Desalination 167 (2004) 369376

Transport coefficients and cadmium salt rejection in nanofiltration membrane

Guy Tiama Ballet, Lassaad Gzara, Amor Hafiane, M. Dhahbi*
Laboratoire Eau et Technologies Membranaires, INRST, BP 95, Hammam-Lif 2050, Tunisie Tel +216 (71) 430044 ; Fax +216 (71) 430934; e-mail: mahmoudd@inrst.rnrt.tn

Received 11 March 2004; accepted 19 March 2004

Abstract Cadmium is one of the main toxic pollutants generated by industrial activities. Many methods have been used to remove cadmium from wastewater issued from these industries. In the present study removal of cadmium Cd(II) ions from aqueous streams was investigated through a nanofiltration membrane process. The retention was studied as a function of the counter-ions, the ionic force and pH. The transport through the TFCS membrane was described by irreversible thermodynamics. The well-known Speigler-Kedem model was applied in order to deter-mine phenomenological parameters and Ps respectively, the reflection coefficient of the membrane and the solute permeability of ions. The convective and diffusive parts of the mass transfer were quantified. Keywords: Nanofiltration; Cadmium removal; Charge exclusion; Phenomenological parameters; Speigler-Kedem model

1. Introduction Cadmium is one of the main toxic pollutants characterised by a long environmental persistence and biological half-time that accounts for its bioaccumulation in individuals. Cadmium has
* Corresponding author

the potential to cause kidney, liver and blood damage and the maximum contaminant tolerated (MCL) has been set at nearly 5ppb. Cadmium is released to the environment through a variety of industrial operations. It is an impurity found in zinc, a by-product of mining and electroplating pigment, and plasticizer production contain cadmium. Cadmium makes its way into

Presented at the EuroMed 2004 conference on Desalination Strategies in South Mediterranean Countries: Cooperation between Mediterranean Countries of Europe and the Southern Rim of the Mediterranean. Sponsored by the European Desalination Society and Office National de lEau Potable, Marrakech, Morocco, 30 May2 June, 2004. 0011-9164/04/$ See front matter 2004 Elsevier B.V. All rights reserved

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water supplies as a result of the deterioration of galvanised plumbing, industrial waste or fertiliser contamination. Cadmium can be removed from wastewater by conventional processes such as coagulation/ filtration, ion exchange, lime softening or by membrane processing, like reverse osmosis (RO), electrodialysis and supported liquid membrane [1]. Nanofiltration was used in softening water, dye recovery, salt removal and wastewater treatment [3]. Nanofiltration, which is a new class of membrane processing can be used when it is not necessary to remove total salt. Compared to RO, nanofiltration has a better selectivity for multivalent and higher flux. This work deals with the recovery of cadmium by nanofiltration in aqueous streams. The retention was investigated as a function of some key parameters such as ionic force, pH and the nature of anions. The Speigler-Kedem model was used to calculate the phenomenological parameters and Ps respectively, the reflection coefficient of the membrane and solute permeability.

Fig. 1. Schematics of the experimental nanofiltration system.

2.3. Nanofiltration The permeations were conducted using a laboratory scale membrane unit P-28 from CMCelfa. A schematic diagram of the apparatus is shown in Fig. 1. Each experiment consists of a permeation of a 500ml of solute at a fixed pressure. No more than 50 ml was collected in any experiment. The permeate obtained at steady state was then analyzed. The cross-velocity applied was 1 m/s, the temperature maintained at 30C and the pressure varied from 311 bars. The permeate flux was calculated by measuring the time corresponding to 10 ml permeate volume. Since the polarization concentration was neglected according to experimental conditions, the cadmium retention rate was calculated as:
Cp R = 1 .100 Cf

2. Materials and methods 2.1. The nanofiltration membrane The membrane tested was a flat sheet aromatic polyamide thin-film denoted TFCS from the fluid system. The membrane was soaked in water for 24 h in order to eliminate conservation products. Then pure water permeability was determined. 2.2. Chemicals Cadmium salts CdSO4, Cd(NO3)2, CdCl2 and sodium salts NaCl, NaNO3 and Na2SO4 were provided respectively from Merck and Aldrich. They were used as received. The purity of all the salts was over 98%. Solutions were prepared with ultrapure water produced by Milli-Q Gradient unit (Millipore).

where Cp and Cf were respectively the solute concentration in the permeate and in the feed solution. 2.4. Analytical methods The concentration of cadmium was measured by conductivity in single solute systems and by atomic absorption spectrophotometry

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(analytiKjna AAS Vario 6) in the mixture systems. The pH was measured by an ionometer Consort C832. 2.5. Transport equations The transport of the solute through NF membranes can be described by irreversible thermodynamics where the membrane is considered as a black box. Kedem and Katchalsky [4] proposed the relation of the volume flux Jv and the solute flux Js through a membrane in the following equations:
Jv = Lp (P ) Js = PsC + (1 )CJv

derived by Pusch [5] from the Kedem-Katchalsky model.

1 1 LD 1 Lp. 1 = A1 + A2 . = + 2 . R Lp Jv .Jv (5)

(1) (2)

The fluxes are related to three membrane parameters , Ps and Lp, reflection coefficient, solute permeability and pure water permeability respectively. As can be seen in Eq. (2) the solute flux is the sum of diffusive and convective terms. Solute transport by convection takes place because of an applied pressure gradient across the membrane. A concentration difference on both sides of the membrane causes diffusive transport. Speigler and Kedem used the above equations and obtained the expression of the rejection rate of the solute related to hydrodynamic flux:
Robs = (1 F ) (1 F )

where LD represent the osmotic permeability coefficient. Plotting the experimental values of (1/R) vs. (1/Jv) should confirm the relationship and the intercept permit to calculate . The Speigler-Kedem approach was usually applied when there was no electrostatic interaction between membrane and solute. This is the case when the membrane is uncharged such as RO membrane or when the solute is neutral (organic compounds). Many authors [6,7,8] used this model in retention of electrolyte with an NF membrane that is charged, the parameters and Ps depend on the membrane effective charge and on the concentration of feed solute solution. The mass transfer of a solute through an NF membrane can be described by the following approximate equation
Cp Jv = Jdiff + JvCconv

(6)

where Jv is the solvent flux, Jdiff the solute flux due to diffusion and Cconv is the solute concentration due to convection. The above equation can be rearranged as:
Cp = Jdiff + Cconv Jv (7)

(3)

(1 ) F = exp Jv Ps

(4)

From Cp vs. the reverse of permeate flux (1/Jv) each part of solute mass transfer (diffusion and convection) was determinate. 3. Results and discussions 3.1. Membrane permeability and selectivity Before the cadmium salts retention experiments, we measured the permeability membrane to water at 30C. As shown in Fig. 2 the

Robs is the observed rejection and Jv the water flux. It can be seen that the rejection rate increases with increasing water flux and reaches at infinite volume flux a limiting value of . The values of and Ps were obtained from the experimental data by best-fit method. The parameter was also determined by using Eq. (5)

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Fig. 2. Water flux as a function of applied pressure at T = 30C.

membrane respect Darcy law and the mean value of Lp was 8.57 L/h.m2 bar. This is a typical value of nanofiltration membranes. The permeability measured will be considered as reference to evaluate cleaning procedure, concentration polarisation and fouling.

In Fig. 3 the rejection of three salts, NaCl, Na2SO4 and CdCl2 is plotted against the salt concentration in the feed of the solution. The membrane shows the following salt rejection sequence: R(Na2SO4) >R((NaCl) >R(CdCl2), which is typical of a negatively charged membrane [9]. The observed trends are not in accord with the size of the hydrated ions, thus indicating that Donnan exclusion effect is the predominant mechanism for salt removal by the TFCS NF membrane. It seems that the TFCS membrane has a relatively large pore. In that case the salt rejection is determined by charge effect while for the membrane which was found to have little pore cation bivalent have higher rejection than the monovalent one.[9,10]. In Fig. 4 the rejection of cadmium for the three anions, SO42, Cl and NO3 is plotted against the permeate flux. The membrane shows the following salt rejection sequence: R(CdSO4) > R(CdCl2) > R(CdNO3)2. Since the NF membrane is negatively charged, the sulphate anion is excluded more than the monovalent anion and then enhances the rejection of cadmium cation. The nitrate ions are less hydrated than

Fig. 3. Variation of rejection rates of salts, Cfeed = 103 mol.L1, vs. permeate flux.

Fig. 4. Associated anion effect on cadmium salt rejection as a function of permeate flux, Cfeed = 103 mol.L1, T =30C.

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Fig. 5. Measured and calculated inverse rejection of cadmium salt as a function of the inverse permeate flux, Cfeed = 103 mol.L1, T =30C.

mity with Eq. (7). From the slope we obtained Jdiff the diffusion part of the mass transfer. The intercept corresponds to the convective contribution (Cconv). Table 1 summarized the calculated parameters. Ps values seem to be highly dependent on the type of anion of the electrolyte solute. Strongly solvated anions (SO42) lead to lower values of Ps in comparison with the less solvated anions (NO3). The reflection coefficient is higher for sulphate than monovalent anions. We noted also, that the diffusion part of flux decreases with increasing hydratation energy. The convective contribution was nearly the same for monovalent anions and lower for sulphate. Cconv was higher for cadmium than sodium salts. 3.2. Effect of the ionic strength on the retention of cadmium The effect of the concentration of the electrolyte was investigated as shown in Fig 7 and summarised in Table 2. The experimental results show that at (NaNO3) = 102mol.L1 the cadmium retention increases. Increasing the sodium cations of the solution involves the formation of a screen which gradually neutralizes the negative charge of the membrane. The total charge of the membrane decreases and the retention of the cadmium increases since the electrostatic effects of the membrane become weaker. For
Table 1 Transport coefficients and single salt flux distribution, Cfeed = 103mol.L1, T = 30C Ps (L/h.m2) 12.79 8.16 1.92 24.06 17.72 8.01 103. Jdiff (mol.h1.m2) 5.9 3.3 0.4 5.8 5.4 3.4 103. Cconv (mol.L1) 0.1 0.1 0.08 0.3 0.3 0.1

chloride ions resulting in less rejection of cadmium associated to nitrate. The hydration energy of SO42, Cl and NO3 are respectively 1047, 325 and 310 KJ/mol1. The theoretical linear relationship of Eq. (5) is shown to be in agreement with experimental finding by Fig. 5 where 1/R is plotted as a function of 1/Jv for different cadmium salts. The solid lines in Fig. 3 and Fig. 4 are values calculated using the Spiegler-Kedem equation with the best fitted and Ps. As illustrated in Fig. 6 the concentration of cadmium in the permeate vs. the reverse of permeate flux, revealed a linear relation in confor-

Fig. 6. Permeate cadmium concentration vs. the reverse of permeate flux for single salts Cd, NO3,2, CdCl2, CdSO4, Cfeed=103 mol.L1, T= 30C.

NaNO3 NaCl Na2SO4 Cd(NO3)2 CdCl2 CdSO4

0.910 0.860 0.916 0.746 0.785 0.882

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higher support electrolyte, cadmium retentions were rather low. These results can be linked to the dependence of the effective charge density of the membrane on the electrolyte concentrations [11,12,13]. The charge is not constant but depends very much on the salt and on the concentration. The decrease of the retention can be ascribed to the adsorption of the nitrate ions on the membrane materiel that lead to a more negative membrane at higher electrolyte concentrations. 3.3. Effect of pH on cadmium removal Fig. 8A shows the retention of cadmium salts at various pH values .The pH was adjusted by the addition of HCl and NaOH. The concentration of the salt was fixed at 103 mol.L1 and the transmembranaire pression was fixed at 9 bar. The effect of the pH on the rejection has been studied by many authors. It depends especi-

Fig. 7. Cadmium rejection at different NaNO3 feed concentration as a function of permeate water flux, Cd, NO3,2,feed = 103 mol.L1, T = 30C.

Table 2 Transport coefficients and mixture salt flux distribution at T = 30C [CdCl2] = 1mmol.L1 [NaCl] (mmol.L1) 0.0001 0.001 0.05 0.1 [NaNO3] (mmol.L1) 0.01 0.1 0.5 [NaSO4] (mmol.L1) 0.0001 0.001 0.05 0.1 Ps (L/h.m2) 17.72 29.60 21.96 21.79 37.13 103. Jdiff (mol.h1.m2) 103. Cconv (mol.L1)

0.785 0.905 0.810 0.870 0.815

5.4 11.6 8.2 8.4 6.7

0.3 0.2 0.2 0.2 0.3

[Cd(NO3)2] = 1mmol.L1

0.746 0.787 0.734 0.689

24.06 14.85 17.91 17.45

5.8 4.7 4.4 3.2

0.3 0.2 0.3 0.3

[CdSO4] = 1mmol.L1

0.882 0.874 0.878 0.863 0.767

8.01 8.65 10.67 10.30 8.47

3.4 3.9 5.0 1.9 3.4

0.1 0.2 0.2 0.2 0.3

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Fig. 8A. Retention of cadmium salts at various pH values.

Fig. 8B. Water flux as a function of pH for cadmium salts at T = 30C.

ally on the nature of the surface ionic groups of membrane [14,15,16] and changes on the speciation on solution [8,17]. The charge of a membrane varies with the pH around its isoelectric point. The electrostatic effect of a membrane, which affects the retention factor and permeate flux, varies therefore with the pH. The TFCS membrane used in this study is a polyamide active layer. For low pH value the membrane is charged positive corresponding to the protoned species A-NH3+. At pH above isoelectric point the membrane is charged negative, corresponding to the anion of the carboxylic group R-COO. At an acidic pH the increase of the cadmium retention rate can be attributed then to the repulsion between cadmium Cd2+ and the positive charge of the membrane. The minimum rejection obtained at pH5 corresponds to the isoelectric point. Increasing retention below isoelectric pH is attributed to repulsion between the nitrate anion and negative charge of the membrane. On the other hand the permeate flux, as can be seen in Fig. 8B, decreases when the pH increases. The pH dependence of the flux shows a more complex pattern since the flux and rejection are not interrelated as in process-driven processes like NF and RO. Accord-

ing to Freger et al. [18] and Capelle et al. [16] the decrease of membrane permeability is due to shrinking of the skin layer due to differences of hydratation of ionised groups of the membrane. 4. Conclusion When treating a salt solution with a TFCS NF membrane, it was shown that the sodium salts retention sequence is R(Na2SO4) > R(NaCl) > R(CdCl2) and cadmium salts R(CdSO4) > R(CdCl2) > R(CdNO3)2. The data indicate that the membrane is negatively charged, and the Donnan exclusion mechanism seems to play an important role. We have used the Speigler-Kedem model. The results of the application of this model show that there was a good agreement between theoretical and experimental curves. Phenomenological parameters and Ps were calculated. They depend highly on the type of anion of the electrolyte solute. We concluded also, that the rejection of cadmium and flux depends on the pH. The results show that the NF is a very promising method of the treatment of acidic stream charged with cadmium.

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