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System Troubleshooting

and
Membrane Cleaning

Data Normalization

Salt Passage

Salt Passage is affected by:

Feed TDS

Feedwater Temperature

Permeate Flow

Semi-Permeable Membrane

Semi-Permeable
Membrane

Allows only water and gas to pass through


Does not allow dissolved Salts to pass through

Effect of Feed TDS on Salt Passage

Diffusion is the movement of molecules from a


high area of concentration to a low area of
concentration due to random Motion.

Effect of Feed TDS on Salt Passage


CF = 1000 ppm

CAVG

CC

CP = 10 ppm
75%
Recovery

4000 ppm

% Salt Passage =
where:

CP
x 100
CAVG

CAVG = Average Concentration of Feed


CP
= Concentration of Permeate

The ratio of TDS in the permeate water to the average


TDS across the feed side of the membrane, expressed
as a percentage.

Effect of Temperature
on Salt Diffusion

As temperature rises, salt molecules gain energy and


move at a faster speed. This increases the rate of
diffusion across the membrane

Improved Salt Rejection with


Increased Permeate Flow

Salt Diffusion is Independent of Applied Pressure. As


permeate production increases diffused salts are diluted

Permeate Flow

Permeate flow of the RO system is affected by:

Feedwater temperature

Feed TDS

Feed pressure

Permeate back pressure

Pressure drop through the system


(decreases net driving pressure)

Effect of Temperature
on Permeate Flow

Permeate Flow Rate increases with Increased


Water Temperature due to reduced viscosity

Osmosis
semi-permeable
membrane

Low TDS

High TDS

The partial charges of the water molecules are so attracted to the


oppositely charged salt ions that they flow to the high TDS side
overcoming the back pressure caused by the weight of the water
column.

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

Net Driving Pressure


Feed Pressure, Osmotic Pressure, P, Permeate Back Pressure
Pa

Pnet = (Pa - Po -P - Pp)


where:
Pnet =
Pa =
Po =
P =
Pp =

Po

Pa > Po

Net Driving Pressure


Applied Pressure
Osmotic Pressure
Hydraulic Pressure Losses
= Permeate Back Pressure

Po+ =
Po = ( - ) =
Po (psi) TDS (ppm)
100

Effect of Net Driving Pressure


on Permeate Flow

Permeate Flow Rate increases with


Increased Net Driving Pressure

What is Normalized Permeate Flow?


Available Membrane Surface Area is
decreased when scaling or fouling occurs, and
results in reduced permeate flow
However, variations in feed water temperature
can also increase or decrease permeate flow
And variations in Net Driving Pressure (NDP)
will have a significant impact on permeate
productivity
NDP is affected by variations in TDS but also
by fouling and scaling

Pressure Drop

Pressure Drop = P = Feed P Conc.P

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

Factors Influencing RO Performance


Increasing

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

In order to monitor changes in


Permeate Flow
Salt Passage
Pressure Drops

Software is available from membrane


manufacturers.

What is Normalized Permeate Flow?


Normalization is a technique that allows us to
compare operation at the current conditions to
operation at Day 1 (1st day of normal plant
operation after commissioning)
Normalized Permeate Flow (NPF) data allows
us to identify loss of permeate flow due to
fouling or scaling by accounting for variations
in temperature, TDS and Feed Pressure (all of
which also impact permeate flow)

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

Normalized Salt Passage


%SPnorm = [EPFo/EPFs] x [STCFo/STCFs]
x [Cfcs/Cfco] x [Cfo/Cfs] x %SPo
Where:
%SPnorm = normalized % salt passage
EPF = average element permeate flow
STFC = salt transport temperature correction factor
Cf = concentration of the feed mg/L
s = Standard or reference condition (start up)
o = operating condition (today)
Cfc = feed TDS x([ln1/(1- recovery)])/recovery
%SPo = 1 [(membrane TDS perm TDS)/membrane TDS x 100]

Normalized Differential Pressure


Normalized DP = Actual DP x Correction Factor
Correction Factor = (2 x CFs + PFs)1.5 / (2 x CFo +PFo)1.5
Where:
CF = Concentrate Flow
PF = Permeate Flow
o = Actual Operating Condition (today)
s = Standard or Reference Condition (start up)

Normalized Permeate Flow


Qnorm = Pfs (Ps/2) Pps fcs + ps
Pfo (Po/2) Ppo fco + po

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

Understanding the Chemistry


Behind Membrane Cleaning

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.

Organic and Biofouling Symptoms


Decreased Normalized Permeate Flow

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

Evenly Distributed Biological/Organic/Suspended Solids


Matrix

Suspended solids and organics can be a problem even in well water!

Biofoulants and Organic Foulants


Biofoulants:

Organic Foulants:

Bacteria

Dead Bacteria

Biofilms

Dead Microorganisms

Microorganisms

Decaying Organisms

Fungi

Decaying Vegetation

Algae

Oils and Greases

Hydrocarbons

NOM

Biofouling/Organics/Suspended Solids
Foulant Matrix

Bacteria are clearly visible within the biofilm

Concentration Polarization

Biological Fouling: Biofilm- Enhanced Osmotic Pressure due to stagnation of


crossflow within the biofilm or organic cake layer, and hindered back-diffusion of
salt ions through the biofilm/organic cake results in reduced permeate production

Effects of Scaling and Fouling on


Permeate Flow
Available Membrane Surface Area is
decreased when scaling or fouling occurs, and
results in reduced permeate flow
Systems that use a Variable Frequency Drive
(VFD) to adjust the output of the high
pressure pump will see an increased feed
pressure.

Effects of Scaling and Fouling on


Permeate Flow
Increased feed pressure will maintain system
permeate flow through reduced available
membrane area.
This results in localized permeate production
at higher flux rates and a resulting increase in
the rate of fouling.

Effect of Membrane Surface Area on Flux


Permeate Flow Through Membrane Surface Area

10,000 gpd/200 ft2 = 5 gfd


Gal/Day

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.

Effect of Flux on Cell-Adhesion

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

Organic and Biofouling Symptoms


Increased Normalized Differential Pressure P

First Stage

Second Stage

The biofilm will grow into the channels of the feed spacer,
restricting water flow and resulting in pressure loss

Differential Pressure (P)


Pressure Drop = P = Feed P Conc.P
P 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)

Organic and Biological Fouling

Feed Spacer
(34 -27 mil)
Biological
growths can
block feed
spacer

Cross Sectional View of two membrane leaves

Membrane surface and feed spacers


blocked by biofilms and organics

Differential Pressure (P)

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?

Silt and Suspended Solids Fouling

Organic and Biofouling Symptoms


Increased Normalized Salt Passage

First Stage

Second Stage

Decreased Salt Passage initially as biofilm covers imperfections; but eventually


water TDS increases as foulant builds up

Manufacturing Imperfections in Membrane

Inorganic Fouling Symptoms


Increased Normalized Salt Passage

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.

Improved Salt Rejection with


Increased Permeate Flow

When Permeate Production is Reduced, Diffused Salts


are not Diluted to the Same Extent.

Cake-Enhanced
Concentration Polarization

Biological Fouling: A higher salt concentration at the membrane boundary due to


cake-enhanced concentration polarization results in a higher salt flux across the
membrane and therefore a higher TDS in the permeate.

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

Natural Organic Matter (NOM):


Suwannee River Humic Acid

Reference: Professor Menachem Elimelech, Yale University, Mechanisms of Organic Fouling and Chemical
Cleaning of RO/NF Membranes

Carboxyls and Phenols are Weak Acids:


R-COOH R-COO- + H+

Biofilms Carboxyl Groups


EPS

TA

M CM

Cy

CH2
OH

COO

COO-

CH2
OH

CH2
OH
CH2

forces

OH

OOC

Repulsive forces:
prevent collapsing

Ca2+ Ionic attractive

CH2
OH
OH
CH2

COO-

+ +

- - - -

Biofilm Symposium: Professor Hans-Curt Flemming, Biofilm Centre, University of


Duisburg-Essen
Mayer et al., 2001

Ionized Carboxylic Acids at High pH

O
||

R -C- O

O
||

- O -C- R

Organics with carboxylic and phenolic groups repel


each other at high pH, and repel away from the
membrane which also becomes more negatively
charged due to carboxyl groups on its surface

R-COOH R-COO- + H+

pH Effect on Organics - Deprotonation

Effect of Organics Dissolution on


Cleaning Solution pH
R-COOH R-COO- + H+
Deprotonation means that Organic Acids release acid
protons into solution at High pH.
The free acid lowers the pH of the high pH cleaning
solution.
More alkaline cleaner should be added to raise the pH
back up to the target level in order to continue
dissolving organic acids.

58

SWMOA

Caustic Hydrolysis of Organics


Sodium hydroxide reacts with fats by hydrolysis
to form soap (saponification).
Proteins are also hydrolyzed by caustic to
amino acids.
For Fat and Protein, the resulting molecules are
carboxylates (gains negative charge at high pH)

R-COOH R-COO- + H+
Polysaccharides can be hydrolyzed into lower
molecular weight sugars that are more soluble.

Interaction of Water with Ionized Species


Dissolution of Salts

Na+

Cl


The partial negative charge of the oxygen atom in the H2O

molecule is attracted to the positively


chargedsodium
The partial positive charge of the Hydrogen in the H2O molecule
is attracted to the chloride.

Low pH Cleaning on Organics?


Never clean with low pH when organics or
biofilm are present in the water!
At pH<4, carboxyl groups are fully protonated
so they lose their repulsive negative charges

R-COO- + H+ R-COOH
They can now easily be compacted into the
membrane by permeation drag.

61

SWMOA

Low pH vs High pH Effect on Organic

Reference: Hong and Elimelech, Natural Organic Matter (NOM) Fouling of NF Membranes, 2001

Loose fouling layer at high pH is easier to penetrate by cleaning chemicals

Low pH vs High pH Effect on Organic


Acid hydrolyzes proteins into amino acids which protonate to
become cationic at low pH can irreversibly bind to the
membrane

Generic Cleaning Recipes

64

SWMOA

Chelants (EDTA) for Organic/Biofouling

Reference: Professor Menachem Elimelech, Yale University, Mechanisms of Organic Fouling and Chemical
Cleaning of RO/NF Membranes, 2006

Calcium Bridging Organic/Biological Fouling

Polyvalent Cations electrostatically attract the negatively charged


carboxylic functional groups in the NOM
Reference: Professor Menachem Elimelech, Yale University, Mechanisms of Organic Fouling and Chemical
Cleaning of RO/NF Membranes, 2006

Cohesion of Organics w/ Biofilm - Calcium Bridging

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

Biofilm/Organics Collected from Lead Element

Superimposed Elemental Imaging of Biofilm Layer

Biofilm and silt particles on lead element

Polyphosphates (STPP)
Calcium Sequestration and Colloidal Particle Dispersion

Polyphosphates such as STPP adsorb to the surfaces of inorganic particles.


Inorganic particles are dispersed due to the negative charge of the polyphosphates
Polyphosphates also sequester calcium to reverse bridging

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

Bacteria Fatty Acids in Outer Membrane

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.

Hydrophobic Properties of Biofilm

Contact Angle of Membrane


surface fouled with biofilm

Contact Angle of Membrane


surface after cleaning
76

SWMOA

Wetting Properties of Surfactant

Wetting allows better spreading of cleaning chemical on foulant surface

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 Air/Water Interface

Surfactants Foaming

Cleaning Chemical Selection


Organic and
Biological Foulants
Biofouling
Organics
Hydrocarbons
Heavy Organic Fouling

Recommended Cleaner
High pH Cleaner:
C-226, C-237
Organics Penetrator:
C-227

Cleaning Temperature

Kinetics: All reactions are faster at higher


temperature

Foulants will react more quickly with cleaning


chemicals at higher temperatureand so will
the membrane do not exceed max allowable
temperatures for the membrane.

Warmer temperature improves foulant


penetration to clean better but it mainly
helps to clean faster.

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

DONT WAIT TO REACH TARGET


TEMPERATURE BEFORE YOUR START
CLEANING!

Cleaning chemicals are effective at all


temperatures Turn on heater and let solution
warm up as you clean.

Time wasted waiting for solution to get warm


(4 6 hours) defeats the purpose of the faster
rate of cleaning at higher 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

Low Flow (gpm/PV)

2.5 - 3.0

8.0 9.0

Medium Flow (gpm/PV)

5.0 6.0

15.0 18.0

10.0 12.0

35.0 45.0

High Flow (gpm/PV)

DO NOT INCREASE FLOWRATE IF > 10 PSI/MEMBRANE

Clean Stages Separately for Optimized Flow Rates


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

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).

Surface Water S.S. Membrane Fouling - SWRO

Debris, sand and insoluble organics on feed element of seawater RO membrane

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

Reference: Professor Menachem Elimelech, Yale University

Interaction of Cleaning Solution with


Foulant

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

Inorganic Scales and Precipitates


1. Carbonate and Phosphate Scales Soluble in low pH
2. Sulfate Scales Not soluble in low pH, slightly soluble
at high pH
3. Silica and Silicate Scales Soluble at high pH, only
soluble in low pH when fluoride ions are present
4. Metal Hydroxide Precipitates Typically soluble at
both pH extremes

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.

Inorganic Scale Formation


10-15% flow
8.4 ppm

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

Inorganic Scale Formation


Scaling: Formation of salt crystals due to concentration of the
solvent to a point beyond its saturation limit

Ca+2 SO4-2 Ca+2

Ca+2 SO4-2 Ca+2

SO4-2 Ca+2 SO4-2

SO4-2 Ca+2 SO4-2

SO4-2 Ca+2

Ca+2 SO4-2 Ca+2

Ca+2

Dilute

Concentrated

(Weak Attraction)

(Shorter distance results


in stronger attraction)

Ca +2 + SO4 2

CaSO4 (Gypsum)

Scale Symptoms
Decreased Normalized Permeate Flow

First Stage

Second Stage

Ions are concentrated to supersaturation levels in the final elements of the


second stage and therefore precipitate as scale.

Scale Formation

Calcium Carbonate Scale

Calcium Sulfate Scale

Calcium Carbonate W/ Silts in Tail Element

Calcium Carbonate W/ Silts in Tail Element

Amorphous Silica Scaling inTail Element

Scale Formation

Feed Spacer
(34 -27 mil)
Scale growth
can block feed
spacer

Cross Sectional View of two membrane leaves

Membrane surface and feed spacers


blocked by scale

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

Increased permeate TDS in the second 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.

AWC
WATER
ANALYSIS
SHEET

ANTISCALANT PROJECTION PROGRAM


for
Reverse Osmosis Systems

Calculates potential for scale formation.

Helps identify possible causes of existing scales in


a system receiving incorrect pretreatment.

Selects
Suitable Antiscalant
Proper dosage
Optimum operating conditions

ANTISCALANT PROGRAM

ANTISCALANT PROGRAM

Acid Soluble Scale Removal


Scale

Cleaning
Solution IN
Membrane
Surface

Cleaning
Solution OUT

Dissolve Carbonate/Phosphate Scale Using:


1. Low pH
2. Warm Temperature
3. High Flowrate
4. Heavier Scaling Requires Longer Cleaning

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 Dissolution with Acid


Ca2+ + CO32-

CaCO3
Calcium Carbonate

Calcium Ion Carbonate Ion

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

Factors Affecting Solubility


Carbonate Speciation dependency on Water pH

Factors Affecting Solubility


Carbonate Speciation dependency on Water pH
Carbonic Acid

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

Phosphate Speciation Dependence on


Solution pH
Mole Fraction

H3PO4

H2PO4-

HPO42-

PO43-

Low pH Cleaning Guidelines


When performing a low pH cleaning, soaking does not improve
dissolution of scale it is actually counterproductive.
The acid is consumed instantly by carbonates or phosphates and
the cleaning solution rises in pH.
For an effective low pH cleaning, the solution must be maintained
between pH 2 3 for the entire cleaning.
pH should be checked every 15 minutes, and if it increases above
pH 3, then more low pH cleaning chemical should be used.
However, when using a low pH cleaning to improve salt rejection
after a high pH cleaning, soaking appears to help by allowing
better contact of the acid with the membrane surface.

Effect of Low pH on Scale


The solubilities of the following
compounds are NOT pH dependent and
CANNOT dissolve in low pH:
Calcium Sulfate
Barium Sulfate
Strontium Sulfate
Calcium Oxalate
These are irreversible scales and cant be
reversed back into their ionic components.
Ca2+ + SO42 + H2O

Ca SO4 * H2O

Cleaning Chemical Selection


Type of Scale

Recommended Cleaner

Carbonate Scales

Low pH Cleaner:
C-205, C-234
Scale Pulverizer:
C-238
Scale Sequestration:
C-239

Sulfate Scales

CaSO4 Scale removal


For heavy scaling as seen below, specialty
chemicals are required to chemically pulverize
CaSO4 scale into a slurry that can be flushed off
membrane surface.

Calcium Sulfate Scale

CaSO4 Slurry formed after


cleaning w/ AWC C-238

Sulfate Scale removal


Barium Sulfate, Strontium Sulfate and Calcium
Sulfate must be cleaned by chelation
Chelation is the removal of the metal from its
salt through chemical binding to the cation
The unpaired sulfate ions now dissolve in water

Aluminum vs. pH
Al3+

Al(OH)4-

Al(OH)2++

Al(OH)2+
Al(OH)3

Reference:J.Gregory,J.Duan, Hydrolyzing metal salts as coagulants, Pure Appl.


Chem., Vol. 73, No. 12, 2001, 20172026

Hydrolysis Reactions: Ferric Ions


0.7 mol NaCl solution, 25C

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

[(OH)4SiOH]- + HOSi(OH)3 (OH)


Si-O-Si(OH)3 + H2O + OHOH 3
OH
Reference: R.K.Iler, The Chemistry of Silica, Wiley (1979)

Si
OH

OH

Silica Concentration (mM)

Effect of pH on Silica Solubility in D.I. Water

H4SiO4

H+ + H3SiO4-

H3SiO4-

H+ + H2SiO42-

Ionized Silicic Acid

OH
|
HO-Si-O
|
OH

OH
|
- O-Si-OH
|
OH

Ionized silica ions and silica polymers repel each


other, and repel OH- ions that catalyze silica
polymerization

Silica Dissolution by HF and ABF


Hydrofluoric Acid:
SiO2 + 4 HF SiF4(g) + 2 H2O
SiO2 + 6 HF H2SiF6 + 2 H2O
Ammonium Bifluoride:
SiO2 + 4 [NH4FHF] SiF4 + 4 [NH4]F + 2 H2O

Cleaning Chemical Selection


Inorganic Foulant
Iron
Manganese
Aluminum

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

Normalized Differential Pressure


Texas RO Plant

Pattern indicates significant reduction in P


after each cleaning

Normalized Permeate Flow Texas


RO Plant
No improvement in NPF after each cleaning despite
significant improvement in P

Prismatic Elemental Mapping:


Silica Scale on Membrane Surface

The membrane cleaning was effectively removing iron but not silica

Scalant / Foulant Matrix


Scalants such as calcium carbonate can
precipitate together with inorganic foulants such as
iron and silica
Biofilms and organic foulants can deposit on the
membrane surface along with iron hydroxide
precipitates and colloidal silica deposits
Bacteria are living organisms and due to their
ability to reproduce, fouling of the second stage is
possible. In such cases, a matrix of biofilm can
form with scalants and inorganic foulants.
When cleaning is performed, the chemical being
used may not be fully capable of infiltrating certain
components of the matrix, making repeated
cleanings necessary

Specialty Cleaners
vs. Generic Chemicals
Generic Chemicals

Specialty Cleaners

Can damage membrane if added


in excess

Self-Buffering to protect
membranes in case of accidental
over-addition

Limited in scope of foulants /


scalants that can be cleaned

Can remove multiple types of


scalants / foulants at the same
time

Requires multiple repetitions of


high pH and low pH cleaning

High pH specialty cleaners also


penetrate scale reducing or
eliminating requirement for
multiple cleanings.

After cleaning, some scalants or


foulants remain promoting faster
deposition of new scalants and
foulants

Infiltrates and completely removes


all scalants and foulants to allow
longer time between membrane
cleaning

General Cleaning Guidelines


Always alternate between circulating and soaking multiple
times for high pH cleaning.
Total high pH cleaning time should be at least 4 6 hours for
effective removal of all organic and biological foulants
In the case of severe organic or biological fouling, a pH of 12
is necessary for effective removal, even with the use of
specialty chemicals.
When performing a low pH cleaning, soaking does not
improve dissolution of scale it is actually counterproductive.
However, when using a low pH cleaning to improve salt
rejection after a high pH cleaning, soaking appears to help by
allowing better contact of the acid with the membrane surface.

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:

Prepare the Cleaning Equipment

Ensure that cartridge filters in cleaning skid are clean.


Ensure that piping is clean and does not have residual from
old cleaning
Rinse the cleaning tank with permeate water
Fill the cleaning tank with permeate water to appropriate level
We assume approximately 10 Gal of cleaning solution per 8
element
Tank capacity in gallons should not be less than 10 x N
Where: N = Number of 8x 40 membranes per cleaning
stage

Step 2:

Prepare the Cleaning Solution

Mix chemicals as directed


Stabilize the cleaning solution pH and temperature by recirculating the
cleaning solution for the cleaning tank though the cleaning pump to the tank
again. Add more cleaning chemicals until you reach the recommended pH.
Adjust the flow rate of the cleaning solution by pump throttle valve.
Permeate
Fill

Chemical Mixing

DP
pH

PI

TI

Heater

FI

Cartridge Filter

Cleaning Pump

Strainer

Cleaning Tank

Step 3:

Check the RO System

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:

Clean the First Stage

a. Connect the CIP discharge port to the feed cleaning port of


the first stage.
b. Connect the concentrate return port of the first stage to
drain.
c. Connect the permeate return line to the cleaning tank.
d. Discharge the cleaning solution from the CIP to the first
stage at low flow.
e. Displace the water in the vessels to drain.
f. Discharge 15-20% of the cleaning solution from the first
pass to drain.

Step 4:

Clean the First Stage

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

Recommend Feed Flow Rate Per Pressure


Vessel
Element Diameter
inches

Feed Pressure*
(psig)

2.5
4
6
8
8.5
16

20-60
20-60
20-60
20-60
20-60
20-60

Feed Flow Rate


gpm

4-6
6 -10
12- 20
24 45
27 48
96 -160

*Dependent on number of elements in pressure vessel

DO NOT INCREASE FLOWRATE IF > 10 PSI/MEMBRANE

Step 4:

Clean the First Stage

g. Route the concentrate return to the cleaning tank in a closed


loop.
h. Recirculate the solution for 5-15 minutes at low flow rate. (we
do not want to dislodge a huge amount of foulant all of the
sudden, which may plug the feed channels).
i. Continue to recirculate the solution for another 5-15 minutes
at medium flow.
j. Recirculate at high flow rate for 30-60 minutes.
k. Allow the first stage to soak while cleaning the second stage.

Step 4:

Clean the First Stage

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

Clean the second stage by repeating the steps (a) through (j).

Step 5:

Clean the Second Stage

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:

Clean the Second Stage

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:

Clean the Second Stage

Allow the first stage to soak while recirculating the second


stage for 15-60 minutes.
Repeat the soaking and recirculation of the two stages as
needed.
Flush each cleaned stage with pH and temperatureadjusted permeate water to drain (or to neutralization tank).
Flush out as much water as the capacity of the cleaning
tank.
Flush each cleaned stage again with normal permeate
water to drain (or to neutralization tank). Flush out as much
water as the capacity of the cleaning tank.

Permeate Valve
Always make sure that permeate valve is
fully open when cleaning!
Causes delamination at concentrate end
of tail element

152

Feed, Permeate and Concentrate


(Based on 75% Recovery)
8.4
ppm

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

Blistering due to Closing of


Permeate Valve during Cleaning

156

Membrane Oxidation

Chlorine

Sodium Hypochlorite

Ozone

Hydrogen Peroxide

Oxidation and Chemical Damage


Oxidizers can cause membrane damage by reacting with
the polyamide surface, breaking its chemical bonds
Examples of oxidizing chemicals are hydrogen peroxide
(H2O2), Hypochlorous acid (HOCl-), O3 (ozone), Chlorine
dioxide (ClO2)
Damage by oxidation is especially detrimental in the
presence of transition metals such as iron (oxidizes from
Fe2+ to Fe3+).
The oxidation of iron on the membrane surface results in
release of heat at the point of contact with the membrane
resulting in localized melting.

Oxidation and Chemical Damage


Increased Normalized Permeate Flow

High Chlorine Concentrations or


No Transition Metals or Low
presence of transition metals
Chlorine Concentration
If transition metals are present, the heat of reaction will result in
membrane damage mostly in the first stage. This can also occur with a
sudden discharge of chlorine at high dosage.
If no transition metals are present, hypochlorous acid can concentrate and
also cause damage in the second stage

Oxidation and Chemical Damage


Normalized Differential Pressure P

First Stage

Second Stage

Oxidation and Chemical Damage


Increased Normalized Salt Passage

High Chlorine Concentration or


Presence of Transition Metals

Low Chlorine Concentration or


No Transition Metals

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

SILT DENSITY INDEX TEST (SDI)


Estimates the rate of fouling by suspended solids
having a particle size larger than 0.45 micron
Will not clog as easily by larger particles such as sand
Used mostly to approximate fouling by colloidal sized
particles which tend to be smaller than 0.5 micron
Bacteria are also in this size range and their presence
can provide a misleading SDI reading

SILT DENSITY INDEX TEST (SDI)

SILT DENSITY INDEX TEST (SDI)


SDI TEST PROCEDURE
1. Connect the test kit without filter paper for pretest flush.
2. Flush the test kit and supply line for five minutes to remove any
possible contaminants.
3. Measure the temperature of the water.
4. Make sure that the O-ring is in a good condition and properly placed.
5. Set the pressure to 30 psig. Supply pressure to the kit is
recommended to be > 35 psig.
6. Open the filter holder and carefully place a 0.45 membrane filter
(shiny side up) on the support plate of the holder. Handle the
membrane filter only with lab tweezers and avoid touching with the
fingers.
7. Close the top of the filter holder loosely.

SILT DENSITY INDEX TEST (SDI)


SDI TEST PROCEDURE
8. Open the feed valve slightly. Allow the water to over flow from the filter
holder to displace any trapped air. Tighten the top of the filter holder.
9. Open the ball valve completely and simultaneously begin measuring
the time (T1) in seconds that is required for filling 250 ml. (normally for
good water it takes 7-9 seconds).
10.Leave the valve open to allow a continued flow for 15 minutes.
11.Measure the time (T2) required to fill additional 250 ml of sample.
(normally for good water it takes <15 seconds).
12.Calculate SDI using the following formula:

SDI =

[1 - T1/ T2 ]
15

x 100

Flow and Mass Balance


When unusual permeate flows or conductivities are
observed a flow or mass balance helps ensure that
instrument readings are correct
A flow balance can be used to verify flow meters
Feed Flow = Permeate Flow + Concentrate Flow
A mass balance can be used to verify conductivity
meters
Total Solids In = Total Solids Out

Flow Balance
Permeate

Feed

75 gpm

100 gpm

Brine
25 gpm

75%
Recovery

QF = QP + QC
where:

QF = Flow of Feed Water


QP = Flow of Permeate
QC = Flow of Concentrate

Mass Balance

QF . CF = QP . CP + QC . CC
L
min

mg
L

L
min

mg
L

L
min

Assuming 1 min, units will be in mg


where:

QF
CF
QP
CP
QC
CC

= Flow of Feed Water


= Concentration of Feed Water
= Flow of Permeate
= Concentration of Permeate
= Flow of Concentrate
= Concentration of Concentrate

mg
L

Pressure Vessel Profiling


When conductivity of the permeate increases abruptly, each
pressure vessel should be looked at individually.
This helps differentiate between overall membrane damage or a
local problem that can be isolated specifically to one or more
pressure vessels.
The conductivity of the permeate of each pressure vessel is
measured and recorded.
The readings should be observed for inconsistency within the
same stage of the system that would pinpoint the problem to the
pressure vessel with the inconsistent reading.
21

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

(Based on 75% Recovery)

Mark the starting and ending points of each of the consecutive


membranes along the length of a flexible tubing.
Insert the flexible tube through the permeate port of the lead
element
Permeate water will flow out the flexible tubing
Take samples and measure conductivity from the beginning and
end of each membrane position

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