DREW

INDUSTRIAL
CONTROLLING
MICROBIOLOGICALLY
INFLUENCED CORROSION
AND BIOFOULING
2
Microbiological Control Is The Key To Success
Or Failure In Cooling Water Treatment Programs
3
How Biofilms Form
4
Biofilms Must Be Controlled
Will provide insulating barrier and
reduce heat transfer rates
Will trap debris and promote plugging
Concentration cell forms beneath and
corrosion accelerates (MIC)
Provides a host for anaerobic
bacteria such as SRBs and other
acid formers
How MIC occurs
How MIC occurs
Biofilm on exchanger
Biofilm on exchanger
5
Biofilms Must Be Controlled
Top layer
Aerobic bacteria
Nitrifying, iron oxidizing and
manganese bacteria are
typical
Middle layer
Facultative bacteria
Prefer aerobic, but survive in
anaerobic 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
6
7
Pitting
Biofilm provides anaerobic environment for SRB proliferation
SRB attack in anaerobic environments results in pitting in all
metallurgy
8
Chlorination
Cl
2
+H
2
O 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 NH
3
, forming chloramines
9
Chlorine and Ammonia
Cl
2
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
1 2 1 NH
2
Cl
4 1 2 OCl
-
200 100 200 HOCl
Virus Spores Bacteria
Relative Effectiveness
(Related to Kill Time)
10
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
O
R
P

m
V
NH2Cl HOCl
Target min ORP Target max ORP
Area of
optimum
kill
11
Chloramines Are Very Poor Biocides
12
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
13
Bromination
Very effective at pH 8
+
in uncontaminated systems
Most economical is to activate a sodium bromide
solution with chlorine source
NaBr + Cl
2
+ H
2
O NaCl + HOBr + HCl
At higher pH levels:
HOBr OBr
-
+ H
+
14
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
P
e
r
c
e
n
t

d
i
s
s
o
c
i
a
t
i
o
n
HOCl
HOBr
Br
2
Better Than Cl
2
at Higher pH
Br
2
Better Than Cl
2
at Higher pH
15
Bromamines Have Very Low Half Life and Flash
Off Over the Tower
16
Chlorine Dioxide
Overcomes the Problems
Associated with Chlorine
and Bromine
O O
O O
Cl Cl
O O
O O
Cl Cl
17
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
18
Why ClO
2
Is Effective In Biofilm Removal
ClO
2
ClO
2
ClO
2
ClO
2
ClO
2
ClO
2
ClO
2
ClO
2
ClO
2
ClO
2
ClO
2
ClO
2
ClO
2
ClO
2
ClO
2
enters cells un-depleted & kills from within
Stops protein production by disrupting DNA
Once DNA is disrupted, life ceases
Low O
2
pH <1 ClO
2
**
ClO
2
-
ClO
2
**
19
Many Organics Do Not React With ClO
2
Ammonia
Ammonium salts
Primary amines
Alkanes
Alkenes
Alcohols
Glycols
Diols
Aldehydes
Ketones
Ethers
Acids
Unsubstituted aromatics
20
Non-Oxidizing Biocide Effectiveness
S
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A
m
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o
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y
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G
l
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t
a
r
a
l
d
e
h
y
d
e
0
500
1000
1500
2000
2500
Dosage Required For 99.999% Kill (5-Log Reduction) in 60 Seconds
21
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
P
e
r
c
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n
t

d
i
s
s
o
c
i
a
t
i
o
n
HOCl
HOBr
ClO2
ClO
2
Not pH Dependent
ClO
2
Not pH Dependent
22
Bromine Vs Chlorine Dioxide In Presence of
Ammonia- 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
Dose rate mg/L
O
R
P

m
V
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
A
T
P
:


%

k
i
l
l
Bromine ORP ClO2 ORP
Target min ORP Target max ORP
Bromine % kill ClO2 % kill
23
Oxidizing Biocide Requirements in
Contaminated Systems
Demand (mg/l) Refinery
(with minor
leaks)
Petrochemical
(hydrocarbon
leakage)
Fertilizer (~5
mg/l NH
3
)
Grain Processing (high
organic loading in recycle
water used as MU)
Chlorine 1.0 15.5 23.8 280.0
Bromine - 5.5 12.4 88.0
Chlorine Dioxide 0.2 2.1 2.8 1.5

Demand in mg/l
24
Gaseous Chlorine Generation
2NaClO
2
+ Cl
2
2ClO
2
+ 2NaCl
Sodium Chlorine Chlorine Sodium
Chlorite Dioxide Chloride
25
Bleach Generation
GENEROX III
2NaClO
2
+ NaOCl + 2HCl 2ClO
2
+ 3NaCl + H
2
O
Sodium Sodium Hydrochloric Chlorine Sodium Water
Chlorite Hypochlorite Acid Dioxide Chloride
26
Advantages Of Chlorine Dioxide
Remains gas in water--
no hydrolyzation
Wont react with NH
3
or
organics
Better MB control
Not as corrosive as Cl
2
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
27
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 processing
applications
No THM & AOX formation
No harmful by-products
No air emissions
28
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 ClO
2
programs
DREW
INDUSTRIAL
The Next
Generation of
Microbiological and
Biofilm Control
Ultrasonic Microbial Control Ultrasonic Microbial Control
30

No chemical biocide usage

No chemical biocide usage

Superior microbial control

Superior microbial control

Excellent Legionella control

Excellent Legionella control

Improved heat transfer

Improved heat transfer

Reduced maintenance
Reduced maintenance
Ultrasonic Microbial Control Ultrasonic Microbial Control
31
SONOXIDE Ultrasonic Treatment
Development
Initial work and patent
for the application of
ultrasound in medical research
In 1999, discovered effectiveness on algae and
bacteria in water systems
32
SONOXIDE
Technology Highly
Recognized
Medicine honors
Apoptosis work
MIT Professor among those
honored

Three scientists received the 2002 N

obel
Three scientists received the 2002 N
obel
Prize for M
edicine
Prize for M
edicine
for determ
ining that organism
s develop and
for determ
ining that organism
s develop and
m
aintain
m
aintain
-
-
-
-
-
-

Q
u
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m

s
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g

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b
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c
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r

Program
m
ed cell death has allowed
experts to understand the m
echanism
s at
play with viruses and bacteria
Chemical & Engineering News/Science Weekly Archive/Microbe Warfare: Bacterial Communication
33
SONOXIDE Ultrasonic System
Patented
Low-power
High-frequency
Special orientation
Air microbubbles
System water Air Bubbles
Emitters
34
The SONOXIDEUnit
Ultrasonic
Treatment
Cell
Venturi
air inlet
Water inlet
(Tower sump)
Water outlet
(Opposite
side of inlet)
Sonoxide
recirculating
pump
Electrical
& controls
panel
Transparent
pipe showing
air bubbles
35
Cavitation
Intense bubble
formation and collapse
Necrosis
Immediate destruction of cell
Apoptosis
Programmed cell death
Inability to reproduce
Produces signaling proteins
SONOXIDE Bio Control Mechanisms
Healthy cells before treatment
Healthy cells before treatment
Sick cells after treatment
Sick cells after treatment
36
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 (Quorum
Sensing)
Treated Cell
SONOXIDE
Low power
High frequency ultrasound
+ microaeration
Initiates PCD
Signaling Molecules
Healthy Cell Biofilm
Quorum Sensing
Sonoxide: Mechanism - Apoptosis
37
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 cell
death
Ultrasonic
Treatment
Chamber
38
39
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
40
0
2
4
6
8
10
0 1 2 3 4 5
Days
A
l
g
a
e

c
o
n
c
e
n
t
r
a
t
i
o
n
(
1
0
6
)
No Treatment Under Sonoxide Treatment
Sonoxide Effect on Green Algae
41
Biofilm and Algae Control
Before SONOXIDE treatment
Before SONOXIDE treatment
3 week of SONOXIDE treatment
3 week of SONOXIDE treatment
No evidence of biofilm or algae Visible biofilm & algae
42
SONOXIDE

Treatment Typical Impact on

Microbiologically Influenced Corrosion Control
Mild Steel 1.3 mpy Mild Steel 1.3 mpy
Copper 0.1 mpy Copper 0.1 mpy
Pre
Pre
-
-
SONOXIDE
SONOXIDE
55-day exposure
Mild Steel 0.3 mpy Mild Steel 0.3 mpy
Admiralty Brass <0.1 Admiralty Brass <0.1
mpy mpy
SONOXIDE
SONOXIDE
35-day exposure
Pre- and post- SONOXIDE treatment corrosion coupon comparison on cooling tower.
43
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.
44
ST Microelectronics, Singapore
Wafer fab plant
Chiller tower system
RR = 1,400 m
3
/yr
V = 43 m
3
SONOXIDE replaced program
comprised of continuous bleach
addition with intermittent feed of
non-oxidizing biocide
Unit installed on tower without any
precleaning
45
ST Microelectronics, Singapore
Total Bacteria Count Readings During SONOXIDE Application
1
10
100
1, 000
10, 000
2
5
/
3
/
0
4
8
/
4
/
0
4
2
0
/
4
/
0
4
2
9
/
4
/
0
4
1
3
/
5
/
0
4
1
9
/
5
/
0
4
3
/
6
/
0
4
1
7
/
6
/
0
4
3
0
/
6
/
0
4
1
4
/
7
/
0
4
2
8
/
7
/
0
4
1
1
/
8
/
0
4
1
8
/
8
/
0
4
1
/
9
/
0
4
1
5
/
9
/
0
4
6
/
1
0
/
0
4
2
0
/
1
0
/
0
4
Da te
T
B
C

(
c
f
u
/
m
l
)
SONOXIDE Commissioned
Legionella Bacteria Counts
82
31
36
2
7
1
0
0
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
L
B

C
o
u
n
t

(
c
f
u
/
m
l
)
46
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
47
Some of Our Many Customers Who Have
Benefited 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
48
Use Of ORP To Enhance Control Of
Oxidizing Biocides
49
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 counts
for specific cooling system
50
Why Use ORP Technology?
ORP allows you to achieve optimum MB control
ORP allows you to continuously control halogen
feed
ORP responds to changes in system conditions
pH, demand, sunlight, etc. contribute to higher
MB loading
Prevents under and overdosing
ORP allows you to find system leaks
51
Simple to Automate and Control
Simple to Automate and Control
Output &
control of
halogen
Controller
with ORP
ORP probe
52
ORP Controls Biofouling
Refinery
300.00
350.00
400.00
450.00
500.00
550.00
600.00
650.00
1/
15
/9
6
1/
16
/9
6
1/
16
/9
6
1/
17
/9
6
1/
17
/9
6
1/
17
/9
6
1/
18
/9
6
1/
18
/9
6
1/
19
/9
6
1/
19
/9
6
1/
20
/9
6
1/
20
/9
6
1/
21
/9
6
1/
21
/9
6
1/
22
/9
6
1/
22
/9
6
1/
22
/9
6
1/
23
/9
6
1/
23
/9
6
1/
24
/9
6
1/
24
/9
6
1/
25
/9
6
1/
25
/9
6
1/
26
/9
6
1/
26
/9
6
1/
27
/9
6
1/
27
/9
6
1/
28
/9
6
1/
28
/9
6
1/
28
/9
6
1/
29
/9
6
1/
29
/9
6
1/
30
/9
6
1/
30
/9
6
Time
O
R
P
-200
-150
-100
-50
0
50
100
150
200
ORP
FOULING
53
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
Effect Of pH on ORP in Chlorinated
Systems
54
ORP Allows Better Control At Reduced Cost And
Chemical Usage
Halogen fed on Halogen fed on
demand demand
Tight ORP Control Tight ORP Control
55
Examples of ORP Control Systems
56
Summary
Microbiological control is the key to success in cooling water
treatment programs
Classical oxidizing biocides (i.e., Cl
2
and Br
2
) work well in the
right types of systems
Unique chemical technology ClO
2
provides excellent
microbial 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
DREW
INDUSTRIAL
Thank
You