Heavy metal removal from aqueous solution by complexation membrane separation

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1 University of Pannonia Doctoral School of Chemical Engineering and Material Sciences Heavy metal removal from aqueous solution by complexation membrane separation Ph.D. teheses Author: Gábor Borbély environmental engineer (MSc) geoinformatical expert engineer Supervisor: Endre Nagy professor Uinersity of Pannonia Research Institute of Chemical and Process Engineering 2011

teheses Author: Gábor Borbély environmental engineer (MSc) geoinformatical expert engineer

2 ABSTRACT Abstract In these dissertation heavy metal ions (nickel and zinc) separation from aquatic solution was showed by polymer enhanced membrane filtration. The essence of this process is the metal bounding to a high molecular weight polymer molecule in reversible reaction. After that the solvent is separated from compound by micro- or ultrafiltration. Issues of the process are 2 streams: a high concentrated metal complex solution and pured water could be flowed into surface water. Metal-complexation agents were applied some different polymer, such as poly(ethylene imine)s (M W = and g/mol), poly(ethylene glycol) (M W = g/mol) and poly(amido amin) dendrimers (M W = and g/mol). It was investigated the effect of some parameters such as initial concentration of metal and polymer solutions, polymer-metal molar ratio to the separation. It was concludes, to work on suitable parameters about % of metal ions can be separated by the tested membrane filtration process. The most effective complexation agent polymer was the poly(ethylene glycol). For minimization of waste streams, it should be investigated the possibility of the dissociation of the evolved polymer-metal complexes, the regeneration of complexation agents by electrodialysis with bipolar membrane. To show the potential environmental and economic advantages of the tested membrane processes, it was made some tests also a traditional process for metal separation from aqueous solution, like adsorption. It was determined that the membrane process, from technological aspect, is more effective than the adsorption. A mass transport model was developed due to theoretical investigation of membrane separation processes, which, accordance out of the models in publications could be observed the main parameters of the mass transport in dependence on spacecoordinates. Keywords: PEUF, EDBM, PEI, PEG, PAMAM, waste, mass transport model 2

Issues of the process are 2 streams: a high concentrated metal complex solution and pured water could be flowed into surface water.

3 THESES Theses ❶ To the best of my knowledge I have proved firstly that Amberlyst 15, known as catalyst in organic chemistry, and Lewatit S 1467, known as water-softener, are suitable for Ni 2+ and Zn 2+ removal from aqueous solution, as cation exchange resins. ❷ ❶ I have proved that poly(ethylene glycol) (M W = g/mol) with -OH function groups and poly(ethylene imine)s (M W = and g/mol) with -NH 2 function groups are proper complexation agents in the complexation-ultrafiltration method with 10 and 20 kda molecular weight cut-off poly(ether sulphone) membranes for removal of Ni 2+ and Zn 2+ from aqueous solution. ❷ ❷ Based on my experimental results I have found that poly(amido amin) dendrimer generation G4.5 (M W = g/mol) with -COOH function groups and poly(amido amin) dendrimer generation G5.0 (M W = g/mol) with -NH 2 function groups can not be recommended as complexation agents in the complexation-ultrafiltration method with 10 and 20 kda molecular weight cut-off poly(ether sulphone) membranes for economical removal Ni 2+ and Zn 2+ from aqueous solution. In Hungary these dendrimers were synthesized in our Institute first time. ❸ ❶ I have found that poly(ethylene imine)s and poly(amido amin) dendrimer generation G5.0, both of them have -NH 2 functional groups, complexed with Ni 2+ and Zn 2+ (See 2.1 and 2.2 theses!) were hardly undone by electrodialysis with bipolar membrane system. The reason for this is that these polymers have -NH 2 groups which can be able to protonated and pass through the cation exchange membrane. 3

❷ ❶ I have proved that poly(ethylene glycol) (M W = 10000 g/mol) with -OH function groups and poly(ethylene imine)s (M W = 25000 and 70000 g/mol) with -NH 2 function groups are proper complexation

4 THESES ❸ ❷ I have found that poly(ethylene glycol) with -OH function groups and poly(amido amin) dendrimer generation G4.5 with -COOH function groups complexed with Ni 2+ and Zn 2+ (See 2.1 and 2.2 theses!) can be easily disrupted by electrodialysis with bipolar membrane system. ❹ It is concluded from 2 nd and 3 rd theses as far as I know I have realized first time complexation-ultrafiltration method with poly(ether sulphone) membrane and poly(ethylene glycol) as complexation agents for Ni 2+ and Zn 2+ removal from aqueous solution so that regeneration of polymer-metal complex also is solved because of waste minimization. My results were compared with 2 conventional methods for Ni 2+ and Zn 2+ removal from aqueous solution, such as adsorption on natural clay minerals and cation exchange resin, and verified the economy of membrane process. ❺ On my work, unlike other published models, I have made a theoretical mass transport model that can take into account the space and time-depending changes of main parameters affecting the mass transport (i.e. D, ν, H, k). Thereby the mass transport rate and in conclusion the efficiency of the whole process can be estimated better than other models. Widening my model, there was a chance to predict more exactly the effect of concentration-polarization on mass transport both in the concentration-polarization and membrane layers than any other previous model. 4

❹ It is concluded from 2 nd and 3 rd theses as far as I know I have realized first time complexation-ultrafiltration method with poly(ether sulphone) membrane and poly(ethylene glycol) as

5 PUBLICATIONS Publications Publications in topic of dissertation Articles Borbély, G., Nagy, E.: Removal of zinc and nickel ions by complexationmembrane filtration process from industrial wastewater, Desalination 240 (2009) (IF 2009 =2,034) (Citations until August 2011: 17) Nagy, E., Borbély, G.: Mass transport through anisotropic membrane layer, Desalination 240 (2009) (IF 2009 =2,034) Borbély, G., Nagy, E.: Nickel and Zinc Removal by Complexation- Ultrafiltration Method, Hungarian Journal of Industrial Chemistry 36 (2008) Borbély, G., Nagy, E.: Komplexképzéssel segített membránszűrés alkalmazása ipari szennyvizek fémtartalmának kinyerésére, Membrántechnika XII. évf. 3. szám (2008) Nagy, E., Borbély, G.: The effect of the concentration polarization and the membrane layer mass transport on the membrane separation, Journal of Applied Membrane Science & Technology 6 (2007) 9-16 Lectures Borbély, G., Nagy, E.: Heavy metal removing by complexation-ultrafiltration process, 35 th International Conference of Slovak Society of Chemical Engineering, Tatranské Matliare, Slovakia, May , Proceedings p. 57 & CD-ROM (Abstract and fulltext) Borbély, G., Nagy, E.: Nikkel és cink eltávolítása ipari szennyvízből membrános eljárással, Műszaki Kémiai Napok 08, Veszprém, április , pp Borbély, G., Nagy, E.: Zn és Ni eltávolítása vizes oldatból komplexképzéssel segített ultraszűréssel, Erdei Ferenc IV. Tudományos Konferencia, Kecskemét, augusztus , Konferenciakiadvány II. kötet, pp

, Borbély, G.: Mass transport through anisotropic membrane layer, Desalination 240 (2009) 54-63 (IF 2009 =2,034) Borbély, G., Nagy, E.

6 PUBLICATIONS Borbély, G., Nagy, E.: Influence of the operating conditions for the membrane separation of Zn 2+ from aqueous solution, 6 th International Conference of PhD Students, Section of Engineering Sciences, University of Miskolc, Hungary, August 2007, pp Borbély, G., Nagy, E.: Különböző paraméterek hatása a Zn eltávolítására membrán alkalmazásával, Műszaki Kémiai Napok 07, Veszprém, április , pp Posters Borbély, G., Nagy, E.: Effect of temperature and transmembrane pressure on the complexation-ultrafiltration, I International Interdisciplinary Technical Conference of Young Scientists InterTech 2008, Poznań, IV 2008, Proceedings pp & CD-ROM Borbély, G., Nagy, E.: Heavy metal removing from industrial wastewater by complexation-membrane filtration process, PERMEA 2007, Siófok, Hungary, 2-6. September, 2007, Book of Abstracts p. 147 & CD-ROM (Abstract and Fulltext) Hegedűs, I., Borbély, G., Kovács, S., Nagy, E.: Synthesis and Industrial Applications of PAMAM dendrimers, 1 st European Chemistry Congress, August 2006, Budapest, Hungary Borbély, G., Nagy, E.: Nehézfémek kinyerése vizes oldatból komplexképzéssel segített membránszűréssel, Műszaki Kémiai Napok 06, Veszprém, április , pp Other publications Articles Jones, H., Visoottiviseth, P., Bux, M. K., Földényi, R., Kováts, N., Borbély, G., Galbács, Z.: Case Reports: Arsenic pollution in Thailand, Bangladesh, and Hungary, Reviews of Environmental Contamination and Toxicology 197 (2008) (IF 2008 =3,321) (Citations until June 2011: 3) 6

Miskolc, Hungary, 12-18. August 2007, pp. 13-20 Borbély, G., Nagy, E.: Különböző paraméterek hatása a Zn eltávolítására membrán alkalmazásával, Műszaki Kémiai Napok 07, Veszprém, 2007. április 25-27.

7 PUBLICATIONS Paulovits, G., Borbély, G., G. Tóth, L., Staszny, Á.: A balatoni halállomány szaporodásának és ívási körülményeinek módosulásai a vízszintváltozás hatására, Acta Agraria Kaposváriensis (2007) Vol. 11 No. 2, 1-12 & CD-ROM Kováts, N., Császár, G., Borbély, G., Rafaey, M.: Reprodukció-gátlás vizuális értékelése ökotoxikológiai tesztekben, Acta Agraria Kaposváriensis (2007) Vol. 11 No. 2, & CD- ROM Borbély, G., Kováts, N., Gajári, J.: A székesfehérvári Sós-tó rekonstrukciót megelőző üledékszennyezettségi vizsgálata, Hidrológiai Közlöny (2006) 86. évf. 2. sz., pp Kováts, N., Borbély, G., Magyar, I., Szép, Zs., Paulovits, G., Pomogyi, P.: Az üledék-toxicitás térbeli eloszlásának vizsgálata a Kis-Balaton Vízminőségvédelmi Rendszer II. ütemének területén, Acta Agraria Kaposváriensis (2006) Vol. 10 No. 1, Kováts, N., Borbély, G., Magyar, I., Szép, Zs., Paulovits, G., Pomogyi, P.: Kis-Balaton védi a nagy Balatont, Térinformatika, 2005/5 augusztus, pp Kováts, N., Borbély, G., Magyar, I., Szép, Zs., Paulovits, G., Pomogyi, P.: Interpretation of spatial distribution of sediment toxicity data, Journal of Hungarian Geomathematics Vol. 2 (2004) Lectures: 7/11 db Paulovits, G., Borbély, G., G. Tóth, L., Kováts, N.: Effects of water level fluctuation on reproduction and spawning habits of fish species in Lake Balaton, Environmental Engineering and Management Journal, September/October 2007 Vol.6 No.5 Proceedings of the 4 th International Conference of Environmental Engineering and Management, ICEEM/04, September 12-15, 2007, Iaşi, Romania, pp (IF 2009 = 0,885 korábban nem rendelkezett IF-ral) (Citations until June 2011: 1) Posters: 3 Scientific report: 1 This work was supported by the Hungarian Scientific Research Fund under Grants OTKA 63615/

, Borbély, G., Rafaey, M.: Reprodukció-gátlás vizuális értékelése ökotoxikológiai tesztekben, Acta Agraria Kaposváriensis (2007) Vol. 11 No. 2, 21-25 & CD- ROM Borbély, G., Kováts, N., Gajári, J.

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