Performance of an acid stable nanofiltration membrane for nickel

removal from aqueous solutions: effects of concentration, solution

pH and ionic strength
O. Agboola
Department of Chemical Engineering, Faculty of Engineering and the Built Environment,
Tshane !niversity of Technology, "retoria, #outh Africa.
Abstract
The performance evaluation of a nanofiltration membrane for the removal of the nic$el ion
as studied as a function of the nic$el concentration, solution p%, and the bac$ground ionic
strength of the solution. &anofiltration is investigated as a means to determine to hat e'tent
the nic$el ions could be removed from acid mine drainage( thus the effect of solution
chemistry on nanofiltration performance is investigated. %igher flu'es )*+.,l-m.-h/ ere
e'perienced at the loer nic$el concentration )01mg-l/ than at )011mg-l/ nic$el concentration
ith flu' of )23.4l-m.-h/ and 511mg-l ith the flu' of )21.+2l-m.-h/ nic$el concentration.
%igher nic$el ion re6ections of )4+7/ ere obtained at the higher nic$el concentrations
)011mg-l and 511mg-l/ than at the loer nic$el concentration )48.,7/. %igher flu'es of *5.5
l-m.-h and 83.2 l-m.-h ere obtained at the higher p% )p% 4/ ith a 1.109 &aCl and 1.159
&aCl bac$ground solution respectively than at loer p% )p% 8, p% * and p% 3/. %igher
nic$el ion re6ections ere obtained at higher p% )p% *, 3 and 4/ for the to ionic strength
bac$ground solutions. %igher flu'es ere also obtained ith the loer &aCl bac$ground
solution. %igher re6ections ere obtained ith both &aCl bac$ground concentration for p% *,
p% 3 and p% 4. :t therefore appears that this nanofiltration membrane should be successfully
applied for the removal of nic$el ions from acid mine drainage.
Keywords: nanofiltration, acid mine drainage, nickel removal, nickel rejection, fluxes, nickel
concentrations, solution pH, ionic strength
1 Introduction
The pollution of surface aters by metal ions originating from acidic effluents )As, "b, Fe,
&i, Cd, 9g, 9n/ from refineries, electroplating effluents )Cu, &i, "b, ;n, Cr/ and from acid
mine drainage )Fe, Al, Cu, 9g, &i, ;n/ can cause serious problems because of their to'icity
<0=8>. These problems have stimulated research the last number of years to study appropriate
1
methods for their removal from ater. &anofiltration is one method that should be effectively
applied for the removal of heavy metal ions from effluents <*>.
#everal studies have been conducted the last number of years to identify the different factors
involved in the re6ection of metal cations by nanofiltration membranes. A$bari et al <5>
investigated the effect of solution chemistry and operating conditions on the nanofiltration of
acid dyes by a nano=composite membrane. Their study shoed that the re6ections of sodium
chloride and sodium sulphate ere moderate and declined ith increasing feed concentration.
:t as also found that by changing the p% that the membrane surface and the dyes charge
changed ith the result that the membrane surface and dyes had different interactions at
different p% values.
Dipan$ar et al <,> studied the effect of solution chemistry on ater softening using charged
nanofiltration membranes. They found that the flu' declined ith increasing ionic
concentration of the feed solution. #hafer et al <+> investigated effects of solution chemistry
on the retention of lo molecular mass acids versus bul$ organic matter by nanofiltration.
Their results emphasi?ed that the charge and si?e of the cations and acids are important for
separation.
Dahmani and Chabene <3> studied the effect of solution chemistry on the performance of a
nanofiltration membrane for nic$el removal from an a@ueous solution. They found that the
solution p%, feed concentration and the ionic strength of the solution affected ion re6ection
and flu'. Choo et al <4> studied the selective removal of cobalt species from simulated
nuclear li@uid aste ith different nanofiltration )&F/ membranes at different solution p%
levels, different cobalt concentrations, and different ion bac$ground concentrations. Their
study provided insight into the understanding of the relationships beteen re6ections of a
target compound )cobalt/ and the chemical e@uilibria of different species in the feed solution
during nanofiltration.
Acid mine drainage containing high concentrations of iron, manganese, cobalt, nic$el, etc., is
of ma6or concern hen it lea$s into the ater environment. An acid stable nanofiltration
membrane hich has the potential to operate at lo p% )p% 2/ has the potential to treat acid
mine drainage effectively. "art 0 of this or$ as presented at the ,
th
international conference
of aste management and the environment 2102 at loer p% of 8 and * and at loer
concentration of 01mg-l and 011mg-l <01>. Therefore, the ob6ective of this investigation is to
2
further evaluate the use of the acid stable membrane for the removal of the nic$el ion at
higher p% values and higher concentration ith this membrane and other membranes.
2. !perimental
2.1 "anofiltration membrane characteristics
A composite nanofiltration membrane )&ano="ro A 8102/ as chosen for this research as
representative of a class of membranes hich are acid stable in ater treatment applications.
According to the manufacturer, the ma'imum operating pressure is *1 bar )531 psi/,
ma'imum operating temperature 51AC )022AF/, alloable p% B Continuous OperationC 1
=02, Decirculation Flo DateC 9inimum 41E-min )2*gpm/, 9a'imum 231E-min )+* gpm/
2.2 Anal#tical $ethod
&ic$el ion concentration as analysed by using inductively coupled plasma optical emission.
9easurements of solution p% and temperature ere made using a p% meter )9ettler Toledo
FF21/ purchased from 9icrosep and thermometer respectively. The ionic strengths ere
calculated using a correlation beteen conductivity and ionic strength of a &aCl standard,
:.#. <9> G0-2HC
i
Z
i
2
)C
i
is the ion concentration and Z
i
is the number of ions/.
2.% &lu! decline e!periments
The e'periments ere carried out ith one liter of solution containing a nic$el sulphate
solution )&i#O
*
/ ith concentrations of 01 and 011 mg-E. The solution p% as varied from 8
and * and the effect of ionic strengths )1.10 9, 1.15 9 as &aCl/ on flu' as investigated.
Flu' decline e'periments ere conducted by using a 0 111=ml dead=end membrane filtration
apparatus )9emcon #outh Africa/ ith magnetic stirrer. A membrane sheet as fitted to the
cell. The membrane active area is about 1.101+5m
2
. The operating pressure as employed via
high=pressure regulator and a nitrogen gas cylinder. The permeate flu' as collected in a
bea$er on the electrical balance and the permeate mass as determined.
2.' &iltration !periments
9embrane sheet stored in 1.+7 - ben?al$onium chloride at 2=81AC as used for the study.
The membrane sheet as initially rinsed in clean distilled ater and as used to measure the
clean ater flu' )CIF/ using distilled ater before each nic$el solution as used ith the
system. The clean ater flu' e'periments ere done to see if membrane did not foul. The
3
clean ater flu' as done at stirring velocity rate of 511 rpm and a pressure of 81 bar. Feed
nic$el solutions ere prepared for each test condition. After filtration as terminated, the
membrane as cleaned ith deioni?ed ater, folloed by a clean ater flu' measurement.
The ater flu'es at different operating conditions ere measured to determine ater flu'
recovery.
2.( )aborator# *ead+nd ,est -ell
The investigation as done using a 9emcon Eaboratory #tirring Cell as shon in Figure 0.
The membrane tested as placed in the cell. A litre of sample as then placed in the cell at
the product inlet. "ressure as then applied ith nitrogen gas and the permeate collected and
its mass determined.
Figure 0C #chematic diagram of laboratory dead=end filtration system.
2.. Anal#sis of /esults
The permeate flu' and re6ection ere investigated as a function of or$ing parameters such
as operating time and ater recovery. The permeate flu' J
v
)l-m
2
-h/ as determined by
measuring the volume of permeate collected in a given time interval divided ith membrane
area by the relationC
A

!
v
=
)0/
Ihere, and A represents flo rate of permeate and the membrane area, respectively.
4
Compressed &itrogen Fas
9embrane
#tirring
Dod
#cale
9agnetic
#tirrer
Feed Deservoir
The observed re6ection hich is the measure of ho ell a membrane retains a solute as
calculated by the folloing relationC

011 / 0 ) 7 =
i
p
C
C
"
)2/
Ihere C
p
and C
i
are the solution concentrations in the permeate and in the initial feed
solution, respectively.
%. /esults and *iscussions
%.1 -lean 0ater flu! as a function of pressure
Clean ater flu' as a function of pressure as done for three different pressures )81, 21, and
01 bar/ before nic$el as added to the feed solutions to establish initial conditions and to
determine the effect of pressure on flu'. The flu'es as a function of time and ater recovery
are shon in Figure 2. The feed pressure had a significant effect on nanofiltration membrane
performance. A relatively high flu' )*,.4* l-m.-h/ as obtained at 81 bar and the flu'
decreased significantly at 21 bar )23.01 l-m.-h/ and 01 bar )0,.24 l-m.-h/. These flu'es are
lo for a nanofiltration membrane and it as decided to conduct all subse@uent runs at a
pressure of 81 bar.
%.2 $emebrane -haracteri1ation
%.2.1 $embrane $orpholog# 23$4
:n nanofiltration separation application, porous membranes separate particles by seiving
mechanism hich is determine by pore si?e of the membrane and particles si?e. &ano="ro=
8102 surface features ere investigated using #E9 and the results are shon in figures 8and
*. Figure 8 shos that there are no visible pores on the surface of the membrane hile figure
shoed some selected pores. :mage analysis as done in image J to select the pores to find
the reason hy the flu'es are lo for a nanofiltration membrane. :t can be seen from figures
8 and * that &ano="ro=8102 has smaller pores that does not even covers the surface of the
membrane thus pushing ater through this membrane re@uires a higher operation pressure.
Figure *c displays the intensity along the selected rectangle, this can be use to find the
thic$ness and the porosity of the membrane.
%.% ffect of solution concentration on flu! and ion re5ection
5
The effects of nic$el ion concentration on permeate flu' and ion re6ection is shon in Figures
5 and ,, respectively. "ermeate flu' as higher at the loer concentration and loer at the
higher concentration )Figure 5/. The loer flu' at the higher concentration could be ascribed
to the higher osmotic pressure of the solution at the higher concentration. "ermeate flu' is
also lo )appro'imately 81 l-m.-h and 28 l-m.-h for the 011 mg-l and 511 mg-l nic$el
concentration respectively and appro'imately *5 l-m.-h for the 01 mg-l nic$el concentration/.
The nic$el ion re6ection as slightly higher at the higher nic$el concentration )4,= 4+7/ for
511mg-l and 011mg-l than at the loer nic$el concentration )3,= 487/ )Figure ,/. The nic$el
ion re6ection did not change much ith increasing ater recovery. These findings for
permeate flu' and ion re6ection as a function of concentration are in correspondence ith
findings of Dahmani and Chabene <3>. They, hoever, used a &F =41 membrane from Do=
Film Tec in their studies.
)a/ )b/
Figure 2C Flu' of deioni?ed ater as function of time and ater recovery )81 bar/.
6
Fig 8. #E9 image )A/ and selection of pores ith :mage J )B/. &o visible pores are seen.
Fig *. #E9 image )A/ and selection of pores ith :mage J )B/. Kisible pores are seen and are
selected in red. )C/ :ntensity along the selected rectangle of the #E9 image.
7
(A) SEM
(B) Analysis of SEM
with Image J to
selet !o"es
(B) Analysis of SEM
with Image J to
selet !o"es
(A) SEM
)a/ )b/
FigureC 5 Effect of solution concentration on flu' decline( )a/ as function of time and )b/ as a
function of ater recovery )81 bar/.

(a) )b/
FigureC , Effect of solution concentration on nic$el ion re6ection( )a/ as function of time and
)b/ as a function of ater recovery )81 bar/.
%.' ffects of solution pH and ionic strength on flu!
The effect of solution p% on flu' is shon in Figure + for a &aCl bac$ground solution of
1.10 and 1.159 )01mg-l nic$el/. A higher permeate flu' as e'perienced at the higher p%
)p% 4/ )*5.5 l-m.-h and 83.0* l-m.-h/ than at loer p% values )p% 8, *, and 3/ for both the
#
1.10 and 1.159 bac$ground solutions. This is also in correspondence ith findings of
Dahmani and Chabene e'perienced <3>.
%.( ffects of solution pH and ionic strength on nickel ion re5ection
The effect of the solution p% on &i ion re6ection for to the to &aCl bac$ground solutions
)1.10 and 1.159/ are shon in Figure 3. %igher &i ion re6ection )appro'imately 44.47 as
e'perienced at the higher p% values )p% *, 3 and 4/ for both bac$ground solutions.. This
could be ascribed to the higher flu' e'perienced at the higher p% values. Eoer ion re6ections
ere obtained at a solution p% of 8. &ic$el ion re6ection as about 45=4,7 at 1.10 9 &aCl
and 42=487 at 1.159 &aCl. Therefore, loer nic$el ion re6ections ere obtained at the
higher &aCl bac$ground )1.15 9/ solution.
)a/ )b/
Figure +C Effect of solution p% on Flu' decline( )a/ 1.109 &aCl )b/ 1.159 &aCl )81bar/
$
%&%1
'a(l
2a4 2b4
Figure 3C Effect of solution p% of on nic$el ion re6ection( )a/ 1.109 &aCl )b/ 1.159 &aCl
)81 Bar/
%.. -lean 0ater flu!es before and after e!posure of the membrane to the nickel
solutions
Determination of clean ater flu' is an important characteristic hen estimating fouling in
membrane separation process. The determination of clean ater flu' as used as basis for
comparison before and after the e'posure of the membrane to the solution. The membrane
productivity is e'pressed as the permeate flu' through the membrane. The initial and final
)after e'posure of the membrane/ clean ater flu'es are shon in Figures 4 and 01. The
initial clean ater flu' as a little bit higher than the clean ater flu'es after e'posure of the
membrane to the solution. This indicated that the membrane surface as somehat affected
by the solution. Therefore, care should be ta$en to pretreat the ater properly prior to
treatment of real acid mine drainage to prevent fouling of the membrane.
1%
%&%1 'a(l
%&%5 'a(l
)a/ 2b4
&igure 6: Flu' of deioni?ed ater as function of )a/ time( )b/ ater recovery )81 bar/
)a/
11
25L(
)b/
&igure 17: Flu' of deioni?ed ater as function of )a/ time( )b/ ater recovery )81 bar/
'. -onclusion
The performance of a nanofiltration membrane for the removal of nic$el ions from an
a@ueous as investigated using a dead=end test cell. Feed pressure has a significant effect on
permeate flu'. "ermeate flu' decreased from about *+ l-m.-h at 81 bar to about 0, l-m.-h at
01 bar. "ermeate flu' as higher )*+.,0 l-m.-h/ at the loer nic$el concentration )01 mg-l/
than at the higher nic$el concentration )011 mg-l( 23.44 l-m.-h/ and )511mg-l( 21.+2 l-m.-h/.
&ic$el ion re6ection as somehat higher )4+7/ at the higher nic$el concentrations )011
mg-l and 511mg-l/ than at the loer nic$el concentration )01 mg-l( 3,.+37/. %igher permeate
flu'es ere e'perienced at the higher p% )p% 4/ for both ionic strength solution. %igher
nic$el ion re6ection )44.47/ as e'perienced at the higher p% values )p% *, 3 and 4/ than at
the loer p% )p% 8( 45.57/. %igher permeate flu'es ere obtained at the loer ionic
strength solution )1.10 9/ than at the higher ionic strength solution )1.15 9/ at all p% values.
%igher nic$el ion re6ection )4,.027/ as obtained at the loer ionic strength )1.10 9/ than
at the higher ionic strength )1.15 9( 42.037/ at p% 8 and nic$el re6ection ere higher
)44.37/ at p% values of *, 3 and 4 for both ionic strength. The clean ater flu' after
e'posure of the membrane to the nic$el solutions as somehat loer than the initial clean
ater flu'. Therefore, some membrane fouling too$ place. The membrane should be suitable
for the removal of the nic$el ion from acid mine drainage. %oever, flu' is lo and other
membranes should also be evaluated. #E9 images of &ano="ro=8102 ere analysed using
12
25L(
the public domain &:% :mageJ softare, version 0.*+v and is available on the internet at
httpC--rsb.info.nih.gov-i6.
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13
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J., 9baya D., Molesni$ov

A., N #choeman J.J. "erformance of an
acid stable nanofiltration membrane for nic$el removal from a@ueous solutionsC
effects of concentration, solution p% and ionic strength. ,
th
:nternational Conference
on Iaste 9anagement and the Environment, ,
th
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14