Chemical Engineering and Processing 105 (2016) 21–29

Contents lists available at ScienceDirect

Chemical Engineering and Processing:

Process Intensification
journal homepage: www.elsevier.com/locate/cep

Comparative study of in-line coagulation and/or ozonization

pre-treatment for drinking-water production with spiral-wound
ultrafiltration membranes
Fátima Rojas-Serrano* , Jorge Ignacio Pérez, Miguel Ángel Gómez
Technologies for Water Management and Treatment Research Group, Department of Civil Engineering, University of Granada, Campus de Fuentenueva s/n
18071, Granada, Spain

A R T I C L E I N F O A B S T R A C T

Article history:
Received 10 June 2015 The application of pre-treatments is a common approach for improving ultrafiltration membrane
Received in revised form 20 March 2016 limitations. However, most studies have been performed for lab-scale hollow-fibre or flat-sheet
Accepted 12 April 2016 membrane modules. The present study was conducted to test the performance of fullscale spiral-wound
Available online 14 April 2016 ultrafiltration (UF) membranes for potabilization of influents rich in humic and fulvic acids under
different scenarios: (i) direct UF, (ii) with in-line pre-coagulation, (iii) with pre-ozonation, and (iv) with
Keywords: both pre-treatments combined. The membranes were polyvinylidene fluoride with 0.03 mm effective
Ultrafiltration pore size. Permeate flow rate was fixed, 1.0 m3/h, equivalent to 48 LMH flux. Membrane performance was
Spiral-wound
compared for the aforementioned cases with the following results: feed water pretreatment was
Pre-coagulation
required since the effluent quality achieved with direct ultrafiltration was poor and fouling increased.
Pre-ozonation
Humic-fulvic-rich influents Between pre-ozonation and pre-coagulation, the former was disregarded given the negligible
Membrane fouling improvement achieved with respect to single ultrafiltration. By contrast, coagulation-flocculation
results were remarkably better for both organic matter removal and fouling control. The application of
the two pretreatments in series resulted in effluent qualities comparable to those achieved with
coagulation-flocculation but fouling rates were much lower and transmembrane pressure growth was
minimal, this constituting a promising option for fouling control.
ã 2016 Elsevier B.V. All rights reserved.

1. Introduction transmembrane pressure, TMP, vacuum vs. pressure driven, etc.),

The use of ultrafiltration membranes for water treatment has
spread worldwide because of its multiple advantages. The
separation mode is size exclusion, by molecular sieving through
fine pores [1]. These membranes are effective in screening out
bacteria and suspended solids [2] while avoiding the disadvan-
tages of chemical disinfection. Moreover, the minor footprint and
the simple operation of the systems [3], together with the rising
competitiveness of the membrane prices [4], make this technology
an attractive alternative for drinking-water production. In fact,
vigorous research is currently being focused on membrane
materials (ceramic, polymeric, metallic, etc.), configurations
(hollow fibre, flat-sheet, tubular, spiral-wound, etc.) and operation
modes (dead-end vs. cross-flow, constant flux vs. constant
* Corresponding author.
E-mail address: rojas_f@ugr.es (F. Rojas-Serrano).
increasing the versatility of the systems.
Nevertheless, the main drawbacks of the membranes remain
unsolved. Firstly, the poor screening of small-sized natural
organic matter (NOM) constitutes a serious handicap, especially
for surface water. Secondly, the membranes are porous materials
subject to fouling, i.e. permeability loss from the accumulation of
aquatic substances on or inside the membrane matrices [5].
Fouling obligates the operation to stop periodically for back-
washing, cleaning or relaxation periods, thus shortening mem-
brane life [6] and increasing operational costs. Depending on their
nature, foulants can be classified as colloidal, organic, scaling,
biofouling, etc. [7] although NOM is considered the worst
constraint for drinking-water applications [8].Thus, membrane
fouling and low retention of NOM are related and require
integrated solutions.
Two different approaches to this problem can be found in the
literature: (i) the optimisation of the operating conditions and (ii)
the application of pre-treatments, [4,5]. In fact, in a previous work
[9], our research group optimised the operating conditions for a

http://dx.doi.org/10.1016/j.cep.2016.04.004
0255-2701/ ã 2016 Elsevier B.V. All rights reserved.
22 F. Rojas-Serrano et al. / Chemical Engineering and Processing 105 (2016) 21–29

drinking-water production unit by means of direct ultrafiltration. 2. Materials and methods

We found that operating conditions certainly influenced mem-
brane performance since the right combination of variables could
lower the TMP increase and the resulting energy consumptions.
Nonetheless, even when the best combination was applied, the
feasibility of the process was questioned as the permeate recovery
was reduced as well. As a result, the pre-treatment option seems
more realistic, especially when the influents are of low quality.
Several studies have combined ultrafiltration and pre-treat-
ments, offering widely different possibilities: coagulation [10–
12], adsorption [13], pre-filtration [14], pre-oxidation [15,16], etc.
However, most studies have used laboratory-scale membranes
with only a few exceptions [12,17]. On the other hand, despite the
potential of spiral-wound (SW) modules for drinking water
production, SW membranes having higher filtration surface and
packing density [18], hollow fibres [10,12–16,19,20] or to a lesser
extent flat sheets [11,14,21,22] have traditionally been preferred
to the detriment of the former. Thus, a comparative study was
conducted to evaluate the performance of full-scale spiral-wound
membranes in different scenarios: direct filtration and ultrafil-
tration preceded by other processes.
Of the possible pre-treatments to be applied, coagulation-
flocculation (CF) was chosen for being the most promising, as
shown by a great number of CF-UF works. Indeed, it has been
successfully applied to increase organic matter removal as well as
to improve membrane performance [22–25]. On the other hand,
ozonation (OZ) was selected as well, since few examples of the
combination OZ-UF were found in the literature, possibly because
of the incompatibility of many polymeric membranes with ozone
[4]. In fact, to date, most studies have used ceramic membranes in
which permeability after ozone application increased with respect
to single ultrafiltration [26,27]. Both pre-treatments involve the
addition of chemicals although their mechanisms sharply differ.
On the one hand, CF consists of adding an agent (coagulant) that
destabilises the colloidal particles in the influent, making their
aggregation possible. The resulting aggregates are presumably
filterable through the membrane. By contrast, OZ involves
oxidising the organic matter present in the water by adding
ozone. The size and nature of the fragments generated depend on
the extent of the oxidation reaction, affecting the success of the
process.
Finally, the main purpose of this study was to determine which
combination of the following was more effective in terms of
fouling reduction and NOM removal: direct ultrafiltration, CF-UF
and OZ-UF. In addition, the combination of the three was also
tested in different sequences, to verify whether the order had any
influence. In this way, CF-OZ-UF and OZ-CF-UF were tested as
well.
2.1. Influent water
The influent was synthetic but the matrix water came from
Canales Reservoir in Granada (Spain), with the following physico-
chemical parameters: pH 8.00; turbidity 5.0 NTU and UV254
0.4 m
1. The dissolved organic carbon (DOC) was 0.5 mg/L and the
suspended solids concentration (SS) was negligible. As a result, the
organic load was increased in order to simulate medium- to low-
quality surface water. A mixture of humic and fulvic acids
(Carbotecnia Húmico 10-10, Carbotecnia S.L., Spain) was dissolved
in the source water so that the resulting influent DOC was
7.5  1 mg/L, although this concentration could vary slightly
according to the changes in the matrix water. The influent
characterization is included in Table 1.
2.2. Ultrafiltration modules
The membrane modules used were commercially available
spiral-wound SpiraSep 960 by TriSep Corporation (Goleta,
California, USA); made of polyvinylidene fluoride (PVDF), with
20.9 m2 filtration area and 0.03 mm effective pore size. The
modules operate submerged and driven with a vacuum, with

0.7 bar being the threshold transmembrane pressure (TMP).
2.3. Description of the experimental plant
The matrix water was drawn from the inlet channel to be
discharged into a PVC intermediate tank (2000 L). A centrifuge feed
pump sucked the water from the intermediate tank and fed the
experimental plant, with the humic/fulvic acid solution being
injected upstream of the feed pump for proper mixing inside the
pump body. The feed flow rate was adjusted to 1.1 m3/h.
The facility was designed to work in different scenarios, so that
the pipe downstream of the feed pump branched off (Fig. 1).
Depending on the position of the manual valves, the influent water
could follow three possible paths:
(a) Direct ultrafiltration: The first branch entered the membrane
tank, where the water was filtered from outside to inside
driven by the permeate pump. The operation was flux constant,
48 LMH, and part of the permeate was reversed through the
membrane during backwashing every 10 min with 2 m3/h flow
rate and 30 s duration. Aeration was continuous (18 Nm3/h).
These operating conditions were fixed according to a previous
study [9]. The operation was dead-end and without a reject.
(b) Coagulation-flocculation pre-treatment: The second branch
was connected to a static mixer through which the coagulant

Table 1
Average physicochemical characteristics of the influent and the different effluents.

Description Influent UF effluent CF-UF effluent OZ-UF effluent CF-OZ-UF effluent OZ-CF-UF effluent

Value Value % rem.

Turbidity, NTU 5.39  0.16 1.83  0.29 65.56 0.95  0.06 81.45 1.17  0.41 80.02 1.00  0.00 81.11 1.00  0.00 80.9
DOC, mg/L 7.55  0.16 6.34  0.10 13.66 4.41  0.58 42.86 5.35  0.28 29.81 4.30  0.06 40.32 4.71  0.24 39.75
UVA254, m
1 18.49  0.14 11.07  0.40 40.07 3.42  0.37 81.3 10.85  0.71 41.89 3.60  0.10 80.74 3.67  0.06 80.15
SUVA, m
1/mg/L 2.49  0.10 1.75  0.04 30.6 0.78  0.11 68.32 2.03  0.18 17.06 0.84  0.01 66.27 0.78  0.05 68.67
Colour436, m
1 3.01  0.11 1.33  0.15 54.62 0.20  0.05 93.04 1.03  0.08 66.96 0.22  0.05 92.54 0.23  0.06 92.43
Fe3+, mg/L 0.00  0.00 0.00  0.00 – 0.06  0.02 – 0.00  0.00 – 0.01  0.00 – 0.01  0.00 –
pH 8.21  0.04 8.23  0.04 – 7.85  0.08 – 8.18  0.08 – 7.91  0.04 – 7.86  0.09 –
 F. Rojas-Serrano et al. / Chemical Engineering and Processing 105 (2016) 21–29
Fig. 1. Flow diagram of the experimental set-up.
was injected. A ferric chloride matrix solution was prepared by
dilution of 40% (m/m) FeCl3 solution, (Brenntag, Germany) in
pure water, enabling a rate of 50 mg FeCl3/L in the influent, the
coagulant dose being fixed according to previous experiments
[28] .The coagulant-influent mixture entered the in-line
flocculator, which consisted of a PVC pipe, with 50 mm
external diameter (2.4 mm thickness) and 100 m long. The
flocculator outlet was connected to the membrane tank. Then,
ultrafiltration was carried out as described under (a).
(c) Ozonation pre-treatment: A third by-pass connected the feed
pump discharge to a venturi for ozone injection. Ozone was
produced from pure oxygen (Air Liquide S.A.), by means of a
generator (C-L010DTI, AirTree Ozone Technology Co., Ltd.,
Taiwan) operating at 1.2 bar. The oxygen flow rate applied was
0.2 Nm3/h.
An in-line ozone analyser (Mini-HiCon, In USA Corp., USA)
allowed measuring the ozone concentration in the gas line. After
ozone injection, the water-ozone mixture entered a 12-min
retention-time contact column to favour the ozone transfer, and
then left the column through an overflow, separating the gas and
water. The ozonated water was conducted to a separate tank, from
which it was pumped to the ultrafiltration circuit following the
same route as mentioned above. The non-reacting gas was released
in the upper part of the overflow, ending at a destruction cell,
where the ozone reacted with saturated solution of NaHSO3
producing O2. Nonetheless, before ozone destruction, the off-gas
ozone concentration was measured by a second in-line ozone
analyser (Mini-HiCon built in SC010, In USA Corp., USA). Thus, the
transferred ozone dose, TOD, could be calculated with Eq. (1),[29].
Q gas

TOD ¼  ½O3 0
½O3 res
Q liq
where TOD is the transferred ozone dose (g O3/L), Qgas and Qliq are
the flow rates for the inlet gas (Nm3/h) and the feed water (L/h),
respectively, and [O3]0 and [O3] res are the ozone concentrations
(gO3/Nm3) in the inlet gas and the off-gas streams, respectively.
Mozia et al. [30] have successfully tested pre-ozonation with doses
up to 0.6 (mg/mg) O3:TOC. Therefore the inlet ozone concentration
23
was maintained constant at 25 g O3/Nm3 in order to achieve a O3:
DOC ratio of 0.6 (mg/mg), assuming full ozone transfer.
The experimental facility was enclosed and insulated so that the
temperature variations were insignificant. However, temperature
together with TMP and O3 concentrations were recorded by a data
register (RSG30, Endress Hauser, Switzerland).
Furthermore, the facility was provided with by-passes allowing
the simultaneous operation of all the processes described above.
Sample points were available for influent, permeate, and also for
the mixture influent-coagulant, i.e. flocculated water, and for the
mixture influent-ozone, i.e. ozonated water.
2.4. Experimental procedure
The whole study was conducted over approximately one year
divided into different stages:
1. Direct ultrafiltration (UF).
2. Coagulation-flocculation followed by ultrafiltration (CF-UF).
3. Ozonation followed by ultrafiltration (OZ-UF).
4. Coagulation-flocculation in series with ozonation followed by
ultrafiltration (CF-OZ-UF) and vice versa (OZ-CF-UF).
Each stage lasted eight weeks, after which the membrane
module in operation was removed and replaced by a new one. The
only exception was stage 4, for which one single membrane
module was used for the two options tested. Each combination was
tested for eight weeks also, but with a four-week relaxation period
in between.
The operation consisted of 6 working-days/1 relaxation-day
with 240-min-long assays. The influent and effluent were sampled
ð1Þ daily to determine which configuration was more effective in
terms of permeate quality. In addition, ozonated and flocculated
water samples were also taken during stage 4 in order to determine
the water quality in the intermediate phases of the combined
process. On the other hand, the transmembrane pressure (TMP)
was registered every 20 s for fouling evaluation. Ozone concen-
trations in the inlet and off-gas lines were also registered with the
same frequency.
24 F. Rojas-Serrano et al. / Chemical Engineering and Processing 105 (2016) 21–29

0.25
0.20
0.15
0.10
TMP, bar 0.05
0.00
-0.05
-0.10
-0.15
-0.20 y = -4.10E-06x-0.10
R2 = 0.99
-0.25
0 2000 4000 6000 8000 10000 12000 14000 16000
Time, s
Fig. 2. TMP time course for a normal operating period within direct UF stage.

After each assay, the membrane was soaked in clean water.
Furthermore, cleaning in place (CIP) was carried out the last
working day of each operating period, during which the membrane
tank was emptied and filled with permeate while NaClO (50 mg/L)
was dosed. After the membrane tank was filled, recirculation
between that and the permeate tank was conducted for 20 min.
Then, the membrane tank was emptied again and filled with tap
water until the next operation period.
2.5. Analytical methods
Physicochemical analyses were performed daily for the influent
and effluent as well as for intermediate samples in the last stage.
Samples were integrated, 100 mL being collected every 30 min for
the whole operation time.
Turbidity, DOC, UVA254, colour436 nm, and pH were determined.
In addition, the iron content was analysed for the effluents
resulting from the application of pre-coagulation. Turbidity was
determined as a measurement of the scattered light (DINKO D-112,
Spain) while Fe3+ concentration was measured by means of a
spectrophotometric test kit (Merck KGaA, Germany). UV–vis
spectrophotometer Helios g (Spectronic Unicam, USA) was used
for the analysis of colour436nm, UVA254nm, and Fe565nm, with 1 cm
quartz cell. Glass-fibre filters (Millipore AP4004705) were used to
obtain filtrated samples for DOC measurement, made by combus-
tion TOC Analyser (Formacs HT, SKALAR, The Netherlands). Specific
ultraviolet absorbance (SUVA) index was calculated as UV254 nm
 100/DOC (mg/L).
2.6. Fouling evaluation
Given that the operation was flux constant, membrane fouling
was indirectly quantified by means of the time course of TMP.
Linear regression was applied to TMP values immediately prior to
backwashing vs. operation time for each assay. The resulting slopes
were called fouling rates. The comparison of the average fouling
rates for each stage allowed an assessment of which scenario was
more favourable in terms of fouling avoidance.
2.7. Statistical analyses
Regression models were built for fouling-rate calculation. In
addition, analysis of the variance tests (ANOVA) were made in
order to compare the quality of the samples and to determine
whether there were statistically significant differences among
them at a significance level of 5%, p < 0.05.
3. Results
3.1. Direct ultrafiltration
The physicochemical parameters of the effluents resulting
from the ultrafiltration as a single treatment are shown in Table 1.
The yields for turbidity were acceptable for the entire operating
period. However, the colour removal was poor (55%) and, in fact,
the colour of the effluent samples was visible to the naked eye. On
the other hand, even when the efficiency for UVA254 was medium
(40% average), DOC removal was very low, with yields of less than
15%.
Fig. 2 shows the TMP time course for a normal operating period
within stage 1. The positive values correspond to backwashing
whereas the negative correspond to permeate production.
Table 2 summarizes membrane fouling rates for the different
stages. According to the high coefficients of determination found
for direct ultrafiltration (average R2 = 0.99), linear regression
closely fit the data. The fouling rate reached for the first working
period was
2.6  10
6 bar/s, with
0.05 bar TMP increment after
240 operating min. The fouling rate continued to increase up to

4.1 10
6 bar/s during the first week. Then, although TMP build-
up continued throughout the entire experimental period, the slope

Table 2
Summary of fouling rates, Vf, results for the whole study.

Process Starting Vf, bar/s Average Vf, bar/s Maximum Vf, bar/s Minimum Vf, bar/s R2 Average TMP, bar
UF
2.6E-06
5.0E-06
5.5E-06
2.6E-06 0.99
0.07
CF + UF
1.1E-06
5.0E-07
2.7E-06 2.2E-07 0.75
0.01
OZ + UF
2.5E-06
1.7E-06
2.8E-06
1.4E-06 0.87
0.02
CF + OZ + UF
3.0E-07 3.5E-07
3.0E-07 4.3E-07 0.33 0.00
OZ + CF + UF
4.1E-07 2.9E-07
4.1E-07 8.3E-07 0.37 0.00
 F. Rojas-Serrano et al. / Chemical Engineering and Processing 105 (2016) 21–29 25

0.30
0.25
0.20
0.15
0.10
TMP, bar 0.05
0.00
-0.05
-0.10
-0.15
-0.20
y = -1.64E-06x-0.15
-0.25 R2 = 0.82
-0.30
0 2000 4000 6000 8000 10000 12000 14000 16000
Time, s

Fig. 3. TMP time course for a normal operating period within CF-UF stage.

growth began to slow, the maximum value being
5.5  10
6 bar/s.
The average value for the whole stage was
5.0  10
6 bar/s
whereas the average TMP increment for operating periods was

0.07 bar. However, the CIP and relaxations applied were very
effective and the TMP threshold value was never reached.
performance of the respective membrane modules with the same
criterion. The best fouling slope was positive, 2.2  10
7 bar/s,
whereas the maximum fouling resulted in
2.7  10
6 bar/s rates.
The average TMP increment for each working period was less than

0.01 bar (Table 2).

3.2. Coagulation-flocculation prior to ultrafiltration 3.3. Ozonation prior to ultrafiltration

The application of coagulation-flocculation before ultrafiltra-
tion considerably improved the effluent quality, as shown in
Table 1.The yields registered for organic matter removal were
medium in terms of DOC, i.e. 43% average, but high in terms of
UVA254, i.e. 81% average. Colour removal was significant also, with
very high yields, averaging 93%. The turbidity of the effluent also
improved, the average value being below 1 UNT. In addition, the
maximum Fe effluent concentration according to Directive 98/83/
EC for water intended for human consumption, 0.2 mg Fe/L, was
never reached, although the pH slightly fell.
The fouling rate was initially
1.1 10
6 bar/s but gradually
decreased,
5.0  10
7 bar/s being the average value for the stage.
Fig. 3 shows the TMP time course for a normal operating period
within CF-UF stage. The figures fluctuated frequently and the
correlation factors were weaker, with average R2 values of around
0.75. In any case, linear regression was still the best fit and it was
necessary to maintain the same model in order to compare the
Despite the high ozone concentration applied, 25 g O3/Nm3,
TOD was lower than expected, as there was always residual ozone
in the off-gas line, 4.2 g O3/Nm3 on average. The average TOD was
3.7 mg/L, the ozone dose being equivalent to the O3: DOC ratio of
0.5 (mg/mg).
The effluent characteristics resulting from the application of
ozonation as a pre-treatment are shown in Table 1. Ozonation
proved adequate for the removal of turbidity but less effective for
organic matter reduction, according to the DOC and UVA254 yields
(30 and 42%, respectively). On the other hand, the average colour-
reducing efficiency was 67%, while the pH barely changed.
The initial fouling rate was
2.5  10
6 bar/s but after several
days of operation, values decreased almost one point, averaging
around
1.7  10
6 bar/s (See Table 2). Fig. 4 shows the TMP time
course for a random operating period within OZ-UF stage. The
coefficients of determination, R2, were strong, between 0.85 and
0.9, although no positive fouling slopes were found in this case.

0.30
0.25
0.20
0.15
0.10
TMP, bar

0.05
0.00
-0.05
-0.10
-0.15
-0.20
y = -2.71E-06x-0.16
-0.25 R2 = 0.90
-0.30
0 2000 4000 6000 8000 10000 12000 14000 16000
Time, s

Fig. 4. TMP time course for a normal operating period within OZ-UF stage.
26 F. Rojas-Serrano et al. / Chemical Engineering and Processing 105 (2016) 21–29

0.30
0.25
0.20
0.15
0.10
TMP, bar
0.05
0.00
-0.05
-0.10
-0.15
-0.20 y = 0.32E-06x-0.11
-0.25 R2 = 0.37
-0.30
0 2000 4000 6000 8000 10000 12000 14000 16000
Time, s

Fig. 5. TMP time course for a normal operating period within CF-OZ-UF experiments.

However, the rates were very similar from one day to another. The
average TMP increment for working periods was
0.02 bar but
TMP growth was controlled by means of the weekly CIPs and
relaxation periods. Additionally, the application of ozone did not
compromise the integrity of the PVDF membrane throughout the
operation period.
3.4. Combined pre-treatments before ultrafiltration
Ozonation followed by coagulation and subsequent ultrafiltra-
tion resulted in very similar effluent characteristics to those found
with the opposite combination. In fact, no statistically significant
differences (p-value > 0.05) were found. The average parameters
for the corresponding effluents are listed in Table 1. The yields for
the removal of DOC and UVA254 were around 40 and 80%,
respectively. Nonetheless, the best results were achieved again for
turbidity and colour, with 81 and 92% removal percentages. The Fe
content of the effluents was consistently below 0.2 mg/L.
The analyses of the intermediate samples showed no remark-
able differences for the flocculated water regardless of whether
coagulation-flocculation was performed before or after ozonation.
On the contrary, the ozonated water was influenced by the order
applied. In general the values for turbidity, colour or UVA254 were
considerably higher when coagulation-flocculation was the first
pre-treatment applied. By contrast, ozonated-water DOC was
7.03 mg/L when ozonation was applied first, whereas the same
parameter was 4.97 mg/L when coagulation-flocculation was
performed first.
Concerning the membrane performance, the initial fouling
rates were
4.1 10
7 bar/s and
3.0  10
7 bar/s for OZ-CF-UF
and CF-OZ-UF, respectively (Table 2). However, after the first
operation hours, most of the fouling slopes turned positive for the
two alternatives tested, as reflected in Fig. 5 and Fig. 6. In fact, the
average values for the overall operating period were positive for
both cases, 2.9  10
7 bar/s and 3.5  10
7 bar/s, respectively. The
pressure time course for a normal working period was almost
constant, varying by only a few thousandths of a bar. Nevertheless,
the correlations were very weak, with average R2 coefficients
around 0.4.
4. Discussion
4.1. Effluent quality
The application of direct ultrafiltration with spiral-wound
membranes proved insufficient for the production of drinking
water from influents rich in humic/fulvic content. The permeate
was heavily coloured and DOC and UVA254 removal percentages

0.30
0.25
0.20
0.15
0.10
TMP, bar

0.05
0.00
-0.05
-0.10
-0.15
y = 0.76E-06x-0.10
-0.20
R2 = 0.40
-0.25
-0.30
0 2000 4000 6000 8000 10000 12000 14000 16000
Time, s
Fig. 6. TMP time course for a normal operating period within OZ-CF-UF experiments.
 F. Rojas-Serrano et al. / Chemical Engineering and Processing 105 (2016) 21–29
were very low. Such high organic content in the effluent
compromises the organoleptic properties of water, making it
unsuitable for human consumption. Moreover, the addition of
chlorine would be necessary, which in turns would relocate the
risks of the disinfection by-products (DBPs) in the drinking-water
distribution networks [31].
However, the combination coagulation-flocculation-ultrafiltra-
tion proved quite effective in lowering the organic matter content,
especially the aromatic part, since UVA254 elimination averaged
81%. The yields for DOC removal were the highest for all the
scenarios tested, the results being consistent with those reported
by other authors for lab-scale hollow-fibre membranes [32–34]. On
the other hand, the slight drop in pH was due to the acidification of
the water caused by iron hydroxide formation, but the average
value was in all cases within the requirements of the Council
Directive 98/83/EC. Furthermore, the efficiency of the CF pre-
treatment for the removal of colour and turbidity was remarkable
and the maximum iron content met EU standards.
By contrast, the removal of UVA254 with ozonation pre-
treatment was only slightly better than for single ultrafiltration,
and the DOC removal achieved indicated that complete minerali-
zation of the organic matter was far from being reached. In fact, the
SUVA index changed slightly with respect to the influent. In
addition, instead of the strong colour degradation expected
according to other authors [35,36], the maximum yield recorded
was only 67%, this implying a serious shortcoming, since humic
and fulvic acids are highly responsible for colouring natural waters.
These data indicate that the ozone transfer could have been
insufficient for the nature and relatively high concentration of
organic matter in the influent water. According to Eq. (1) [29], for a
given gas-to-liquid ratio, TOD can be increased by minimizing the
residual ozone concentration and/or raising the one at the inlet.
Throughout the experimental period the ozone-water contact was
lower than expected, since residual ozone was constantly found in
the off-gas line. Thus, the resulting 0.5 (mg/mg) O3:DOC ratio
would have been inadequate. Byun et al. [35] reported that DOC
rejection increased only from 11% to 26% when raising the O3:DOC
ratio from 0.2 to 0.9 (mg/mg) for a PVDF-UF membrane. Similarly,
for ceramic membranes, Szymanska et al. [37] found that the
quality of the permeate could not be further improved even when
the ozone dosage was increased up to 3.1 (mg/mg) O3:TOC ratios
for a flat-sheet microfiltration membrane. The results of these
authors, for 11.7 mg DOC/L and 8 mg TOC/L influents, respectively,
suggest that even when the ozone transfer had been greater, DOC
removal would have barely increased.
Concerning the application of the two pre-treatments in series,
physicochemical parameters for the final effluents were very
similar regardless of the order applied, and the soaking period in
between did not appear to influence the effluent quality. However,
ozonated-water analyses revealing much lower DOC, when
coagulation-flocculation was performed first, confirmed that the
success with the combined process was attributable to coagula-
tion. Jeong et al. [38], recently testing combined coagulation-
ozonation-ultrafiltration for lab-scale hollow-fibre membranes,
also concluded that coagulation was mainly responsible for
decreasing DOC in the effluent. In any case, given that the removal
efficiency was slightly lower than that achieved with pre-
coagulation-flocculation, double pre-treatment was disregarded
as a means of improving the final water quality.
From the results for permeate quality, coagulation-flocculation
was deemed the most recommendable pre-treatment for spiral-
wound ultrafiltration membranes, given that the organic matter
removal was considerably higher than for ozonation and nearly the
same as for double pre-treatment. These findings confirm the
potential of this type of membrane for drinking-water production,
although further research is needed before this technology can be
27
fully applied to any water source. Ozonation results could be
potentially improved if higher ozone transfer was achieved. This
would involve increasing the contact ozone-water by enlarging the
column-retention time or providing a packing, together with the
application of higher inlet ozone concentrations. Both measures
entail higher investment in equipment and energy and, although a
cost analysis lies beyond the scope of the present study, according
to our results and those of other authors [39,40], the resulting
permeate quality does not appear to justify the cost rise, making
pre-ozonization unadvisable for ultrafiltration of influents with
high organiccontent. By contrast, although there is a margin for
improving coagulation-flocculation, e.g. testing new coagulants or
optimising the coagulant injection, the process is much cheaper
and easier to control, making this option preferable among all the
scenarios tested.
4.2. Membrane fouling
The application of pre-treatments was found to help control
fouling, given that the resulting average rates were considerably
lower for any of the combined processes. In fact, ultrafiltration
without pre-treatment was the only case where the starting
fouling rate continued to increase over the entire stage.
Between coagulation-flocculation and ozonation, the former
was demonstrably better. Fig. 4 shows that the slope for OZ-UF
descended more sharply than that for CF-UF, Fig. 3, indicating that
the membrane became fouled more quickly. Compared to single
ultrafiltration, the average fouling rates were one order of
magnitude lower, this difference not being as significant for
ozonation (Table 2). The starting fouling rates were also lower for
CF-UF. On the other hand, although the average rate for the CF stage
was negative, some positive values resulted within this stage,
indicating a certain degree of pressure recovery during operation.
This fact could not be attributed to any particular condition but to
the coagulation-flocculation process itself, as the same coagulation
parameters were applied throughout the stage. Nonetheless,
correlation factors were better for OZ-UF, a result which can be
explained by considering that linear regression perfectly fit the
TMP time course for direct ultrafiltration; and given that ozonation
barely decreased the organic content of the water going through
the membrane, it seems logical that OZ-UF correlation factors were
similar to those for UF and stronger than for CF-UF.
The results reached for full-scale CF-UF with spiral-wound
membranes were consistent with works with other types of
membranes, where the coagulant was found to be responsible for
the formation of a porous cake that could ease the filtration process
[41,42]. The role of ozone in fouling is less discussed in the
literature. Lee et al. [40] found the fouling layer to be thinner for
hybrid ozonation-microfiltration than for single microfiltration.
Likewise, according to Szymanka et al. [37], the higher the ozone
dosage and flow rate, the lower the membrane fouling for ceramic
membranes. Both studies used flat-sheet membranes. In our case,
the comparison of the average TMP increments reached for single
ultrafiltration and for hybrid ozonation-ultrafiltration indicated
that the application of ozone also helped delay the fouling of spiral-
wound membranes. From the rates being similar from one day to
another it could be deduced that fouling generation was more or
less stabilized. However, unlike the CF-UF process, no positive
values were found, implying that the fouling layer that formed was
less reversible. Nonetheless, fouling mechanisms occurring as a
result of the application of in-line CF-UF or OZ-UF should be further
studied by means of respective membrane-module autopsies.
Finally, the application of the two pre-treatments in series
provided the best membrane performance. The starting fouling
rates were the lowest for the entire study and average fouling rates
were positive regardless of the order applied, signifying that there
28 F. Rojas-Serrano et al. / Chemical Engineering and Processing 105 (2016) 21–29
was pressure recovery throughout the respective operational
periods, as reflected by the ascending slopes in Figs. 5 and 6. The
CF-OZ-UF figures proved slightly better than OZ-CF-UF, which
could be the result of having used the same membrane module for
both experiments. Despite the relaxation period in between, CF-
OZ-UF being tested first could have affected the results but the
differences were not relevant and the average TMP increments
were on the order of thousandths of a bar in both cases.
Nonetheless, the coefficients of determination for both alternatives
were the worst reached throughout the study, indicating very
weak data correlations, probably as a consequence of the stronger
changes in the influent water with the double pre-treatment.
These results indicate that the combination of the two pre-
treatments can successfully reduce depositions on membrane
surface apparently because of the changes in the chemistry of the
influent water, making the membrane less prone to fouling. These
findings were corroborated by Jeong et al. [38], who recently
reported that the flux decline was remarkably better after
ozonation together with coagulation than only with coagulation.
However, the results of the present study should be completed
with more exhaustive analyses of the effluent, flocculated and
ozonated water samples as well as membrane autopsies, in order
to identify which changes in molecular size and functional groups
in the water entering the membrane explain the lower TMP
increase and fouling.
In summary, the hybrid process was a suitable option to control
membrane fouling. Nevertheless, although cost analysis is beyond
the scope of this study, the energy consumption of the combined
pre-treatments is higher than for a single one. Therefore, the
economic feasibility of combined processes compared to single
coagulation-flocculation pre-treatment should be assessed as well.
5. Conclusion
The present study on the performance of full-scale spiral-
wound ultrafiltration membranes confirms the potential of this
configuration for drinking-water production. However, the mem-
branes must be used together with appropriate pre-treatment
since the humic/fulvic acid removal achieved with direct filtration
was very poor, DOC and UVA254 rejection being, respectively, 14%
and 40%. Furthermore, membrane fouling increased without any
pressure recovery over time, with the risk of quickly reaching
threshold transmembrane pressure.
Pre-treatments such as ozonation or coagulation-flocculation
offer better effluent quality and improve membrane performance.
However, the effect of ozonation is less remarkable than that of
coagulation-flocculation. The first option is not recommended
given the scant upgrade achieved with 0.5 mg/mg O3:DOC ratios
(3.7 mg O3/L) and the higher investment needed to potentially
improve the effluent quality. By contrast, coagulation-flocculation
prior to ultrafiltration has proved to be the most effective pre-
treatment to reduce the organic matter content in the permeate
among the possibilities tested, with 43% and 81%, DOC and UVA254
removal, respectively. In addition, average fouling rates, being
three times lower than for ozonation-ultrafiltration and one order
of magnitude lower than for direct ultrafiltration, indicate that pre-
coagulation helps substantially to delay fouling.
Both pre-treatments applied in series led to effluent quality
similar to that achieved with single coagulation-flocculation,
meaning that double pre-treatment is useless from the standpoint
of permeate quality. However, the combination of ozonation and
coagulation-flocculation minimizes fouling rates, in such a way
that transmembrane pressure barely changes during operation (on
the order of magnitude of thousandths of a bar) and pressure is
recovered throughout the operating period, as positive average
fouling rates demonstrate. These findings make this combination a
promising option for fouling control.
Acknowledgements
This study, CTM2010-18899-TECNO, was supported by the
Spanish Ministry of Science and Innovation. It was held at the
Institute of Water Research (University of Granada) and Parque de
las Ciencias, Granada (Spain) with the collaboration of CADAGUA S.
A. Thanks are also extended to Mr. José Manuel Quesada Gallego,
from Ozono Electronica Iberica S.L., for his support during
ozonation start-up and to Mr. David Nesbitt, professional transla-
tor, for reviewing the English of the manuscript.
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