DESALINATION

Desalination 145 (2002) 321-327

ELSEVIER www.elsevier.com/locate/desal

Application of membrane techniques in a water softening process

MichaIi Bodzek”*, Stanislaw Koterb, Klaudia Wesolowska”

“Institute of Water and Wastewater Engineering, Silesian University of Technology,
Konarskiego 18, 44-100 Gliwice, Poland
Tel./Fax +48 (32) 237-2368; email: boa!zekm@polsl.gliwice.pl
bFacul@ of Chemistry, Nicolaus Copernicus University, Gagarina 7, 87-100 Torud Poland

Received 5 February 2002; accepted 20 February 2002

Abstract
The paper presents the results of tests carried out on selected membranes, SEPA (Osmonics Inc., USA). The
efficiency of membrane water softening was evaluated on the basis of permeate flux and the physicochemical analysis
of raw water and permeate. The transport-separation properties of the membranes were determined using (a) the model
solutions of NaCl and MgSO, and (b) the natural waters of high degree of hardness. The performed tests indicate that
the DSS-DK and DS3-SE membranes may be applied to the softening of water for drinking and household purposes.
The model based on the extended Nemst-Planck and the Donnan equations has been quantitatively fitted to the
experimental data. The obtained values of model parameters indicate that in the case of RO membranes a mechanism
other than the Donnan exclusion is responsible for the high retention of ions. The membrane filtration modelling will
be performed in the next stage of project.

Keywords: Membrane techniques; Water treatment; Nanofiltration; Water softening

1. Introduction
A rising demand for high-quality water
observed recently has created a necessity of
rationalisation of processes connected with
softening of hard and very hard water in Poland.
In accordance with the Decree of the Health and
Social Welfare Minister, No. 82 dated 4th
*Corresponding author.
September 2000, item 937, drinking water and
water for economic purposes should be charac-
terised by hardness (CaCO,) 60-500 mg/dm3.
The removing of excessive amounts of calcium
and magnesium from drinking water would make
healthy feeding and healthy organism functioning
possible. At the same time it could ensure a long-
lasting operation of household equipment (pre-
venting scale deposits).

Presented at the International Congress on Membranes and Membrane Processes (ICOW, Toulouse, France,
July 7-12, 2002.
001 l-9164/02/$- See front matter 0 2002 Elsevier Science B.V. All rights reserved
PII: SO0 1 l-9 164(02)00430-7
322 M. Bodzek et al. /Desalination 145 (2002) 321-327

2. Objectives the total hardness was carried out applying the

complexometric titration with EDTA, while the
The research is aimed at testing selected
concentration of chloride was determined by the
membranes produced by Osmonics Inc. under
Mohr method.
laboratory conditions with respect to their
technological application to the process of water
4. Results and discussion
softening for drinking and household purposes.
The results of the tests show that the effi-
3. Materials and methods ciency of the membrane DS-5-DK (J, = 25 x 10d6
m3/m2s (Fig. 2b) is several times higher than that
The scheme of the installation is presented in
of the membrane DS-3-SE (J,, = 7x low6 m3/m2s,
Fig. 1. The basic element of installation is the flat
Fig. 2a). The retention coefficients of Cl- and
membrane module produced by Osmonics Inc.,
Mg2+ ions obtained while testing the membranes
type SEPA CF-HP, high-pressure version,
with the model solutions are as follows: R,, =
adjusted for carrying out reverse osmosis and
12%, R,, = 98% for the NF membrane DS-5-DK,
nanofiltration. The effective membrane area was
and R,, = 95.1%, R,, = 98.2% for the RO
155 cm’. In the experiments the NF and RO
membrane DS-3-SE.
membranes DS-5-DK, DS-3-SE (Osmonics) were
Furthermore, it has been observed that in the
used. The membrane filtration was carried out for
case of DS-5-DK the volume flow in the NaCl
5 h at constant process parameters, i.e., working
filtration is much higher than that in the MgSO,
pressure 2 MPa, flow over the membrane surface
1 m/s, T= 25°C. 5.5 -
a)

l
The effectiveness of a membrane water treat-
ment process was evaluated on the basis of - 9
5.0 -
permeate flux. The transport separation charac- z
.+ c 0.5% MgSO,
teristics of tested membranes were determined in
s - 0.5% NaCl
relation to the model solutions of NaCl and z
4.5 -
52
MgSO,. In the next stage of the experiment the r _ . - * . . . .
membrane filtration of natural hard water was . .
carried out and a physicochemical analysis ofraw 4.0 I I I I I I I I I I I I I I
water and permeate were made. The determi- 0 15 30 45 60 75 90105120135150165160195210
time[min]
nation of concentration of Mg2+, Ca2’ ions and of
b) *
16.0 - ' -

iz 16.0 -
"E
- Os%MgSO,
?
a 14.0 - ++ 0.5% NaCl
0
L
_) .z f - .
12.0 -

10.0 I I I I I I I I I I I I I(
0 15 30 45 60 75 SO 1051201351501651601Q5210
time[min]

Fig. 2. Time dependence of volume flux through:

Fig. 1. Scheme of pilot installation for membrane (a) membrane DS-3-SE, (b) membrane DS-5-DK. Feed:
filtration. 0.5% NaCI, 0.5% MgSO,.
 M. Bodzek et al. /Desalination 145 (2002) 321-327 323

filtration, whereas for DS-3-SE the situation is
opposite (Fig. 2). This phenomenon can be
explained (partly at least) by the different
osmotic pressure differences, AIT,ofthe feed and
permeate solutions developed during the filtra-
tion of NaCl and MgSO,. Using the layer model
of concentration polarisation for the calculation
of the salt concentration near the surface of
membrane:
necessary for the calculation of
It has been estimated that for DS-3-SE An;is
equal to ca. 0.44 (NaCl) and 0.10 MPa (MgSO,),
whereas for DS-5-DK, An; = 0.08 (NaCl) and
0.16 MPa (MgSO,). Thus, remembering that
Ap = 2 MPa, the effective force (Ap- ATT)is
substantially higher in the first case for MgSO,,
than in the second case for NaCl. To characterise
the membranes, the model based on the extended
Nernst-Planck equation (ENPE):
concentration of fixed charges. In that model the
rejection mechanism of ions is based on the
Donnan effect and their transport (the diffusion
and convection parts of ENPE) is affected by the
so-called hindrance factors K,,d,K,,,, depending on
the ratio of solute to pore radius, ri/r,. Assuming
the straight pores of radius rp = 1 nm for both
membranes, it was found that the ratio of the
active membrane layer to its porosity, 1,/V,, is
equal to 12 (DS-5-DK) and 44 pm (DS-3-SE). If
the VP of both membranes were the same, it
would mean that either the thickness of the active
layer of DS-5-DK was ca. four times smaller than
that of DS-3-SE or that the radius of the pores of
ATC: DS-5-DK was twice that of DS-3-SE.
According to the model, the concentration of
fixed charges in the pore solution, C, for DS-5-
(2)
DK is 0.5 M as calculated from the NaCl data,
assuming rp = 1 nm, Z, = 50 pm. Using the
MgSO, data, however, the model calculations
yield 100 times higher values of C,. These
unexpectedly high values of C, mean that the
steric effect, larger for MgSO,, plays an
important role here (the radii of ions calculated
from their mobilities are 0.348 (Mg”) vs. 0.184
(Na’), 0.231 (SO:-) vs. 0.121 (Cl-) nm). In the
case of DS-3-SE for both electrolytes, the C,
calculated is also much too high (ca. 20 M). Here
for the explanation of salt rejection the surface

1
force-pore model of Matsuura and Sourirajan can
~..,Fdl
dc.
be applied [2,3].
dx “RTdx
Four types of water characterised by different
total hardness (H,,) were used in the experiment.
and on the Donnan equation: They were the well waters taken from Jaworzno
(H,,, =:500 mg CaC0,/dm3), Bedzin (H,,> 500 mg
- l/z, _ llZk l/Z, _llZk
a = f(feed), p (permeate) CaC03/dm3) and Gliwice (H,, > 600 mg CaCO,/
‘i,cc ‘k,a =cia , ,
Cka
dm3), and the tap water for comparison.
Fpr both DS-5-DK and DS-3-SE membranes,
ci - zici+a,F, = 0 (475) the highest J, is observed for tap water and the
well water from Gliwice, characterised by the
developed by Bowen et al. [ 11, has been applied. lowest total hardness H,,, (Fig. 3a and 3b).
In the above equations C,, c, denote the concen- It was observed that at the first tests both
tration of ion i in the pore solution and in the membranes showed slightly higher volume flux
external solution, respectively, and C, is the (J,,) then that after the repeated use of a given
324 M Boclzek et al. /Desalination 145 (2002) 321-327

a)

5.0 , , , , , , , , , , , , , , , , , , , ,
0 30 60 90 120 150 180 210 240 270 300
0 30 60 90 120 150 160 210 240 270 300 time [min]
time [min]

Fig. 3. Time dependence ofvolume flux through: (a) membrane DS3-SE, (b) membrane DS-5-DK. Feed: well water from
Bedzin, Jaworzno and Gliwice.

Table 1
Time dependence of J,, J,=a log(t/min) + b, and the determination coefficient R* for membranes DS-3-SE, DS-5-DK

Water intake DE-3-SE membrane DS-5-DK membrane

J, [10e6 m’/m*xs] R2 J, [1O-6 m’/m*xs] R*

0.5% NaCl - 0.0333 log(t) + 4.42 0.687 -0.0490 log(t) +1s.39 0.911
0.5% MgSO, - 0.0909 log(t) + 5.57 0.914 -0.0946 l(t) + 12.65 0.989
Tap water -0.198 log(t) + 7.27 0.779 -0.736 log(t) + 23.00 0.827
Jaworzno -0.0514 log(t) + 6.25 0.946 - 0.224 log(t) + 15.07 0.951
Bedzin - 0.127 log(t) + 6.62 0.724 -0.528 log(t) + 15.53 0.94
Gliwice -0.0669 log(t) + 5.89 0.971 -0.671 log(t) + 16.84 0.955

membrane. This fact indicates a partial, irrevers- The highest values of retention coefficient of
ible blocking of pores (fouling) which slightly total hardness, Htot, were obtained while filtering
reduced the efficiency of water filtration. the hard waters through the DS-3-SE membrane
The dependence of volume flow on time can (Fig. 4).
be approximated by the logarithmic function J, = The rejection coefficient of ions contributing
a log(t) + b. The parameters of that function, to the total hardness exceeded 80% for municipal
including the determination coefficient R2, for the and well water from Jaworzno, whereas for the
investigated membrane systems are listed in well waters of Bqdzin and Gliwice it amounted to
Table 1. less than 70% (Fig. 4b). The high decrease of the
It has been found that during the process of temporary hardness (Fig. 6), the content of Ca2’
softening of natural waters, the retention coeffi- and Mg2’ ions, inorganic carbon and of the
cients of Cl- and Mg2+ ions were lower than those conductivity was observed for both tested mem-
obtained for the model solutions (0.5% NaCl and branes. In contrast to DS-5-DK, the DS-3-SE
MgSO,). This is due to the multicomponent membrane shows a good retention of all ions,
nature of the natural waters as well as different both mono- and divalent ones (R>90%,
concentrations of the ions in the treated waters Figs. 4aAa).
and the model solutions. The results of analytical determinations
 M. Bodzek et al. /Desalination 145 (2002) 321-327 325

I 3.0
3.0
time [h]
time [hl

Fig. 4. Retention coefficients of I&,,: (a) membrane DS3-SE, (b) membrane DS+DK.

time[h] 1.5 3.0

time (h]
Fig. 5. Retention coefficients of Cl- ions: (a) membrane DS-3SE, (b) membrane DSSDK.

4 100 w 100

T L
E 75 L 75
g
.s
! 50 0 5.

p
5 25 wshrtliwice j 25 water GWii
‘g P,
0 0
15 3.0 5.0
15 3.0 5.0
time [hl
time [h]

Fig. 6. Retention coeffkients of H,: (a) membrane DS3-SE, (b) membrane DS-5-DK.

(Table 2) allow to state that the well waters after
the membrane filtration, using the DS-5-DK
membrane, meet the requirements of the Decree
of the Minister of Health concerning the well
water use for consumption aims. Eventually, a
soft water (Jaworzno), a light hard water
(Bedzin) and a medium hard one (Gliwice) have
been obtained.
Analysing the parameters of the hard waters
after the filtration through the DS-3-SE mem-
brane, one can state that none of them meets the
requirements of the Decree because of the low
concentration of Ca*’ and Mg*+ ions. In order to
make this water potable, it might be mixed with
the water treated by other (e.g., conventional)
methods.
326 M. Bodzek et al. /Desalination 145 (2002) 321-327

Table 2
Results of water softening applying DS-3-SE and DS-5-DK membranes

Component unit Water intake Concentration, mg/dm3

DS-3-SE membrane DS-5-DK membrane

Feed 1.5 h 3.0 h 5.0 h Feed 1.5 h 3.0 h 5.0 h

H,,,, mg CaC0,/dm3 Tap water 90 12.0 10.0 8.0 144 18.0 20.0 22.0
Jaworzno 504 10.0 10.0 10.0 498 88.0 72.0 80.0
Bedzin 532 12.0 12.0 10.0 572 172 196 190
Gliwice 596 8.0 12.0 12.0 596 300 244 194
Cl-, mg Cll/dm3 Tap water 35.4 14.2 14.2 14.2 35.4 28.3 28.3 28.3
Jaworzno 163 21.2 14.2 14.2 184 127 113 120
Bedzin 92 7.1 7.1 7.1 92.0 70.8 70.8 70.8
Gliwice 347 35.4 28.3 28.3 347 297 283 269
Mg*+, mg Mg2+/dm3 Tap water 6.3 1.0 1.5 1.0 8.7 0.5 1.0 0.5
Jaworzno 58.3 0 0.5 0.5 56.9 8.7 6.8 7.8
B&dzin 46.6 1.0 1.9 1.5 43.7 15.6 21.4 21.9
Gliwice 12.6 0 1.0 1.0 29.2 24.3 20.4 16.0
Ca*‘, mg Ca*‘/dm’ Tap water 25.6 3.2 1.6 1.6 43.2 6.4 6.4 8.0
Jaworzno 106 4.8 3.2 3.2 106 20.8 17.6 19.2
Bedzin 136 3.2 1.6 1.6 157 43.2 43.2 40.0
Gliwice 218 3.2 3.2 3.2 190 80.0 64.0 51.2
H,, mg CaCO,/dm’ Tap water 70.0 10.0 10.0 7.5 105 15.0 20.0 20.0
Jaworzno 265 10.0 10.0 10.0 270 85.0 70.0 80.0
Bedzin 315 10.0 10.0 10.0 360 145 155 155
Gliwice 395 7.5 10.0 10.0 395 220 200 180
Conductivity, mS/cm Tap water 0.20 0.022 0.021 0.021 0.282 0.068 0.075 0.083
Jaworzno 1.26 0.046 0.042 0.043 1.231 0.541 0.524 0.539
Bedzin 1.09 0.039 0.035 0.033 0.986 0.502 0.577 0.558
Gliwice 1.98 0.054 0.062 0.062 2.12 1.39 1.29 1.20
Inorganic carbon, Tap water 15.5 1.83 1.89 1.82 24.5 7.29 8.11 8.88
mg/dm3 Jaworzno 62.5 1.91 1.71 1.79 80.1 34.5 33.9 33.4
Bedzin 72.6 2.26 1.97 1.92 87.0 35.9 39.2 36.4
Gliwice 97.4 3.1 2.92 2.61 103 54.8 48.2 42.5

The presented data show that the retention of modelling of the filtration of multi-ionic solu-
a given ion depends on the composition of the tions (natural well waters) will be presented.
solution to be filtered. In the next paper the
 M. Bodzek et al. /Desalination 145 (2002) 321-327 327

5. Conclusions 4 - Flux of ion i (based on membrane

1. Using DS-3-SE and DS-5-DK membranes, area), mol m-*5-’
a considerable reduction of the hardness of Jv - Volume flux (based on membrane
extremely hard well waters has been achieved. area), mxs-’
The total hardness of permeate did not exceed the Kr,c,
K,,, Hindrance factor for convection
permissible value for drinking water. At the same and diffusion
time, the substances that make up the taste and 4 - Thickness of polarisation layer, m
nutritional quality of water have been removed to rp,r, - Radii of pores and of ion i, nm
only a small extent. R - Gas constant, =8.3 14 Jx moll’x
2. It has been observed that DS-5-DK is a K-’
typical NF membrane. It sufficiently reduces the T - Absolute temperature, K
hardness of the tested waters and shows rela- VP - Volume fraction of pores
tively higher productivity than the DS-3-SE x - Distance normal to membrane, m
membrane. Thus, the DS-5-DKmembrane can be z, - Charge number of ion i
recommended for the production of potable and
household water.
3. It was proven that the RO process is not
Osmotic pressure, Nxm-*
favourable for the production of drinking water
Osmotic coefficients of the feed
because of too high retention of micro and macro
and permeate solutions
elements. These elements are responsible for the
Electric potential inside the pores,
water health virtues. The water softened on RO
V
membranes can be mixed with water softened by
other methods.
Acknowledgements
4. The model based on the extended Nernst-
Planck and Donnan equations can quantitatively This research project is a part of the research
be fitted to the experimental data; however, the program,“Application of membrane techniques in
obtained values of model parameters indicate that water softening process”, performed as part of
in the case of RO membranes, a mechanism other Grant No. 3T09C08919.
than the Donnan exclusion is responsible for the
high retention of ions.
References
6. Symbols Ul W.R. Bowen, A.W. Mohammad and N. Hilal, Char-
acterisation of nanofiltration membranes for predic-
CI/,C,,
, , - Concentrations of electrolyte in the
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atomic force microscopy, J. Membr. Sci., 126 (1997)
c,, c, - Concentrations of ion i and the
91.
fixed charges, moles per m3 of pore
solution
PI T. Matsuura, Synthetic Membranes and Membrane
Separation Processes, CRC Press, BocaRaton, 1994.
Q - Diffusivity of ion i, m*xs-’
[31 H. Mehdizadeh and J.M. Dickson, Theoretical modi-
0s - Bulk diffusivity, rn’xs-’ fication of the surface force-pore flow model for
F - Faraday constant, = 96,500 Cx reverse osmosis transport, J. Membr. Sci., 42 (1989)
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