating resin functionalized with 2,3-dihydroxy benzoic acid for Fe(III) determination in water samples by flame atomic absorption spectrometry, *Reactive and Functional* 

Hubicki, Z., Jakowicz, A., Łodyga, A. (1999) *Application of the ions from waters and sewages*, In: Adsorption and its applications in industry and environmental protection. Studies in surface science and catalysis, ed. A. Dąbrowski, Elsevier, Amsterdam, New York. Hyvönen, H., Orama, M., Saarinen, H., Aksela, R. (2003) Studies on biodegradable chelating ligands: complexation of iminodisuccinic acid (ISA) with Cu(II), Zn(II), Mn(II) and

Hyvönen, H., Aksela, R. (2010) Complexation of 3-hydroxy-2,2'-iminodisuccinic acid (HIDS) with Mg2+, Ca2+, Mn2+, Fe3+, Fe2+, Co2+, Ni2+, Cu2+, and Zn2+ ions in aqueous solution,

IDS Na-salz (1998) Eine neue umweltfreundliche alternative zu klassischen

Irving, H., Williams, R.J.P. (1953) The stability of transition-metal complexes. *Journal of* 

Ivanov, V.A., Timofeevskaya, V.D., Gorshkov, V.I., Drozdova, N.V. (1996) The role of temperature in ion exchange processesof separation and purification, *Journal of* 

Jeyakumar, S., Mishra, V.G. Das, M.K., Raut, V.V., Sawant, R.M., Ramakumar K.L. (2011) Separation behavior of U(VI) and Th(IV) on a cation exchange column using 2,6 pyridine dicarboxylic acid as a complexing agent and its application for the rapid separation and determination of U and Th by ion chromatography, *Journal of Separation* 

Jones, K.C., Pyper, R.A. (1979) Copper recovery from acidic leach liquors by continuous ion-

Fe(III) ions in aqueous solution, *Green Chemistry,* Vol. 5, pp. 410-414.

*Journal of Coordination Chemistry,* Vol. 63, pp. 2013-2025.

komplexierungsmitteln. Bayer AG brochure, Leverkusen. Ion exchange resins and adsorbents (2006) Dow Chemical, Co. brochure.

*Radioanalytical and Nuclear Chemistry*, Vol. 208, pp. 23-45.

exchange and electrowinning, *Journal of Metals,* Vol. 4, pp. 19-25.

*Chemical Society*, Vol. 162, pp. 3192-3210.

*Science*, Vol. 34, pp. 1-8.


Muraviev, D., Gonzalo, A., Valiente, M. (1995) Ion exchange on the resin with temperatureresponsive selectivity. 1. ion exchange equilibrium of Cu2+ and Zn2+ on iminodiacetic and aminomethylphosphonic resin, *Analytical Chemistry,* Vol. 67, pp. 3028-3035.

236 Ion Exchange Technologies

*Extraction and Ion Exchange*, in press.

*Hydrometallurgy*, Vol. 86, pp. 6-12.

*and Technology*, Vol. 29, pp. 481-486.

*Chemistry*, Vol. 322, pp. 47-52.

*Roumaine de Chimie*, Vol. 54, pp. 107-117.

pp. 3756-3766.

359-371.

solutions, *Hydrometallurgy,* Vol. 54, pp. 107-115.

*of Applied Polymer Science,* Vol. 59, pp. 1271-1283. Kunin R. (1958) *Ion Exchange Resins*, 3rd Ed; Wiley: New York. Kunin, R. (1979) Amber-Hi-Lites 161, Rohm and Haas Co.

ion-exchange resin, *Desalination*, Vol. 129, pp. 1-6.

Jachuła, J., Kołodyńska, D., Hubicki, Z. (2011) Sorption of Cu(II) and Ni(II) ions in presence of novel chelating agent methylglycinediacetic acid by microporous ion exchangers and sorbents from aqueous solutions, *Central European Journal of Chemistry,* Vol. 9, pp. 52-65. Jachuła, J., Kołodyńska, D., Hubicki, Z. (2012) Methylglycinediacetic acid as a new complexing agent for removal of heavy metal ions from industrial wastewater, *Solvent* 

Kononova, O.N., Kholmogorov, A.G., Kachin, S.V., Mytykh, O.V., Kononov, Y.S., Kalyakina, O.P., Pashkov, G.L. (2000) Ion exchange recovery of nickel from manganese nitrate

Krongauz, V.V., Kocher, C.W. (1997) Kinetics of ion exchange in monodisperse resin, *Journal* 

Kurama, H., Çatlsarik, T. (2000) Removal of zinc cyanide from a leach solution by an anionic

Lee, M.S., Nicol, M.J. (2007) Removal of iron from cobalt sulphate solutions by ion exchange with Diphonix resin and enhancement of iron elution with titanium(III),

Li, P.; SenGupta, A.K. (1998) Genesis of selectivity and reversibility for sorption of synthetic aromatic anions onto polymeric sorbents, *Environmental Science and Technology,* Vol. 32,

Li, C.W., Qi, T., Wang, F.A., Zhang, Y., Yu, Z.H. (2006) Variation of cell voltage with reaction time in electrochemical synthesis process of sodium dichromate, *Chemical Engineering* 

Luca, C., Vlad, C.D., Bunia, I. (2009) Trends in weak base anion exchangers resins, *Revue* 

Lührmann, LM., Stelter, N., Kettrup, A. (1985) Synthesis and properties of metal collecting phases with silica immobilized 8-hydroxyquinoline, *Fresenius Journal of Analytical* 

Marhol, M., Beranová, H., Cheng, K.L. (1974) Selective ion-exchangers containing phosphorus in their functional groups. I. Sorption and separation of some bivalent and trivalent ions, *Journal of Radioanalytical and Nuclear Chemistry*, Vol. 21, pp. 177-186. Marhol, M., Cheng, K.L. (1974) Some chelating ion-exchange resins containing

Melling J., West, D.W. (1984) Proceedings of the International Conference on Ion-Exchange,

Minczewski, J., Chwastowska, J., Dybczyński, R. (1982) *Separation and preconcentration* 

Society of Chemical Industry, Cambridge, England, p. 724.

*methods in inorganic trace analysis*, Wiley-VCH, New York.

ketoiminocarboxylic acids as functional groups, *Talanta*, Vol. 21, pp. 751-762. McClain, A., Hsieh, Y.L. (2004) Synthesis of polystyrene-supported dithiocarbamates and their complexation with metal ions, *Journal of Applied Polymer Sciences*, 92 (2004) 218-225. Mendes, F.D., Martins A.H. (2004) Selective sorption of nickel and cobalt from sulphate solutions using chelating resins, *International Journal of Mineral Processing,* Vol. 74, pp.


determination by flame atomic absorption spectrometry, *Analyst*, Vol. 124, pp. 1847- 1851.

Tewari, P.K., Singh, A.K. (2000) Amberlite XAD-7 impregnated with Xylenol Orange: a chelating collector for preconcentration of Cd(II), Co(II), Cu(II), Ni(II), Zn(II) and Fe(III) ions prior to their determination by flame AAS, *Fresenius Journal of Analytical Chemistry*, Vol. 367, pp. 562-567.

238 Ion Exchange Technologies

Reynolds T.D. (1982) Unit operations and processes in environmental engineering, BC

Ripperger K.P., Alexandratos, S.D. (1999) Polymer-supported phosphorus-containing ligands for selective metal ion complexation. In: Adsorption and its applications in industry and environmental protection. Studies in surface science and catalysis, ed. A.

Saygi, K.O., Tuzen, M., Soylak, M., Elci, L. (2008) Chromium speciation by solid phase extraction on Dowex M 4195 chelating resin and determination by atomic absorption

Sahni, S.K., Reedijk, J. (1984) Coordination chemistry of chelating resins and ion exchangers,

Sahni, S.K., Van Bennekom, R., Reedijk, J. (1985) A spectral study of transition-metal complexes on chelating ion exchange resin containing aminophosphonic acid groups,

Samczyński, Z., Dybczyński, R. (1997) Some examples of the use of amphoteric ion exchange resins for inorganic separations, *Journal of Chromatography*, Vol. 789, pp. 157-167. Samczyński, Z., Dybczyński, R. (2002) The use of Retardion 11A8 amphoteric ion exchange resin for the separation and determination of cadmium and zinc in geological and environmental materials by neutron activation analysis, *Journal of Radioanalytical and* 

Saxena, R., Singh, A.K., Rathore, D.P.S. (1995) Salicylic acid functionalized polystyrene sorbent Amberlite XAD-2. Synthesis and applications as a preconcentrator in the determination of zinc(II) and lead(II) by using atomic absorption spectrometry, *Analyst*,

Scheffler, A. (1996) Lewatit-MonoPlus. The latest generation of monodisperse ion exchange resin with outstanding properties for optimising water treatment system, Technical

Sharma, R.K., Pant, P. (2009) Solid phase extraction and determination of metal ions in aqueous samples using Quercetin modified Amberlite XAD-16 chelating polymer as metal extractant, *International Journal of Environmental Analytical Chemistry*, Vol. 89, pp.

Sherrington, D.C. (1998) Preparation, structure and morphology of polymer supports,

Smolik, M., Jakóbik-Kolon, A., Porański, M. (2009) Separation of zirconium and hafnium using Diphonix® chelating ion-exchange resin, *Hydrometallurg,* Vol. 95, pp. 350-353. Stamberg, J., Valter, V. (1970) Entfärbungsharze - Anwendungsprinzipien, charakterisierung und verwendung (Decolourizing resins - principles of application, characterization and

Tandy, S., Bossart, K., Mueller, R., Ritschel, J., Hauser, L., Schulin, R., Nowack, B. (2004) Extraction of heavy metals from soils using biodegradable chelating agents,

Tewari, P.K., Singh, A.K. (1999) Amberlite XAD-2 functionalized with chromotropic acid: Synthesis of a new polymer matrix and its applications in metal ion enrichment for their

use). Akademie-Verlag, Berlin, Akadbmie-Verlag, Berlin, p. 63.

Environmental Science and Technology, Vol. 38, pp. 937-944.

spectrometry, *Journal of Hazardous Materials*, Vol. 153, pp. 1009-1014.

Engineering Division, Edition II, Boston, MA.

Dąbrowski, Elsevier, Amsterdam, New York.

*Coordination Chemistry Reviews*, Vol. 59, pp. 1-139.

*Polyhedron,* Vol. 4, pp. 1643-1658.

*Nuclear Chemistry*, 254 (2002) 335-341.

*Chemical Communications,* pp. 2275-2286.

Vol. 120, pp. 403-405.

Bulletin, Bayer AG.

503-514.

