Electrochemical Monitoring for Process

Optimization
Dr. Russell D. Kane – iCorrosion LLC
Houston, Texas
Organization
 Background
 Conventional corrosion control approaches
 What new approaches does electrochemical (echem)
corrosion monitoring bring for controlling corrosion and
process improvement?
 Proven Applications
 Amine gas processing
 Cooling water
 Black & white liquor
 Developing Areas
 Issues and Potential Problem Areas
 Summary
Background
What the Chemical Industry Wants
to Know About Corrosion…
Process
Design: Optimization:
Which is the most How can I better
efficient metal for operate my process
my application?
to maximize
production but
control corrosion?

Troubleshooting:
Why did is Asset
material fail by Management:
pitting corrosion? What will be the
remaining asset life
at run rate X ?

Bottom Line:
How do I know my
What solutions should I recommendations are
recommend to keep the plant working?
operating?
 “Corrosion Control 101”
 Methods of Corrosion Control
 Selection of materials

 Chemical treatment

 Cathodic/Anodic protection

 Coatings

What about a new paradigm? Include:

 Better Process Control

 However, a New Paradigm
Requires a Different Approach
 Need to view corrosion as a “real-time” variable
 In minutes, hours & days

 Not weeks, months & years

 Then, correlate corrosion with operations and specific

process conditions; develop automated processes that
prevent, minimize or repair corrosion damage.
Offline to Real-time Corrosion
How Can Corrosion Technology be Applied?
Monitoring
See only cumulative damage See only long term changes See periods of max. corrosion

Corrosion Rate

Corrosion Rate
M etal Loss


  
 

Date/Time Date/Time Date/Time

Off-line Online Online, Real-Time

Weight Loss Periodic UT Super ER SuperLPR technology
Advanced
Coupon • multiple technique
Off-line ER On-line ER Conventional LPR Electrochemical
electrochemical monitoring
Visual Inspection Monitoring
(New data every 7 minutes)
UT inspection (Data in minutes and differentiate
pitting from general corrosion)
Time
TimeFrame
Frame- -months Time
months TimeFrame
Frame––days/weeks
days/weeks Time
Mostly
Mostlymanual
manualtechniques:
techniques: Time
Timeframe
framestill
stilltoo
toolong
long
TimeFrame
Frame- -minutes
minutes
Only
Time
Timeframe
frametoo
toolong
long for process correlation;
for process correlation; Onlytechnology
technologyconsistent
consistent
with
for process correlation;
for process correlation; Good
Goodfor
forcumulative
cumulativedamage
damage withdirect-to-DCS
direct-to-DCSfor
forprocess
process
Good correlation & optimization
Goodfor
forcumulative
cumulativedamage
damage correlation & optimization

Timing

MONTHS DAYS MINUTES

 Online Corrosion Information
Changes the Game
 This new approach is also consistent with CPI corrosion control needs:
 Faster, accurate and requires less manual labor.
 Provides integration with plant automation systems.
 Distributes important information and promotes better decision making,
increases work efficiency and aides documentation & follow-up, enabling:

Identify Correlate Optimize Closed-loop

Critical Events to Process to Corrosion
Corrosion process reduce mitigation
Events changes Corrosion Solutions

Update Automate
inspection & Instructions,
maintenance follow-up
Planning Reports & KPIs
 New Capabilities of Advanced
Electrochemical Monitoring
 Corrosion Rate
 Technique: Linear Polarization Resistance Wireless Antenna

 Prime variable for control of general corrosion activity in system. Real-

time measurements in minutes. IS Self-powered
Transmitter
 B Value Housing
 Technique: Harmonic Distortion Analysis
 Correction factor (often assumed to be a constant) that is actually
determined by the mechanism and kinetics of the corrosion process;
used to increase accuracy of LPR corrosion rate.
 Pitting Factor (PF)
 Technique: Electrochemical Noise
 Measure of the stability of the corrosion process (defined as standard Extended
Cable
deviation of the corrosion current vs. corrosion current) (6-12 ft)
 Corrosion Mechanism Indication (CMI) Access Fitting &
 Technique: Low frequency impedance measurement Electrode (Sensor)

 Correlates with film formation/destruction and surface adsorption

(inhibition) processes Direct to DCS
 Measurement time Corrosion
 Variable Monitoring
Proven & Developing Applications
of Electrochemical Monitoring
 Cooling Water

Corrosion
rate

 Online monitoring of water treatment resulted in reduced corrosion rate /

pitting and 85% reduction in copper dissolution rate of HX system. Most
importantly, the corrosion control was implemented online without
changing other critical plant variables.
Overview of Applications: Gas
Processing - Amine Unit
TREATED GAS
Corrosion Problem Areas

LEAN AMINE

C
O
ACID
N
FILTERS GASES
T
A
ACCU
C
M.
T
O S
R
T
A
Lean To R
Rich
B I
Amine
S P
Heat Exch.
O
R
P
B E Amine
SOUR GAS E R Reboiler
FEED R

RICH AMINE
* Highlighted areas can
be monitored by
Amine
Make-up electrochemical
techniques.
Amine Process Upset vs.
Real-Time Corrosion Rate
Spike in
differential  Real-time corrosion rate
pressure across (black line) during an upset
the regenerator
event.
 Upset was related to specific
events: ΔP and rapid change
in stream rates to reboiler.
 Corrosion rate changed from
0.15 mm/yr to 1.25 mm/yr
 Corrosion rate remained high
even after regenerator
regained some stability.
 Loss of protective corrosion
Corrosion rate films from period of local
turbulence.
 Lesson: Corrosion was not an
“always on” process, but
correlated with process
conditions and could be
controlled.
 Pulp & Paper White Water:
Pitting vs. Neutralizer Control
 Pitting Factor from
electrochemical monitoring
indicated episodes of pitting
in plant white water system.
 Further examinations showed
the key role of white water
neutralizer selection in
determining its potential for
localized corrosion.
 Monitoring usage of different
neutralizers clearly shows
importance of properly

pH & Neutralizer
selected dosage rate and
type of neutralizer.
 Switch to new neutralizer
(marked as B) resulted in a
significant reduction in pitting
tendency.
 Successful and Developing Applications
Critical catalyst feed rate
 Impact of water upset in HC
process environment (Rohm &
Haas and BASF)
 Corrosion in multiphase
(oil/gas/brine) environment
(USDOT field pipeline study).
New relationship  Refinery ADU, VDU & FCCU
with neutralizer feed rate systems (West Pacific Refinery)
 Amine gas processing (Shell
Canada)
 Pulp & paper plant white water
(SCA Ortvikens)
Relationship with
 Biodegradation of VOCs using
Inorganic feed rates trickle-bed bioreactor (Plant
Demonstration Project)
 H2S-containing environments
(Extensive Lab Trials / Canadian
Pipeline)
Present Experience-based Limits
for Echem Monitoring
 Need an electrically conductive environment; electrodes must be wetted
 > 100 µS - Use of standard finger-electrode or flush-mounting probes
 10-100 µS - Requires larger, more closely spaced electrodes
 <10 µS – Requires use of a special low conductivity probe

 High H2S content environments may lead to formation of a

conductive iron sulfide film on electrodes
 In severe cases, can lead to disruption of data
 Use of measured B value improves corrosion rate accuracy
 B value and CMI indicate interference of conductive films (indication to
operator to clean electrodes).

 Hydrocarbon environments can prevent accurate measurements

 Need separate aqueous phase or condensation on probe
 May require proper selection of probe type (sensor configuration)
 Turbulence to keep HC and aqueous phases mixed
 Need to know phase and flow behavior of water in system
 Minimize Problems for Echem
Monitoring
HC Product
HC Product Pipeline
Pipeline Profile
Profile
 Need to understand
(general and local)
process conditions:
 Phase behavior of process
constituents (esp. liquid
water & dew point)
 Tool: thermodynamic/ionic
modeling
 Flow dynamics (turbulent /
stratified flow)
 Tool: Flow modeling / CFD
 Anticipated local corrosivity
 Tool: Corrosion modeling
 Determine probe locations System can be modeled by Predict ®-Pipe and/or Predict to
indentify locations of water drop-out and hold-up in system.
and type for max. success The highlighted locations can be electrochemically monitored
for corrosion in the local aqueous phase.
 Echem Monitoring Benefits & Value
Delivered: Chemical Industry
Decrease asset replacement, extend Mitigate production losses; increase
asset service life throughput

Proactively identify susceptibility to Identify critical & risk areas; inspect

localized corrosion where most needed

Optimize materials-friendly processes Define compatible process & materials

envelope

Prevent emissions and hazardous Mitigate process and product

effluents contamination

Opportunity Value Estimates

Reduce Lost Production >$300,000 per leak
Improved Material Selection up to $500,000 per unit
Summary
 Electrochemical corrosion monitoring is a real-time and
accurate method to assess plant corrosion.
 Can be integrated with plant process control; allows process
optimization for reduced corrosion.
 Works most effectively in conductive media or subject to upsets
involving conductive media (e.g. water)
 Modern electrochemical monitoring is compatible with
modern plant control systems
 The best transmitter will not work if the wrong probe type or
monitoring location is used
 To be successful, need to understand phase behavior, fluid
dynamics and variability of corrosion in the system.
 Process, ionic and flow modeling are of great value.
 Need to understand the probe type required for accurate system
measurements.
 Emphasize:
 Probe location – Probe location – Probe location
 Probe type – Probe type – Probe type
Acknowledgement
 Honeywell Corrosion Solutions
 Dawn Eden
 Juan Hernandez
 Phil Ng
 Slawomir Kus
 David Eden