Coagulation-Ceramic Membrane Filtration

Process for U.S. Surface Water Treatment:

The Effects of Coagulation and Membrane Fouling
Literature Review
Water Research Foundation Project #4292
Principal Investigator:
James E. Amburgey, Ph.D.
University of North Carolina at Charlotte
Co-Principal Investigators:
Tanju Karanfil, Ph.D. (Clemson University)
Jaehong Kim, Ph.D. (Georgia Tech)
Yonggyun Park, Ph.D. (GS Engineering)

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Introduction
To meet the growing water demands as well as higher water quality standards, membranes have
been successfully tested and recognized as an alternative to conventional water treatment
methods. Typical conventional water treatment processes include coagulation, flocculation,
sedimentation, filtration, and disinfection. Membrane systems can be single-unit processes that
rely only on particle size exclusion as their mode of treatment. Some have pore sizes in the range
of 1 m to 0.01m (e.g., microfilters and ultrafilters) and can filter out bacteria, protozoa,
viruses, and large organic molecules. While others are effectively non-porous (e.g., reverse
osmosis membranes) and can filter out compounds with low molecular weights such as salts.
Microfiltration (MF) membranes are gaining interest in this part of the world for their ability to
produce high quality water at relatively low operating pressures. Membranes of this type are
principally made of either organic polymers or ceramic materials (Cermades et al., 2007).
Polymeric membranes are more commonly used for water treatment applications because they
are cheaper to manufacture. However, it is only recently that ceramic membranes for drinking
water treatment have gained popularity; mainly because of their numerous advantages over
polymeric membranes. According to Lehman et al. (2007), ceramic membranes are superior to
polymeric membranes and more resistant to severe chemical and thermal environments, allowing
them to perform more efficiently under extreme operating conditions. In addition, ceramic
membranes can operate at higher fluxes, produce higher feed water recoveries, withstand high
pressure backwash operations, operate at extended backwash intervals, and have a longer life
without breakage (Lehman et al., 2007).
The major limiting factor of using any membrane system for water treatment is fouling. Fouling
is caused by the accumulation or concentration of particles, organics, or biological substances on
the membrane surface. The effects of fouling can decrease the membrane flux, increase the
transmembrane pressure (TMP), decrease product quality, and shorten the membrane life (Lee et
al., 2000). As a result, the focus of much of the research done on membrane systems today is on
ways to inhibit or prevent membrane fouling. Pretreatment is commonly thought to be the most
effective way of inhibiting fouling. By adding a dispersant or removing the fouling agents before
membrane filtration, fouling can be slowed down or in some cases be prevented. A drawback of
using MF is that particles typically in the size range of viruses and small organics (<0.1 m) can
easily pass through the pores.
Coagulation has been shown to be an effective pretreatment for microfiltration membrane
systems for control fouling (Matsushita et al., 2004). According Loi-Brgger et al. (2006)
coagulation before membrane filtration is advantageous since particles, colloids, and higher
molecular substances get incorporated into the flocs that can be easily removed by the MF
membrane.
The system being tested in this project is a ceramic microfiltration membrane with a nominal
pore size of 0.1 m. The system can be operated in a dead-end flow configuration with
2
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coagulation and pH adjustment prior to membrane filtration. Inline static mixers can be used to
mix the chemicals with the influent water stream. Regular backwashing will be implemented in
between filtration runs using product water.
The objective of this literature review is to summarize previous research studies completed on
ceramic membrane systems that incorporated coagulation as a pretreatment stage. The primary
goal was to gather information on operating parameters such as coagulant doses, pH levels, and
backwash intervals. Furthermore, studies done using polymeric membranes with similar
configurations were compared with studies done on ceramic membranes to compare their
operating parameters and performance.
Ceramic Membrane System Parameters
One of the merits of using membrane filters is the possible elimination of coagulation,
flocculation, and sedimentation stages from the process train. For a ceramic MF membrane (like
the one used in this study) with a nominal pore size of 0.1 m. It is expected that the removal of
viruses in the water would be poor. In a test run done by Matsushita et al. (2004) using 0.1 m
ceramic MF membranes, the authors observed that there was no reduction in virus levels in the
experiments done without the addition of coagulants. On the other hand, they observed a 6.4 log
to 7.4 log virus removal when a coagulant was added.
Similar to conventional water treatment, coagulation in combined MF systems is generally
applied to aggregate foulants to form particles large enough to be rejected by the membrane
(Kennedy et al., 2003). Kennedy et al. (2003) stated that increasing the size of foulants (such as
dissolved organic matter and viruses (<0.1 m)) in dead-end systems is expected to: (i) reduce
their chance of penetrating membrane pores and adsorbing on the pore walls, (ii) form a porous
cake on the membrane surface that can reduce fouling, and (iii) simplify cleaning so that flushing
and/or backwashing with product water can remove the permeable cake layer. In order to
accomplish this, a suitable coagulant (e.g., iron or aluminum salts) has to be fed into the raw
water stream at the proper dosage and pH (Lerch et al., 2005).
For ceramic MF membrane systems that incorporated coagulation as a pretreatment stage in the
published literature, a range of coagulant types and doses, pH values, and backwash intervals
have been used. Table 1 summarizes the studies. It should be noted that not all of the studies in
Table 1 focused on finding the optimum coagulant dose or pH. For example, the study done by
Kanaya et al. (2007) only listed the coagulant dosage being used by a full-scale ceramic
membrane drinking water treatment plant in Japan and did not justify how they arrived at that
number.

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Table 1. Summary of Ceramic Coagulation/MF System Operating Parameters

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Lehman et al. (2007) showed that with the same coagulant dosage (2 mg/L as Al) in-line
coagulation produced better results than a 2-stage coagulation/flocculation. Their results showed
that with the flocculated water, the specific flux declined to 78% of the initial water flux after 40
hours of operation. With in-line coagulation and the same coagulant dose with 20 seconds of
retention time, 91% of initial specific flux was maintained after 40 hours of operation. Similar
research by Lerch et al. (2007) and Meyn et al. (2008) also reported less fouling with inline
coagulation.
Matsushita et al. (2004) and Matsui et al. (2003) studied the removal of viruses by combining
coagulation with a ceramic membrane MF system. Matsui et al. (2003) found that the ceramic
membrane performed best in terms of virus removal when the coagulant dose was greater than
1.0 mg/L as Al at pH 7.0. However, the authors observed a slightly better removal when they
used mechanical mixers as opposed to static mixers, 7.5 log and 6-7 log, respectively. They
attributed the enhanced removals in the mechanical mixers to both the adsorption of the viruses
onto aluminum floc particles and virus inactivation in the coagulation process. Matsushita et al.
(2004) found that a PACl dosing at 1.08 and 1.62 mg Al/L at a pH of 6.8 achieved a virus
removal of 6.4 log and 7.4 log respectively. The authors concluded that coagulation had the
greatest influence on the removal of viruses and recommended a dosing of at least 1.08 mg/L to
produce satisfactory removal results. They also determined that coagulation time only had a
slight effect on the removal of viruses.
Meyn et al. (2008) investigated the performance of the ferric chloride coagulant in removing
dissolved organic carbon (DOC) under various pH levels. They found that the best DOC removal
was achieved at the lowest applied pH of 4.5 and the lowest removal was at pH 6.5. In addition,
they found that at a lower pH the effects of reversible fouling were almost absent, whereas at
higher pH levels it was more evident.
Meyn and Leiknes (2010) performed a study on different coagulants under varying
coagulation/flocculation conditions to investigate their respective impact on the membrane
filtration performance. They compared two different coagulants, polyaluminum chloride (PACl)
and ferric chloride (FeCl3). For the PACl coagulant they chose doses of 2, 3, and 5 mg Al/L;
while for the FeCl3 coagulant the chose doses of 4,6, and 10 mg Fe/L. The investigated pH range
was from 4.5 to 7.0 for both coagulants. Both configurations used coagulation/flocculation tanks
with a hydraulic retention time of 21 minutes in total, 7 minutes in the fast mixing tank and 14
minutes in the slow mixing tank. They found an optimum pH for DOC removal at 5.5 and 4.5
for PACl and FeCl3, respectively. They also observed better DOC removal with the PACl
coagulant than the FeCl3 coagulant. In terms of DOC removal, the optimum PACl dose was
found to be at 5 mg Al/L, and the optimum FeCl3 dose was found to be at 10 mg Fe/L. In terms
of reversible membrane fouling, the optimum dose where fouling minimized was found to be at 2
mg Al/L.

5
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Based on the parameters found in this literature review, the following initial ranges of operating
parameters for the pilot study are proposed. The following parameter values will be used to
establish a baseline for the preliminary trials. The optimum coagulant dose and pH are likely to
change due to variability in raw water quality. The system will need to be optimized to determine
the best parameters for each source water in this study.

Table 2. Proposed Initial Operating Conditions for Ceramic Coagulation/MF System.

Parameter

Aluminum (Al)

Ferric (Fe)

Coagulant

0.5 to 3.5 mg/L as Al

1 to 6 mg/L as Fe

pH Range

5.5 to 38.5 mg/L as alum*

6.5 to 7.0

(2.9 to 17.5 mg/L as FeCl3)

4.5 to 5.5

Backflush Interval

1 hour

1 hour

* Alum chemical formula of Al2(SO4)3 14.3 H2O, Mol. Wt. = 600 g/mol

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Polymeric Membrane System Parameters

A review on polymeric MF with coagulation as pretreatment was also performed. The coagulant
dose, pH levels, and backwash intervals were compared to determine how similar or different the
polymeric and ceramic membranes were. A total of 7 papers were reviewed that had similar
operating parameters as the papers reviewed in the previous section. Table 3 summarizes the
parameters that the authors used.
Berube et al. (2002) investigated the use of PACl as pretreatment steps prior to MF membrane
treatment for the removal of organic material and trihalomethane (THM) precursors contained in
water. The authors used a 0.2 m hollow fibre microfiltration membrane that was backwashedback pulsed once every 22 minutes. PACl dosages that resulted in concentration of 0.6, 1.2, and
2.5 mg/L as AL were investigated. In addition, soda ash was used to adjust the pH to
approximately 6.2. They concluded that the MF system with pre-coagulation removed
approximately 75% of the organic material and THM precursors. Also, they found that there was
no benefit to using a concentration of coagulant greater than approximately 0.3 mg/L as Al, to
achieve high removal efficiencies for organic material and THM precursors. A point worth
noting is that since the membrane is being operated in a dead-end mode, the actual coagulant
concentration within the membrane system is likely to increase consecutive filtration cycles
(Berube et al., 2002).
Farahbakhsh and Smith (2002) evaluated the effect of pretreatment with coagulation on the
performance on the 0.2 m MF membrane system. They decided to use doses of 2, 4, and 8
mg/L of PACL and maintained a pH between 5.9 and 6.2. A backwash interval of 22 minutes
was used during the membrane operation. They found that the highest reductions in the rate of
membrane fouling resulted from coagulation at a PACl dose of 4 mg/L. Overall, they concluded
that the pretreatment with coagulation was effective.

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Table 3. Summary of Polymeric Coagulation/MF System Operating Parameters

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Fiksdal and Leikens (2006) investigated the effectiveness of pre-coagulation/flocculation

combined with a 0.2 m MF membrane for virus removal. Using 3 and 5 mg Al/L of alum and
PACl coagulants, the authors observed an average of 6.7 log removal values for both coagulants.
Thus concluding that MF filtration in combination with coagulation was effective in removing
viruses in drinking water.
Howe and Clark (2006) conducted laboratory studies to understand the effects of coagulant,
coagulant dose, and application condition on membrane performance. They selected five
coagulant doses to fulfill the following treatment objectives: (1) no coagulant, used as a control
experiment, (2) dose for ineffective coagulation, (3) dose for optimal turbidity removal, (4) dose
midway between 3 and 5, and (5) dose for enhanced coagulation. The study was conducted using
dead-end 0.2 m flat-sheet membrane disks. The authors showed the effectiveness of coagulants
with different water sources. With some waters the coagulant had negative effects on the
membrane flux (i.e., it fouled the membrane) while with others it improved the membrane flux.
The range of alum dose and pH optimum for turbidity removal of 5 different water sources was
10 to 15 mg/L and 7.2 to 7.8, respectively.
Compared to ceramic membrane systems, the most significant difference appears in the
backwash interval times. The polymeric systems were backwashed more frequently (<1hr) than
ceramic membrane systems. However, the coagulant doses and pH level used were similar. A
key concept to explore in this research will be in using coagulant dosages that would be
considered suboptimal in conventional drinking water treatment plants for ceramic membrane
application. In a study by Choi and Dempsey (2004), the authors concluded that under-dose
coagulation conditions (relative to conventional treatment) should be considered for polymeric
UF applications. The under-dose conditions improved contaminant removal and reduced fouling
while also producing a smaller volume of waste solids due to decreased coagulant dosage (Choi
and Dempsey, 2004). The under-dose conditions offer many potential advantages and appear
consistent with the lower coagulant dosages cited in previous studies.

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References
Brub, P., D. Mavinic, et al. (2002). "Evaluation of adsorption and coagulation as membrane
pretreatment steps for the removal of organic material and disinfection-by-product precursors."
Journal of Environmental Engineering and Science 1(6): 465-476.
Choi, K.Y., and B.A. Dempsey (2004). In-line Coagulation with Low-pressure Membrane
Filtration. Water Research 38(2004): 4271-4281.
Farahbakhsh, K. and D. Smith (2002). "Performance comparison and pretreatment evaluation of
three water treatment membrane pilot plants treating low turbidity water." Journal of
Environmental Engineering and Science 1(2): 113-122.
Fiksdal, L. and T. Leiknes (2006). "The effect of coagulation with MF/UF membrane filtration
for the removal of virus in drinking water." Journal of Membrane Science 279(1-2): 364-371.
Howe, K. and M. Clark (2006). "Effect of coagulation pretreatment: on membrane filtration
performance." Journal-American Water Works Association 98(4): 133-146.
Judd, S. and P. Hillis (2001). "Optimisation of combined coagulation and microfiltration for
water treatment." Water Research 35(12): 2895-2904.
Kanaya, S., S. Fujiura, et al. (2007). The World Largest Ceramic Membrane Drinking Water
Treatment Plant, American Water Works Association, 6666 West Quincy Avenue, Denver, CO,
80235-3098, USA.
Lehman, S., S. Adham, et al. (2008). "Performance of new generation ceramic membranes using
hybrid coagulation pretreatment." Journal of Environmental Engineering and Management 18(4):
257-260.
Lerch, A., S. Panglisch, et al. (2005). "Direct river water treatment using coagulation/ceramic
membrane microfiltration." Desalination 179(1-3): 41-50.
Loi-Brgger, A., S. Panglisch, et al. (2006). "Ceramic membranes for direct river water
treatment applying coagulation and microfiltration." Water Science and Technology: Water
Supply 6(4): 89-98.
Matsui, Y., T. Matsushita, et al. (2003). Virus removal by ceramic membrane microfiltration
with coagulation pretreatment, IWA Publishing.
Matsushita, T., Y. Matsui, et al. (2005). "Effect of membrane pore size, coagulation time, and
coagulant dose on virus removal by a coagulation-ceramic microfiltration hybrid system."
Desalination 178: 21-26.

10
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or thirdparty copyrighted materials, nor has the accuracy of its information or conclusions been evaluated.
Accordingly, the information is not considered published and is not available for general distribution. Until the
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Meyn, T., A. Bahn, et al. (2008). "Significance of flocculation for NOM removal by coagulationceramic membrane microfiltration." Wat Sci and Tech: Wat Supply 8: 691-700.
Meyn, T. and T. Leiknes (2010). "Comparison of optional process configurations and operating
conditions for ceramic membrane MF coupled with coagulation/flocculation pre-treatment for
the removal of NOM in drinking water production." Journal of Water Supply: Research and
Technology - AQUA 59: 81-91.
Mo, L. and X. Huanga (2003). "Fouling characteristics and cleaning strategies in a coagulationmicrofiltration combination process for water purification." Desalination 159(1): 1-9.
Yonekawa, H., Y. Tomita, et al. (2004). "Behavior of micro-particles in monolith ceramic
membrane filtration with pre-coagulation." Water Science and Technology 50: 317-325.
Yuasa, A. (1998). Drinking water production by coagulation-microfiltration and adsorptionultrafiltration. Proceedings of 1997 Workshop on IAWQ-IWSA Joint Group on Particle
Separation, July 1, 1997 - July 2, 1997, Sapporo, Jpn, Elsevier Sci Ltd.

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Significant Findings
Based on the literature review, it appears that by using coagulant dosages that would be
considered suboptimal in conventional drinking water treatment plants (i.e., those resulting in
inadequate charge neutralization for good floc formation, settling/flotation, or filtration) might be
ideal for ceramic membrane pretreatment applications. The under-dose conditions show
potential for reducing operating costs (both chemical costs and disposal costs) while improving
operation (by improved contaminant removal and reduced fouling) and appear consistent with
the lower range of coagulant dosages cited in previous studies. While there are not yet any
research results to support this with from the current study, the range of coagulant dosages
investigated in this study will include coagulant dosages lower than those typical of conventional
surface water treatment plants. This idea was not included in the original proposal, which said
based on similar research with polymeric membranes, low coagulant dosages will be avoided
due to fouling concerns and is offered up for discussion/comments at this time.
Applicability of Findings to the Drinking Water Community
The finding that intentional under-dosing in membrane coagulation pretreatment relative to
conventional coagulation pretreatment may offer a significant financial advantage to some
utilities and offer greener (i.e., more sustainable) treatment options as well. This finding has not
yet been supported experimentally, but it could be explored in the current experimental plan for
this project. So, no applicable findings are being reported at present.

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