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Membrane Cleaning
Data Normalization
Salt Passage
Feed TDS
Feedwater Temperature
Permeate Flow
Semi-Permeable Membrane
Semi-Permeable
Membrane
CAVG
CC
CP = 10 ppm
75%
Recovery
4000 ppm
% Salt Passage =
where:
CP
x 100
CAVG
Effect of Temperature
on Salt Diffusion
Permeate Flow
Feedwater temperature
Feed TDS
Feed pressure
Effect of Temperature
on Permeate Flow
Osmosis
semi-permeable
membrane
Low TDS
High TDS
Osmosis
semi-permeable
membrane
Low TDS
High TDS
When sufficient force is applied, the water molecules will be pulled away from the
salt ions and pushed back to the other side of the membrane. The salt ions
cannot pass through the semi-permeable membrane.
The force required to pull the water molecules away from the salt ions is known
as the osmotic pressure.
Reverse Osmosis
Permeate
Low TDS
High TDS
Concentrate
When applied pressure exceeds the osmotic pressure, water from the high
concentration side can be forced into the low concentration side. This process is
known as Reverse Osmosis.
The salt molecules on the low TDS side are now further diluted resulting in very
pure water called permeate
Po
Pa > Po
Po+ =
Po = ( - ) =
Po (psi) TDS (ppm)
100
Pressure Drop
is related to:
Feedwater temperature (proportional to
viscosity of water)
Flow rates (due to friction losses)
Fouling and Scaling conditions (narrowing
of feed spacer friction losses)
Pressure Loss
Due to Fouling/Scaling
Permeate
Flow
Effective Pressure
Temperature
Recovery
Feed Salt Concentration
19
Salt
Passage
Data Normalization
We standardize (normalize) for the effects of
Feed Temp
Feed TDS
Feed Pressure
Normalized Data
Each membrane manufacturer provides software
that normalizes data that is entered daily by the
plant operators.
Normalized Data is then plotted into curves:
Normalized Permeate Flow
Normalized Pressure Differential (P)
Normalized Salt Passage
Data Normalization
Normalized Permeate Flow allows us to detect
possible scaling, fouling, membrane oxidation, and
mechanical damage
Normalized Salt Passage allows us to detect
possible scaling, fouling, membrane oxidation, and
mechanical damage
Normalized P allows us to detect possible scaling
and fouling
When the data from all 3 normalized curves are
compared side by side, we can isolate the most likely
causes
X (TCFs/TCFo) x Qo
Where:
Pf = feed pressure
P/2 = half the pressure drop
Pp = product pressure
fc = osmotic pressure of feed/concentrate
p = osmotic pressure of the permeate
TCF = temperature correction factor
Q = permeate flow
s = standard or reference condition (start up)
o = operating condition (today)
26
Data Normalization
Normalized Permeate Flow
3.00
2.50
GPD
2.00
1.50
1.00
0.50
0.00
Jan-07
Feb-07
Mar-07
Apr-07
May-07
Jun-07
Jul-07
Aug-07
Sep-07
Data Normalization
Normalized Salt Passage
1.20
1.00
0.80
0.60
0.40
0.20
0.00
Jan-07
Feb-07
Mar-07
Apr-07
May-07
Jun-07
Jul-07
Aug-07
Sep-07
Data Normalization
Normalize Differential Pressure
60.0
50.0
PSI
40.0
30.0
20.0
10.0
00.0
Jan-07
Feb-07
Mar-07
Apr-07
May-07
Jun-07
Jul-07
Aug-07
Sep-07
Time to Clean?
As a general rule of thumb, normalized
permeate flow (NPF) should never be allowed
to decrease more than 15% without cleaning
the membranes
If the membranes are allowed to be fouled
excessively, there can be a permanent loss of
performance.
First Stage
Second Stage
The growth of biological film is initially slow but builds up very quickly as
the sticky surface starts to trap organics which will be utilized by the
bacteria as a carbon source
Organic Foulants:
Bacteria
Dead Bacteria
Biofilms
Dead Microorganisms
Microorganisms
Decaying Organisms
Fungi
Decaying Vegetation
Algae
Hydrocarbons
NOM
Biofouling/Organics/Suspended Solids
Foulant Matrix
Concentration Polarization
Gal/Dayft2 = 10 gfd
10,000 gpd/100
Permeate Flow
(Gallon)
=
= GFD
Flux =
2
Membrane Area
(ft ) (Day)
The flow of permeate water through a unit surface
area of membrane per unit of time.
Interplaybetweeninterfacialpermeatedrag(PD),vanderWaals+electrostatic+acidbase(XDLVO),andstericinteractionson
microbialadhesiontomembranesgivingriseto(a)subcriticalflux,(b)criticalflux,and(c)supercriticalfluxcelladhesion.
Reference: Biofilm Symposium, Eric M.V. Hoek, Associate Professor, California NanoSystems Institute, UCLA
First Stage
Second Stage
The biofilm will grow into the channels of the feed spacer,
restricting water flow and resulting in pressure loss
Feed Spacer
(34 -27 mil)
Biological
growths can
block feed
spacer
Time to Clean?
Most membrane manufacturers recommend
cleaning when Normalized P increases by
10 - 15%.
If a 7M first stage with a P of 25 PSI
increases to 28.75 PSI, is a cleaning
justifiable?
First Stage
Second Stage
First Stage
Second Stage
Increased permeate TDS in the first stage is directly related to reduced permeate
production. The salts that diffuse across the membrane at a constant rate will
become more concentrated when permeate production is lower.
Cake-Enhanced
Concentration Polarization
Fouling Removal
Cleaning should be performed using the following:
1. High pH Cleaner
2. High Temperature
3. High Flow Rate
4. Periodic Soaking
5. Heavier Fouling Requires Longer Cleaning
Organic/Biological Foulants
Different types of organics with different properties:
1. Weak Acid Groups in NOM (Natural Organic
Matter) and Biofilm (Carboxyl, Phenol)
2.Bacterial outer membrane carries negative charge
(Techoic acid in Gram positive,
Lipopolysaccharides in Gram negative)
3. Polar Organics (Hydrophilic)
4. Non-Polar Organics (Hydrophobic)
5. High Molecular Weight Organics Hydrophilic
and Hydrophobic Ends
Reference: Professor Menachem Elimelech, Yale University, Mechanisms of Organic Fouling and Chemical
Cleaning of RO/NF Membranes
TA
M CM
Cy
CH2
OH
COO
COO-
CH2
OH
CH2
OH
CH2
forces
OH
OOC
Repulsive forces:
prevent collapsing
CH2
OH
OH
CH2
COO-
+ +
- - - -
O
||
R -C- O
O
||
- O -C- R
R-COOH R-COO- + H+
58
SWMOA
R-COOH R-COO- + H+
Polysaccharides can be hydrolyzed into lower
molecular weight sugars that are more soluble.
Na+
Cl
The partial negative charge of the oxygen atom in the H2O
R-COO- + H+ R-COOH
They can now easily be compacted into the
membrane by permeation drag.
61
SWMOA
Reference: Hong and Elimelech, Natural Organic Matter (NOM) Fouling of NF Membranes, 2001
64
SWMOA
Reference: Professor Menachem Elimelech, Yale University, Mechanisms of Organic Fouling and Chemical
Cleaning of RO/NF Membranes, 2006
Organics and Biofilms can gel together due to calcium bridging, resulting in
increased fouling on the membrane surface.
Reference: Professor Menachem Elimelech, Yale University, Mechanisms of Organic Fouling and Chemical
Cleaning of RO/NF Membranes, 2006
Polyphosphates (STPP)
Calcium Sequestration and Colloidal Particle Dispersion
Uncharged Organics
Not all organics gain a charge at high pH that only
applies to those that carry weak acid groups
(carboxyl, phenol).
Hydrophobic groups attract to other Hydrophobics
Hydrophilic groups attract to other Hydrophilics
Uncharged hydrophobic organics are attracted to
the membrane surface because membranes are
significantly hydrophobic.
Uncharged Organics
Contact angle determines the hydrophobicity of a
surface
Surfactants
Surfactants
The hydrophobic end of a surfactant attaches to
hydrophobic organics and biofilm.
The bacterial cell membrane contains fatty acids
which the surfactant can emulsify into water.
The surfactant also attaches to the membrane
surface, making it more hydrophilic, which prevents
organic and biological foulants from re-depositing
during cleaning.
SWMOA
77
SWMOA
Surfactants
0.29%
0.23%
0.06%
0.14%
Reference: Professor Menachem Elimelech, Yale University, Mechanisms of Organic Fouling and Chemical
Cleaning of RO/NF Membranes, 2006
Surfactants Foaming
Recommended Cleaner
High pH Cleaner:
C-226, C-237
Organics Penetrator:
C-227
Cleaning Temperature
EffectofTemperatureonWaterMolecules
Water molecules move more quickly as they gain energy from heat
Increased bombardment of the foulant surface and higher rate of back
diffusion of dissolved foulant Kinetics of dissolution
More space for polar organics and ionized species to fit between water
molecules
Cleaning Temperature
Fouling Removal
High Flow Rate
Shearing forces result in mechanical removal
Faster removal of hydrated surface foulant
molecules results in substrate foulant being
exposed more quickly.
Moving solution keeps cleaning chemical
molecules in motion which increases collision
with the foulants and leads to a faster reaction
rate (Kinetics).
Flow Rates
4 Vessel
8 Vessel
2.5 - 3.0
8.0 9.0
5.0 6.0
15.0 18.0
10.0 12.0
35.0 45.0
PI
Concentrate Return
Permeate Return
Second Stage
DP
pH
PI
TI
Heater
FI
Cartridge Filter
Cleaning Pump
Strainer
Cleaning Tank
Drain
Feed Line
Chemical Mixing
Fouling Removal
Flow Direction
In some cases, cleaning in Reverse Flow can
be highly beneficial
Reverse Flow refers to feeding cleaning
solution from the concentrate end and
returning it to the cleaning tank from the feed
end.
Reverse Flow cleaning is highly beneficial for:
1. Persistent biofouling regrowth
2. Heavy suspended solids deposition on feed
elements
Impact of Feed-spacers on
Bacterial Deposition
Water cross-flow velocity is slowed at points of contact with feedspacers, allowing for
deposition of bacteria
Reference: X. Huang, G.R. Guillen, E.M.V. Hoek, A New High-Pressure Optical Membrane Module for Direct
Microscopic Observation of Seawater RO Membrane Fouling, Journal of Membrane Science (2010).
Fouling Removal
Reverse Flow Cleaning
Caution! No thrust ring on feed end, so
reverse flow cleaning is risky!
Even if thrust ring is installed, shims will
prevent full protection in reverse flow.
Never exceed 2/3 of normal cleaning flow
rates (~30 GPM max reverse flow rate)
Cleaning in reverse flow does not substitute
normal cleaning in the forward flow direction
Reference Hydranautics Technical Service
Bulletin TSB 125.02
Fouling Removal
Fouling Removal
Membrane Soaking
Soaking the membranes refers to turning off
circulation of cleaning chemicals but not flushing
them out.
Soaking allows prolonged contact of the cleaning
chemicals with the foulants for better penetration.
Soaking works best when used for 15 min 1 hour
alternated with circulation of cleaning chemicals.
Extended overnight soakings do not provide
additional benefits Periodic circulation is necessary
to remove locally saturated solution and deliver more
active cleaning solution to the membrane surface.
Fouling Removal
Chemical cleaning of organic and biologically
fouled membranes involves two steps:
Chemical step: Reaction between the chemical cleaning
agent and the foulant need favorable chemistry and
stoichiometry
Physical step: Mass transfer of cleaning agent into the
fouling layer and of foulants away from the surface
Membrane Surface
Circulate
Soak
Membrane Soaking allows time for diffusion of cleaning chemical across the
liquid/solid interface and into the foulant.
Lack of turbulence ensures contact between chemical and foulant accross the entire
liquid/solid interface, allows for diffusion into foulant layer.
Cross-flow allows removal of loosened foulant and exposes next layer of foulant to
chemical.
Circulation also constantly replaces cleaning agents consumed locally by the foulant
Scale Symptoms
1. Decreased Normalized Permeate Flow (NPF).
2. Increased Normalized Differential Pressure (NP)
in the last stage.
3. Increased Normalized Salt Passage in the last
stage.
Feed
Permeate
1000 ppm
1st Membrane
10-15% flow
12.3 ppm
85-90% flow
1264 ppm
2nd Membrane
10-15% flow
20.1 ppm
85-90% flow
1675 ppm
3rd Membrane
85-90% flow
2410 ppm
4th Membrane
10-15% flow
40.9 ppm
Scale
Formation
Concentrate
85-90% flow
3959 ppm
SO4-2 Ca+2
Ca+2
Dilute
Concentrated
(Weak Attraction)
Ca +2 + SO4 2
CaSO4 (Gypsum)
Scale Symptoms
Decreased Normalized Permeate Flow
First Stage
Second Stage
Scale Formation
Scale Formation
Feed Spacer
(34 -27 mil)
Scale growth
can block feed
spacer
Data Normalization
Pressure Drop
Scale Symptoms
Increased Normalized Differential Pressure P
First Stage
Second Stage
Scale precipitation in the final stage will block the membrane feed spacers
resulting in restricting water flow and causing increased pressure drop.
Scale Symptoms
Increased Normalized Salt Passage
First Stage
Second Stage
AWC
WATER
ANALYSIS
SHEET
Selects
Suitable Antiscalant
Proper dosage
Optimum operating conditions
ANTISCALANT PROGRAM
ANTISCALANT PROGRAM
Cleaning
Solution IN
Membrane
Surface
Cleaning
Solution OUT
EffectofTemperatureonSaltMolecules
Salt molecules in crystal lattice vibrate more quickly as they gain energy from
heat
As the salt ions move further apart, water molecules can fit more easily between
the salt ions to penetrate into the scale
Rate of back diffusion into bulk solution increases with higher temperature
CaCO3
Calcium Carbonate
CO32- + H+
HCO3-
Carbonate Hydronium
Ion
Ion
Bicarbonate
HCO3
+ H+
H2CO3
Bicarbonate Hydronium
Ion
Ion
Carbonic Acid
H2CO3
H2O + CO2
Carbonic
Acid
Water
Carbon
Dioxide
Bicarbonate
Carbonate
Hydroxide
1.00
0.90
Mole Fraction
0.80
0.70
0.60
0.50
0.40
P-alkalinity
endpoint
M-alkalinity
endpoint
0.30
O-alkalinity
endpoint
0.20
0.10
0.00
8
9
Water pH
10
11
12
H3PO4
H2PO4-
HPO42-
PO43-
Ca SO4 * H2O
Recommended Cleaner
Carbonate Scales
Low pH Cleaner:
C-205, C-234
Scale Pulverizer:
C-238
Scale Sequestration:
C-239
Sulfate Scales
Aluminum vs. pH
Al3+
Al(OH)4-
Al(OH)2++
Al(OH)2+
Al(OH)3
OH
OH
OH
OH
Si
OH
OH
H
Si
OH
OH
OH
OH
OH
OH
OH
OH
H
OH
OH
H
OH
Si
OH O
H
OH
OH
Si
OH
OH
H4SiO4
H+ + H3SiO4-
H3SiO4-
H+ + H2SiO42-
OH
|
HO-Si-O
|
OH
OH
|
- O-Si-OH
|
OH
Colloidal Silica
Silt
Clay
Recommended Cleaner
Low pH Cleaner:
C-205, C-234
Or
Specialty Iron Cleaner:
C-225 (neutral pH cleaner)
C-237 (high pH iron removal)
High pH Cleaner:
C-226, C-237
Silica Cleaner:
C-236
The membrane cleaning was effectively removing iron but not silica
Specialty Cleaners
vs. Generic Chemicals
Generic Chemicals
Specialty Cleaners
Self-Buffering to protect
membranes in case of accidental
over-addition
Cleaning Procedures
Cleaning Equipment
Clean-In-Place (CIP)
Permeate
Fill
Chemical Mixing
DP
pH
TI
Heater
FI
PI
PI
DP
FI
pH
TI
Cartridge
Filter
Cleaning
Pump
Pressure Indicator
Differential Pressure Indicator
Flow Indicator
pH Indicator
Temperature Indicator
Strainer
Cleaning Tank
Drain
Throttle Valve
Closed Ball Valve
Open Ball Valve
Safety Precautions
During cleaning, do not exceed membrane manufacturers
recommendations for flow rates, temperature, pressure and pH.
Always add chemicals slowly to an agitated batch of make-up water.
Always wear safety glasses and appropriate protective gear when
working with chemicals.
Dont mix concentrated low pH cleaners with concentrated high pH
cleaners.
Always perform a high pH clean before the low pH clean.
Be sure all hoses and piping can handle the temperatures,
pressures and pH which will be encountered during cleaning.
Thoroughly rinse the 1st cleaning solution from the R.O. system
before introducing the next solution.
Step 1:
Step 2:
Chemical Mixing
DP
pH
PI
TI
Heater
FI
Cartridge Filter
Cleaning Pump
Strainer
Cleaning Tank
Step 3:
First Stage
Isolate the RO system from the feed and the Point-Of-Use (P.O.U).
Ensure that all the cleaning valves are working properly.
Set all the cleaning valves in the closed position.
Permeate
Feed Line
Concentrate
Second Stage
Step 4:
Step 4:
First Stage
PI
15-20%
Permeate Return
Second Stage
Drain
DP
pH
PI
TI
Heater
FI
Cartridge Filter
Cleaning Pump
Strainer
Cleaning Tank
Drain
Feed Line
Chemical Mixing
Feed Pressure*
(psig)
2.5
4
6
8
8.5
16
20-60
20-60
20-60
20-60
20-60
20-60
4-6
6 -10
12- 20
24 45
27 48
96 -160
Step 4:
Step 4:
First Stage
PI
Concentrate Return
Permeate Return
Second Stage
DP
pH
PI
TI
Heater
FI
Cartridge Filter
Cleaning Pump
Strainer
Cleaning Tank
Drain
Feed Line
Chemical Mixing
Step 5:
Clean the second stage by repeating the steps (a) through (j).
Step 5:
First Stage
Drain
PI
Permeate Return
Second Stage
DP
pH
PI
TI
Heater
FI
Cartridge Filter
Cleaning Pump
Strainer
Cleaning Tank
Drain
Feed Line
Chemical Mixing
Step 5:
First Stage
PI
Permeate Return
Second Stage
DP
pH
PI
TI
Heater
FI
Cartridge Filter
Cleaning Pump
Strainer
Cleaning Tank
Drain
Feed Line
Chemical Mixing
Step 5:
Permeate Valve
Always make sure that permeate valve is
fully open when cleaning!
Causes delamination at concentrate end
of tail element
152
12.3
ppm
20.1
ppm
40.9
ppm
19.4
ppm
Permeate
Feed
Concentrate
1,000
ppm
Feed
1,264
ppm
Feed
1,675
ppm
2,410
ppm
3,959
ppm
Permeate
Concentrate
Membranesareplacedinsidepressurevesselsthatallowtheconcentrate
fromeachmembranetoflowtothefeedsideofthenextmembrane.
Permeateflowsfromonemembranetothenextwithinthepermeatetubesof
eachmembranethroughinterconnectors
Feed
Channels
Permeate Back Pressure
Feed
Channels
Permeate Back Pressure
Feed
Channels
Permeate Back Pressure
Feed
Channels
Membrane Pouching
Less severe outcome of closing permeate valve during cleaning, but still results
in some loss of rejection due to mechanical deformation of membrane at glue
lines, and compression of membrane surface against feed spacers
156
Membrane Oxidation
Chlorine
Sodium Hypochlorite
Ozone
Hydrogen Peroxide
First Stage
Second Stage
Since the membrane surface is damaged, feed water salts will no longer
be removed and feed water will flow directly into the permeate resulting
in high TDS
Troubleshooting
and
Problem Analysis
SDI =
[1 - T1/ T2 ]
15
x 100
Flow Balance
Permeate
Feed
75 gpm
100 gpm
Brine
25 gpm
75%
Recovery
QF = QP + QC
where:
Mass Balance
QF . CF = QP . CP + QC . CC
L
min
mg
L
L
min
mg
L
L
min
QF
CF
QP
CP
QC
CC
mg
L
72
19
20
25
18
22
21
34
36
30
32
First Stage
Second Stage
Membrane Probing
8.4
ppm
12.3
ppm
20.1
ppm
40.9
ppm
Feed
19.4
ppm
Permeate
Permeate
Concentrate
1,000
ppm
1,264
ppm
1,675
ppm
2,410
ppm
3,959
ppm
Membrane Probing
An inconsistency in conductivity indicates an O-ring leak
A leak in the first O-ring will result in mixing between the
feed-water and the permeate
A leak in O-rings of the 2nd through the last membrane of
the pressure vessel would result in mixing between the
concentrate and permeate streams
Thank you
Mo Malki, American Water Chemicals
E-mail: momalki@membranechemicals.com
www.membranechemicals.com