CHEMICAL CLEANING OF MF AND UF MEMBRANES IN

WATER TREATMENT

By: Javier Lopetegui, PhD in Science (*); Rakel Gutiérrez, Industrial Enginner (*); Elena
Meabe, Chemical Engineer (**); Luis Sancho, PhD in Science (**).

(*) Likuid Nanotek S.L.

PºManuel Lardizábal 15
20018 San Sebastián
Tel.: 943 223 841
Web: www.likuidnanotek.com

(**) Centro de Estudios e Investigaciones Técnicas de Gipuzkoa (CEIT)

PºManuel Lardizábal 15
20018 San Sebastián
Tel.: 943 212 800
Web: www.ceit.es

ABSTRACT: The successful operation and maintenance of a filtration system, as well as

membrane average life will depend on membrane fouling phenomena. To optimize that, a good
membrane system design is critical, considering both water and membrane features and
proposing good operational conditions. Therefore, the establishment of proper and versatile CIP
protocols, with the use of good and specific cleaning detergents is being more and more
important. Those protocols must be dynamics and must work all together with useful membrane
lab analysis and works.

A membrane is a semi permeable thin layer, able to separate different substances according to
their physical and chemical properties when driving force is applied through it.

Pressure-driven membrane operations (other operations known as GP and DIA) can be

classified in four groups mainly: IO, NF, UF and MF. OI and NF (also known as OI at low
pressure) are mainly used for salt removal (water desalination) and water softening respectively.
In this kind of operation, membrane fouling can generate production stops, high preventive
maintenance and shorten/reduce membranes’ average life.

The number of OI plants and their size has grown exponentially in recent years, being a very
attractive market for large water companies settled in international markets.

However, UF and MF market has grown steadily over the last 10 years, with annual growth
above 10 and 15%. Despite the fact that the type of installation is not as big as the latest
generations of OI plants, the problem of membrane fouling remains critical for the viability of the
system.
Global market for MF and UF tangential filtration systems, including modules and associated
equipment, was 3,8 billion dollars during 2006 [1], and it is expected to reach 5 billion dollars by
2010.

This kind of membrane can be applied on several sectors, such as agro-food sector (wine
clarification, filtration of milk-based products, juice clarification etc.), biopharma (crop
separation, metabolite concentration, etc.), chemical (oil separation and recycling etc.) and of
course, water market. Specifically in applications for water treatment, MF and UF membranes
are used for:

Surface water and groundwater purification.

Pre-treatment of NF and OI plants.

Wastewater treatment (Direct filtration and MBR).

Sludge treatment.

The appearance, development and growth of new technologies such as MBR, are essential for
the increase associated to water treatments, and the fact that the use of MF membranes in
purification is increasing.
The EU Water Framework Directive 2000/60/EC of the European Parliament favors MBR
technology, in cases like urban water with very strict requirements of effluent quality. In the
industrial sector IPPC directives and the Best Available Technology concept clearly favour the
application of this technology.
With reference to purification, MF provides water quality and reliability compared to
conventional technologies; it eliminates or minimizes the continuous addition of chemical
reagents and the formation of undesirable by-products.

The average life of a membrane used for water treatment range from 3 to 10 years. At this
point, it is important to take into account the properties of the fluid to be treated, to operate the
membranes under appropriate conditions and, to introduce a monitoring and a fouling detection
system. Moreover, it is important to develop, optimize and introduce cleaning protocols
(especially with industrial water) in order to extend the membrane’s life and to minimize
preventive and corrective maintenance (Table 1).

Purpose of the filtration Quality, performance, operating costs

Properties of the fluid to be treated
Operating conditions
Cleaning and recovery protocol
DOM, COM, SS, SM, viscosity, hardness, FI
T, TMP, CFV, VCF
Periodicity, type of reagent (acid, alkaline, enzymatic,
degreaser, etc.), cleaning temperature, CT reagent
combination, pH, etc.

Table 1. Points that should be taken into account for the design and operation of a tangential filtration
system of MF and UF MBR.

In order to optimize operating conditions and cleaning protocols, laboratory studies as well as
destructive tests of Membrane Autopsy are becoming extremely necessary (Figures 1 and 2).
These tests enable to locate, evaluate and correct fouling, breakages and malfunction in
membrane systems.
 Figure 1. SEM Microscopy room – Membrane Laboratory at Likuid-CEIT

Figure 2. Jar-test to optimize cleaning protocols of organic membrane – Laboratory at Likuid-CEIT.

Types of fouling
There are several types of fouling that are classified in three main categories: inorganic, organic
and biofouling. The latter is mainly organic and presents some peculiarities that will be
explained forward (that will be further developed).

Inorganic
Silica
Silica deposits are very hard, fragile and looks like/seem to porcelain. Precipitation of silicates is
always related to the presence of iron or aluminum, forming silico-aluminates of calcium and
iron. The cleaning of siliceous precipitates should be done in alkaline pH values and under
temperatures as high as possible with detergent products.

Aluminum
The aluminum found in membranes might have three origins: ionic, colloidal (aluminum
silicates) and an excess of coagulants (alumina sulfate and aluminum polychloride).
As these coagulants are very difficult to clean, frequently high pH and temperatures are used in
order to enhance the detergents’ action.
 Iron
The iron from pipes’ corrosion, etc. is not problematic. However, there might be some problems
with the iron in solution, which is deposited in membranes as ferric oxide, as well as the iron
from coagulants, usually chloride and ferric sulfates as they originate a dark brown colored
deposit.
To eliminate this kind of deposits, they should be dissolved with acid solutions at high
temperatures if possible. Citric acid works very well, and if it is combined with surfactants agents
it works even better.
If the cleaning is done with pH around 4,1 the removal of iron is optimized, due to the fact that
the mentioned pH corresponds to maximum iron solubility.

Calcium Carbonate, CaCO3

Calcium Carbonate precipitates quickly, forming granulated and porous precipitates. Initially the
treatment is simple, since any kind of strong acid solution will redissolve it. Even small doses of
weak acids such as citric, working at pH 6,5-6,8 will eliminate this deposit

Calcium Sulfate, CaSO4, (gypsum)

It forms hard, dense and fragile precipitates. Its removal is more complicated than in the
previous case because it is highly insoluble in water, requiring a strong acid combined with
other elements as chelating agents.

Calcium Phosphate, Ca3(PO4)2

Phosphate deposits have a brown-gray colour and they are eliminated with a medium-soft acid
cleaning, although alkaline surfactants may also be used.

Barium Sulfate, BaSO4 and Strontium, SrSO4

Barium Sulfate is insoluble in water. It is eliminated with chelating agents.

Organic Material / Matter

The accumulation of particles on the surface of the membrane is controlled by two opposite
mass transfer processes: convection of particles towards the membrane, because of the
permeate flux, and diffusion of particles from the membrane due to the shear produced by the
tangential flow of the retentate [2]]. Although the membranes are operated in cross flow mode,
to minimize the accumulation of soluble and colloidal material in the boundary layer near the
membrane’s surface (concentration – polarization), part of the feed water’s colloids are
transported to the membrane’s surface where they are adsorbed, forming a thing fouling layer
[3]]. The size or degree of fouling depends on those summarized in Table 1, among others.

In order to minimize fouling problems, it is important to reduce as much as possible COM

especially in cases that the molecular size is similar to the pore size of the membrane. This is
not easy to control; therefore, a pre-coagulation system or coagulation/flocculation previous to
the membrane is commonly used, thus reducing the amount of COM in the circulation loop of
the membrane.
MBR systems present several advantages in this sense, as the biological system located just
before the membrane, eliminates efficiently the BOM. Thus, the design of the MBR should be
focussed on eliminating the BOM as much as possible, reducing the maximum COM in the
circuit of the membranes.
Temperature factor is also very interesting when minimizing organic biofouling. As MBRs
3
eliminate high volumetric loads (kgBODm d) in exothermic processes, the temperature of
reactors is usually high. This favors the dissolution of colloidal species that might otherwise be
potential “blockers” of pores.
In general, this kind of biofouling can be treated with a combination of sodium hydroxide and
hypochlorite. In the case that organic fouling is nor effectively removed with these reagents, the
use of alkaline detergent with enhancers and other complementary reagents is recommended to
obtain higher removal efficiency. In some cases, the use of enzymatic detergents with protease
and lipases, which act specifically over certain compounds, is recommended, as well as
additives to eliminate fat, etc.

Biofouling
As in the previous case, the microorganisms are transported towards the surface of the
membrane where they are adsorbed; they grow and multiply at the expense of water’s nutrients,
forming a biological layer or bio-layer that can condition the performance of the system.
The bio-layers formed may or may not cover the membrane uniformly. However they usually
consist of multiple layers of alive and dead microorganisms together with their extracellular
products (EPS, glycoprotein, lipids, etc.)
This type of fouling is critical to IO systems and MF/UF systems that filtrate directly the water,
especially when this water has a high organic load. This effect is diminished in MBR systems
due to the low BOM concentration in the membrane circuit, despite the presence of a large
amount of biomass, in form of.
One of the critical factors in order to reduce biofouling is to work with higher CFV which drag
and prevent the consolidation of bacterial layers on the membrane’s surface.

The chemical cleaning suitable for this kind of biofouling is very similar to that described before,
but sometimes the cleaning action might be combined with biocide agents, chelating agents as
EDTA and some enzymatic detergents that denature certain proteins of the bacterial cell
membrane.

Types of membranes and cleaning protocols

There are many kinds of membranes depending on their composition, geometry, etc. In order to
simplify and in relation to MF and UF for water treatment, the most commonly used nowadays
are organic (HF tubular and flat) and inorganic (ceramic tube).
In all cases the principle of performance is cross-flow filtration, and due to the high sheart
imposed, a cake layer is not quickly formed on the surface of the membrane, enabling a
continuous performance during a long period of time. On the other hand, in submerged systems
the CFV necessary for this continuous “self-cleaning” is given by the air flow injected into the
bottom of the membrane module. In external membranes, CFV is created by recirculation of
water along the membrane.

External membranes’ cleanings protocols are more developed compared to those for
submerged membranes. There are several reasons for this:

Costs: submerged membrane plants predominate in urban sector, with very high flow
rates and volumes. Working with these volumes and with a large number of
membranes, the purpose is to save as much as time and reagents as possible.
However, this might not be the best option considering the global system.

Type of fouling: the operation of submerged system with urban wastewater generates a
repetitive fouling nature, generally less severe than in the industrial systems. Moreover,
fouling is generated at lower TMP values. All this favors the efficiency of the chemical
cleaning, despite the comments of the preceding paragraph.

The gradual introduction of submerged membrane systems in MBRs for industrial water
treatment is generating more complicated fouling problems and they are becoming more difficult
to treat. On the other hand, the use of submerged membranes in industrial MBRs is usually
associated to medium-low size plants. Therefore, the use of detergents with combined and
potentiated formulas instead of hypochlorite or a combination with it, is becoming widespread
and optimized from a technical-economic point of view.
 Tubular Membrane – Ceramic or Organic

Tubular membranes are mainly used in external configuration of medium-small size plants, and
cleaning protocols have been adapted to industrial sector’s necessities. Therefore, there are
already a large number of chemical agents used for different cleaning protocols adapted to each
case (Table 2).

Chemicals commonly used in membrane cleaning

Caustics Hydroxide, carbonates and phosphate
Oxidants/disinfectants Hydrogen peroxide, peroxyacetic acid, sodium
hypochlorite and metabisulphite
Acids Citric, nitric, phosphoric
Chelating agents EDTA, citric acid
Surfactants Anionic, nonionic
Enzymes Proteases y lipases
Table 2. Chemical agents mainly used for cleaning membranes.
Taken from “Universidad de Granada-Tesis Doctoral 2006-José Edgar Zapata Montoya”

In general, the tubular membranes are less sensible than HF, for example, to changes in
viscosity, SS, T and BOM as they can be adapted to to a wide range of TMP and CFV, in a
more intensive operation that requires less membrane surface to be installed and thus reduce
the inversion.

Tubular membranes do not need a small mesh size pre-filtration of the influent and they are
easy cleaned. In the case of ceramic membranes (Figure 3), the recovery that can be achieved
is the best of all, as it is possible to use a wide range of pH and temperature. This also affects
the average life of the membrane, which can approximately duplicate lifetime of an organic
membrane.

Figure 3. Likud’s multitubular inorganic membrane samples

The cleaning protocol must be adapted to the operating conditions of the modules which can
vary significantly in the case of external membranes. TMP values between 0.5 and 6 bar can be
applied, together a wide range of CFV values.

In general, it would be advisable:

Maintenance cleaning, low foam medium alkaline chlorinated detergent at 0,6-1%
during 40-60 min.

Clean shock, with a medium-high alkaline detergent (depending on the tolerance of the
membrane to pH) followed by a mild acid detergent at 0,5-1% during 30-60 min.

In the case of difficult fouling associated to proteins, grease or other substances, it is necessary
to use specific enzymatic products, degreasers, etc.
 Hollow Fiber (HF)

FH membrane is usually used with outside-inside filtration mode. The permeate is collected
inside the fiber, which can be as thin as 0.5 mm. Hollow fiber is used both in external and
submerged configuration. In the external one, HF is applied to treat superficial and underground
waters with low turbidity and low OM concentrations. In MBR systems the submerged
configuration is mainly used, with reinforced fibers of 2 mm diameter.
HF usually gets more clogged in the end of the fibers (Figure 4), because the degree of
agitation of the fiber in these areas is lower.

Figure 4. Solids accumulation and organic material on the top of HF module.

However, before initiating discontinuous cleaning protocol it is recommendable, if possible, to

flush the membranes with tap water at high pressure

In the case of HF membranes, apart from optimizing the chemical cleaning protocol, it is highly
important to operate the system in the optimum conditions in order not to vary the
characteristics of the solution to filter. This fact is due to the low pressure applied for the
filtration, which makes the membrane performance to be highly influenced by any change in the
liquid to filter. For example, in hollow fiber membranes applied to MBR processes, the control of
SS and BOM concentration, as well as the temperature, is critical for the good performance of
the system. An increase in SS, which generates an increase in the viscosity, is the cause of two
important deficiencies:
1. Filterability of mixed liquor decreases.
2. Coalescence of air bubbles occurs, reducing the scouring on the membrane surface
and consequently, the “cross-flow” efficiency.

Chemical cleanings have been shown to be very efficient. In lab scale, filtration tests are done
in specific devices (filtration cells Figure 5), operating in dead-end filtration mode). By using
these techniques and trying different cleaning solutions, it is possible to obtain interesting
recovery graphics (Figure 6) in order to optimize the cleaning protocol.

As an example of a standard cleaning protocol:

Backwashes: 2-5 ppm of hypochlorite in opposite direction, with a flux 2.5 times higher
than nominal flow.

Maintenance cleaning:
o 200-800 ppm of hypochlorite.
o 200-800 ppm of hypochlorite combined with medium alkaline detergent with low
foaming potential.

Recovery cleaning:
o 600-1.000 ppm of hypochlorite combined with medium alkaline detergent (low
foaming potential), followed by citric acid at 1% concentration.
As in the previous case, in cases of severe fouling of the membranes, adaptation of cleaning
protocols is needed: more specific reagents are used and cleaning conditions (contact time,
temperature, etc) are modified.

Figure 5. Dead-end filtration cell AMICON 8200.

45
40 y = 509.13x
35 y = 250.55x
J(20ºC) (l/hm2)

30
25 y = 215.27x
20
15 y = 95.994x
10
5
0
0 0.05 0.1 0.15 0.2 0.25
TMP (bar)

New Fouled Alk. Cl. Acid Cl.

Figure 6. Clean water permeability evolution (slope of each line) after different chemical cleanings.

Flat-sheet organic membrane

Organic flat-sheet membranes can be used in external and submerged configuration. In both
cases, fouling nature and chemical cleaning protocols are similar to those mentioned previously
for tubular and HF membranes, respectively.
These membranes do not have any particular characteristic which can affect the fouling
mechanisms and the chemical cleaning conditions.
A fragment of PAN organic membrane is shown in Figure 7, before and after being cleaned
with several acid solutions. Clean water permeability was measured after each cleaning test. In
this specific case, as alkaline cleaning was shown to be inefficient, it was concluded that the
membrane presented inorganic fouling. Afterwards, different acid cleanings were made in order
to compare their efficiency. It must be highlighted that the low efficiency of nitric and oxalic acids
are due to the pH and temperature limitations typical of organic membranes, which make not
possible to apply high concentrations of these acids and require the use of other commercial
detergents with moderate pH values.
 2
REAGENT CWP (l/hm bar)
DIVOS 35 475
Citric acid 400
Nitric acid 190
Oxalic acid 60

Figure 7. Fragments of PAN flat-sheet organic membrane before and after being cleaned with acid
DIVOS35 reagent. Clean water permeability values after the cleaning with different solutions are included.
Summary
For a correct design of a MF/UF system, it is necessary to consider the characteristics of both
the wastewater and the membrane, as well as select the most appropriate operating conditions
in order to find the optimum combination between them.
In addition, a correct chemical recovery of the membrane, no matter what kind it is, is essential
so as to fulfill the technical-economic requirements of a filtration system.

When a chemical cleaning protocol is settled, it is necessary to adapt it to the nature of fouling
that will be generated, especially when working with industrial wastewater and variable
composition water.
Consequently, the maintenance operations are minimized and membrane’s lifetime is extended.

Adaptation of cleaning protocol can be based on CIP procedures or on lab tests. These
observations can be complemented with a membrane autopsy when membrane performance
and cleaning efficiency is not good.

The basis for a good cleaning protocol is almost the same independently of the configuration
(tubular, HF, flat-sheet) and operation mode (external or submerged). Nevertheless, it is
necessary to adapt the chemical cleanings to the specific operation conditions under normal
operation of the membrane (TMP and temperature).

In the case of fouling by organic material and/or biofilm, temperature and pH are very important.
Thus; the higher they are, the better the efficiency of the cleaning.
Finally, the effectiveness of the cleaning will depend directly on the type of membrane, as
Depending on it, stronger products and higher pH, temperature and contact time can be
selected.

The same happens with acid cleanings, where higher cleaning efficiency is obtained with lower
pH values. Temperature is also very important.

If the fouling is inorganic, the efficiency of the cleaning will depend on the type of active principle
used, and the adjustment of the pH in relation to the solubility index of the compound intended
to be removed from the membrane.

As a general rule, it is important to ask the membrane manufacturer for advice if there are any
doubts concerning the pH, temperature or active principle that will be used during the cleaning
protocols.
Acronyms
BOM Biodegradable Organic Matter
CIP Cleaning In Place
CFV Cross- flow velocity
COM Colloidal Organic Matter
CT Contact Time
CWP Clean Water Permeability
DIA Diafiltration
FI Fouling index
GP Gaseous Permeation
HF Hollow Fiber
IO Inverse Osmosis
MBR Membrane Bioreactor
MF MicroFiltration
MOD Dissolved Organic Matter
NF NanoFiltration
OM Organic Matter
PAN Polyacrylonitrile
SS Suspended Solids
TMP Transmembrane pressure
UF UltraFiltration
VCF Volumetric concentration factor

References
[1] News. (September 2005). Membrane Technology, pg.4.
[2] Wang, L and Song, L. (1999), Flux decline in microfiltration and ultrafiltration:
experimental verification of fouling dynamics. Journal of Membrane Science 160, pp.41-
50.
[3] Lepore, J.V. and Ahlert, R.C., 1988, “Fouling in Membrane Process”, in B.S. Parekh
(ed.), Reverse osmosis Technology:Application for High Purity Water Production,
Marcel Dekker, New York, pp. 141-184.