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DREW
INDUSTRIAL
CONTROLLING
MICROBIOLOGICALLYINFLUENCED CORROSION
AND BIOFOULING
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Microbiological Control Is The Key To Success
Or Failure In Cooling Water Treatment Programs
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How Biofilms Form
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Biofilms Must Be Controlled
Will provide insulating barrier andreduce heat transfer rates
Will trap debris and promote plugging
Concentration cell forms beneath and
corrosion accelerates (MIC)
Provides a host for anaerobicbacteria such as SRBs and otheracid formers
How MIC occursHow MIC occurs
Biofilm on exchangerBiofilm on exchanger
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Biofilms Must Be Controlled
Top layer Aerobic bacteria Nitrifying, iron oxidizing and
manganese bacteria aretypical
Middle layer Facultative bacteria
Prefer aerobic, but survive inanaerobic conditions
Denitrifying
Bottom layer Anaerobic SRB, iron reducing
Provides protective barrier for all types of microorganisms and
creates environment to enable all species to flourish
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Pitting
Biofilm provides anaerobic environment for SRB proliferation
SRB attack in anaerobic environments results in pitting in all
metallurgy
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Chlorination
Cl2 +H2O HCl + HOCl
HOCl H+ + OCl-
Lowest cost alternative in right systems-- Narrow pH
range below ~8.5
Uncontaminated systems
Attacks nucleus not slime layer Poor biofilm penetrant
Reacts with organics and loses ability to kill bacteria
Reacts with NH3, forming chloramines
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Chlorine and Ammonia
Cl2 reacts in 10:1 ratio to form
chloramines
Far less effective than HOCl
and OCl-
Initially forms
monochloroamine
Positive FRC reading Significantly lower ORP Much lower killing power
121NH2Cl
412OCl-
200100200HOCl
VirusSporesBacteria
Relative Effectiveness
(Related to Kill Time)
ff f C C
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Effect of Free Chlorine and Chloramines
on ORP (pH = 7.5)
Effect of Free Chlorine and Chloramines
on ORP (pH = 7.5)
200
250
300
350
400
450
500
550
600
650
700
750
800
0.00 0.01 0.10 1.00 10.00 50.00 100.00
Free Available Halogen
ORPm
V
NH2Cl HOCl
Target min ORP Target max ORP
Area of
optimum
kill
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Chloramines Are Very Poor Biocides
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Effects Of Over-Chlorination
Acceleration of corrosion rates
Increased chloride-- SCC of SS
Aggressive to copper
Delignification of wood
Reaction/deactivation of some
inhibitors/ deposit control agents
Lower cycles of concentration when
chloride is limiting factor for COC
Severe delignification
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Bromination
Very effective at pH 8+ in uncontaminated systems
Most economical is to activate a sodium bromidesolution with chlorine source
NaBr + Cl2 + H2O NaCl + HOBr + HCl
At higher pH levels:
HOBr OBr- + H+
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0
10
20
30
40
50
60
70
80
90
100
6.5 6.7 6.9 7.1 7.3 7.5 7.7 7.9 8.1 8.3 8.5 8.7 8.9
pH
Percentdissociation
HOCl
HOBr
Br2Better Than Cl2at Higher pHBr2Better Than Cl2at Higher pH
B i H V L H lf Lif d Fl h
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Bromamines Have Very Low Half Life and Flash
Off Over the Tower
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Chlorine Dioxide
Overcomes the Problems
Associated with Chlorine
and Bromine
OO
OO
ClCl
OO
OO
ClCl
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What is Chlorine Dioxide?
Powerful and highly effective oxidizer
Not affected by pH because it is a dissolved gas Wont react with many organic contaminants - including
ammonia compounds
Excellent biofilm removal - rapidly penetrates and oxidizes
biofilms
Can destroy odors caused by microorganisms and organics
Does not form disinfection by-products such as
trihalomethanes and oxidized aromatics
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Why ClO2 Is Effective In Biofilm Removal
ClO2
ClO2
ClO2
ClO2
ClO2
ClO2
ClO2
ClO2
ClO2
ClO2
ClO2
ClO2ClO
2
ClO2
ClO2 enters cells un-depleted & kills from within
Stops protein production by disrupting DNA
Once DNA is disrupted, life ceases
Low O2 pH
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Many Organics Do Not React With ClO2
Ammonia
Ammonium salts
Primary amines
Alkanes
Alkenes
Alcohols
Glycols
Diols
AldehydesKetones
Ethers
Acids
Unsubstituted aromatics
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Non-Oxidizing Biocide Effectiveness
S
accharomyc
escerevisi
n
Staphylococcusaureu
Psue
domones
aeneginone ChlorineDioxid
AcidifiedQuatern
ar
QuaternaryAm
moniu
SodiumHypochlorit
Glutaraldehyde
0
500
1000
1500
2000
2500
Dosage Required For 99.999% Kill (5-Log Reduction) in 60 Seconds
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0
10
20
30
40
50
60
70
80
90
100
6.5 6.7 6.9 7.1 7.3 7.5 7.7 7.9 8.1 8.3 8.5 8.7 8.9
pH
Percentdissociation
HOCl
HOBr
ClO2
ClO2 Not pH DependentClO2 Not pH Dependent
Bromine Vs Chlorine Dioxide In Presence of
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Bromine Vs Chlorine Dioxide In Presence ofAmmonia- ORP & Dose Rate Vs % Kill
200
250
300
350
400
450
500
550
600
650
700
750
800
0.0 1.4 2.7 5.4 6.8 8.1 13.5 20.0 30.0 40.0 50.0
ORPmV
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
ATP:%
kill
Bromine ORP ClO2 ORP
Target min ORP Target max ORP
Bromine % kill ClO2 % kill
Oxidizing Biocide Requirements in
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Oxidizing Biocide Requirements in
Contaminated Systems
Demand (mg/l) Refinery(with minor
leaks)
Petrochemical(hydrocarbon
leakage)
Fertilizer (~5mg/l NH3)
Grain Processing (highorganic loading in recycle
water used as MU)
Chlorine 1.0 15.5 23.8 280.0Bromine - 5.5 12.4 88.0
Chlorine Dioxide 0.2 2.1 2.8 1.5
Demand in mg/l
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Gaseous Chlorine Generation
2NaClO2 + Cl2 2ClO2 + 2NaCl
Sodium Chlorine Chlorine Sodium
Chlorite Dioxide Chloride
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Bleach Generation
GENEROX III
2NaClO2
+ NaOCl + 2HCl 2ClO2
+ 3NaCl + H2O
Sodium Sodium Hydrochloric Chlorine Sodium Water
Chlorite Hypochlorite Acid Dioxide Chloride
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Advantages Of Chlorine Dioxide
Remains gas in water--no hydrolyzation
Wont react with NH3 or
organics
Better MB control
Not as corrosive as Cl2
Effective over wide pH ranges
Lower dosage, less SCC
problems, no chance of
delignification, more effective
than chlorine
Excellent on algae, SRB, other
anaerobes and slime
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Advantages Of Chlorine Dioxide
Safe to operate and use
Completely
environmentally friendly
and safe
50 years of experience
Built in safety features
Extensively used in drinking
water and food processingapplications
No THM & AOX formation
No harmful by-products
No air emissions
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Biodispersants Effectively Penetrate Biofilm
Biodispersants are molecules with surface acting properties
Enhance ability of biocides to better penetrate biofilm
Important to use when applying chlorine and bromine
May not be required with ClO2 programs
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DREW
INDUSTRIAL
The Next
Generation of
Microbiological andBiofilm Control
Ultrasonic Microbial ControlUltrasonic Microbial Control
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No chemical biocide usageNo chemical biocide usage
Superior microbial controlSuperior microbial control
Excellent Legionella controlExcellent Legionella control Improved heat transferImproved heat transfer
Reduced maintenanceReduced maintenance
Ultrasonic Microbial ControlUltrasonic Microbial Control
SONOXIDE Ultrasonic Treatment
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SONOXIDE Ultrasonic Treatment
Development
Initial work and patent
for the application of
ultrasound in medical research
In 1999, discovered effectiveness on algae andbacteria in water systems
bles
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SONOXIDETechnology Highly
RecognizedMedicine honors
Apoptosis workMIT Professor among those
honoredThreescientistsreceivedthe2002NobelThreescientistsreceivedthe2002NobelPrizeforMedicinePrizeforMedicine
fordeterminingthatorganismsdevelopand
fordeterminingthatorganismsdevelopandmaintainmaintain------
Quorumsensing
enables
bacteriatocoord
inatetheir
behavior
Programmedcelldeathhasallowed
expertstounderstandthemechanismsat
playwithvirusesandbacteria
Chemical & Engineering News/Science Weekly Archive/Microbe Warfare: Bacterial Communication
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SONOXIDE Ultrasonic System
Patented
Low-powerHigh-frequency
Special orientation
Air microbubbles
System water Air Bubbles
Emitters
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The SONOXIDE Unit
Ultrasonic
Treatment
Cell
Venturi
air inlet
Water inlet
(Tower sump)
Water outlet
(Opposite
side of inlet)
Sonoxiderecirculating
pump
Electrical
& controls
panel
Transparent
pipe showing
air bubbles
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Cavitation
Intense bubbleformation and collapse
Necrosis Immediate destruction of cell
Apoptosis Programmed cell death
Inability to reproduce Produces signaling proteins
SONOXIDE Bio Control Mechanisms
Healthy cells before treatmentHealthy cells before treatment
Sick cells after treatmentSick cells after treatment
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Healthy Cell
Programmed Cell Death is
triggered by low energy high
frequency ultrasound Signaling molecules are released
which affects healthy cells and
removes biofilm in remote areas
of water system (QuorumSensing)
Treated Cell
SONOXIDE
Low powerHigh frequency ultrasound
+ microaeration
Initiates PCD
Signaling Molecules
Healthy Cell Biofilm
Quorum Sensing
Sonoxide: Mechanism - Apoptosis
A t i
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System water Air Bubbles
Apoptosis
Healthy bacterial cells exposed to: Frequency, Power Ultrasound
Micro bubble aeration
Bacterial cell is genetically altered
Apoptotic cells exit chamber
Biofilm cells subjected to programmed celldeath
Ultrasonic
Treatment
Chamber
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Total Bacteria Control
Total Bacterial Counts
100
1000
10000
100000
1000000
10000000
12/2 12/12 12/22 1/1 1/11 1/21
Start SONOXIDE
Sonoxide Effect on Green Algae
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0
2
4
6
8
10
0 1 2 3 4 5Days
Algaeco
ncentration
(106)
No Treatment Under Sonoxide Treatment
Sonoxide Effect on Green Algae
Bi fil d Al C t l
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Biofilm and Algae Control
Before SONOXIDE treatmentBefore SONOXIDE treatment 3 week of SONOXIDE treatment3 week of SONOXIDE treatment
No evidence of biofilm or algaeVisible biofilm & algae
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SONOXIDE T t t Bi fil C St d
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SONOXIDE Treatment Biofilm Coupon Study
Condition of biofilm coupon upon start-up of
SONOXIDE system. Biofilm is evident.
Condition of biofilm coupon upon start-up of
SONOXIDE system. Biofilm is evident.Same biofilm coupon removed after 4 months
of SONOXIDE operation. No evidence of slime.
Same biofilm coupon removed after 4 months
of SONOXIDE operation. No evidence of slime.
Biofouling study using biofilm coupons. Biofilm coupon was examined prior
to SONOXIDE start-up and re-examined after 4 months of SONOXIDE
operation. All biofilm was cleaned up and no evidence of slime exists.
S S
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ST Microelectronics, Singapore
Wafer fab plant
Chiller tower system
RR = 1,400 m3
/yr V = 43 m3
SONOXIDE replaced program
comprised of continuous bleachaddition with intermittent feed of
non-oxidizing biocide
Unit installed on tower without any
precleaning
ST Mi l t i Si
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ST Microelectronics, SingaporeTo tal B acteria C ou nt R ead ing s D ur ing S ON OX ID E App lication
1
10
100
1,000
10,000
25/3/04
8/4/04
20/4/04
29/4/04
13/5/04
19/5/04
3/6/04
17/6/04
30/6/04
14/7/04
28/7/04
11/8/04
18/8/04
1/9/04
15/9/04
6/10/04
20/10/04
Date
TBC(cfu/ml) SONOXIDE Commissioned
Legionella Bacteria Counts
82
31 36
2 7 1 00
20
40
60
80
100
14/5/04 6/3/04 30/6/04 7/7/04 21/7/04 1/9/04 6/10/04
Date
LBCount(c
fu/ml)
SONOXIDE S t Ad t
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Performance Improvements Reduction in bacteria counts No visible biofilm Improved corrosion rates
Improved heat transfer Control of algae Reduced maintenance costs Potential to increase COC
Quality Improvements Eliminate biocide Improved reliability Reduced corrosion potential
EH&S Benefits Better Legionella compliance Eliminate biocide discharge issues
Improved risk management Improved personnel safety
SONOXIDE System Advantages
Some of Our Many Customers Who Have
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yBenefited From SONOXIDE
Ford Motor
Bridgestone Firestone
AGA Gases
Kodak
Hines Properties
Cummins Engine
Ashland Chemical
Bayer
Procter and Gamble
Roche
Sasol Wax
MIT
BMW
Schiphol Airport
Alcoa
Daimler Chrysler
Kraft Foods
Superfos
BASF
Owens Corning
Use Of ORP To Enhance Control Of
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Oxidizing Biocides
What Is ORP?
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What Is ORP?
Measures the oxidizing or
reducing ability of a solution
Correlates death rate of
organisms
All systems are different-- Must
relate ORP vs. bacterial countsfor specific cooling system
Why Use ORP Technology?
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Why Use ORP Technology?
ORP allows you to achieve optimum MB control
ORP allows you to continuously control halogenfeed
ORP responds to changes in system conditions pH, demand, sunlight, etc. contribute to higherMB loading
Prevents under and overdosing
ORP allows you to find system leaks
Simple to Automate and ControlSimple to Automate and Control
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Simple to Automate and ControlSimple to Automate and Control
Output &
control of
halogen
Controllerwith ORP
ORP probe
ORP Controls Biofouling
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ORP Controls Biofouling
300.00
350.00
400.00
450.00
500.00
550.00
600.00
650.00
1/15/9
1/16/9
1/16/9
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1/17/9
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Time
OR
-200
-150
-100
-50
0
50
10 0
15 0
200
ORP
FOULING
Effect Of pH on ORP in Chlorinated
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440.00
450.00
460.00
470.00
480.00
490.00
500.00
510.00
520.00
530.00
ORP
6.60
6.65
6.70
6.75
6.80
6.85
6.90
6.95
7.00
pH
ORP
PH
p
Systems
ORP Allows Better Control At Reduced Cost And
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Chemical Usage
Halogen fed onHalogen fed ondemanddemand
Tight ORP ControlTight ORP Control
Examples of ORP Control Systems
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Examples of ORP Control Systems
Summary
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Summary
Microbiological control is the key to success in cooling water
treatment programs
Classical oxidizing biocides (i.e., Cl2 and Br2) work well in theright types of systems
Unique chemical technology ClO2 provides excellentmicrobial control in high pH and contaminated systems
New SONOXIDE ultrasonic treatment controls
microorganisms without the use of chemicals
Oxidation Reduction Potential (ORP) is an excellent tool to
control feed of oxidizing biocides
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DREW
INDUSTRIAL
ThankYou