MBR Course

Membrane Fouling & Cleaning

October 16 & 17, 2012
Hamid Rabie

Effect of Fouling on Permeability

initial permeability

Permeability

Irreversible fouling
Restored permeability

Reversible fouling

Permeability after time t

Time
Irreversible fouling is a relative terminology

Fouling
Loss of productivity due to various factors (physical/chemical):

membrane compaction
adsorption
membrane deposits and solid build up
pore plugging and precipitation
gel compaction
concentration polarization (less important for MBR)

Fouling prevention is major design/operational issues

Fouling can be controlled by

Membrane Modification (pore size, porosity, structure, nature)

Pre-treatment (screening, pre-oxidation, )
Process Considerations (flux, recovery, sludge age, )
Maintenance Cleaning (back pulse, regular chemical cleaning, relaxation, ...)
Hydraulic Improvements (tank design, air distribution, ...)

Structure of an Asymmetric Membrane

Fouling can occur on surface
or inside membrane structure.
Membrane compaction
changes membrane structure
and reduces porosity resulting
in higher resistance to flow.

Adsorption Capacity

Water permeability (gfd/psi)

30

Adsorbed material may be

removed by extensive water
rinsing or chemical cleaning.

25

Rate of Decline in Permeability

With 15min initial
permeation

20

Without initial permeation

0.05 gfd/psi/day
With 15min initial permeation
0.24 gfd/psi/day

15
0

10
Tim e (day)

Fibres were soaked in bioreactor and

clean water permeability was
measured at different times

15

20

Cake Formation and Concentration Polarization

High molecular weight solutes

1. Decrease in back diffusion

due to established sub-layer
(concentration polarization)

CS

Bulk flow

2. New condition at membrane

JW

JW

CP

Cb
sub-layer

Membrane

Gel layer or cake

Note: Cs > Cb

may exceed the limit (e.g., 0.02% for silica)

3. Increase in CP (due to Cs > Cb )

4. Cake layer resistance

At Steady State:
Rate of solutes coming towards
membrane due to filtration =
Rate of migration of solutes away
from membrane due to diffusion,
shear and back pulse

What Fouls the Membrane?

All components in feed can foul the membrane
In many systems, the main foulant exists in trace amount
Common Foulants:
Scaling: CaCO3, CaSO4, BaSO4
Metal Oxides: iron, aluminum
Inorganic Colloids: silt
Silica
Organics: oil, NOM
Biofilms: bacteria and EPS (protein, nucleic acid, lipopolysaccharides,
DNA, )

Foulant is a mixture of chemicals usually in a complex

matrix

Membrane Biofouling

Accumulation and attachment of microorganisms

(e.g.., bacteria, fungi, microalgae)

Complete growth of biofilm: bacteria is hidden in

EPS matrix. Note fibrous structure.

Biofilm is in multilayer of living and dead cells and associated EPS.

Biofouling is more severe on MF and UF since nutrients can pass through.
Biofouling may result in degradation of membrane and joint glue.

Cleaning Fundamentals

Cleaning Mechanism
1. Competitive adsorption
2. Solubilization
Changing solubility (e.g., increasing T)
Emulsifying
Dispersing

3. Chemical Modification

Hydrolysis of fats and oils (e.g., at high pH)

Oxidation (e.g., organics)
Degradation of proteins
Chelating (e.g., divalent cations)
Reaction of metal oxides and acids

Common Cleaners
1. Acids: HCl, HNO3, H3PO4, C3H4(OH)(COOH)3
2. Alkalis: NaOH
3. Surfactants:
anionic (sulfonates, sulfates, phosphates), cationic (quaternary ammonium
salts), nonionic (PEO: -O-CH2), competitive adsorption, emulsifying, micelle

4. Chelators: ethylenediamine tetraacetic acid (EDTA)

5. Oxidizers: NaOCl, ClO2, HOBr, H2O2, ozone, UV
6. Enzymes:
degrade proteins, starch, fat, oil, cellulose, cleave peptide linkage in proteins
in specific sites, it is very selective and bacteria can adopt, very slow reaction

Acid Cleaning
CaCO3 + 2HCl

CaCl2 + H2O + CO2

Fe2O3 + 6HCl

2FeCl3 + 3H2O

HCl

cheap, high rate of reaction and yield, corrosive

H2SO4

cheap, moderate rate of reaction and yield, corrosive

HNO3

also oxidant for organics and biological, moderate

rate of reaction and yield, too corrosive

H3PO4

chelating, pH buffering, less corrosive, uses too much

for pH < 2.3, Ca phosphates has limited solubility, too
expensive, not recommended for P removal processes

Citric acid

good chelating with Ca, its complex with ferrous ion

has low solubility, low kinetic, high yield

Alkalis Cleaning (NaOH)

1. Dissolves: silica

some inorganic colloids (dispersion)

many biological and organic foulant

2. Sanitizer
3. Neutralizes fatty acids and humic acids (R-COOH)
4. Hydrolysis fats and oils
C3H5-(OOCR)3 + 3NaOH
ester

C3H5(OH)3 + 3NaOOCR
soap

NaOOCR has emulsification properties

NaOOCR is insoluble at low pH, also precipitate with Ca, Mg, add in
presence of chelating agent (EDTA) to remove Ca, Mg

5. Hard to maintain pH, measure pH during cleaning

NaOCl (Oxidizer/Disinfectant)
1. Extremely effective specially for pore fouling
2. Disinfection property (biofouling control)
damage to cell wall
alteration of cell permeability
inhibition of enzyme activity
3. Alkali cleaning property (increases pH)
NaOCl + H2O

HOCl +

NaOH

active component

widely used and inexpensive

more effective at low pH and also more corrosive
harmful by-products (e.g., THM)

Cleaning Sequence/Condition
Depends greatly on types of foulant and membrane and the
way membrane has been fouled (see examples)
1. Biofilm (dominant) + Inorganic
Alkalis/Oxidizer/Acid (initial acid cleaning increases adhesion of humic material,
initial caustic cleaning can remove significant organic so oxidizer cleaning becomes
more efficient.)

2. Inorganic (dominant) + Organic + Biofilm

Mixture of Acids and Chelators/Oxidizer or Alkalis
Conditions:
Type of Cleaner, Temperature, Concentration, Contact Time
Certain relations exists, for example: bacteria kill is related directly to dosage

The best sequence and condition can be obtained after

identifying foulant and preliminary tests.

Operational Considerations of
Cleaning

Cleaning Methods
Mechanical Cleaning
1. Scrubbing:

solid removal

2. Back Pulse:

reverse TMP and drive permeate backward

3. Relaxation:

eliminate TMP, allow gel layer to dissipate

Chemical Cleaning
1. In-Situ/Empty Tank: back wash regularly with chemicals in CIP from top only,
in pulses at moderate flow for uniform distribution

2. In-Situ/Full Tank:

the same as empty tank except back wash from both ends

3. Soak:

soak in chemical solution for extended period

Backwash
Use clean filtrate to backwash membranes. A reverse flow from the CIP
tank is fed to the inside of the membrane fibers cleaning from the inside out
Cleaning chemicals are optional and not always necessary.
Process Tank Water

Backwash Cleaning
Clean-In-Place Tank

(Reverse Flow with Filtrate)

(Filtrate from membrane)

X-section

Cleaning Methods (Another Classification)

Maintenance cleaning
Used for maintaining permeability (conditioning rate of decline)
frequent, short contact time such as: back pulse, relaxation,
in-situ/full tank

Recovery cleaning
Used for restoring permeability close to one of new membrane, not
frequent, long contact time, such as: soak.

Flux Distribution in Fibres during Back Wash

Empty Tank Back Wash

Full Tank Back Wash

(only from top)

(from both sides)

Calculation is done based

on a true permeability of
10 gfd/psi

1.2

1.6

Normalized Flux

Normalized Flux

1.6

0.8
30 gfd

0.4

15 gfd

Calculation is done based

on a true permeability of
10 gfd/psi

1.2

0.8
30 gfd

0.4

15 gfd

0
0

0.5

1.5

Fiber Length from top (m)

0.5

Fiber Length from top (m)

Why using pulsed back wash at

higher flow rates ?
1. uniform distribution
2. low chemical consumption

1.5

Long pipe lines reduces

back wash performance

Any Cleaning Should not Exceed:

1. Membrane Limitations
pH
Temperature
Chemicals
2. Process Limitations
Bioreactor (e.g., nitrifiers sensitive to chlorine and pH)
Drinking Water (e.g., THM, residual chlorine)

Steps Towards Identifying

Problem(s)

Check List
1. Solid build up
2. Aerator Status
3. Fibre appearance (black, brown, damaged, )
4. Fluctuations in designed operating conditions (flux, pH, )
Operating at, for example, high solid or flux can foul membranes in short
time but it takes long before membranes recover.

5. Record any changes in operation, cleaning results, and any

suspected chemicals.

Identifying Nature of Foulants

Fully characterise the feed
Cleaning of fouled fibres and analysis of extracts
Extraction of foulant and analysis (GS/MS, Pyrolysis, ...)
Autopsy of fouled membrane

ESEM (environmental scanning electron microscopy) for morphology

TEM (transmission electron microscopy) for biological fouling
EDX (energy dispersive x-ray) for elemental analysis
MWCO (molecular weight cut-off)
Pore size

Conclusions
Membrane fouling can be controlled
Essential to diagnose what is the cause
Crucial to understand fluid dynamics and mass transfer
Crucial to understand chemical interactions with membrane
Develop rational pretreatment and cleaning protocols

Membrane Biofouling (STEM micro-graph)

1 micron

Note significant biofouling on the surface of membrane

STEM micro-graph after Maintenance Cleaning

1 micron

Note that the fouling has been controlled

Fouled Membrane in Tap Water

Note the disperse/loose structure of foulant

Burlington tap water

Dead-end filtration

Fouling is mainly due to

fibrous organic matter;
moderate microbial and
inorganic fouling.
0.5 micron

STEM micro-graph of foulant

MBR Pilot with Ferric Addition

ESEM Micro-graph
of fouled membrane

0.5 micron

(Foulant Analysis)

Foulant is mainly inorganic:

iron and calcium precipitate
(almost 10 to 1 ratio)
Iron precipitates in different forms
which have different optimum pH
values for precipitation

EDX examination of foulant on

membranes used in an MBR pilot

(Foulant Structure)
Problems
Structure of inorganic fouling.
Membrane pores were plugged with
precipitates. Further analysis also
showed bacteria growth typical of
sewage treatment plants.
Conventional cleanings (chlorine or
acid) did not recover permeability.

Solutions
A mixture of chelating agents and
acid for cleaning
Regular maintenance cleaning with
formulated chemical according to the
Manual
Control of inorganic fouling: pH
adjustment, flash mixer, low dosage

ESEM analysis of foulant at an MBR pilot