Chemical Papers 67 (4) 380–388 (2013)

DOI: 10.2478/s11696-012-0280-x

ORIGINAL PAPER

Comparison of polymeric and ceramic membranes performance

in the process of micellar enhanced ultrafiltration of cadmium(II)
ions from aqueous solutions

Katarzyna Staszak*, Zofia Karaś, Karolina Jaworska

Institute of Technology and Chemical Engineering, Poznan University of Technology,

Pl. M. Sk
lodowskiej-Curie 2, 60-965 Poznań, Poland

Received 26 March 2012; Revised 12 September 2012; Accepted 14 September 2012

A comparison of polymeric and ceramic membranes in the ultrafiltration process was studied and
presented. This study was conducted on the separation of cadmium(II) ions, with particular refer-
ence to parameters such as hydrodynamic permeability coefficient, membrane fouling, amount of
surfactant in the permeate, efficiency, and effectiveness of the process. The effect of ionic (SDS) and
non-ionic (Rofam 10) surfactants or their mixture was investigated. The hydrodynamic permeabil-
ity coefficient of the ceramic membrane was found to be much lower in comparison to those of the
polymeric ones (1.69 × 10−7 m3 h−1 m−2 Pa−1 , 5.66 × 10−7 m3 h−1 m−2 Pa−1 , and 9.26 × 10−7
m3 h−1 m−2 Pa−1 for ceramic, CA, and PVDF, respectively). However, filtration of the surfactants
solutions did not cause permanent blocking of pores and the surface of the ceramic membrane in
contrast to the polymeric ones. No significant differences in surfactants permeation through the
membranes tested were observed. Concentration of the surfactant in the permeate was lower than 1
CMC for the Rofam 10 solution and exceeded the CMC by about 40 % for the SDS solution. Better
separation properties of polymer membranes for the separation of cadmium(II) ions from micellar
systems were identified.

c 2012 Institute of Chemistry, Slovak Academy of Sciences

Keywords: ultrafiltration, ceramic and polymeric membrane, cadmium(II) ion

Introduction hanced ultrafiltration (Huang et al., 2009; Juang et

Traditional methods of elimination or recovery
of heavy metals, i.e. cadmium(II) ions, include pre-
cipitation, ion exchange, crystallization, evaporation,
liquid–liquid extraction (Sadegh Safarzadeh et al.,
2007; Staszak et al., 2011), etc. In most cases, the
ultimate goal of the recovery process is not metal, but
its removal from the effluent. However, the recovery of
heavy metals allows their subsequent re-use and thus
provides further economic and environmental benefits
by contributing to the reduction of costs and saturat-
ing the demand for raw materials (Kurniawan et al.,
2006).
A promising technique for the decontamination of
wastewater containing these metals is the micellar en-
al., 2003; Scamehorn et al., 1986) or polymer enhanced
ultrafiltration (Cañizares et al., 2008; Palencia et al.,
2009; Rivas et al., 2007). Membrane processes provide
high permeate flux and high rates of elimination at low
costs of energy and mild conditions. In addition, mem-
brane separation can be carried out continuously and
it can also be easily combined with other separation
techniques. This method is used for the separation of
low molecular mass solutes and macromolecules.
Basic idea of micellar enhanced ultrafiltration
(MEUF) is that the surfactant solution, with the
concentration higher than the critical micelle con-
centration (CMC), is added to the solution contain-
ing the separated compounds (e.g. metal ion, organic
materials, or low molecular mass solute). When the

*Corresponding author, e-mail: Katarzyna.Staszak@put.poznan.pl

 K. Staszak et al./Chemical Papers 67 (4) 380–388 (2013)
Fig. 1. Scheme of micellar enhanced ultrafiltration.
surfactant concentration is above the CMC value,
micelles with their hydrodynamic diameter signifi-
cantly larger than the pore diameter of the ultrafil-
tration membrane are formed. Dissolved organic com-
pounds are usually soluble in the micelles while dis-
solved ions are usually adsorbed on the micelles sur-
face due to electrostatic binding on the surface of the
opposite-charged micelles. Micelles containing solubi-
lized/bound contaminants with diameter larger than
the membrane pore size are rejected by the mem-
brane during the ultrafiltration process, thus only wa-
ter, unsolubilized contaminants, and the monomeric
form of the surfactant pass through the membrane.
The MEUF phenomenon is illustrated in Fig. 1.
The surfactant used in the micellar enhanced ultra-
filtration can be recovered by precipitation with one
or multivalent counterions, which is one of the advan-
tages of this method (Li et al., 2009). This makes the
entire process more economical. An important advan-
tage of micellar enhanced ultrafiltration is also the low
power consumption and high efficiency of metal ion
solubilization by micelles. Metal ions are bound in the
so-called Stern layer with the temporary surface of the
micelle. The Stern layer is an electrical double layer
formed by charged ions and counterions. In this layer,
about 60–70 % of the micelle charge is neutralized.
The most popular membrane materials are poly-
mers. Due to the variety of materials and sufficient
selectivity effect during the transport, polymeric mem-
branes were unrivaled until inorganic membranes, in-
cluding the ceramic ones, have been introduced. Since
then, their popularity grows and the number of exper-
imental studies conducted to demonstrate the effec-
tiveness of their use in various fields increase. Ceramic
membranes have a lot of advantages: (i) they are au-
toclavable, (ii) allow sterilization by superheated wa-
ter, steam, or oxidizing agents, (iii) show high tem-
peratures resistance, (iv) acids and bases resistance,
(v) solvents resistance, (vi) excellent mechanical re-
sistance, (vii) long working life, and (viii) they are
environment friendly (Barredo-Damas et al., 2010).
Despite their many advantages, ceramic membranes
381
have also disadvantages: large mass and costly pro-
duction of ceramic components. However, these disad-
vantages are acceptable because of their long lifespan
and high chemical and thermal resistance, which is
especially important for their application. The main
advantages of polymeric membranes are the possi-
bility to synthesize novel polymers with well-defined
structures, as ‘tailored’ membrane materials, and low
cost of their production. Unfortunately, these mem-
branes have generally no resistance to harsh environ-
ment (chemical, degradation, pH, temperature, etc.)
(Basile & Gallucci, 2011).
Particular attention was paid to wastewater con-
taining cadmium because of the threat to human
health and environment. Sources of environmental
pollution by cadmium can vary and they are gener-
ally associated with the use of cadmium. Cadmium
is present in fuel oil and in oil for diesel engines;
it can also be used in the electronics, electrical and
metallurgy industry, in batteries, as an additive in al-
loys, in the synthesis of cadmium-based pigments, or
in the manufacture of paints, ceramics, and glazes.
It is also used as a stabilizer in plastics (PVC), and
it is also a component of the production of fertiliz-
ers (Eichler, 1989). In Poland, the most serious prob-
lem concerning cadmium is the zinc industry, produc-
ing primary zinc. Until 1992 (when metallic cadmium
production was stopped), domestic demand for metal-
lic cadmium and its compounds was satisfied by the
Non-Ferrous Foundry “HM Szopienice” in Szopienice
using domestic waste materials as raw materials, in-
termediates from the lead–zinc industry, so-called cad-
mic sponge or crude cadmium carbonate. Much of
the metallic cadmium was and is used in the pro-
duction of chemical compounds. From this perspec-
tive, the production of only metallic cadmium from
cadmium-containing ores (as was done previously in
Poland), has never been rational, both because of
the inconvenience of the metallic cadmium produc-
tion, and complicated dissolution of the metal salts.
It is preferable to produce cadmium salts directly
from industrial waste materials by the hydrometallur-
gical process using extraction or membrane techniques
(Staszak et al., 2011). The recovery of metals from
hydrochloric acid solutions has gained importance be-
cause of the chloride-based leaching in hydrometal-
lurgy. Extraction of cadmium from a chloride medium
can be applied in NiCd batteries recycling, for example
in the Toegepast-Natuurwetenschappelijk Onderzoek
(TNO) method (Romano Espinosa et al., 2004).
The aim of this study was to compare the proper-
ties of ceramic and polymeric membranes in the pro-
cess of micellar enhanced ultrafiltration. Experiments
included the following steps: (i) determination of the
hydrodynamic permeability coefficient of distilled wa-
ter, (ii) determination of the membrane fouling, (iii)
determination of the amount of surfactant in the per-
meate, (iv) filtration of cadmium(II) ions using classic