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Water Research 38 (2004) 593600

Metal ions removal from wastewater or washing water from contaminated soil by ultraltrationcomplexation
Raffaele Molinari*, Saverio Gallo, Pietro Argurio
Department of Chemical and Materials Engineering, University of Calabria, Via P. Bucci, Cubo 45/A, Rende (CS) I-87030, Italy Received 18 September 2002; received in revised form 10 September 2003; accepted 14 October 2003

Abstract In the present paper a process for removal of ions from wastewater or from washing water of contaminated soil by using the weakly basic water-soluble polymer polyethylenimine (PEI) as chelating agent and the Cu2+ ion as model in combination with an ultraltration process was investigated. The complexing agent was preliminarily tested to establish the best operative conditions of the process. Next, ultraltration tests by using ve different membranes were realised to check membrane performance like ux and rejection. Finally, the possibility for recovering and recycling the polymer was tested in order to obtain an economically sustainable process. Obtained results showed that complexation conditions depends on pH: indeed, at a pH>6 PEICu2+ complexes are formed, while at pHo3 the decomplexation reaction takes place. Saturation condition is 0.333 mg Cu2+/mg PEI, meaning a ratio PEI/Cu2+=3 (w/w). UF tests showed good results using the PAN 40 kDa membrane reaching an average copper concentration in the permeate of 2 mg/l and a ux of 135.4 and 156.5 l/h.m2 at 2 and 4 bar, respectively. Metal rejection, permeate ow rate, and possibility to regenerating and recycling the polymer makes the polymer-assisted ultraltration process (PAUF) very interesting for metal ion removal from waters. r 2003 Elsevier Ltd. All rights reserved.
Keywords: Ultraltrationcomplexation; Polymer-assisted ultraltration; Cu (II) ion removal from water; Wastewater treatment; Soil remediation

1. Introduction Water treatment plays an important role in the wide subject of pollution problems solving and represents today one of the most important elds of study. In fact, a rational hydrologic resource management is necessary because of increased worlds demand of water, particularly in these last years owing to lacking of this resource. Other than in the Mediterranean Middle-East, it is known that in some regions of Southern Italy the service of water distribution is not continuous, and this phenomenon is happening also in Northern Italy because of anomalous climatic changes, especially in
*Corresponding author. Tel.: +39-0984-496-699; fax: +390984-496-655. E-mail address: r.molinari@unical.it (R. Molinari).

winter. In this situation some textile industries of Northern Italy, which request big water consumption, have taken into account to review their operational system, treating and recycling wastewater, in order to nd a remedy for unoptimistic prevision for the future. So, the approach of a pondered water consumption and its purication and recycling has become very important as stated also by the European Commission (Council Directive 96/61/EC) for achieving integrated prevention and control of pollution through the application of Best Available Techniques (BAT) to obtain a high level of protection of the environment as a whole. The engineered systems associated with wastewater reclamation, recycling and reuse can play an important role in the natural hydrologic cycle. An overview of the cycling of water from surface and groundwater resources to water treatment facilities, irrigation,

0043-1354/$ - see front matter r 2003 Elsevier Ltd. All rights reserved. doi:10.1016/j.watres.2003.10.024

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municipal, and industrial applications, and to wastewater reclamation and reuse facilities is described elsewhere [1]. This scheme takes into account that in most cases the reuse of wastewater can produce water for non-potable applications. Metal contamination is a dangerous cause of water pollution: indeed, e.g., Cu2+ ions are essential nutrients, but when people are exposed to Cu levels of above 1.3 mg/l for short period of time, stomach and intestinal problems occur. Long-term exposure to Cu2+ leads to kidney and liver damage. Separation processes for metal ions removal from aqueous solutions are a major industrial activity covering processes ranging from production of potable water, to leaching and recovery of metals from contaminated soil or from ores, to detoxication of process water and wastewater, also for water recycling and reuse. A variety of separation processes for metal ions have been developed up-to-date for industrial need: e.g., in water softening (Mg2+, Ca2+ removal) the rst studied traditional process is the lime-soda method, which causes a precipitation of hardness [2]. This technique, like the others, consisting practically in an induced sedimentation, produce water within international health standards, but has two important drawbacks: they produce big amount of sludge [35] containing residual of reagents used, which result in a pollution problem, and treated water may contain residual coagulants if the process is not correctly controlled or operated [6]. Another important method for metal removal from polluted water is the ion exchange process, which produces water within international quality standards, but it is not a continuous process, because of regeneration necessity [2]. Membrane processes play today an important role in the eld of wastewater purication and reuse. This well consolidated technology is very interesting because of low operative costs, conceptual simplicity, modularity, and optimal quality of treated water. Furthermore, the use of new materials permits to obtain very resistant membranes, both on chemical and mechanical point of view, for various applications [68]. For separating species with ionic dimensions, reverse osmosis membranes are required but they will result in high operative costs, low permeate ow rate and low ions selectivity. In order to overcome these problems, the ultraltrationcomplexation, also named polymerassisted ultraltration (PAUF), was introduced. Ultraltration can be used for removal of trace metals from aqueous streams, provided that these metals are primarily bound to water-soluble polymers [9]. The unbound metals pass through the membrane, whereas the polymers and their complexes are retained. This PAUF process can be applied for various purposes such as the treatment of waste efuents, groundwater and seawater. The advantages of this method are the

low-energy requirements involved in the ultraltration and the high removal efciency because of effective binding [10]. Several research efforts have been carried out to study the applicability of PAUF in metal removal from water of various origins. Pivot of the study are the consideration on technical and economical feasibility, to respect the limits xed by pollution laws: Juang and Shiau [10] studied the metal removal from aqueous solutions using chitosan-enhanced membrane ltration, and in other two works [11,12] the authors considered the problem of technical feasibility on the use of PAUF for brackish water softening, or wastewater treatment by using three weakly basic, water-soluble polymers like chitosan, polyethylenimine (PEI), poly(diallyl dimethylammonium chloride) to remove ions like Ca2+, Mg2+, Na+, K+, Cu2+ and Zn2+. Tabatabai et al. [13] studied the feasibility of PAUF for water softening in the removal of Ca2+ and Mg2+ ions from hard water by using the polymer sodium polystyrene sulfonate (PSS). They demonstrated (with some economical considerations) that the PSS needs to be recovered from the retentate and regenerated appropriately, to be reused. Steenkamp et al. [14] considered the Copper (II) removal from polluted water with alumina/chitosan composite membrane, giving attention prevalently to the problems related to the synthesis of their composite support and to the factors which inuence metal removal efciency, like pore radii variation with temperature and powder mixtures used, and chitosan coating thickness. Vieira et al. [15] studied an application of PAUF in metal removal from pulp and paper industry wastewater. All the cited works consider the PAUF and its applicability in metal removal from water, but they use polymers that in their complexing action to complex ions of interest, release other ions, like Na+ or H+, which results in a potentially modication of water characteristic, or they do not consider the use of the polymers at their maximum complexation ability, saturation conditions and chemistry of polymermetal complexation. In the present work, some results of a study on metallic ions removal from wastewater and from washing water of contaminated soils by means of PAUF are reported. The determination of complexation, de-complexation and chemical conditions of saturation are discussed; the results of ultraltration tests on ve different membranes realised by using the weakly basic poly(ethylenimine) as the selective polymer and the copper as model ion are reported. This polymer has the advantage of no release of other ions in treated water because it does not work by means of ionic exchange reaction, but it complexes also counter-ions to form neutral complexes. A criterion to nd the membrane with the best performance is also reported.

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2. Materials and methods Copper sulphate penta-hydrate (CuSO4 5H2O) from Fluka Chemika (purity>99%) was used for preparing Cu2+ solutions. Poly(ethylenimine) 50% wt solution in water from Sigma-Aldrich (MW 10,000 and 60,000) was the polymer utilised. Other chemicals used were H2SO4 (purity 9597%) purchased by Riedel de Haen and NaOH (purity>99%) from Merck. The used ultraltration plant (Fig. 1) permitted to test simultaneously ve different UF membranes. It was constituted by three sections: electric panel, to control plant working; alimentation section, constituted by a feed reservoir of 25 l, in which a cooling coil was immersed with a thermostat and a level control sound; ultraltration section, with a centrifugal pump LOWARA CKM 70/34 that generates the ow (max ow rate=1.5 m3/h; max pressure=4.5 bar), ve steel plane cells (useful membrane surface area 14.18 cm2) equipped with manometers and ow meters to control operative transmembrane pressures and tangential ow rates of the concentrate (retentate). The thermostatic system controlled the operative temperature, resulting isothermal ultraltration runs (t 25 C). The coolant was simply tap water. Before each ultraltration run the membranes were characterised with demineralised water in the same plant, in order to evaluate the relative membrane permeability and the membrane fouling after the ultraltration runs. During this characterisation, operative transmembrane pressure was xed rst at 4 bar to stabilise the compaction, and later it was decreased to 2 bar. Ultraltration tests were carried out setting the operative pressure rst at 2 bar and after increased at 4 bar, because it is known that fouling tendency

increases with transmembrane pressure. The plant was operated in batch mode recycling the ve permeates to feed reservoir. Every 30 min (starting by the time t 0 min) permeates were collected for 2 min and their volumes measured in order to calculate instantaneous ux; they were also analysed to determine copper concentration. Each ultraltration run was stopped (or pressure was changed) when steady state was reached, that means permeate ux and copper concentration were practically constant. The average time to reach the steady state was between 2.5 and 3 h. Permeates collected in the steady-state condition were also submitted to total organic carbon (TOC) measurements, in order to verify if the polymer passed through the membranes. The thermostat LT 100-1, the photometer LASA 100 and the analytical kits LCK 380 and LCK 381 (depending on the concentration of the total carbon estimated in the sample) from Dr. Lange, were used for carrying out TOC measurements. Five different UF membranes were tested measuring retention and water permeate ux. Some of their characteristics are reported in Table 1 where uxes measured with distilled water at 2 and 4 bar are also reported. The retention RTC ; for the target component (TC), was measured by using its denition: RTC 1 CTC;P =CTC;F ; where CTC;P and CTC;F are the concentrations of the TC (Cu2+) in the permeate and in the feed solution, respectively. The other important parameter, the volume permeate ux (J), generally expressed as the volume obtained per unit time (t) and per unit of membrane surface (S), was

Flow meters Pump

Plane cells

Feed reservoir

Retentate header

Feed header

Permeate header

Permeates

Fig. 1. Flowsheet of the ultraltration laboratory plant able to tests simultaneously ve UF membranes.

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596 R. Molinari et al. / Water Research 38 (2004) 593600 Table 1 Some characteristics of the tested UF membranes Membrane type Iris 10 FS 40 PP GR 40 PP Iris 30 PAN 40 Material Polyether sulphone (PES) Fluoride-polypropylene Polysulphone-polypropylene Polyether sulphone (PES) Polyacrylonitrile Cut-off (kDa) 10 40 40 30 40 Producer Tech-Sep Dow Dow Tech-Sep Tech-Sep Water ux (l=h m2 ) (24 bar) 33.8555.00 220.0397.7 220.0444.3 114.2207.3 291.1528.9

measured by the following equation: J V =tS: Determination of copper concentration was carried out by using an analytical kit (Carlo Erba Reagenti), based on a colorimetric reaction and absorbance reading at a 600 nm wavelength. Absorbance reading was performed by using a Recording Spectrophotometer UVVisible 160 A (Shimadzu Corporation-Analytical instruments division). A pH meter (Orion Research IncorporatedExpandable ion Analyzer EA 920) with a combined glass electrode was used for pH measurements.

Fig. 2. Idealised structure of the polymeric complex PEI copper (II) ions.

3. Results and discussion The water-soluble polymer PEI was considered in this preliminary phase of our work. It shows a good afnity for the model ion Cu2+ and has the advantage of no release of counter ions in the treated water with respect to polymers that work with an ion-exchange mechanism. In Fig. 2, the mechanism of PEIcopper interaction is reported [16], where the lone-pair of nitrogen binds the copper according to the acid and base Lewis theory. The mechanism of PEIcopper interaction can be described by the following equilibrium reactions: PEI nH2 O"PEIHn nOH ; n PEI aCu2 "PEICu2a ; a 1 2

where 0pnpn and 0papa with n equal to the number % % % of monomers contained in a single polymeric chain and a representing the maximum complexation ratio of the % polymers with copper ions (a n=4 as showed in the % % idealised structure previously reported). In particular, considering the longer polymeric chain (MW 60 kDa) and considering the monomeric unit CH2CH2NH (MW 43.062 Da) we obtain that n 1393: % Reactions (1) and (2) are competitive for the polymer because, depending on pH conditions, it is able to complex copper ions by means of Eq. (2) or stays in aqueous solution like PEI Hn at low pH incapable to n interact with copper. Measuring the pH of PEI in aqueous solutions, the Keq of Eq. (1) was practically

equal to zero, meaning that this equilibrium reaction is hardly shifted at left. So, the polymer at its natural pH in water stays prevalently as PEI, and not in the form PEI Hn : n First step of this research consisted in the determination of optimal chemical conditions (pH) for copper complexation (bound) and de-complexation (release). The determination of release condition is fundamental for recovering and recycling the binding polymeric agent. Indeed, it should be taken into account that the PAUF process appears to be economically more feasible if the polymer could be regenerated and reused, so that the process should be represented as reported in Fig. 3. Complexation and de-complexation conditions were determined by means of some tests conceptually very similar to LL extraction. They were carried out in isothermal conditions at a temperature of 2571 C by preparing 20 ml of aqueous solutions containing polymer and copper at concentrations respectively of 150 and 50 ppm, and changing the pH. In order to evaluate the inuence of polymer molecular weight on copper complexation, these experiments were realised both with PEI 10,000 and PEI 60,000. To quantify the copper polyethylenimine (CuPEI) complex formation, the spectrophotometric technique was used. By previous scanning of various samples, the peaks of absorbance vs. wavelength showed a maximum absorbance for CuPEI complex in aqueous media at a wavelength of 620 nm. By taking advantage of complex reading at this wavelength whilst no reading was observed for Cu2+ alone, it was possible to establish if the complex was or not formed by simple experiments in test tubes without using the membrane separation process. The complexationdecomplexation process was quantied by plotting

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Polymer make-up Permeate (water to reuse or discharge)
MEMBRANE

597

Metal containing Feed

Complexation
STEP

Retentate

Polymer Regeneration

Recovered Metal solution

Polymer Recycle

Fig. 3. Schematic principle of the PAUF separation process.

100 80 C%
C%

100 80
300/50 150/50 50/50

60 40 20 0 2 4 6 pH 8

60 40 20 0

PEI 60000 PEI 10000

10
(a)

30

60

90

120

150

Copper concentration [mg / l]

120

Fig. 4. CuPEI complex formation C% ABS=ABSmax 100 vs. pH in complexation tests of PEI 10,000 (300, 150 and 50 mg/l) with copper (50 mg/l).
[Cu2+ ]max

80 40 0 0 100 200

the complexation percentage C% ABS=ABSmax 100; where ABSmax is the maximum value of the absorbance obtained from the experiments which corresponds to the maximum amount of complex (100%). Obtained results for PEI 10,000, reported in Fig. 4, show that this polymer is able to complex copper ion at pH 6 or higher, while the decomplexation happens at pHo3 C%o10%: The results of complexation tests with PEI 60,000 are not reported because the obtained data were practically equal to that ones obtained with the smaller chain-polymer. Indeed, the number of single complexes in Fig. 2, [Cu2+(NH)4], depends only on total monomeric units present in the overall polymer chains and not on polymer molecular weight. Similar results were obtained by working at different polymer concentrations (300 and 50 ppm), showing that pH of maximum bonding does not depend also on polymer concentration. These results agree with the chemical mechanism of polymercopper interactions. Indeed, at high pH the complexation reaction (2) takes place. In order to determine the bonding capacity (saturation condition) of PEI (maximum copper amount, e.g. grams, that can be complexed by a xed amount, e.g. 1 g, of polymer), some complexation tests were carried out with a polymer concentration of 150 mg/l (volume=20 ml) and changing copper concentration at a

R2 = 0.9857

300

400

(b)

Polymer concentration [mg/l]

Fig. 5. (a) CuPEI complex formation C% ABS=ABSmax 100 vs. copper concentration (initial PEI concentration= 150 mg/l, pH=6) and (b) determination of the binding capacity of PEI 60,000 (pH=6).

xed pH value (equal to 6). It should be taken into account that one important cost of PAUF process is represented by polymer consumption and its bonding efciency: this justify the convenience to use the polymer at its maximum complexation capacity. Obtained results, reported in Fig. 5a for PEI 10,000 and 60,000, show that maximum copper that can be complexed by 150 mg/l PEI is equal to 50 mg/l, that is 0.333 mg Cu2+/ mg PEI. This value is also conrmed in Fig. 5b for various concentration values of Cu2+ and polymer. The excess of copper remains in solution like hydroxide. In fact, taking into account that the solubility product constant Ksp CuOH2 Cu2 OH 2 1019:9 ; at 25 C, maximum feed pH to avoid copper hydroxide formation

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300 Flux [l/h*m ]

and precipitation is approximately 5.6 for an aqueous concentration of copper equal to 50 mg/l, while in these complexation tests operative pH was 6. Important result of the complexation tests is the identical binding capacity obtained operating with PEI 10,000 and 60,000. This is a consequence of the concentration unit used: in fact, PEI binding capacity depends only on the number of complexation sites that are the same for a same weight amount of polymer. Obviously, this is not applicable when referring to molar concentration (polymer moles/litres of solution). Adding the previous consideration on identical operative pHs and binding capacity for the two size of PEI used and taking into account that in PAUF the complexation step is followed by a membrane ltration, the PEI 60,000 is more interesting than the smaller one, permitting the use of membranes with bigger pores for obtaining low operating costs. From the above results the operative conditions for ultraltration tests were ratio PEI/Cu2+=3(w/w) and pH=6. Ultraltration tests were carried out using ve different membranes (see Table 1), two operative trans-membrane pressures (2 and 4 bar), pH approximately equal to 6 and three different weight concentrations of PEI and Cu2+ (150/50, 375/125, 600/200). Working at increasing PEI/Cu2+ concentrations permitted to simulate the increase of retentate concentration in a hypothetical industrial plant where the permeate free of metals is withdrawn using the PAUF technique. We used this approach because of the small volume of permeate collected during an ultraltration run (as a consequence of the small useful membrane surface area); indeed, the increase of concentration in the retentate by a direct withdrawn of permeate would require a lot of working hours of the laboratory plant. Each test, at different copper and polymer concentrations, was carried out by starting with a new set of the ve membranes: in fact, to realise a process with an industrial applicability it is certainly important to evaluate membrane fouling, regeneration and reuse, but goal of our preliminary tests was to evaluate and compare membrane performances at increasing retentate concentrations, which practically results in an increase of membrane fouling and/or concentration polarisation. Obtained results, summarised in Figs. 68, show that increasing copper and then polymer concentration (ratio PEI/Cu2+=3 xed) in the retentate, the separation efciency (R%) decreases, that will results in a copper and polymer concentrations increase in the permeate and a little decrease of permeate ux. By increasing polymer concentration in the retentate (Fig. 8), rejection rst decreases, because of fouling, but increasing retentate concentration this tendency changes, because of the formation of a selective dynamic layer (by

200

100

Iris 10 kDa PAN 40 kDa DOW GR 40 DOW FS 40 PP Iris 30 kDa

0 150 300 450 600 Polymer concentration in the retentate [mg/ l]

Fig. 6. Comparison of ux through the ve membranes by increasing polymer concentration (values at steady state, P 2 bar, PEI=Cu2 3).

10 8 6 4 2 0 150
Iris 10 kDa PAN 40 kDa DOW GR 40 DOW FS 40 PP Iris 30 kDa

Copper Cp [mg/l]

300 450 Polymer concentration in the retentate [mg / l]

600

Fig. 7. Comparison of copper concentration in the permeate (Cp ) for the ve membranes by increasing polymer concentration (values at steady state, P 2 bar, PEI=Cu2 3).

100.0

R%

Iris 10 kDa

98.0

PAN 40 kDa DOW GR 40 DOW FS 40 PP Iris 30 kDa

96.0 150

300

450

600

Polymer concentration in the retentate [mg/l]

Fig. 8. Comparison of copper rejections (R%) for the ve membranes by increasing polymer concentration (values at steady state, P 2 bar, PEI=Cu2 3).

concentration polarisation) that improves the separation. This causes a little permeate ux decrease too, because of mass transfer resistance increase. The inspection of the membranes at the end of each run permitted to conrm cake formation: in fact, each used membrane presented a thin layer on its ltering surface. This cake was cerulean, practically the colour of the polymercopper complex, but it not gave too much intensity of the fouling after simple washings with tap

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water. Indeed, the initial water permeate ux obtained with demineralised water (see Table 1, column at 2 bar) was about the same of that one obtained in operating conditions (see Fig. 6). It should be taken into account that an optimal PAUF processes should generate high permeate ux (JP ) with low copper concentration (Cp ). So, in order to compare membrane performances, an appropriate parameter Jp =Cp was introduced. This parameter has no dimensional signicance, but it answers to the previous requirements to optimise PAUF processes. Data of our optimisation parameter Jp =Cp ; reported in Figs. 9 and 10 at 2 and 4 bar, respectively, show that the PAN 40 kDa membrane gives the best combination of the two parameters. Furthermore, it is better operating at P 2 bar rather than at 4 bar as the higher Jp =Cp value shows. The economical feasibility of PAUF process depends also on polymer regeneration, so some UF tests were carried out in the laboratory plant, with a set of ve membrane previously used and with the following operative conditions: PEI=150 ppm; Cu=50 ppm; pH=3 (de-complexation conditions). The permeates withdrawn at established time were analysed to determine copper and TOC concentrations: obtained data
800
Iris 10 kDa

showed that all the copper passed through the membrane, while the polymer remained in the retentate (rejection of 95% with PAN 40 kDa membrane), that means a good possibility of polymer regeneration, recovery and reuse.

4. Conclusions The described study on polymer assisted ultraltration shows: (i) the importance to use optimal chemical conditions to obtain a maximum binding capacity of the polymer; (ii) the role of different types of UF membranes in order to employ this process in metal ions removal from various types of wastewaters. In the case of Cu2+ removal by its complexation with PEI best results were obtained for the membrane PAN 40 kDa, reaching an average copper concentration in the permeate of 2 mg/l and a ux of 135.4 and 156.5 l/h.m2 at 2 and 4 bar, respectively. The obtained results show that use of PAUF process with PEI does not reach a complete removal of the metal, but can reach the objective of the purication process that is to decrease metal concentration down a certain value required by reuse or xed by water laws for discharge.

Acknowledgements The authors wish to thank the National Interuniversity Consortium Chemistry for the Environment (INCA) which partially supported this work within the Sisifo Project and the National INCA Plane Remediation of contaminated soil.

600 (Jp / Cp)

PAN 40 kDa DOW GR 40 Iris 30 kDa

400

DOW FS 40 PP

200

0 150

300 450 Polymer concentration in the retentate [mg / l]

600

References
[1] Asano T, Levine D. Wastewater reclamation, recycling and reuse: past, present and future. Water Sci Technol 1996;33(1011):114. [2] Brisi C, editor. Chimica applicata. Torino: Libreria Editrice Universitaria Levrotto & Bella; 1990. [3] Kruithof JC, Kopper HMM. Experiences with groundwater treatment and disposal of the eliminated substances in the Netherlands. Aqua 1989;38:20716. [4] Drioli E, Molinari R. Operazioni a membrana nel trattamento di acqua civili ed industriali, 3 Convegno di Terra dOtranto: LAcqua fattore di crescita del territorio: qualit" , trattamento, riuso e gestione, Lecce 2526 a Maggio 1995. p. 271. [5] Molinari R, Grande C. In: Palmisano L, editor. Processi innovativi a Membrana nel Trattamento delle Acque. Abbiategrasso, MI: Edizioni spiegel; 2000. p. 15986 [Chapter 9, ISBN 88-7660-159-7]. [6] Scott K. Handbook of industrial membranes. Oxford: Elsevier Advanced Technology; 1995.

Fig. 9. Comparison of Jp =Cp for the ve membranes by increasing polymer concentration (values at steady state, P 2 bar, PEI=Cu2 3).

600
Iris 10 kDa PAN 40 kDa DOW GR 40 Iris 30 kDa DOW FS 40 PP

(Jp /Cp)

400

200

0 150

300 450 Polymer concentration in the retentate [mg /l]

600

Fig. 10. Comparison of Jp =Cp for the ve membranes by increasing polymer concentration (values at steady state, P 4 bar, PEI=Cu2 3).

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600 R. Molinari et al. / Water Research 38 (2004) 593600 [12] Juang RS, Chiou CH. Feasibility of the use of polymerassisted membrane ltration for brackish water softening. J Membr Sci 2001;187:11927. [13] Tabatabai A, Scamehorn JF, Christian SD. Economic feasibility study of polyelectrolyte-enhanced ultraltration (PEUF) for water softening. J Membr Sci 1995;100: 193207. [14] Steenkamp GC, Keizer K, Neomagus HWJP, Krieg H. Copper (II) removal from polluted water with alumina/ chitosan composite membranes. J Membr Sci 2002;197: 14756. [15] Vieira M, Tavares CR, Bergamasco R, Petrus JCC. Application of ultraltrationcomplexation process for metal removal from pulp and paper industry wastewater. J Membr Sci 2001;194:2736. [16] Geckeler KE, Volchek K. Removal of hazardous substances from water using ultraltration in conjunction with soluble polymers. Environ Sci Technol 1996;30(3):72534. [7] Aptel P, Vial D. Membranes in water treatment and potabilization. In: Haber C, Drioli E, editors. Proceedings of the Membrane Separation Processes. Brazil: Rio de Janeiro; 1992. p. 291. [8] Mulder M. Basic principles of membrane technology. Dordrecht, Holland: Kluwer Academy Publishers; 1991. [9] Rumeau M, Persin F, Sciers V, Persin M, Sarrazin J. Separation by coupling ultraltration and complexation of metallic species with industrial water soluble polymers. Application for removal or concentration of metallic cations. J Membr Sci 1992;73:31322. [10] Juang RS, Shiau RC. Metal removal from aqueous solutions using chitosan-enhanced membrane ltration. J Membr Sci 2000;165:15967. [11] Juang RS, Chiou CH. Ultraltration rejection of dissolved ions using various weakly basic water-soluble polymers. J Membr Sci 2000;177:20714.