SEPARATION SCIENCE AND ENGINEERING

Chinese Journal of Chemical Engineering, 19(4) 586ü591 (2011)

Investigation of Mg2+/Li+ Separation by Nanofiltration*

YANG Gang (ཷ‫**)ذ‬, SHI Hong (ಮ‫)܁‬, LIU Wenqiang (ঞำஜ), XING Weihong (໺ฯ‫)܃‬
and XU Nanping (༗઒଼)
State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing University of Technology, Nanjing
210009, China

Abstract The Mg2+/Li+/Cl solutions were filtrated with a commercially available DK nanofiltration membrane to
investigate the possibility to enrich the lithium component. The investigation was significant as such an approach
might be a competing substitute for the present lithium purification industry and the environmental protection pur-
pose. The Donnan steric pore model (DSPM) was implemented for the prediction. The separation of Mg2+/Li+ was
mainly affected by the working pressure (or the permeation flux) and a limiting separation factor was found around
0.31. The effective membrane charge density was evaluated and its dependence on the permeation flux as well as
the ion pattern was discussed. For predicting an actual separation of electrolytes, the experimental investigation
seems necessary for the reliability and efficiency.
Keywords nanofiltration, lithium recovery, DSPM model, separation factor

1 INTRODUCTION used for the characterization of the DK membrane.

Analytical grade LiCl and MgCl2 were used to make
New technologies are urgently demanded in re- the Mg2+/Li+/Cl solutions shown in Table 1. Their
cent years for saving energy and reducing waste. mass ratios Mg2+/Li+ are around that of the crude
Membrane separations have therefore been focused on, brine in the East Taijinaier Salt Lake [8], and the lith-
among which nanofiltration (NF) [13] is acknowl- ium ion concentrations change within a limited scope.
edged as an efficient process. Such approaches were All water used was pretreated with reverse osmosis
used for water softening in early days [4], and then membrane and ion exchange resin with the conductiv-
were found to be a best choice for the treatment of ity less than 0.5 Ps·cm1. Table 2 lists the bulk diffu-
process fluids. The mode is now being extended to the sion coefficients and Stokes radii of the solutes, which
environmental protection area to recover valuable were incorporated in the mathematical computation.
components. The interest herein is the NF rejections The data for lithium ion were from [9], while the rest
of lithium ions, which is often used for hygroscopic were from [10].
purpose or elsewhere (e.g. lithium battery). Actually
membrane processes [5, 6] concerned this refrigeration Table 1 Brine compositions
agent, though a few ideas [7] did not seem practical Simulated brine cLi /g·L1 (Mg2+/Li+)/g·g1 [mol·mol1]
yet. In nature the lithium element is basically stored in
the brine. Its enrichment process is featured with Feed A 0.26 18 [5.1]
evaporations, by which a variety of ions are removed Feed B 0.16 22 [6.3]
through crystallizations. The work [8] on NF of the Feed C 0.1 24 [6.9]
crude lithium brine was comprehensive, but the results
almost led to a negative evaluation since the crude
brine was too complicated. In the present industrial Table 2 Bulk diffusion coefficient and Stokes radii
process it is able to evolve the lithium-containing Solute Di’×109/m2·s1 rs/nm
stream into Mg2+/Li+ mixture. A proper implementa- +
tion of the NF technique might facilitate the removal Li 1.03 0.238
of ions such as Mg2+ with less energy consumption. In Mg 2+
0.72 0.348
this paper, experimental investigations and theoretical Na+ 1.33 0.184
predictions are given to elucidate the selective rejec-
Cl 2.03 0.121
tions of Mg2+/Li+.
Glucose 0.69 0.365

2 EXPERIMENTAL
The cation concentrations were determined by
2.1 Chemicals and analysis Inductively Coupled Plasma (Shimdzu, Japan). The
glucose concentrations were determined by TOC (total
Analytical grade NaCl, MgSO4 and glucose were organic carbon) analyzer (Shimdzu, Japan).

Received 2010-12-09, accepted 2011-04-15.

* Supported by the National Natural Science Foundation of China (20576052) and the Joint Innovation Fund of Jiangsu Prov-
ince (BY2009107).
** To whom correspondence should be addressed. E-mail: yanggang@njut.edu.cn
 Chin. J. Chem. Eng., Vol. 19, No. 4, August 2011
2.2 Membrane and apparatus
The spiral-wound Desal DK membrane element
(GE Osmonics) of nominally 8 m2 membrane area
was used. The parental solution was fed into the
membrane element through a feeding pump and then a
pressure-boosting pump. The later was equipped with
a transducer for a smooth start-up and easy process
adjustment. The inlet pressure and retentate flow rate
were controlled with accuracy through the adjustment
valve and the transducer. The retentate flow rate and
the permeate flux were monitored with two electronic
flowmeters, while the permeate flux records were
calibrated to avoid the temperature, density and me-
chanical deviations. The storage tank jacket was cir-
culated with cooling water to stabilize the feeding
temperature at (35r1) qC.
2.3 Experimental procedure
All experiments were carried out at the
cross-flow rate of 3 m3·h1, at which the concentration
polarization is negligible [11]. The temperature was
kept constant at 35 °C. Both the retentate and perme-
ate flew back to the feed tank. The constant process
parameters and the relevant samples were available in
the cycling. The permeate flux as well as the concen-
trations at both membrane sides were determined as
the transmembrane pressure stepped up every 0.2 MPa
from 0.8 MPa to 1.6 MPa. The membrane separation
587
the theoretical calculation seems deviated while the
empirical or semi-empirical treatment works better.
On the other hand, the dielectric exclusion is weak-
ened at a high feed concentration, which is the case
for the brines in [8, 21] and this paper. Therefore, only
the simplified DSPM model is used herein for the
process prediction and concise evaluation for rejec-
tions of the Mg2+/Li+ system. The model parameters,
i.e. effective membrane pore radius (rp), effective
membrane thickness (ǻx/Ak) and effective membrane
charge density (Xd), are obtained through the charac-
terization experiments. With the numerical treatment
procedure [22], the extended prediction is available.
4 RESULTS AND DISCUSSION
4.1 Separations of Mg2+/Li+ mixture
The ion rejection and SF of Mg2+/Li+ are shown
in Fig. 1. For Feed A, the Mg2+ rejection increases
while the Li+ rejection decreases with the increase of
permeation flux. A strong Donnan effect is observed.
In the permeation flux range, the SF decreases from
0.49 to 0.31. The Mg2+ rejection for Feed B (as well as
Feed C) is similar, but the Li+ rejection is different,
which increases slightly only at a higher flux. Negative
 cMg2 cLi permeate
factor (SF) is calculated as SF ,
 cMg2 cLi  retentate
where cMg 2 and cLi+ are the magnesium and lithium
concentrations, respectively. When SF 1, no differ-
ential retention occurs. When SF<1, Li+ penetrates
preferentially and is enriched more in the permeate if
SF is lower. On the contrary, when SF>1, Mg2+ takes
the place of Li+.

3 SIMULATIONS

Modeling of nanofiltration based on the

black-box treatment or the Nernst-Planck equations
were reported [1216]. A simplified Donnan steric pore
model (DSPM) [17, 18] and its new version [10] were
typically impressive. Much work was reported on the
improvement [19]. The endeavors partly aimed at
in-depth probing fundamental aspects of the mass
transfer. Unfortunately, the prediction-oriented utiliza-
tion is complicated, since it is difficult to obtain the
physicochemical parameters such as dielectric con-
stant or streaming potential [20]. And, the model pa-
rameters changes with process conditions. For a solu-
tion with components of relatively high concentrations,
or a real wastewater that is apt to foul the membrane, Figure 1 Ion rejection and SF vs. permeation flux
588 Chin. J. Chem. Eng., Vol. 19, No. 4, August 2011

rejections of 40%20% are observed. The opera- their single electrolyte solutions, the rejection decreases
tions for the 3 mixtures started at the same working as the corresponding concentration increases, as
pressure, so their beginning permeation fluxes in- shown in Fig. 3. It is interesting that their rejections
creased with their resistant osmotic pressures. The are quite close and Li+ rejection is even a little higher.
initiate values of SF for Feeds B and C decrease. It is The different dependencies very the electric functions
interesting that the starting SF for Feed B is lower that Mg2+ and Li+ exert at the membrane surface and
than that of Feed C. This is supposed to be caused by inside the pore. This imply that an optimized opera-
the permeation fluxes, the ion concentrations and the tion is possible to obtain the Li+-enriched permeate.
ratios. The trend is evident within the flux range, sug-
gesting the phenomena are governed not only by the
Donnan exclusion.
Normally a multi-valent anion is preferentially
rejected by a negatively charged NF membrane if
there exists a univalent anion. Herein the divalent and
univalent cations are selectively rejected. This is en-
couraging from the perspective of field applications.
The selection may be due to the electric properties and
the geometric sizes of the ions. Other factors such as
the dielectric properties, which are difficult to charac-
terize, might also help lead to the above occurrences.
The dependency of the Mg2+/Li+ SF on the Li+
concentration is shown in Fig. 2, where the parental
Mg2+/Li+ concentration ratio falls within 1824. Un-
der a given operating pressure, SF changes within a
narrow range with the Li+ concentration or the
Mg2+/Li+ concentration ratio. Differently, the depend-
ence of SF upon the operating pressure is manifest. For

Figure 3 Rejection variations of Mg2+ and Li+

ǻp/MPa:ƶ0.8;ƻ1.0;Ƹ1.2;ͪ1.4; 1.6

4.2 Evaluation with a simulation model

With the retention data of the neutral solutes, the

Figure 2 Variations of SF with retentate Li+ concentra-
tion and Mg2+/Li+ ratio
ǻp/MPa:ƶ0.8;ƻ1.0;Ƹ1.2;ͪ1.4; 1.6
membrane pore radius (rp) and the effective mem-
brane thickness (ǻx/Ak) were calculated as 0.53 nm
and 3.42 μm, respectively, through the best-fit method.
This is slightly deviated from the data reported, which
may be due to the different conditions that the mem-
branes were produced and utilized. The effective
membrane charge density (Xd) greatly relies on condi-
tions such as pH and ionic strength [20, 23]. Several
reports have used the adsorption isotherm of
s
ª n
º
Xd q «1/ 2¦ zi ci (0 ) » [20, 24] to relate it with the
¬ i 1 ¼
ionic strength. In this study, the constants q and s are
regressed from the rejections and fluxes and listed in
 Chin. J. Chem. Eng., Vol. 19, No. 4, August 2011 589

Table 3. The results prove that Xd is greatly influenced purification of Li+ component. The temperature factor
by the solution composition, and even its sign is is still left for investigation, but its influence on the
changed with Mg2+ added. membrane pore size and charge density is limited. In
most cases room temperature is recommended due to
the comprehensive consideration of the membrane
Table 3 Xd fitted with the DSPM model as function of
feed characteristics service life, energy consumption and operation con-
venience.
Ionic system q s R2
Na+/Cl 2.03u1016 6.07 0.87

+
Li /Cl 2.20u105 1.95 0.98

2+
Mg /Cl 2.54u1025
8.84 0.69
Li+/Mg2+/Cl 2.09u1012 4.75 0.96

Figure 4 gives the predicted relationship of SF

and the permeation flux. The trial with Xd obtained
from the other ionic systems leads to a complete fail-
ure. Good conformity is found when Xd is regressed
from experiments with the Li+/Mg2+/Cl mixture.
When extended to a moderately broader working pres-
sure range, the predicted SF evolves forward smoothly.
The factor decreases as the permeation increases, but
the extent is gradually narrower. The factor seems to
approach a limit value about 0.31. The encouraging
preferential rejection of Mg2+ is similar with the result
in the nanofiltration of the SO 24 /Cl/Na+ solution.
Their difference is that a peak rejection of Cl often
emerged is not so clear here for Li+ (as instructed in
Fig. 2). Such an extremity of the Donnan effect does
not appear since Mg2+ is not rejected completely.
Nevertheless the trend shown here suggests a techni-
cally viable membrane approach for enriching Li+.

Figure 5 Predicted SF vs. Mg2+/Li+ ratio and retentate Li+

concentration

4.3 Dependency of effective membrane charge

density

A typical treatment of Xd is the regression ap-

Figure 4 DSPM predictions of SF
experiment
ƻ (Feed A);ƶexperiment (Feed B);Ƹexperiment
(Feed C); DSPM (Xd of Mg2+/Li+); DSPM (Xd of Na+)
The evaluated dependencies of SF upon the re-
tentate Mg2+/Li+ ratio as well as the retentate Li+ con-
centration are given in Fig. 5. At the given working
pressure, SF is basically not sensitive to the two pa-
rameters and maintains around 0.34. The rejections for
two ions change, but are in the same trend. Apart from
the membrane choice, the operation pressure seems to
be a significant adjustment measure for an optimized
proach [10, 17, 19, 2528], or it may be evaluated via the
Gouy-Chapman double electric layer theory and ex-
perimental determination of the tangential membrane
surface potential [20, 21, 29, 30]. However, Xd is an
inenarrable variable [31] as it relates with membrane
property, ionic adsorption and ambient pH condition.
In this paper, Xd is also found dependent of the per-
meability, as shown in Fig. 6. An increase appears for
the monovalent cation but a decrease occurs for the
cation Mg2+. The contradicted trends seem to be af-
fected by the cation valency other than the process
phenomenon such as the concentration polarization.
The permeate flux might affect the intrapore elec-
trokinetic effect by its contribution to the slip plane
movement of the adsorption layer. The absolute value
of Xd tends to decrease as the permeate flux increases.
This deserves attention in the future modeling. On the
other hand, Xd value is intensively dependent on the
590 Chin. J. Chem. Eng., Vol. 19, No. 4, August 2011
Figure 6 Dependency of intrapore charge density on flux
+
Li+;ƶMg2+;ͪMg2+/Li+
ƻ Ni ;Ƹ
cation pattern. Xd is negative for the monovalent ion
but positive for the divalent ion. The trend is similar to
the reports in literature [17, 28]. The Xd variation is
likely caused by the ionic adsorption that changes
with the ion valency. And, the Xd value for the
Mg2+/Li+/Cl mixture is between those for Mg2+ and
Li+ systems. The component Mg2+ preponderates for
the charge density, but with the limited data, no evi-
dent linearity is found among them yet.
The Donnan potential at the pore entrance shown
in Fig. 7 also changes with the permeation flux. The
linearity is good but the slope and the intercept change
with ion pattern. The positive slope for the monovalent
ions and the negative one for the divalent cations show
the diversion of the charge property. This is similar
with the dependence of the streaming potential on the
driving pressure, which is also linearly related [32].
Figure 7 Dependency of Donnan potential on flux
ƻ Ni+;ƸLi+;ƶMg2+;ͪMg2+/Li+
5 CONCLUSIONS
A DK brand membrane was used to investigate
the possibility of separating Li+ from the Mg2+/Li+
mixture. The prediction with the DSPM model was
carried out for an extending analysis. Within the con-
cerned concentration range, the Mg2+/Li+ ratio and the
Li+ concentration were found basically not affecting
their separation factor, while the working pressure, or
the permeation flux, seemed significant. Higher driv-
ing pressure helped raising separation potential. The
limiting SF of 0.31 was technically possible for richen
Li+ with membrane technologies. Actually, the integral
membrane process design was able to facilitate a high
Li+ recovery at a relatively high purity. The data
analysis disclosed the dependence of the intrapore
membrane charge density on ion pattern, ion concen-
tration and driving pressure force. The empirical ex-
pression of Xd for the mixed electrolyte solution is still
necessary for the probe of the separation possibility.
NOMENCLATURE
c concentration, g·L1
Di,’ bulk diffusion coefficient, m2·s1
Jv volumetric permeate flux, m·s1
ǻp pressure on both sides of the membrane
q empirical parameter, mol·m3
R rejection
R2 correlation coefficient
rp effective membrane pore radius, m
rs stokes radius, m
s empirical parameter
SF separation factor
Xd effective membrane charge density, mol·m3
z ionic valence
ǻx/Ak effective membrane thickness, m
0 feed side
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