DESALINATION

ELSEVIER Desalination 164 (2004) 105-110

www.elscvier.com/1oca&deaa l

Removal of heavy metals from wastewater by membrane

processes: a comparative study
Hani Abu Qdais a* , Hassan Moussab
'Department of Civil Engineering, Department of Chemical Engineering, Jordan University of Science and Technology,
PO Box 3030, Irbid 22110, Jordan
Tel . +962 (2) 709-5111 ; Fax +962 (2) 709-5018 ; email : hgdais@just.edujo

Received 28 October 2002 ; accepted 14 August 2003

Abstract
Wastewater containing copper and cadmium can be produced by several industries . The application of both reverse
osmosis (RO) and nanofiltration (NF) technologies for the treatment of wastewater containing copper and cadmium
ions to reduce fresh water consumption and environmental degradation was investigated . Synthetic wastewater samples
containing Cu" and Cd2+ ions at various concentrations were prepared and subjected to treatment by RO and NF in
the laboratory . The results showed that high removal efficiency of the heavy metals could be achieved by RO process
(98% and 99% for copper and cadmium, respectively) . NF, however, was capable of removing more than 90% of the
copper ions existing in the feed water . The effectiveness of RO and NF membranes in treating wastewater containing
more than one heavy metal was also investigated . The results showed that the RO membrane was capable of treating
wastewater with an initial concentration of 500 ppm and reducing the ion concentration to about 3 ppm (99 .4%
removal), while the average removal efficiency of NF was 97% . The low level of the heavy metals concentration in
the permeate implies that water with good quality could be reclaimed for further reuse .

Keywords : Heavy metals ; Reverse osmosis ; Nanofiltration ; Removal efficiency ; Industrial wastewater

1 . Introduction accelerated in recent years and has begun to find

Reverse osmosis (RO) and nanofiltration (NF)
are relatively new processes, which were initially
developed for the production of potable water
from saline and brackish water . However, the
development of these processes has been
*Corresponding author .
applications in the treatment of industrial waste-
water . Recent research indicates that wastewater
reclamation by RO offers great promise for a
sustainable reduction in cost, conserving natural
resources, as well as marked improvements of
pollutant removal efficiency .
Wilf and Alt [1] applied RO for the
reclamation of municipal wastewater . They found

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1 06 H.A . Qdais, H. Moussa /Desalination 164 (2004) 105-110
that RO was capable of treating secondary
effluents. Ujang and Anderson [2] illustrated the
feasibility of using a low- pressure RO process
for the removal of Zn2' and Cu z+ from wastewater
in the presence of EDTA as a chelating agent .
Steenkamp et al . [3] manu-factured a tubular
alumina/chitosan composite membrane and used
it to remove Cu" ions . An effluent of Cu" ions
below 1 mg/l was achieved . Durham et al . [4]
applied microfiltration prior to using RO to treat
municipal wastewater to reduce capital and
operating costs of the RO treatment process .
Redondo [5] presented trends for using RO to
treat low-quality feed water . He discussed the
various benefits and problems encountered in
using RO for treating wastewater . Padilla and
Tavani [6] studied the removal of trivalent
chromium from tanning wastewater using RO .
The study revealed effective removal of the
chromium from wastewater . Okazaki et al . [7]
demonstrated that the use of the RO process in
combination with a microfiltration system
removed cadmium from wastewater produced by
electronic microchip manufacturing to below
detectable levels (i .e ., <0 .01 mg/l) .
Berg et al . [8] applied NF to remove pesti-
cides and other micropollutants . Their study
revealed that at neutral pH values complete
rejection of polar organics is possible with NF .
Tang and Chen [9] applied NF for the treatment
of textile wastewater . The investigation showed
that 98% dye rejection was achieved at an applied
pressure of 500 kPa. Koyuncu [10] investigated
the effect of cross flow velocity and feed
concentration on the removal of reactive dyes
using NF . His study showed a removal greater
than 99% can be achieved by NF mem-branes
containing vinylsulphone dyes . Del Re and
Giacomo [11] coupled NF and supercritical water
oxidation to remove and destroy toxic
micropolluting organic compounds from waste-
water. They claimed that such coupling reduces
both the investment and the operating costs of
removing toxic and dangerous micropollutants
present in the wastewater and produces water of
high level of purity . Schafer et al . [12], Hong and
Elimelech [13] and Cho et al . [14] applied NF for
the removal of natural organic matter and studied
NF membranes fouling behavior by its presence .
Heavy metals are considered as one of the
serious environmental contaminants because of
their high toxicity . Wastewater containing copper
and cadmium can be produced by a variety of
industries such as metal finishing, batteries
manufacturing, electrical cables and electronic
microchip manufacturing, and the mining indus-
try . Legal requirements oblige industries to install
effective wastewater treatment systems . Since the
price of the noble materials such as heavy metals
is constantly increasing, interesting processes are
those capable, in addition to wastewater
purification, of recovering metals . RO and NF
may be such processes .
Membrane separation processes are increas-
ingly used as an alternative to conventional
industrial wastewater treatment . There are several
advantages of using membranes in water and
wastewater treatment [15] . Reuse of water from
industrial processes is an important business goal,
especially when the industry is using large
amounts of water . This goal can be achieved
through industrial wastewater treatment by
membrane processes . Using these processes will
also enable the industry to comply with the
effluent standard limits imposed by environ-
mental regulations [16] .
The conventional and most commonly used
method for the treatment of industrial wastewater
containing heavy metals is the chemical preci-
pitation method [17] . However, this process
requires a large amount of treatment chemicals to
decrease the heavy metals to levels imposed by
the regulations . In addition, the sludge produced
from the precipitation process has to be subjected
to dewatering and disposal into landfills, which
adds an additional cost to the treatment process .
 H.A . Qdais, H. Moussa /Desalination 164 (2004) 105-110 107

Therefore, it is important to recover the valuable The initial concentration of the metal sulfates
materials (metals and water) and prevent environ- used in the experiments ranged from 25 to
mental degradation . The purpose of this study is 200 ppm for both CuSO 4 and CdSO 4 . A bench-
to evaluate the performance of the RO and NF scale membrane unit was used to carry out the
processes in removing heavy metals from experiments consisting of a module containing
industrial wastewater . two tubular spiral-wound membranes arranged in
series . The system is fed by a plunger pump,
which provides high pressure . The experimental
2. Materials and methods set-up is shown in Fig. 3, and the membrane
Synthetic samples of wastewater were pre- characteristics are presented in Table 1 .
pared by adding different amounts of copper and Initially the experiments were conducted using
cadmium as cupric and cadmium sulfates to cupric and cadmium sulfates separately . After
distilled water . To monitor the performance of the that, a mixture with various ratios of
RO and NF processes, the total dissolved solids CuSO 4 :CdSO4 (1 :3, 1 :1 and 3 :1) were subjected
(TDS) concentration was used as an indicator of to treatment by both RO and NF processes .
performance . Several solutions were prepared
with different concentrations of copper and
cadmium sulfates . The TDS was measured each
time at 19°C, and the calibration curve between
the added concentration and TDS was prepared .
Figs . 1 and 2 show good correlation between the
added concentration of copper and cadmium and
TDS (R2 is 0 .984 and 0 .995 for copper and
cadmium, respectively) . The high correlation
obtained suggests that TDS is a good indicator for
measuring the concentration of the heavy metals
in the solution .

160

Fig . 2 . Calibration curve using TDS as an indicator to

measure CdSO 4 concentration.

MEMBRANE ASSEMBLY

Pressure
gauge

0 0 .5
Tank
Initial concentration, mM
Fig . 1 . Calibration curve using TDS as an indicator to
measure CuSO4 concentration. Fig . 3 . Schematic diagram of the membrane unit .


108 H.A . Qdais, H. Moussa /Desalination 164 (2004) 1 05-110

Table 1
Membrane specifications used in the experiments

Characteristics RO NF
membrane membrane

Membrane material Polyamide Polyamide

Membrane configuration Spiral wound Spiral wound
Membrane surface area, m 2 2 .5 2 .5
Allowable operating pH range 4-11 2 .5-11
Maximum operating temperature, °C 45 45
Maximum feed turbidity, NTU 1 1
Maximum feed SDI, 15 min 5 5

3. Results and discussion 0.11 ppm with average removal efficiency of

98.5%, while the cadmium removal efficiency of
The efficiency of RO and NF processes in
the NF ranged from 82 to 97% . This implies that
removing Cu+2 and Cd2+ from wastewater is
membrane techniques such as RO and NF are
presented in Figs . 4 and 5 . As shown from Fig . 4,
efficient processes for removing heavy metals
Cu" ions were successfully removed from the
from wastewater, so as to reclaim this water for
wastewater by both RO and NF . The concen-
further uses. The results obtained also show that
tration of Cu" in the product water (permeate) for Cd2+ ions were removed at a slightly higher
RO was reduced to an average value 3 .5± efficiency compared to Cu e+ . This might be due to
1 .7 ppm with an average removal efficiency of the fact that the size of the Cd2+ is larger than that
97% . On the other hand, the removal efficiency of Cu e+ . A somewhat similar result was found by
of Cue{ by NF ranged from 84% to 96% for an Ujang and Anderson [2], who reported that Zn 2+
initial feed concentration of 25 and 200 ppm, ions can be removed at a slightly higher
respectively . The same result can be observed for efficiency compared to Cu e+ . This was also con-
Cd2+ ions (see Fig . 5) where its concentration in firmed by the higher removal of cadmium than
the permeate from RO was reduced to 1 .77± the copper under the same pressure by RO, as
shown in Fig . 6 .
10 10
• RO 0
• RO
0 ONF
O NF 0
0 E
CL 0 0
O O 0 0
0 0
O O 0
0
• • f-
2 • • • • • • • •
0
0 50 100 150 200 250 0 50 100 150 200
Initial concentration, ppm
Initial concentration, ppm
Fig . 4 . Concentration of CuSO4 in the permeate from RO Fig . 5 . Concentration of CdSO4 in the permeate from RO
and NF for different feed concentrations . and NF for different feed concentrations


H.A . Qdais, H. Moussa /Desalination 164 (2004) 1 05 -110 109

Table 2
RO efficiency in treating the mixture of copper and cadmium salts

Solution Concentration Concentration TDS in the feed Permeate

no . of CuSO4 , ppm of CdSO4, ppm to the RO, ppm concentration, ppm

1 125 375 500 3 .09

2 250 250 500 3 .20
3 375 125 500 3 .34

Table 3
NF efficiency in treating the mixture of copper and cadmium salts

Solution Concentration Concentration of TDS in the feed Permeate

no . of CuSO 4, ppm CdSO4 , ppm to the RO, ppm concentration, ppm

1 125 375 500 12 .34

2 250 250 500 13 .16
3 375 125 500 13 .58

The effectiveness of RO and NF membranes

in treating wastewater containing mixed heavy E
CL
metals was tested. Three different solutions were CL
prepared which contained concentrations of
CuSO4 and CdSO4 with different ratios so as to
achieve a solution with TDS of 500 ppm . The
ratios of CuSO 4 and CdSO4 concentrations in the
solutions are given in Tables 2 and 3 . The con- EL
d
s
centration of the ions in the permeate from the Q

RO was found to be about 3 ppm (99 .4% removal 0

efficiency), whereas it was 13 ppm from the NF
experiment (97 .4% removal efficiency) . This is a
clear indication that RO and NF are also capable
of treating wastewater containing more than one
heavy metal . The results also show that RO is
more effective than NF in obtaining water with
lower heavy metal concentration as obtained in
the single heavy metal cases .
The local Jordanian standards of industrial
wastewater discharges (JS 202/1991) require that
the concentration of Cu 2T and Cd2+ in discharge
water should not exceed I and 0 .01 ppm, respect-
ively . Slightly higher values were obtained in the
experiments performed . The concentration of the
above ions can still be lowered by further treating
5 7 9 11 13 15
Applied pressure (bar)
Fig . 6 . Effect of the applied pressure on permeate con-
centration for both cadmium and copper by RO (feed
concentration 500 ppm) .
the permeate in another RO unit or increasing the
operating pressure . Fig . 6 shows the effect of the
applied pressure on the concentration of the ions
in the permeate from RO . The results confirm that
lower concentration can be achieved by
increasing the applied pressure . It can also be
seen from this figure that the removal of Cd +2 is
always higher than Cu +2 for the same pressure and

110 H.A . Qdais, H. Moussa /Desalination 164 (2004) 105-110
initial concentration . The results obtained in this
study are of great importance for a country like
Jordan where water is scarce, and it is necessary
to investigate all means to prevent water
resources degradation and to conserve freshwater
for domestic use .
4. Conclusions
Wastewater containing copper and cadmium
is produced by several industries . Environmental
regulations oblige industries to treat the waste-
water containing heavy metals to reduce their
concentration to acceptable levels . The present
study suggests that membrane processes are very
successful techniques for the removal of heavy
metals such as Cu" and Cd 2+ from wastewater
streams . They are capable of reducing the heavy
metal concentration in the effluent stream to low
levels that are accepted and recommended by
local Jordanian standards for industrial waste-
water discharge . Reuse of industrial wastewater
containing heavy metals after treatment by RO
and NF is feasible and can contribute in
alleviating the pressure on conventional water
resources. This is especially important in a
country like Jordan, which suffers from a chronic
water shortage . Membrane process should be
explored further for the possibility of heavy
metals recovery .
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