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Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l
a r t i c l e i n f o a b s t r a c t
Article history: Wastewater reclamation requires processes and technologies having the ability to reduce the presence of
Accepted 8 November 2008 micropollutants which are not wholly treated in conventional WWTP. Due to the complexity of membrane–
Available online 12 October 2009 solute interactions and the diversity of secondary treatment effluent (STE) matrices, deeper investigations
are required to identify the major foulant species and more specifically their behaviour at high concentration
Keywords:
in real waters. This study investigates the rejection and fouling potential of nanofiltration (NF) and low-
Domestic wastewater reuse
Nanofiltration
pressure reverse osmosis (RO) membranes with two STEs sampled from i) a conventional activated sludge
Reverse osmosis process coupled with ultrafiltration (CAS-UF) and from ii) a membrane bioreactor MBR (AquaRM®, SAUR
Membrane fouling (France)). Whatever the origin of the effluent, RO seems to be the best solution to prevent pollution of
Micropollutant retention tertiary effluents (expected result) but also to obtain low fouling levels. The different composition and
molecular weight distribution of MBR and CAS-UF effluents can explain the different fouling behaviours that
were observed.
© 2009 Elsevier B.V. All rights reserved.
0011-9164/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2008.11.052
834 M. Jacob et al. / Desalination 250 (2010) 833–839
UF before RO). The impact of volume reduction factors (VRF) over Table 1
fouling has also been studied by Garcia-Figueruelo et al. [12]. Their Membrane characteristics.
study shows that, up to a VRF of 3, there is not any fouling of the RO Membrane NF-lo NF-ti RO-m
membrane when filtrating real STE. Deeper investigation of the
Salt retention 40–60% CaCl2 85–95% CaCl2 N98% CaCl2
influence of VRF, concentration factor and trans-membrane pressure N97% MgSO4 N97% MgSO4
(TMP) would allow to improve the full water reuse process in terms of Water permeability at 20 °C (L h m2 bar) 12.1 6.2 3.6
energy and water saving. Experimental measurements +/−1.1 +/−0.6 +/−0.1
Contact angle (°) 28 63 69
Then, the following study focuses on the comparison of two
Zeta potential at pH7 (mV) Negative Negative Negative
different secondary and tertiary treatment processes and thus to the − 19.7 − 14.2 − 7.7
following treatment lines: CAS-UF + RO/NF and MBR + RO/NF as
shown in Fig. 1.
Analysis of TOC, conductivity, UV at 254 nm, UV at 210 nm and
volume reduction factor (VRF = V0 / (V0 − Vp)) were calculated versus
HPLC-SEC chromatography provide information about retention
filtration time.
capacities of the membranes under different experimental conditions.
At the end of each filtration, membranes were washed with ultrapure
Filtration performances are determined by flux decline measurements
water. The water permeability after rinsing was then measured and
(fouling velocities) and autopsies of the membrane surface by
compared with the water permeability before filtration. The difference of
scanning electronic microscopy (fouling structure). The effect of
permeability enabled to measure the flux decline due to irreversible
VRF, STE's matrix and TMP on the RO and NF membrane performances
fouling (or reversible only by addition of chemicals).
in terms of filtration and retention performances is investigated at lab
The fouling resistance (Rc) is given by Darcy's law (Eq. (1)):
scale with real effluents.
TMP−Δπ
J= ð1Þ
2. Materials and methods μ⋅ðRm + Rc Þ
STEs were sampled from two MBRs (AquaRM®, SAUR (France)) 2.3.1. UV/VIS spectroscopy (JASCO V-530)
and one CAS-UF process treating domestic wastewater was used as Absorbances at 210 nm, 254 nm and 280 nm were performed.
feed effluent for RO or NF filtrations (properties of these effluents are The wavelength at 210 nm enables to detect most of the organic
given in Section 2.4). compounds such as aldehydes, carboxylic acids, esters, nitrites, etc…
Ultrafiltration was performed with a module containing NORIT Absorption at 254 nm is characteristic of aromatic molecules.
hollow fibers (MWCO = 200 kDa) at an average flux of 70 to 100 L h− 1 Absorbance at 280 nm is mainly used to detect proteins.
m− 2 at constant pressure equal to 0.5 bar.
A 500 mL (V0) stirred filtration cell was used for filtration of STEs 2.3.2. High performance size exclusion chromatography (HPLC-SEC)
by RO and NF membranes at constant pressure (4–6–8–12 bars) and Size exclusion chromatography enables the determination of the
constant stirring. The velocity of the mixer at the blade extremities molecular size of organic molecules. A SHODEX SB802.5 column was
was equal to 0.3 m s− 1. For each experiment, a new piece of mem- used. The mobile phase consisted of 25 mM Na2SO4 and phosphate
brane of 0.0045 m2 was used. During filtration, the volume of reten- buffer as defined by Her et al. [13]. The system was calibrated using
tate decreased according to the volume of filtrated permeate. In order dextran molecules (1, 5, 12, 20 kDa) and operated at 0.4 mL min− 1
to compare each experiment, the normalized flux (J/J0) and the with 100 µL injections and detection of UV at 210 nm and 254 nm.
Fig. 1. Study case: impact of CAS-UF and MBR secondary treatments on tertiary treatment membranes (NF or RO) performances.
M. Jacob et al. / Desalination 250 (2010) 833–839 835
MBR-1 effluent MBR-2 effluent CAS + UF effluent 3.1. Performance of reverse osmosis membrane
UV 254 nm 0.148 0.155 0.215
UV 210 nm 3.207 1.579 1.880 Table 3 summarizes rejections of RO-m for the 3 effluents at
UV 280 nm 0.128 0.115 0.163 different TMP and VRF.
TOC (mg L− 1) 8.0 6.0 7.6 Firstly, as expected, it can be observed that RO-m presents reten-
COD (mg L− 1) 12 13 18
tions higher than 90% for every indicator. Furthermore, a slight in-
SUVA 1.9 2.6 2.8
SS (mg L− 1) b2 b2 b2 fluence of the TMP can be noticed on the indicator UV at 210 nm. The
Mg2+ (mg L− 1) 9.8 8.9 23.3 VRF does not influence the retention capacities as well. The average
Ca2+ (mg L− 1) 28.4 25.0 24.1 retentions are also the same whatever the feed water. Consequently,
Conductivity (µS cm− 1) 894 631 1300 the composition of effluent in the filtration cell has no effect on RO-m
Nitrates (mg L− 1) – 2 –
performances in terms of retention capacities.
– : not measured. Fig. 2 shows the flux decline of the RO-m for the 3 STEs tested at
the same pressure equal to 8 bars.
On the one hand, similar flux declines, for all effluents, can be
Total organic carbon (model “TOC-VCSH/CSN”, Shimadzu), chemical
observed from the beginning of the experiment to VRF equal to 2.3
oxygen demand (COD) (AFNOR NFT 90-101), suspended solids (SS)
(zone A). On the other hand, from VRF equal to 2.5 to the end of
(standard NF EN 872), conductivity (standard NF EN 27888) and
filtration (zone B), the flux decreases abruptly (around 60%/VRF unit)
concentration of magnesium and calcium by atomic absorption spec-
for MBR-1 and CAS effluents. Then, two different fouling mechanisms
troscopy were also measured. Autopsies of the membranes were
occur in zones A and B except for MBR-2 effluent. Indeed, the MBR-2
performed by scanning electronic microscopy (SEM) (JEOL 5410 LV
effluent exhibits a constant slight linear flux decline versus VRF (5%/
instrumentation).
VRF unit) until the end of the filtration. Furthermore, the effluent
Samples of feed (STE), retentate at the end of the filtration, and
that is less concentrated (MBR-2), particularly in organic matter and
permeate (4 samples of permeate for each experiment according to
conductivity, shows also the lower flux declines compared to MBR-1
VFR= 1.1; 1.4; 2.0 and 3.3) were collected for each experiment. Then,
effluent.
solute concentrations of the retentate (Cr) and permeate (Cp) enabled to
Fig. 3 displays SEM analysis of a clean RO-m and two RO-ms at the
calculate the observed solute retention capacity (Robs) of the membrane
end of MBR-1 and MBR-2 effluent filtrations at 8 bars.
(Eq. (2)). TOC, UV at 210 nm, UV at 254 nm and conductivity are the
No filtration cake was observed with the MBR-2 effluent which is
indicators used in this study to calculate these observed retention
consistent with the low flux decline observed, whereas MBR-1 ef-
capacities.
fluent causes formation of a visible cake. Furthermore, after water
rinsing of these membranes, more than 95% of permeability recovery
was obtained for both effluents. Consequently, the two fouling ten-
Cp
Robs = 1− ð2Þ dencies described previously are the results of a reversible fouling.
Cr
Then, the first mechanism could be due to the rise of the osmotic
pressure or electrostatic interactions. The second mechanisms could
be the result of a cake formation.
Robs observed retention capacity As the more important flux decline was observed with MBR-1
Cp permeate concentration (kg m− 3 or mg L− 1) effluent, it was decided to study the influence of pressure on per-
Cr retentate concentration (kg m− 3 or mg L− 1) formances of filtration of the MBR-1 effluent. Thus, Fig. 4 presents the
effects of the TMP on the flux decline during the filtration of MBR-1
effluent with the RO-m.
TMP does not act on RO-m performance in terms of flux decline.
2.4. Secondary treatment effluent characteristics Same results about TMP effects were obtained with the other effluents
(MBR-2 and CAS), which means that, in this range of pressure (4 to
The characteristics of the effluent used in this study are described 12 bars) cake deposits are not compressible.
in Table 2.
Organic and mineral contents of the CAS effluent are globally 3.2. Performance of nanofiltration membranes
higher than MBR ones. Compositions of MBR effluents are very close.
Nevertheless, conductivity, TOC, calcium and magnesium, and UV210 Table 4 summarizes rejections of NF-ti and NF-lo for the 3 effluents
are lower for MBR-2 than for MBR-1. at different TMP and VRF.
Table 3
RO-m retention capacities (%).
UV210 UV254 TOC Cond UV210 UV254 TOC Cond UV210 UV254 TOC Cond
MBR-2
VRF = 1.1 91 96 91 97 95 N98 91 97 96 97 92 98
VRF = 1.4 90 89 91 96 97 N98 95 97 97 N98 96 98
VRF = 2 92 N98 96 96 95 N98 96 97 96 N98 97 98
VRF = 3.3 90 N98 95 96 94 N98 97 97 97 N98 98 98
Average 91 95 93 96 95 N98 95 97 97 N98 96 98
MBR-1
Average 94 97 97 98 97 N98 97 98 96 N98 97 98
CAS + UF
Average 93 N98 96 96 94 97 96 97 96 N98 96 98
836 M. Jacob et al. / Desalination 250 (2010) 833–839
Fig. 2. RO-m's flux decline versus VRF at 8 bars for MBR-1, MBR-2 and CAS effluents. Fig. 4. RO-m's flux decline versus VRF at 6, 8 and 12 bars for MBR-1 effluent.
High retention (N90%) of aromatic molecules (UV at 254 nm), (4 and 6 bars), there is a low flux decline (10%/VRFunit) up to VRF
conductivity and TOC were observed for NF-ti but retention is smaller equal to 3 followed by a higher flux decrease (25%/u). At
than 80% for molecules absorbing UV at 210 nm. NF-lo shows retention intermediate pressure (8 bars), the flux drops linearly with the
higher than 90% for aromatic molecules but low retention (b50%) of VRF. Finally, at high pressure (N12 bars), the flux decline is high
molecules absorbing UV at 210 nm and conductivity. Globally, NF-ti, as (80%/u) at the beginning of the filtration and then decreases
it was expected, allows higher retention capacities than NF-lo. The effect according to VRF (~ 15%/u). On Fig. 6, for NF-ti, the flux tends to
of TMP on retentions is higher for NF-lo than for NF-ti. Indeed, for a decrease linearly with the VRF for all the TMPs.
pressure varying from 4 to 12 bars, retention of molecules absorbing UV Furthermore, water rinsing of fouled membranes gives the following
at 210 nm by NF-lo almost doubles when the one of NF-ti rises to about results (Table 5).
10 to 20%. Furthermore, for NF membranes, the higher the VRF, the Permeability recovery is much higher for NF-lo than for NF-ti
higher is the retention. whatever the pressure. Moreover, an increase of TMP causes a rise
Figs. 5 and 6 display the effect of TMP on the flux decline of NF-lo of irreversible fouling. For NF-lo, the flux decline behaviour at low
and NF-ti respectively for the CAS effluent. pressure tends to the one observed with RO. Thus, fouling is also
For both membranes, the higher the TMP, the higher is the flux probably due to osmotic pressure and electrostatic repulsion up to
decline. For NF-lo, three tendencies can be observed. At low pressure VRF equal to 2–3 and then to the formation of a cake. Adsorption
Fig. 3. SEM analysis of three (RO-m)s (×5000): a clean RO-m, RO-m after fouling by MBR-2 and RO-m after fouling by MBR-1.
M. Jacob et al. / Desalination 250 (2010) 833–839 837
Table 4
Retention capacities of NF membranes.
UV210 UV254 TOC Cond UV210 UV254 TOC Cond UV210 UV254 TOC Cond
NF-ti
MBR-1
VRF = 1.1 67 N98 74 90 75 95 82 92 77 97 91 93
VRF = 1.4 72 N98 94 92 79 N98 93 93 80 96 93 95
VRF = 2 76 N98 96 92 81 N98 95 94 82 98 93 95
VRF = 3.3 – – – – 81 N98 93 92 81 97 87 91
average 72 N98 98 91 79 97 91 93 80 97 91 93
MBR-2 67 98 92 91 79 N98 93 93 78 98 93 94
average
CAS + UF – – – – 74 97 96 90 – – – –
average
NF-lo
MBR-1
VRF = 1.1 4 86 – 32 3 92 52 40 10 N98 – 39
VRF = 1.4 11 85 33 7 96 58 42 20 N98 44
VRF = 2 9 93 36 16 98 63 50 22 N98 48
VRF = 3.3 18 94 46 18 N98 72 56 32 N98 56
average 10 89 37 11 96 61 47 21 N98 46
MBR-2
average 26 97 94 35 32 94 91 37 42 96 95 46
– : not measured.
Table 5
Permeability recovery of NF-lo and NF-ti after filtration of CAS-UF effluent at different
pressures.
TMP (bars) 4 6 8 12
Fig. 8. RO and NFs flux declines for CAS and MBR-1 effluents at 8 bars.
4. Conclusion
Table 6
Summary table of RO and NF membranes performances with MBR-1, MBR-2 and CAS-UF effluents.
J/J0 at VRF = 2.5 at 8 bars 0.86 0.58 0.20 0.91 – 0.78 0.82 0.73 0.46
Flux at VRF = 2.5 at 8 bars 23.4 55.1 10.9 22.8 – 56.4 21.8 65.1 26.8
(L h− 1 m− 2)
Permeability recovery by – – – – – – 98.9 90.1 64.0
rinsing (%)
Retention molecules – – – +++ – ++ +++ + ++
1000 Da
Retention molecules – – – +++ – ++ +++ +++ ++
10,000 Da
Retention UV210 (%) 95.5 10.1 78.8 95.4 – 78.8 97.6 32.4 74.0
Retention UV254 (%) 99.9 95.9 98.0 100 – 100 94.4 93.6 98.8
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