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Abstract
Reverse osmosis separation of inorganic salts in aqueous solutions has been studied using polyamide thin film
composite membrane, in spiral wound configuration. Various inorganic salts involving monovalent and divalent
ions have been studied. The solute transport through the membrane and the mass transfer coefficient at the high
pressure feed side of the spiral wound module were determined for each type of salt. The mass transfer coefficient
of each inorganic salt was predicted from the experimental data for the reverse osmosis separation of sodium
chloride as reference and the mass transfer empirical correlations. The values obtained were compared with the
experimental ones. The free energy parameters for monovalent cations, monovalent anions and divalent cations
have been calculated. These parameters were used to predict the reverse osmosis performance of inorganic salts in
spiral wound reverse osmosis module. It was observed that the free energy values of the cations are negative while
those of the anions are positive, suggesting that the surface of the membrane used is positively charged.
Keywords: Reverse osmosis; Inorganic salts; Desalination; Thin film composite membranes; Spiral wound module
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–2 June, 2004.
0011-9164/04/$– See front matter © 2004 Elsevier B.V. All rights reserved
384 M. Khayet and J.I. Mengual / Desalination 168 (2004) 383–390
of their mass transfer coefficient in spiral wound solutes was established earlier and has been dis-
modules are of practical interest. cussed extensively with respect to inorganic or
In RO processes, preferential sorption at mem- organic solutes [4]. The approach is based on a
brane–solution interface is one of the factors modified form of the Born expression for free
governing solute separation. It is a function of the energy of ion-solvent interaction to both the bulk
membrane material, solute and solvent inter- solution phase and the membrane-solution
actions together with the experimental conditions. interface where water is preferentially sorbed. The
These interactions arise in general from the ionic, utility of the free energy of ions for predicting
steric, polar, and/or non-polar character of each solute separations in RO was illustrated with
one of the above three components of the system particular reference to cellulose acetate mem-
involved. In fact, RO separations of inorganic salts branes [4]. The object of this part of the work was
in aqueous solutions have been discussed from to obtain data on free energy for different
different points of view, including partition monovalent and divalent ions in aqueous solutions
coefficient of solute between membrane and liquid with respect to polyamide thin film composite
phases, enthalpy of hydration of ions in the bulk membrane used in spiral wound configuration and
phase solution, partial molar free energy of to compare such data with the corresponding ones
hydration and entropy of ions in the bulk phase applicable for cellulose acetate and polyamide
solution, or relative free energy parameters for membranes reported earlier [4–6]. The theoretical
ions and solutes [1]. The latter approach was approach developed by Matsuura et al. [1,4], based
applied in this study using various inorganic salt on free energy parameter, is applied in this study
types involving monovalent cations, monovalent to predict the RO solute separation of polyamide
anions and divalent cations. thin film composite membrane arranged in spiral
On the other hand, it is well known that the wound module for inorganic salts in aqueous
RO transmembrane water flux leads to the appear- solutions.
ance of the concentration polarization phenomenon
even when the separation of the solute from the
2. Experimental
solvent is not perfect [2]. The solute concentration
at the membrane surface becomes higher than that The experimental study was carried out using
in the bulk phase. Most of the models used in a pilot plant ROI-2 provided by Osmonics [7]. A
characterization of RO membranes make use of stainless steel spiral wound module S2521
mass transfer correlations in order to calculate the (Osmonics), containing polyamide thin film
solute concentration at the membrane surface [2]. composite membrane, was employed in this study.
The most used correlations are those based on the The effective membrane area of the membrane
Chilton-Colburn and Deissler analogies between module was 1.2 m2.
heat and mass transfer. In this study, the mass The inorganic solutes used are listed in Table 1,
transfer coefficient in the feed side of spiral wound along with some relevant physiochemical data.
module, k, and the solute transport through In this study, prior to each salt aqueous solution
polyamide thin film composite membrane (DK/ test, the membrane module was initially subjected
δ) were evaluated based on RO transport equations for pure water experiment to measure the pure
[3]. The obtained value of k, for each inorganic water membrane permeability. All the experiments
salt, was compared with the predicted one based were conducted at fixed feed flow rate of about
on the mass transfer empirical correlations [1,4]. (171 kg/h), feed pressure of 1378.9 kPa and feed
The concept of free energy parameter govern- temperature of approximately 22ºC. The solute
ing RO separations of ionic solutes in aqueous concentrations used were in the range of 0.09–
M. Khayet and J.I. Mengual / Desalination 168 (2004) 383–390 385
Table 1
List of solutes used with some physicochemical and experimental dataa
a
A ≈ 8.88×10–12 m/sPa; bCalculated from Eq. (8); cCalculated from Eq. (6).
0.1 mol/l. The solute concentrations in the feed is pure water, both π2 and π3 are zero, and therefore
and product solutions were measured with a con-
ductivimeter 712 ΩMetrohm and a 692 pH/Iono- J s = A ( P2 − P3 ) (3)
meter ΩMetrohm with the corresponding ion
selective electrode. In each experiment, the solute The solute permeation flux, Jd, is written as:
separation f, was calculated using the following
DK
equation: Jd = ( c2 X 2 − c3 X 3 ) (4)
δ
Solute conc. in feed − Solute conc. in product
f = (1) (DK/δ) is called the solute transport parameter,
Solute conc. in feed the quantity K is the equilibrium constant inde-
pendent of salt concentration, X2 is the solute mole
3. Theoretical approach fraction of the feed solution at the membrane
The following basic equations for RO transport surface, X3 is the solute mole fraction of permeate
have been derived and discussed extensively with solution, c2 and c3 are the total molar concentration
respect to single solute aqueous solution systems including solute and solvent in feed and permeate,
for the case where water is preferentially sorbed respectively.
at the membrane–solution interface [1]. The By using Eq. (4) and the following relation:
solvent flux is given as:
Jd
X3 = (5)
J s = A ⎡⎣( P2 − P3 ) − ( π2 − π3 ) ⎦⎤ (2) Jd + Js
where A is the pure water permeability constant, the solute transport parameter can be calculated
(P2 – P3) is the transmembrane hydrostatic pressure as:
difference, π2 and π3 are the osmotic pressures of DK X3
( c2 X 2 − c3 X 3 )
−1
the feed and the permeate solutions at the mem- = Js (6)
brane surface, respectively. When the feed liquid
δ 1− X3
386 M. Khayet and J.I. Mengual / Desalination 168 (2004) 383–390
The equation for the concentration polarization where DS and DS,NaCl represent the diffusivities of
is given by the film model [1,2]: the solute under consideration and sodium
chloride solute in water, respectively.
⎡ X − X3 ⎤ Jd + Js The concept of free energy parameter govern-
ln ⎢ 2 ⎥= (7) ing RO separations of ionic solutes in aqueous
⎣ X1 − X 3 ⎦ kc1
solutions has been discussed previously [1,4]. The
where k is the mass transfer coefficient at the feed following relationships have been derived by
side of the membrane module. Matsuura et al. [4] to calculate the free energy
Eq. (7) can be solved for k parameter, assuming parameter of ions:
a constant total molar concentration c = c1 = c2 = c3.
⎛ ∆∆G ⎞ ∆Gm ,i − ∆GB ,i
⎛ X − X3 ⎞ −⎜ ⎟ =
Js ⎝ RT ⎠i RT
k= ln ⎜ 1 ⎟ (8) (12)
c (1 − X 3 ) ⎝ X 2 − X 3 ⎠
−1 ⎧⎪⎛ Em ⎞ ⎛ EB ⎞ ⎫⎪
= ⎨⎜ ⎟−⎜ ⎟⎬
On the other hand, the mass transfer coefficient RT ⎩⎪⎝ ri + ∆ m ⎠ ⎝ ri + ∆ B ⎠ ⎭⎪
used in the concentration polarization equation
[Eq. (7)] may be obtained from Sherwood corre- where ∆G represents the free energy of solute–
lation [2] solvent interaction (i.e. the free energy of hyd-
ration of solute in the present study), R is the gas
Sh = α Reβ Sc γ (9) constant, T is the absolute temperature, the sub-
scripts m and B the membrane solution interface
where Sh, Re and Sc are the Sherwood, Reynolds and the bulk solution phase, respectively; the
and Schmidt numbers, respectively and α, β and subscript i refers to the particular ion under con-
γ are characteristic constants, which depend on sideration and E is defined as:
the hydrodynamic conditions of each system. For
spiral wound modules, the following correlation ( zi e0 )
2
⎛ 1⎞
has been reported in [1]. E=N ⎜1 − ⎟ (13)
2 ⎝ εs ⎠
1/ 2
⎛ h f ηsp ⎞ where N is the Avogadro number, zi is the valence
Sh = 1.065 ⎜ ⎟⎟ Re1/ 2 Sc1/3 (10)
⎜ Lsp 2 − ηsp of the ion, e0 is the electronic charge, ri is the radius
⎝ ⎠
of the ion and εs is the dielectric constant of solvent.
where hf is the thickness of feed flow channel, ηsp The free energy parameter is a function of the
and Lsp are the mixing efficiency of spacer and chemical nature of the solute, solvent, and mem-
the spacer mesh width, respectively. brane material. With respect to completely ionized
According to the above correlation, at a given inorganic solutes in water, it has been shown that
Reynolds number, the quantity (Sh/Sc1/3) is a con- the solute transport parameter is related to the free
stant. Matsuura et al. [4], based on Eqs. (9) and energy parameter for the ions by the expression:
(10), stated that when k for NaCl is known, k for
other solutes in dilute solutions can be obtained DK ⎧ ⎛ ∆∆G ⎞ ⎛ ∆∆G ⎞ ⎫
from the following relation: = C * exp ⎨nc ⎜ ⎟ +⎜ ⎟ ⎬ (14)
δ ⎩ ⎝ RT ⎠c ⎝ RT ⎠ a ⎭
2/3
⎛ DS ⎞ where nc and na represent the number of moles of
k = k NaCl ⎜ ⎟⎟ (11)
⎜D cations and anions, respectively and C* depends
⎝ S ,NaCl ⎠
only on the morphological structure of the membrane
M. Khayet and J.I. Mengual / Desalination 168 (2004) 383–390 387
and is independent of the nature of solute. If the solute diffusivities. The pairs of values (k, DS)
free energy parameters of the ions Na+ and Cl– were fitted to a potential function by the least
are known, the value of C* can be calculated from squares method. From Eq. (11), k was calculated
Eq. (13) using experimental data on solute trans- taking sodium chloride as reference solute. The
port parameter. results are also presented in Fig. 1. The agreement
The calculated values of the solute transport between the mass transfer coefficients calculated
parameter and the mass transfer coefficient in the by Eq. (8) and Eq. (11) may be considered good
feed side of the membrane module for each solute (i.e. the discrepancy is less than 4.9%). However,
may then be used to obtain the solute separation, for spiral wound modules the applicability of the
f, using the following expression [4]: empirical mass transfer correlations is not
−1
recommended as both the membrane type and the
DK J d + J s 1 − f ⎡ J + Js ⎤ spacer used in the high-pressure side of the mem-
= ⎢ exp d (15)
δ S f ⎣ Sk ⎥⎦ brane module may cause large errors.
The solute transport parameter (DK/δ) was
where S is the effective membrane area. calculated from Eq. (6). The results are also shown
in Table 1. It can be observed that the solute
transport parameters of the salt involving divalent
4. Results and discussion
ions are lower than those of the monovalent ions.
The concentration of the solute at the mem- Ghiu et al. [6] studied the importance of para-
brane surface was calculated from Eqs. (1)–(3). meters like ionic size, ionic hydrated size, diffus-
Then, the mass transfer coefficient, k, was ivity in solution, enthalpy and entropy of hydration
evaluated from Eq. (8). The obtained values on salt permeation. It was reported that the
together with the data involved in the calculations crystallographic radii cannot explain the order of
are summarized in Table 1. The mass transfer salt type permeation and the hydrated radii must
coefficient is, in general, higher for the inorganic be considered instead of the crystallographic radii.
salt having higher diffusion coefficient. Fig. 1 In fact, the enthalpy of hydration (∆H) as well as
shows the k values obtained as functions of the the entropy of hydration (∆S) represent more
precise quantification of the degree of hydration.
5.0 Both thermodynamic parameters ∆H and ∆S are
0.5444
integrated in the bulk Gibbs free energy (∆G).
y = 0.2658x
4.5 2
R = 0.9733
Furthermore, the interaction ion-solvent must be
taken not only in the bulk feed solution but also
k (10 m/s)
and 750.5 kcal Å/mol and 1.05 Å for divalent divalent cations. Also, Table 2 shows that the
cations, respectively. These data were used to values of (∆∆G/RT)i for the halide anions increase
calculate the free energy of solute-solvent with the increase in ionic radius. This means that
interaction ∆G at the membrane solution interface with respect to solutes involving halide anions,
and at the bulk solution phase of ionic solutes, (DK/δ) increases, and hence solute separation
together with the free energy parameter of each decreases, with the increase of the ionic radius
ion type. The results are shown in Table 2. (Table 1).
Using the experimental data (DK/δ) for NaCl Fig. 2 shows the plot of ln(DK/δ) as function
given in Table 1 and the data on (–∆∆G/RT)i for of Σ(∆∆G/RT)i. A straight line can be plotted
Na+ and Cl– ions given in Table 2, the value of C* between the two parameters which indicates that
was calculated from Eq. (14). A value of the procedure used can be applied also for spiral
9.92×10–8 m/s was obtained. It can be observed wound configuration. It must be mentioned here
that the quantity (∆∆G/RT)i is negative for all
cations and positive for all anions. This indicates
that the anion is attracted and the cation is repelled -15
-16.5
confirms the observation made earlier for
polyamide material [5,6]. In contrast, an opposite -17
Table 2
Free energy parameters for some monovalent cations, monovalent anions and divalent cations
that, for a given membrane, a lower value for in Fig. 1. Fig. 4 shows the variation of both the
Σ(∆∆G/RT)i may result in a lower value for (DK/δ) experimental and the calculated solute separation
and better solute separation can be obtained. with the algebraic sum Σ(∆∆G/RT)i. The predicted
In addition, by using the value of C* and the solute separation (solid line) did not differ
data on (–∆∆G/RT)i for different ions given in significantly from the experimental one. The
Table 2, the values of (DK/δ) for the different highest difference in data on solute separations
inorganic solutes were calculated from Eq. (14). was within 0.2% for CaCl2. The agreement between
The results are presented in Fig. 3 as a function the calculated and experimental results confirms
of the previously obtained values determined from the practical validity of the prediction technique
Eq. (6). Good agreement can be observed between and the numerical values of the free energy used
both values, which indicates that the procedure in this study.
used is adequate.
The values of (DK/δ) calculated from Eq. (14)
5. Conclusions
were used to obtain data on solute separation, f,
using Eq. (15) and the applicable value of mass The transport of various inorganic salts in
transfer coefficient, k, on the high-pressure side aqueous solutions through polyamide thin film
of the membrane obtained from the straight line composite membrane in spiral wound
16
14
DK /δ (10 m/s) from Eq. (14)
12
10
8
Monovalent cations
-8
6
Monovalent anions
4 Divalent cations
100
99.5
Experimental
99 Predicted
f (%)
98.5
98
97.5
Acknowledgement
The authors of this work gratefully acknow-
ledge the financial support of the “Comunidad de
Madrid” through its project Nº 07M/0059/2002.