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Article history: In this study, the nanofiltration of cleaning-in-place (CIP) wastewater was studied using a two-step
Received 24 April 2009 nanofiltration (NF) process. In the first step, the effects of operating parameters including pH, tem-
Received in revised form perature, and transmembrane pressure on the membrane fouling were investigated using a loose NF
29 September 2009
membrane. Also, Taguchi method was applied in order to design the experiments and optimize the
Accepted 1 October 2009
experimental results. The optimum conditions providing the lowest flux decline were estimated. L9 (34 )
orthogonal array for experimental planning and the smaller-the-better response category was selected
Keywords:
to obtain optimum conditions. Analysis of variance (ANOVA) was used to determine the most significant
Nanofiltration
CIP wastewater
parameters affecting the flux decline caused by membrane fouling. The optimum conditions were found
Taguchi method as the second level of pH (7), first level of temperature (25 ◦ C) and first level of transmembrane pressure
ANOVA (12 bar). Under these conditions, flux decline caused by membrane fouling was predicted as 24% that
Flux decline was within the range of confidence limit of the observed value of 20%. Transmembrane pressure was
found to be the most important factor on the flux decline. The effect of pH on the membrane fouling
was also investigated with scanning electron microscopy (SEM) and contact angle measurements. It was
found that pore plugging was dominant at pH 4. In the first step of the treatment; 97% chemical oxygen
demand (COD), 100% sulphate, 50% chloride and 38% conductivity removal was obtained under the opti-
mized conditions. In the second step, the quality of permeate obtained from the first step was improved
using a tight membrane at 20 and 30 bar. Even better rejections were achieved especially for chloride
and conductivity in the second step at 30 bar.
© 2009 Elsevier B.V. All rights reserved.
1383-5866/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2009.10.001
266 Z.B. Gönder et al. / Separation and Purification Technology 70 (2010) 265–273
Table 2 Table 3
Characterization of shampoo CIP wastewater used in this study. Parameters and their values corresponding to their levels studied in experiments.
Parameter Unit Average values Parameters Designation Levels
−1
COD mg L 27,500
1 2 3
Chloride mg L−1 1,600
Sulphate mg L−1 586 pH A 4 7 10
Conductivity s cm−1 4,000 Temperature (◦ C) B 25 35 45
pH – 7 Transmembranepressure (bar) C 12 16 20
268 Z.B. Gönder et al. / Separation and Purification Technology 70 (2010) 265–273
Fig. 1. Permeate fluxes as a function of VRF during the filtration of shampoo wastewater for all the experiments. (a) Trials carried out at pH 4. (b) Trials carried out at pH 7.
(c) Trials carried out at pH 10.
Table 5 example, the mean S/N ratio for A factor at levels 1, 2 and 3 can
Experimental results for flux decline and corresponding S/N ratios.
be calculated by averaging the S/N ratios for the experiments 1–3,
Trial no. Flux (L m−2 h−1 ) Flux decline (%) S/N ratio (dB) 4–6 and 7–9, respectively. The mean S/N ratio for every factor is
calculated similarly.
Jw Jf Fouling (100 − FR)
The S/N ratio averages for each factor at three levels are pre-
1 137 93 32 −30.09
sented in Fig. 2. As seen from figure, overall mean value was
2 255 167 34 −30.75
3 435 221 49 −33.84 calculated as −30.78 from all Taguchi experiment results. On the
4 185 134 27 −28.71 other hand, the maximum variation level was determined as −2.75.
5 315 192 38 −31.59 Also it can be seen that the slopes of the lines between different lev-
6 262 184 30 −29.44 els are not the same for pH and temperature factors. So, the levels
7 234 151 35 −30.96
8 190 147 27 −28.63
have different influence on membrane fouling. The increase in foul-
9 358 199 44 −32.96 ing is bigger when the temperature changes from 35 to 45 ◦ C than
when it changes from 25 to 35 ◦ C. So, it can be said that membrane
fouling was lesser affected from temperature when the tempera-
experiments are presented in Table 5. In order to evaluate the influ- ture is lower than 35 ◦ C. However, the slopes of the lines between
ence of each factor on the flux decline, the S/N ratio for each factor 12–16 bar and 16–20 bar are almost the same.
should be computed. The S/N ratio for a single factor can be cal- Fig. 2(a) shows the effect of pH on the membrane fouling. The
culated by averaging the value of S/N ratios at different levels. For pH of minimum membrane fouling was observed at 7, which is the
Fig. 2. Main effect plots for S/N ratios of flux decline caused by fouling: (a) pH, (b) temperature and (c) transmembrane pressure.
270 Z.B. Gönder et al. / Separation and Purification Technology 70 (2010) 265–273
Fig. 3. SEM images of the top layers’ cross-section of membranes. (a) FM NP010 before filtration. (b) FM NP010 after filtration at pH 4. (c) FM NP010 after filtration at pH 10.
(d) FM NP010 after filtration at pH 7.
medium pH value among the three levels tested in this study. The by the deposition of the particles in the pores. So, it could be seen
value of wastewater pH can affect the membrane surface charge that the membrane was indeed fouled after the filtration at pH 4.
due to the disassociation of membrane’s functional groups. Zeta However, SEM images of the membranes after filtration at pH 7
potential is used to quantify the membrane surface charge. The and 10 were almost similar to clean membrane. Flux decline might
membranes are positively charged at pH values below the iso- result from the surface fouling compared to pore plugging.
electric point whereas they are negatively charged at pH values As seen from contact angle measurements (Fig. 4), contact angle
above the isoelectric point of the groups. The surface charge of of the membrane at pH 7 was similar to that at pH 10. But at pH 4,
the membrane increases because of increasing electrostatic repul- contact angle of the membrane was lower than the others. A higher
sion between a negatively charge solute and membrane [32,33]. FM contact angle indicates an increase in surface fouling. So, it can be
NP010 membrane skin layer is made of polyether-sulfone that has concluded that pore plugging was dominant at pH 4.
dissociable sulphonic acid groups in the chemical structure. For the As a conclusion, it can be said that the FM NP010 membrane
FM NP010 membrane, it is known that isoelectric point is 4.2 [23]. showed the best performance for membrane fouling at pH 7.
The membrane surface was nearly no charged at pH 4. Therefore, According to Fig. 2(b), the S/N ratio was decreased with increas-
there was not an electrostatic interaction between the membrane ing of temperature and hence the highest membrane fouling was
and the solutes in the wastewater. Separation of molecules could be occurred at higher temperature (45 ◦ C). It is known that an increas-
occurred due to size exclusion. So, the flux decline caused by foul- ing in temperature increases the permeate flux. On the other hand,
ing at pH 4 was higher than at pH 7 and 10. At pH 7 and 10, which
are above the isoelectric point, the membrane surface was nega-
tively charged. Thus, the electrostatic repulsion occurred between
the negatively charged membrane and the solutes, preventing the
adsorption of solutes onto the membrane. Also, the flux decline
caused by fouling at pH 10 was higher than that at pH 7. At high
values of pH, electrostatic repulsion between the charged groups
can cause a reduction in pore size and the pores can shrink [32]. This
situation resulted in higher membrane fouling at pH 10. Also, SEM
and contact angle measurements of the new and clean membranes
were determined to visualize membrane fouling on the pores and
membrane surface for different pH values. Fig. 3 represents the FM
NP010 membrane before (a) and after filtration experiments which
were carried out at pH 4 (b) that the highest membrane fouling
(49%) occurred, at pH 10 (c) that the intermediate membrane foul-
ing (35%) occurred and at pH 7 (d) that the lowest membrane fouling
(27%) occurred.
As seen from Fig. 3(a), the pores of clean FM NP010 membrane
are clearly visible. But, for the membrane that has been fouled with
wastewater at pH 4 (Fig. 3(b)), the size of the pores was reduced Fig. 4. Contact angle values for clean and fouled membranes at pH 4, 7 and 10.
Z.B. Gönder et al. / Separation and Purification Technology 70 (2010) 265–273 271
Table 7 Table 10
Optimum working conditions, observed and predicted flux decline caused by Process performance of FM NP030 membrane at 20 and 30 bar.
fouling.
Parameter Permeate quality (percent removal %)
Parameter Value Level
20 bar 30 bar
pH 7 2
Temperature ( ◦ C) 25 1 COD (mg L−1 ) 570 (97.9%) 400 (98.5%)
Transmembrane pressure (bar) 12 1 Chloride (mg L−1 ) 425 (73%) 375 (77%)
Observed flux decline caused by fouling (%) 20 Conductivity (s cm−1 ) 1285 (68%) 1253 (69%)
Predicted flux decline caused by fouling (%) 24
Predicted confidence interval for fouling (%) 10–45
ate quality since concentration polarization has reversible effect on
flux decline.
Table 8 The process performance of the FM NP030 membrane at 20
Characterization of composite permeate obtained from confirmation experiment.
and 30 bar is shown in Table 10. In addition, the rejections were
Parameter Feed wastewater Permeate quality calculated based on the feed concentrations and the composite per-
quality (percent removal) meate concentrations obtained from the FM NP030 membrane at
COD (mg L−1 ) 27,500 820 (97%) the end of the experiments for evaluating the total performance of
Chloride (mg L−1 ) 1,600 800 (50%) the system.
Sulphate (mg L−1 ) 586 0 (100%) The best quality of composite permeate was obtained at 30 bar.
Conductivity (ms cm−1 ) 4 2.46 (38%)
It was observed that the resulting permeate was free from sulphate.
The reduction observed in COD was greater than 98%. But chloride
and conductivity could not be removed effectively.
4. Conclusions
Table 9
The flux decline results of FM NP030 membrane at 20 and 30 bar.
20 53 44 48 17 8 9
30 80 56 71 30 19 11
Z.B. Gönder et al. / Separation and Purification Technology 70 (2010) 265–273 273
Under the optimized conditions 97% COD, 50% chloride and [13] Y. Lin, Y. Chen, D. Wang, H. Lee, Optimization of machining parameters in mag-
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