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Corrosion =
Oxidation reduction
(REDOX) reactions
H2
Reduction of Oxygen
(CATHODE)
O2
OH-
RED OXIDE
o
o
MAGNETITE
BLACK OXIDE
Fe3O4
o
EL
EC
TR
FeOH++ + Fe(OH)+2
ON
FL
H++FeOH+
OW
Evolution
of Hydrogen
(CATHODE) Fe+2
eFe
MAGNETITE
Precipitation of Black
Oxide (CATHODE)
Oxidation and
Hydrolysis
Hydrolysis of
Dissolved Iron
lowers pH
Acid Pit Solution with
Lower Oxygen Content
Oxidation of Iron
ANODE
Reducing conditions
minimize corrosion (more
negative ORP)
The principal of the ORP measurement is
similar to how we measure oxidizing
biocides
Biocides - oxidizing - more positive values
Scavengers reducing - more negative values
Reducing conditions
minimize corrosion
(more negative ORP)
More Reducing
400
200
Oxidizing
-200
-400
-600
0.1
Reducing
1
10
100
Dissolved Oxygen (ppb)
7
1000
Voltage
Bulk
Water
Inert Metal (Pt)
NCSM (V)
+ 300
+200
+100
0
-100
-200
-300
-400
-500
-600
-700
Higher baseline DO
Weaker scavenger
Cooler temperature
More acidic/lower pH
11
Contents
13
Operational
Chemical
System design
metallurgy
Deaerator tray
alignment
Feedwater
heater
Economizer
leaks
Pump leaks
Deaerator
venting, steam
supply
Steam load
changes
Start up and
shut down
Condensate vs
make up ratio
Process leaks
Temperature
Feedwater
demand
Economics
Dissolved oxygen
Oxygen scavenger,
passivator
chemistry & dose
limitations
Scavenger mixing,
residence time
Condensate
treatment recycle
pH
Process
contamination leaks
Corrosion products
14
15
DA brought on line
DA steam flow loss
2nd boiler brought on line
Seasonal operations
Variation in MU to Condensate
16
200
-250
150
-300
100
-350
50
-400
-450
4 Hours
DO Ingress from Pump A
17
250
18
general corrosion
oxygen induced pitting
flow accelerated corrosion
others
Any metallurgy
Any scavenger/passivator chemistry
19
MOC
MOC
Indirect
Direct
Residuals
DA
Inspections
O2
Monitoring
Fe
Testing
NCSM
2009
1940s
20
Scavenger residual
measurement has
limitations
Scavenger residual (FW or BD) does not
mean no DO
Measuring sulfite in BD does not provide
quick response to real corrosion stress
events
Measuring sulfite BD concentrations can
be unrelated to the stress events in the
FW
21
DO measurement is also
limited
DO spikes
& quickly
returns to
low level
The actual
corrosion
event lasts
much longer!
23
-100
-50
RT ORP 6 minute delay
-100
-150
-150
-200
-200
-250
-250
NCSM
-300
-350
9:00
-300
10:00
11:00
Time
-350
12:00
25
RT ORP (mV)
NCSM (mV)
-50
-200
-100
-300
-200
-400
-300
-500
-400
-600
-500
-700
-600
Time (hrs)
26
RT ORP (mV)
NCSM (mV)
-100
ORP mV
Conventional scavenger
feed methods are inferior to
NCSM
Constant fixed feed
Setpoint based on historical/grab samples
Misses dynamic stresses
Conventional
Best Practice
New
Best Practice
Deaeration + Scavenger
Deaeration
+ NCSM
Residuals
Mechanical Deaeration
primary removal
NCSM
secondary response
Feed scavenger based
on MOC corrosion
stresses
Contents
30
Water Out
Active
Platinum
Electrode
Water In
3/8 Stainless
Steel ORP Cell
with Reducing
Unions
Reference
Electrode
Reference
Electrode
Ceramic
Junction
3/8 Stainless
Steel ORP Cell
with 1/4
Reducers
32
33
Contents
34
35
36
37
38
39
Questions?
41
Thank You!
42