DESALINATION

Desalination 165 (2004) 155-160

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Treatment of the tannery effluents from a plant near Algiers by

nanofiltration (NF): experimental results and modeling
M. Taleb Ahmed a, S. Tahab*, T. Chaabane a, J. Cabon b, R. MaachP, G. Dorange b
"USTHB/FGM_GP/GE, bLaboratoire de Chiraie des Eaux et de l'Environnement, ENSCR,
avenue du Gdn&al Leclerc, 35700 Rennes, France
TeL + 33 (2) 23238015; Fax +33 (2) 23238199; email: samirtaha@ense-rennes.fr

Received 23 February 2004; accepted 3 March 2004

Abstract

The treatment of a rejection of tannery effluent was carried out on an organic nanofiltration membrane. The
rejection was recovered from a leather manufacturing plant in the area of Algiers (Rouiba). The effluent of the bath
of tanning and liming charged with chromium ions was the subject of this study. In the case of synthetic solutions,
the experimental variations of the retention ranged from 94-99.9% depending on initial feed concentration. For the
tanning bath, the results indicated that chromium retentions of 60 and 30% were observed respectively in acid and
basic medium. In acid medium, the rejection of the bath of liming has generated a retention of 15%. The use of the
model of Nakao et al. [1] based on the extended modified Nernst Planck equation enabled us to compare the
theoretical retention of chromium ions with the experimental results and to calculate the membrane pore radius.

Keywords: Nanofiltration; Tannery; Chromium; Model; Pore radius

1. Introduction

Tanneries and textile industries are very water

consuming, generate wastewater with of organic
matter and heavy metals in particular chromium
salts and sulfides [2,3]. These effluents cannot be
rejected without pretreatment in the rivers because
o f their toxicity with respect to fauna and the water
*Corresponding author.

flora. As they are not biodegradable, this rejected

water makes the conventional treatment methods
less effective. Since the effluents are discharged
on the Mediterranean coast, they can generate
pollution in various forms. The maximum capacity
of treatment o f the factory [4,5] is 5500 skins/d
transformed into finished leather. In 2001, the
number of treated skins was 3700 skins/d. Thus,
the membrane processes [6-10] present a better

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 l'Eau Potable, Marrakech, Morocco, 30 May--2June, 2004.
0011-9164/04/$- See front matter 2004 Elsevier B.V. All rights reserved
doi; 10.1016/j.desal.2004.06.018

156

M. Taleb Ahmed et al. ~Desalination 165 (2004) 155-160

adapted alternative for this type of effluent. In the

present work, we were interested in the treatment
by nanofiltration of synthetic and industrial solutions containing chromium salts. An organic membrane of negative total charge was used to carry
out nanofiltration of this water. The performance
of this membrane were determined by measurement of the following parameters: pH, electric
conductivity, chromium and sulfide concentrations. The factors of selectivity in nanofiltration
are dependent mainly on the steric effect related
to the size of the membrane pores the electrostatic
effect related to the fixed charged groups and the
effect of solubilization due to the hydration and
swelling capacity [7,8]. Therefore, knowledge of
the characteristics of a NF process can allow for
predictions of the separation behavior of the
membrane [9-12]. In this work, we investigated
the separation behavior and determined the
efficiency of chromium retention and membrane
pore radius using the model ofNakao et al. [1].

2. Theoretical approach
One of the most fundamental ways to predict
the transport through a nanofiltration membrane
is by means of a model using the extended NemstPlanck equation [11-14]. The extended NemstPlanck equation is an equation of transfer (1)
taking into account all the phenomena intervening
in the transport of an ion through a membrane. It
was proposed by Dresner and Schl6gl [ 11] in the
form:
J , = - O ~ dC'
dy

Z~FC'D' d~t t-~3~C~Jv

RT
dy

(1)

By considering that the membrane is a succession of ideal membrane elements and infinitesimal
thickness in balance with diluted and ideal
solutions, Spiegler and Kedem [ 16] have proposed
Eq. (2) giving local flow of solvent.

drI,1
---~y)

By defining the solvent permeability of the

membrane as equal to L# = Pv/Ay, J e a n be put in
the form:

(3)
The integration ofJ~ Eq. (1), on the thickness
of the membrane, gives:
R. _ (1-Fi) 0 ,
1-o,F,
in which the constant F is given by:
F~ =exp(

1-(Y;J v]

(5)

Nakao et al. [1] have proposed to directly

determine the parameters % or o and P; or Ps
relating to the equation of Spiegler and Kedem
[16] starting from the structural and physicochemical data of the membrane and the aqueous
solution. Thus they have obtained the following
expressions:
0 s = 1 HFSF
-

(6)
(7)

where Hpand/-/Dare the steric parameters relating

to the correction factors of the wall effect.
HF =1+ 16~/
9

(8)

HD= 1

(9)

with

and r - - (2)

(4)

(10)
KT

6rq.tD

(11)

M. Taleb Ahmed et al. / Desalination 165 (2004) 155-160

where r is the solute radius and r is the pore

radius of membrane. S e and S o are the partition
coefficients determined by the steric effect of the
aqueous solution and were expressed as follows:
So = ( 1 - ) , , ) 2
SF

(12)

(13)

= 2(1 -)L)2 - ( 1 - ) ~ ) 4

3. Materials and methods

Filtration experiments were performed with a

Millipore laboratory tangential filtration system
(Fig. !). It is equipped with a spiral wound polymeric membrane (Nanomax 50, Millipore USA),
having a filtration area of 0.37 m 2and a pure water
permeability of 22.7x 10-12 m.s-l.Pa-I The Nanomax 50 is a composite membrane with a negatively charged thin skin layer (0.4 ~tm) made of
polyamide arylene on a polysulfone support layer.
Experiments were performed for 1 h in a batch
circulation mode. Both permeate and retentate
were returned to the feed vessel in order to keep a
constant concentration. The temperature of the
recirculation feed solution was maintained at
20-J:0.5C. Chromium salts were purchased from
Prolabo Products (France). Solutions were prepared in demineralized water (pH -- 5.70, conductivity = 1 ~t.s/cm-l). The pH of the feed
4

h.,,-T~dI

(~

157

solutions was adjusted using HC1, HNO 3 and

H2SO4 depending on nature of the anion. This pH
was accurately determined using a probe calibrated on a daily basis. Cation concentrations were
measured by atomic absorption spectrophotomerry (VARIAN AA-1275) and those of anions
were determined by ionic chromatography. We
studied the influence of the concentration, pH,
transmembrane pressure on the synthetic solutions
of CrCI~ (0.5 mole/m 3) as well as the rejections of
tannery (liming and tanning).
4. Results and discussion
4.1. Study o f synthetic solution o f CrCl 3

The experiments were carried out on solutions

of CrCI3, 6H20 of concentration 0.5, 1 and
2 mol.m-3 at pH equal to 4.5. Each solution was
studied at four pressures (1, 2, 3, 5 and 10 bar).
The results show that the retention of chromium
III was not affected significantly by its concentration or applied pressure in the studied range.
The experimental variations of the retention
ranged from 94 to 99.9%. Work of Yaroshchuk
[17,18] and other authors [19,20] confirms these
results and proposes that the dielectric mechanism
of exclusion is dominating in the strong retention
of the trivalent ions. In order to model the experimental results related to the CrC13 solutions, the
8

Ib.._--ff-~
v
3

Fig. 1. Pilot description. 1, feedback; 2, volumetricpump; 3,4, pressure regulation valves; 5, membrane; 6, permeate
recirculation; 7, retentate recirculation; 8, heat exchanger; D, flow meter; P, pressure sensor; T, thermometer.

M. Taleb Ahmed et al./ Desalination 165 (2004) 155-160

158

model parameters ~s and P were determined by

solving Eqs. (4)-(13) and using a computer
program written in Turbo-Pascal software
language. The modeled variation of the ions rejection was then plotted as a function of the volumetric flux. As an example, in Fig. 2, the evolution
of calculated ion rejections versus volumetric flux
can be compared with experimental results. It can
be observed that in all cases, the model estimations
are in good agreement with measured rejections.
It can be concluded that the extended Nernst
Planck equation modified by Nakao et al. [1] can
be successfully applied in the case of CrlII
solutions. The calculated retention and pore radius
are reported in Table 1. The optimum pore radius

Table 1

Determination of pore radius value using the Nakao's

model
Jv 106, m/s
R exp., %
r p, nm
R th, %

1.015
95.23
0.364
95.25

3.045
98.34
0.365
98.97

5.075
98.76
0.366
98.53

10.15
99.17
0.367
99.22

Study conditions: pH = 4.5; [Cr3+] = 0.5 mole/m 3

calculated is 0.365 nm for a concentration ofCrCl 3

equal to 0.5 mole/m 3, a value which approaches
that in experiments given by Jeantet [ 14] which
is 0.47 nm.

4.2. Study of the effluent of tannery

100

99

[]

98
O

97

ta

96
95

Theoretical retention
Experimental retention

r-i

940

6
J v .10

8
10
6 (m/s)

Fig. 2. Comparisonof calculated and experimental values: chromiumretention as a function of permeate flow.
[CrCI3] = 0.5 mole/m3; pH = 4.5.

The principal characteristics of the treated

effluents of Rouiba tannery is described in Table 2.
The analyses of permeate and retentate solutions
were followed by the conductimetric method and
by atomic absorption spectrophotometry. The
operating conditions at the start of the pilot are
mentioned in Table 3. The results are shown in
Figs. 3 and 4. It gives the retention of chromium
in function of applied pressure at pH values of 2
and 7.6 for liming bath and of 4 and 10 for tanning
bath.
As can be observed, in the case of tanning bath,
the results obtained have shown that chromium
retention of 60 and 30% were observed respectively in acid and basic medium. In acid medium,

Table 2
Parameters of pollution of the various baths of the tannery of Rouiba [14]
Bath type

Stage of soaking

Stage of liming

Stage of tanning

Conductivity, [xS/cm
Chlorates, mg/1
BODs, rag/1
COD, mg/1
MES, mg/l
pH
Chrome, mg/l
Sulfates, mg/1

10.87-17.37
3.118-17.250
410-1650
43,000-52,300
774-4400
6.85-7.50
-820-860

8.28-12.50
1.770-4.537
360-4180
10,100-30,500
988-2088
11-12
-83-150

28.20-31
21.000-30.000
-8320-15000
3000-8000
3.20--4.10
5000
110-160

M. Taleb A hmed et al. / Desalination 165 (2004) 155-160

159

Table 3
Study conditions
CrCI3

Stage of soaking

[CrC13] = 0.5 mole/m3

pH = 4.5
Conductivity = 0.013 mS/cm

-[Chrome] = 121 mg/L

pH = 785
pH = 4,02
Conductivity = 2.61 mS/cm
Conductivity =8.08 mS/cm
T= 293C; Applied pressure = 05-10 bar

40
35

Stage of tanning

70[

_m Tanning bath pH = 7.64

60

[] Tanning bath pH = 2

[] Tanning bath pH = 3.94

~30

50

= 25
o

i 4

20

30

15

20

10

10
0

2
3
4
Applied pressure (bar)

Applied pressure (bar)

Fig. 3. Evolution of ion retention according to the pressure: conductimetric method.

Fig. 4. Evolution of ions retention according to the pressure: conductimetric method.

the rejection of the bath o f liming has generated a

retention of 15%.

treatment of tanneries effluents by nanofiltration

have shown that the pH of the medium affect
considerably the ionic rejection. However, other
experiments will be carded out to understand the
behavior o f the membrane against industrial
solutions containing chromium ions in complex
medium.

5. C o n c l u s i o n

In the case of synthetic solutions, the results

have shown that the retention of chromium III was
not affected significantly by its concentration or
applied pressure in the studied range. The experimental variations o f the retention were ranging
from 94-99.9%. The optimum pore radius calculated is 0.365 nm for a concentration of CrC13
equal to 0.5 mole/m 3. In the case of industrial
solutions, as tanning bath, the results obtained
have shown that chromium retention o f 60 and
30% were observed respectively in acid and basic
medium In acid medium, the rejection o f the bath
o f liming has generated a retention of 15%. The

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