3D TRASAR Boiler Technology

Protecting Boiler Assets with

REDOX Stress Control
Technology

Contents

What is REDOX Stress Control?

Why REDOX Stress Control?
Practical considerations
Early Experience in Ammonia Plant

REDOX stress control is

REDOX stress control is achieved by

adjusting scavenger feed to maintain a
set point based on the waters ORP
measured at operating temperature &
pressure.

Corrosion =
Oxidation reduction
(REDOX) reactions
H2

Reduction of Oxygen
(CATHODE)

Precipitation of Red Oxide

Fe2O3

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

ORP indicates the potential

for
water to corrode
Corrosion = REDOX Reactions
REDOX Reactions = ORP voltage (mV)
(Oxidation Reduction Potential)
ORP voltage = bulk FW corrosivity

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

Corrosion control typically negative values

Oxidizing - more corrosive
Reducing - less corrosive

Reducing conditions
minimize corrosion
(more negative ORP)

ORP ( mV) 400F, 204C

More Reducing

400
200

Oxidizing

-200
-400
-600
0.1

Reducing

1
10
100
Dissolved Oxygen (ppb)
7

1000

Nalco Corrosion Stress

Monitor (NCSM) measures
net ORP at operating T & P

Voltage
Bulk
Water
Inert Metal (Pt)

External Pressure Balanced

Reference Electrode
(EPBRE)
8

Examples of how system

factors affect NCSM readings

NCSM (V)
+ 300
+200
+100
0
-100
-200
-300
-400
-500
-600
-700

Higher baseline DO
Weaker scavenger
Cooler temperature
More acidic/lower pH

Advantages of NCSM due to

detecting & reacting at
operating conditions
NCSM - robust, sensitive, accurate & fast
Rated to 500F, 2000psi
Can see effects at hi T not seen at room T
(RT)
Corrosion correlation to actual T & P
Fast since sampling is early in stream
Primarily for Preboiler Corrosion Control
10

How does NCSM control

corrosion stress?

Detects REDOX stress in a boiler feed

water system (ORP at operating T & P)
Determines correct response to REDOX
stress
Delivers the correct amount of scavenger
to minimize the corrosivity of boiler feed
water

11

Example of NCSM operating

ranges for sulfite & carbon
steel system (400F)
NCSM (mV)
+300 Dissolved Oxygen (ppb DO)
>100
+200
30-50
Pitting Attack
+100
0
4-7
-100
Good
0
Confidence Line
Deaerator
-200
Sulfite residual
(ppb DO scavenging
-300
equivalents)
0.8 mpy
-400 30
0.5 mpy
-500 60
0.2 mpy
-600
2500
12

Contents

What is REDOX Stress Control?

Why REDOX Stress Control?
Practical considerations
Early Experience in Ammonia Plant

13

The boiler is the most

dynamic water-using system
in most plants
many MOC factors affect boiler performance
Mechanical

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

Many case studies document

NCSM diagnostic & control
capabilities

Lost scavenger feed

Steam load changes
Using different pumps
Increase in make-up water;
boiler tube leak
Lost amine feed to condensate;
feed water pH change

15

More NCSM corrosion

control & diagnostics MOC
cases

DA brought on line
DA steam flow loss
2nd boiler brought on line
Seasonal operations
Variation in MU to Condensate

16

NCSM handled production

increases & decreases that
caused corrosion stress
-200

200

-250

150

-300

100

-350

50

-400

-450

4 Hours
DO Ingress from Pump A

17

NCSM (mV) 133C

ELIMINOX Pump Speed (%)

Load (MW)
DO (ppb)
Residual Hydrazine (ppb)

250

Condensate Hot-well Pump A

On Off

NCSM protects boiler system

from many variables

Customers running lean, doing more with

less
Boiler criticality puts business/production
at risk
Cost of (lost) production/business is real
Improved ability to reduce/control
variables increases protection asset life
extension

18

NCSM can protect a variety

of boiler systems

Can address corrosion mechanisms

simultaneously

general corrosion
oxygen induced pitting
flow accelerated corrosion
others

Any metallurgy
Any scavenger/passivator chemistry
19

NCSM controls corrosion

more directly
Chemical
Chemical

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

CHEMETS spectrophotometric test

inaccurate, point in time
On-line device like Orbisphere
Susceptible to fouling
Slow response since sample needs to be
cooled
O2 does not always correlate to corrosion
stress
Only measures one MOC corrosive factor
22

The NCSM data shows theres

more to pre-boiler corrosion
stress than dissolved oxygen

DO spikes
& quickly
returns to
low level

The actual
corrosion
event lasts
much longer!

23

NCSM cannot be substituted

by off-the-shelf ORP probes

Off-the-shelf ORP probes

Can become inaccurate (polarized) over
time
Are less sensitive
Can give the wrong indication of what is
happening at T and P
Require cooling the water sample
Changes water chemistry
Lag time reduces responsiveness
24

NCSM 200-1000x more

sensitive than conventional
ORP probes
0

-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

Same event at EO - NCSM

responds to corrosion
products, RT ORP does not
0

-200

-100

-300

-200

-400

-300

-500

-400

-600

-500

-700

-600

Time (hrs)
26

RT ORP (mV)

NCSM (mV)

-100

ORP mV

NCSM responds to stresses in

correct magnitude & direction
ORP variation with CHZ additions 250F
RT ORP
NCSM
0
RT ORP probes can
-100
miss some macro
-200
changes
-300
RT ORP may
-400
respond the wrong
way to the stress
-500
-600
A
B
C
D
E
A B C: Increase CHZ
A= 30 D:
Increase+ 145ppb
CHZO2;
and
E
ppm ELIMIN-OX;
250FDO
D E: Same DO; Increase CHZ even more
27

Conventional scavenger
feed methods are inferior to
NCSM
Constant fixed feed
Setpoint based on historical/grab samples
Misses dynamic stresses

Feed slaved to steam load

Appeals to one stress
May or may not be indicative of corrosion stress

Feed based off inert tracer

Improves control a degree
Confirms product in system
May or may not be indicative of corrosion stress
28

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

Boiler Best Practices

Scavenger feed
point locations
29

Contents

What is Corrosion Stress Control?

Why Corrosion Stress Control?
How to Make the Paradigm Shift
Practical considerations

30

NCSM is robust to withstand

operating temp & pressure
The NCSM system design limit 2000psi &
500F (special considerations above
2000psi)
Typical installation point after main FW
pump (pressure side)
System design for non-hazardous areas
(special considerations for Refineries)
Closely follow manual procedures-safety
31

A tour of the NCSM cell &

electrodes
Disassembled ORP Cell

ORP Cell Internal Configuration

Platinum (ORP) and

RTD Electrodes

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

NCSM sample point is

selected to capture & react
to stressors
Typically pressure side of FW pump
Locate probe close as possible to the
actual sample take-off point; <20ft
Insulate well from tap to probe &
beyond (see manual)
Flow rate 200-500 ml/min
Tubing OD

33

Contents

What is REDOX Stress Control?

Why REDOX Stress Control?
Practical considerations
Early Experience in Ammonia Plant

34

Ammonia Plant Experience

Sample to
NCSM Probe

35

Ammonia Plant Experience

36

Ammonia Plant Experience

37

Ammonia Plant Experience

38

Ammonia Plant Experience

39

NCSM Detects what others cant,

Determines correct response &
Delivers real customer value!

Save energy & water

Potential to optimize cycles
Reduced transport of insulating corrosion
products to boiler

Increase boiler reliability & asset life

Reduced maintenance costs

Better use of labor
Reduced downtime/increased production
Diagnose improvement project needs

Communicate results via 3D TRASAR Web

40

Questions?

41

Thank You!

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