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Acid solutions are used to remove milk-based calcium fouling and water-related hardness issues.The alkaline cycle
is the most complex of the cleaning steps. The solution must be properly buffered to maintain the correct pH,
because the concentration of caustic changes due to its reaction with foulants. Straight caustic is seldom
recommended for membrane cleaning. A combination of nonionic and anionic surfactants will usually provide the
best results. The addition of water-conditioning agents and a buffer to the surfactant cocktail completes the recipe
for an effective additive.
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Membrane Fouling
When a Liqui-Cel Membrane Contactor system is placed between a clarification unit and an RO
unit to remove CO2 from a water stream, watch for changes in water pH. Water may contain
species that are soluble in water in acidic pH ranges but insoluble in alkaline pH ranges. If water
pH increases as the water passes through the contactor (this happens when dissolved CO2 is
removed from water) the insoluble species might precipitate on the membrane surface.
Precipitation of solids can also occur when water is treated with flocculation chemicals followed by
a change in pH. For example, alum (aluminum sulfate) is often used to remove suspended matter
from water. The removal takes place by coagulation, flocculation and precipitation in the water
clarifier tank. The precipitation occurs in the form of polymeric aluminum hydroxide at certain pH
ranges. As CO2 is removed from the feed water, a change in pH may be enough to precipitate
excess aluminum hydroxide or other ionic compounds on the membranes surface. The thin
coating or deposits will prevent normal gas transfer through the membrane and the contactors
Liqui-Cel Membrane Contactors Design & Operating Guidelines
27
removal efficiency will drop. This process is reversible by cleaning the contactor with an acid
solution such as 3% w/w ortho-phosphoric acid solution (refer to the Liqui-Cel Membrane
Contactor Cleaning Guidelines). The acid solution may dissolve surface precipitates on membrane
and will restore the contactor degassing performance to original manufacturer's specifications.
When the contactors are installed downstream from carbon beds, a 2 micron absolute filter should
be installed and the carbon beds should be flushed to drain after the carbon change-out until all
carbon fines are flushed out. Care should also be taken when back flushing carbon beds that are
downstream of membrane contactors. Filtration should be added to keep the contactors free from
carbon particles, which can be difficult or impossible to clean.
When Liqui-Cel Membrane Contactors are installed upstream of RO membranes, a cleaning
cycle is also recommended in order to prevent fouling of the Liqui-Cel Membrane Contactor.
Please refer to the Liqui-Cel Membrane Contactor Cleaning Guidelines available on-line at
www.liqui-cel.com or from your Membrana representative.
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Type of Membrane Fouling, Water Quality I ndicators, and Control Measures
According to the type of fouling materials, four categories of membrane fouling
are generally recognized. They are (a) inorganic fouling/scaling, (b) particle/colloids
fouling, (c) microbial fouling, and (d) organic fouling. A brief description on the nature
of fouling, relevant water quality as indicators, and control measures are summarized
below for each type of membrane fouling.
Inorganic Fouling/Scaling
Inorganic fouling or scaling is caused by the accumulation of inorganic
precipitates such as metal hydroxides, and scales on membrane surface or within pore
structure. Precipitates are formed when the concentration of chemical species exceeding
their saturation concentrations. Scaling is a major concern for reverse osmosis (RO) and
nanofiltration (NF). RO and NF membranes reject inorganic species. Those species
form a concentrated layer in the vicinity of membrane-liquid interface - a phenomenon
referred to concentration polarization. For microfiltration (MF) and ultrafiltration
(UF), inorganic fouling due to concentration polarization is much less profound, but can
exist most likely due to interactions between ions and other fouling materials (i.e.,
organic polymers) via chemical bonding. Some pretreatment processes for membrane
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filtration such as coagulation and oxidation, if are not designed or operated properly, may
introduce metal hydroxides on membrane surface or within pore structure. Inorganic
fouling/scaling can be a significant problem for make-up water of caustic solutions
prepared for chemical cleaning.
Particulate/colloid Fouling
Algae, bacteria, and certain natural organic matters fall into the size range of
particle and colloids. However, they are different from inert particles and colloids such
as silts and clays. To distinguish the different fouling phenomena, particles and colloids
here are referred to biologically inert particles and colloids that are inorganic in nature
and are originated from weathering of rocks.
In most cases, particles and colloids do not really foul the membrane because the
flux decline caused by their accumulation on the membrane surface is largely reversible
by hydraulic cleaning measures such as backwash and air scrubbing. A rare case of
irreversible fouling by particles and colloids is that they have smaller size relative to
membrane pore size. Therefore, those particles and colloids can enter and be trapped
within the membrane structure matrix, and not easily be cleaned by hydraulic cleaning.
Microbial/Biological Fouling
Microbial fouling is a result of formation of biofilms on membrane surfaces. Once
bacteria attach to the membrane, they start to multiple and produce extracellular
polymetric substances (EPS) to form a viscous, slimy, hydrated gel. EPS typically
consists of heteropolysaccharides and have high negative charge density. This gel
structure protects bacterial cells from hydraulic shearing and from chemical attacks of
biocides such as chlorine.
Severity of microbial fouling is greatly related to the characteristics of the feed
water. Water quality parameters that indicate the potential of microbial fouling are
classified into three categories:
(a) Parameters indicating the abundance of microbes,
(b) Parameters indicating nutrient availability,
(c) Parameters indicating environmental conditions for microbial growth,
Organic Fouling
Organic fouling is profound in membrane filtration with source water containing
relatively high natural organic matters (NOM). Surface water (lake, river) typically
contains higher NOM than ground water, with exceptions. For source water high in
NOM, organic fouling is believed to be the most significant factor contributed to flux
decline (Mallevialle et al., 1989; Lahoussine-Turcaud et al, 1990). Microfilters usually
remove insignificant amount of organic matter, as measured by dissolve organic carbon
(DOC). DOC as an indicator for organic fouling is probably neither proper nor adequate.
Efforts to identify the effects of subgroups of NOM on membrane fouling have yet been
able to draw definitive conclusions.
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The effects of various operating strategies against different types of fouling are
summarized in Table 1. As indicated in Table 1, chemical cleaning is an effective control
strategy for all types of membrane fouling.

Membrane Chemical Cleaning
The key issue to understand membrane fouling and cleaning is to understand
interactions a) between fouling materials and membrane, b) between cleaning chemicals
and fouling materials, c) between cleaning chemicals and membrane, and d) among the
fouling materials.
I nteractions Between Fouling Materials and Membrane
Membrane fouling is a complicated phenomenon of which causes of fouling are
multiple and poorly understood. The core of the issue is interactions between fouling
materials and membrane, and between fouling materials themselves. It has been
recognized that electrostatic interaction and hydrophobic/hydrophilic interaction between
membranes and fouling materials have a significant bearing on membrane fouling. This
is particularly true to more difficult fouling problems caused by adsorption of natural
organic matters and biopolymers on the membrane. The balance between the forces of
electrostatic repulsion and hydrophobic adhesion determines the outcomes of membrane
fouling, as well as the efficiency of chemical cleaning
Electrostatic Interactions
Surface charge of membrane media is the results of ionization of particular
functional groups existed on the membrane surface (e.g., carboxyl and amine). Because
ionization of a functional group depends on pH, surface charge of a particular membrane
is also pH-dependent. In pH range of typical natural waters, most membranes appear to
have a neutral to negative net surface charge. On the other hand, colloids, particles, and
dissolved organic matters typically carry negative charges at the pH of natural water.
Therefore, there is a tendency of electrostatic repulsion between membranes and those
constituents.
Natural organic matter, a major factor of membrane fouling, typically contains
about 50% humic substances. Aquatic humic substances (AHS) are polyprotic acids
(Malcolm, 1985). Major acidic functional groups include carboxylic and phenolic
functional groups. About 70% - 80% of total acidity is from carboxylic groups, and rest
is from phenolic hydroxyl groups, as illustrated by a typical titration curve of HAS in
Figure 2 (adapted from Thurman, 1985)