Membrane Cleaning Guide

1 Brief summary of the theory behind membrane blocking

Membrane fouling is the general term used to describe all operations which obstruct mass transfer
through a membrane, including all reversible and irreversible processes which clog up a membrane and
Membrane Fouling result in a reduction of the
reversible, irreversible
Macrofouling Microfouling filtration rate. Figure 1
shows the most important
Sludge accumulation Fouling Scaling Biofouling fouling processes which
occur in membrane-
Organic Anorganic
supported activated
Particulate and col- Dissolved Micro- sludge processes using
loidal Substances Substances Organisms
ceramic microfiltration and
Wastewater-
Activated Sludge Mixture ultrafiltration membranes.

Fig. 1: Different types of membrane fouling

Other technical terms are

presented in Fig. 2. A coating layer is always formed by particles larger than the pore diameter and can
even be caused by a growth of micro-organisms. If the membrane is not cleaned mechanically, the
coating layer would continue to expand until the membrane became completely blocked.

Dissolved organic or inorganic molecules enter the

ADSORPTION d << d
P
membrane pore structure with the filtrate. Depending
Pores become narrow or closed
because of
on the membrane material, the dissolved substance, - dissolved org. oder inorg. substances

the concentrations and the pH value, the substance

can accumulate or adsorb on the membrane. The Coating layer d >> d P

pore structure then becomes narrower and the flow Deposites on the membrane surface
consisting of
- Particulate substances,
rate over the membrane decreases. - Dissolved org. substances because suolubility
Is exceeded (gel layer)

Blocking is the term employed when the pore structure

Blocking d ~ dP

becomes completely closed e.g. by particles, which Pores of particle size become blocked
Or closed because of
have the same size as the pores. However this - Particulate org. or inorg. substances

definition is also used for cases in which there is,

Fig. 2: Technical terms
more or less, a complete break in the flow rate.

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1.1 Macrofouling
This is the term used to describe an accumulation of sludge on the membrane caused by particulate and
colloidally dissolved organic and inorganic substances.

1.1.1 Development
Over the course of operating time, a filter cake forms on the membrane surface owing to the fitration
flow through the membrane during which particulate impurities are separated.

1.1.2 Precautionary or prevention measures

Before entry into the activated sludge tank, sand particles should be removed, in any case, via a
suitable gravity separator (sand trap) while organic, colloidal suspended substances should be broken
down in an efficient biological stage.

1.1.3 Control mechanisms

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Different fouling control strategies are implemented with CFM Systems . These include the following:

1. Shear force is generated perpendicular to the filtration direction by membrane aeration under
the module. The ascending air bubbles produce major shear forces at the phase interfaces
whereby the particulate coating layer is removed. The air bubbles also accelerate the ambient
liquid which results in a continuous cross-flow.
2. Periodic backflushing with permeate (filtrate), which even reaches into the pore structure, is
applied to break off the coating layer from the filter plate, from which it is then removed by the
cross-flow.
3. AMC (Automatic Mechanical Cleaning) Plastic elements with a diameter of roughly 7 mm,
which greatly increase the shear forces, are routed continuously upwards past the membranes
by the flow and hence effectively remove the coating layer on the long term.
4. When system malfunctions occur, a considerable amount of sludge can accumulate on the
module. An easy, highly effective cleaning process using a high-pressure steam cleaner is
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provided for by CFM Systems .

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1.2 Microfouling – Fouling

Fouling refers to the adsorption of dissolved, organic substances on the surface or in the pores of a
ceramic membrane.

1.2.1 Development
Certain surface-active, organic molecules tend to accumulate on surfaces and thus change the
character of the membrane (hydrophilicity) and/or reduce pore diameter. Consequently, this decreases
the flow through the membrane.

1.2.2 Precautionary or prevention measures

The best way to avoid this is by installing an effective biological stage whereby the organically
degradable substances are removed and many of the non-degradable substances are bonded to the
activated sludge flocs. Fouling is reduced effectively on the long term. Certain difficult-to-degrade
substances such as synthetic oils should be prevented from entering the system via a volatile liquid
separator.

1.2.3 Control mechanisms

The biological stage can be controlled regularly by measuring standard parameters such as BOD5 und
COD and optimisation measures, if necessary, can be implemented. Permeate quality is also an
indicator for treatment efficiency in the biological stage. Permeate is fairly colourless (very light yellow)
and almost odour-free if operation runs well.

Backflushing with caustic soda solution and/or oxidants can be applied to remove blocking, which is
caused by fouling and which cannot therefore be removed by permeate backflushing. A good cleaning
effect (e.g. operation during the night at low feed rate) can be achieved by a break in filtration and
aeration only for some hours at adequate filtration capacity.

Fouling can be removed in continuous operation by the automated cleaning system, ADAB, developed
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by CFM Systems (see section 3 for more details).

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1.3 Microfouling – Scaling

Scaling is the term used for precipitation with subsequent deposits of inorganic salts on the membrane
surface and pore structure which reduces pore diameter and may even cause the membrane to become
completely blocked.

1.3.1 Development
If the solubility of inorganic salts is exceeded, these precipitate on surfaces and form layers.

1.3.2 Precautionary or prevention measures

Since inorganic salts cannot bio-degrade nor dissolve by e.g. increasing pH value, precautionary
measures should involve excluding wastewater with high salt concentrations from operations.

In any case, salt concentrations should be determined to detect the possibility of scaling.

1.3.3 Control mechanisms

If scaling occurs, the deposits can usually be dissolved by acids. The standard acid used by
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CFM Systems is citric acid since this bio-degrades easily.

1.4 Microfouling – Biofouling

Biofouling refers to the growth of micro-organisms on the filter plate. These try to become deposited on
the plate via a so-called extracellular polymer layer which is indicated by a greasy surface that cannot
be cleaned under running water.

1.4.1 Development
In activated sludge plants, this is a normal process which can be performed by almost all micro-
organisms. There is an increase in the formation of extracellular polymer layers when micro-organisms
are involved in stress situations in particular.

1.4.2 Precautionary or prevention measures

This is only possible to a limited extent. There is less formation of extracellular polymer layers when
operation in the biological stage is consistent.

1.4.3 Control mechanisms

All the methods for controlling coating layers such as AMC and ADAB are also conducive to reducing
the accumulation of extracellular polymer layers on the membrane. Cleaning with oxidants in this case
has proven very effective.

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Membrane Cleaning Guide

2 Parameters influencing cleaning processes

The significance of physical/chemical/technical parameters varies for the cleaning of industrial plants:

1. Mechanical cleaning: Mechanical cleaning is the most effective method which involves shear
force caused by flow (AMC, trouble shooting using a high-pressure cleaner).
2. Temperature: Basically it is true to say; the higher the temperature, the more effective the
cleaning. Ceramic membranes offer the greatest advantages in this case because temperatures
of up to 90°C can be used in cleaning operations de pending on the type of module.
3. Time: The cleaning time is particularly important for chemical cleaning which is more effective,
the longer the process runs. In this case, a similar cleaning effect can often be achieved at
lower concentrations but at longer reaction times.
4. pH value: It is the pH value, and not so much the concentration which is the decisive factor for
acidic or alkaline cleaning operations. Limits are also set by the biological system in question.
Cleaning solutions should always be in the range between pH 2 and pH 13.
a. Acidic cleaning: This is conducive to the removal of salt deposits. Although organic
acids have the advantage of being bio-degradable, they are considerably weaker than
inorganic acids such as hydrochloric acid.
b. Alkaline cleaning: This is applied to remove organic deposits. Caustic soda is the
standard solution (NaOH) used. Conversion of concentration to pH values for standard
acids and bases can be found in the annex.
5. Oxidation potential: One major advantage of ceramic membranes is their long-term resistance
to strong oxidants. The structure of many organic compounds is broken down and destroyed
(e.g. extracellular polymer layer) and micro-organisms are eliminated. The standard oxidant
used is sodium hypochlorite usually together with the alkaline solution.
6. Surface-active substances: This refers to surfactants which increase cleaning efficiency.
Particularly effective surfactants should be used for membranes contaminated with oil.

®
CFM Systems has succeeded in ensuring long-term, efficient membrane performance in terms of flow
rate and separation properties by skilfully combining the various influencing factors into complex,
automated cleaning processes. Special, manual cleaning regulations are provided to remove all types of
blocking from membranes that have been used incorrectly.

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3 Automated cleaning methods for CFM Systems®

The process is based on MBR operation and basically consists of a bioreactor with activated sludge as
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a biological stage (container 1) and a filtration stage (container 2) with CFM Systems membranes.

Cleaning

Bioreactor 1 Filtration 2

Permeate
Inlet

Blower Blower

Recirculation

Similar to a conventional sewage treatment plant, wastewater is degraded and treated by micro-
organisms in the biological stage. Instead of then separating the activated sludge by sedimentation, a
®
filtration stage is used for separation. The CFM Systems membranes separate the sludge from the
treated water (permeate) depending on their pore size. To prevent concentration occurring in the
filtration stage, a quantity of the return sludge has to be returned to the bioreactor. The volume flow
required can be defined as four times the feed flow.

Filtration

A filtration pump draws the treated water (permeate) through the membrane which retains solids and
micro-organisms. The pump produces a volume flow Qperm and a vacuum pperm. Pressure rises
continuously at constant volume flow as filtration time increases. Volume flow can be kept constant by
increasing the pump speed. Backflushing (variable time setting) begins automatically once the filtration
phase has ended (variable time setting). A certain permeate quantity, which is used for backflushing, is
collected in a storage tank. Excess permeate is routed to a discharge outlet (canal, receiving stream) via
an overflow or is made available as service water.

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3.1 Backflushing with permeate in continuous operation

Periodic backflushing is conducted by reversing the flow in order to remove deposits and coating layers
from the membranes. Intervals can be set between 20 and 60 seconds in the plant. The permeate in the
storage tank is pressed into the membrane by reversing the direction of rotation of the filtration pump
with excess pressure and an adjustable volume flow.

3.2 Backflushing with cleaning solution in continuous operation

Preventive chemical cleaning (ADAB – Automatic Detergent Assisted Backflushing) has been integrated
into the process to ensure filtration performance and smooth operation of the membrane activated
sludge plant. A separate storage tank is available for this purpose and chemicals can be added to the
permeate. Similar to backflushing, this mixed chemical solution is pressed into the membrane in the
opposite direction to filtration.

Two cleaning stages are usually carried out. The first cleaning stage involves an alkaline solution to
which an oxidant has been added (NaOH & NaOCl). In order to increase cleaning activity, a certain
reaction time is set aside for the solution to take effect. This procedure can be repeated as often as
required. An acidic cleaner is used in the second cleaning stage which operates in the same way as the
first. The pipes have to be rinsed after each cleaning stage to prevent the chemicals being mixed.
Rinsing is conducted only once and in the same way as permeate backflushing.

3.3 Intensive automatic or manual cleaning (on-air)

Depending on wastewater composition, intensive cleaning may be necessary. For this purpose, longer
contact times (reaction times) between the membrane surface and the cleaning agent are needed so
that cleaning takes place in air. To this end, the filtration chamber is emptied and its content pumped
back into the activated sludge tank. The ADAB cleaning is started, optionally with heated permeate.
Once cleaning has been completed, the filtration chamber is re-filled and the filtration cycle goes into
operation again. The various process steps are illustrated in the following diagram.

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Membrane Cleaning Guide

4 Sequence of automated cleaning procedure

A reduction in membrane flow is usually a consequence of all the blocking mechanisms illustrated.
Therefore it makes sense to apply the different cleaning options in succession. For this purpose,
automated ADAB cleaning procedures, which will be highlighted in the following flow diagrams, are
provided.

filtration backflushing

no

yes yes yes

cleaning intensive hot water permeate heating

no no

Process-integrated cleaning Intensive cleaning

(ADAB) (on air)

dosing
backflushing NaOH & NaOCl

reaction time emptying of filtration chamber

x repetitions

rinsing with permeate

Process-integrated cleaning
(ADAB)

dosing
backflushing acid

reaction time filling of filtration chamber

x repetitions

end end

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Membrane Cleaning Guide

5 Summary and overview

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Table: Limit values for cleaning with CFM Systems

Max. temperature Min. pH value Max. pH value Max. pressure

Module G-LM 60°C 2 12 2 bar
Module G-HP 60°C 2 12 2 bar
Module A-LM 60°C 2 12 2 bar
Module A-HP 60°C 2 12 2 bar

Table: Overview of recommended membrane cleaning processes

Type of membrane Citric acid Caustic soda Sodium Enzymes

blocking 0.2w% solution hypochlorite
0.1w% 0.2w%
Scaling ++ o
Fouling o ++ ++ ++
Biofouling + ++ +

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Membrane Cleaning Guide

6 Annex
6.1 Cleaning solution properties
Citric acid dissolves inorganic scaling such as limescale or similar substances very well. The standard
solution is 0.2 w% which is equivalent to a pH value in pure water of roughly 2.6. Citric acid of up to a
concentration of 3w% can be used (equivalent to a pH value of 2).

Besides the good dissolution properties for inorganic deposits, citric acid can complex calcium hydroxide
which results in even better cleaning efficiency.

4.0

3.5

3.0

2.5
pH-Value

2.0

1.5

1.0

0.5

0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
w% Citronensäure

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Caustic soda solution is instrumental in dissolving adsorbed organic molecules on ceramic surfaces.
The optimum concentration of 0.1 w% NaOH should be maintained for standard cleaning processes. pH
value is around 12.4. A pH value of max. 13, equivalent to max. 0.4 w% NaOH, can be used only once
for removing particularly stubborn impurities. Reaction time should be restricted to only a few minutes
and temperature to 60°C.

14

13

12

11
pH-Value

10

7
0.0 0.1 0.2 0.3 0.4 0.5
w% NaOH

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Membrane Cleaning Guide

Sodium hypochlorite is a clear, yellow-green, strongly alkaline, caustic, oxidising substance with a
typical odour. It can be mixed in water at any ratio and adsorbs carbon dioxide from air. Sodium
hypochlorite can only be stored to a limited extent because it gradually breaks down into sodium
chlorate (NaClO3), common salt (NaCl) and oxygen (O2) under storage conditions and loses active
chlorine.

Well-known, dangerous chemical reactions:

• Highly explosive nitrogen trichloride is formed with ammonia and ammonium compounds

• Strong reaction with organic peroxides and oxidising substances

• Strong reaction with reducing agents such as sodium acid sulfite solutions or sulphur dioxide

• Large quantities of gaseous oxygen are formed spontaneously with oxidants such as hydrogen
peroxide or potassium permanganate

• Large quantities of extremely toxic, gaseous chlorine are formed spontaneously with all types of
acid and acid salts

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