Corrosion Prediction in Industrial
Systems
Quality Moment
SEEMS LEGIT
Corrosion prediction
Why predict corrosion?
The corrosion challenge
Corrosion basics
Types of prediction and their usage
History and families of CO2 corrosion models
The deWaard equations
Other common methods and software
Strengths and weaknesses
Pointers for success
Corrosion modelling through the design process
Conclusions
The Purpose of
Corrosion Prediction
Why predict corrosion?
Its dangerous.
200 fatalities in US from
pipeline corrosion failures
1989-98 (US GAO 2000)
Gas pipeline corrosion failure in San Bruno, CA 2010.
Four fatalities.
Why predict corrosion?
Its expensive:
Australia: A$13bn p.a. (CSIRO, 2009)
USA: US$279bn p.a. (US FHA, 2001)
Developed world: 3-5% of GDP
Developing world: 10-20% of GDP
66% of pipeline failures (AEUB, 1998)
(most of it preventable or manageable)
Why predict corrosion?
Corrosion prediction determines the design
Design life
Materials selection / corrosion allowances
Corrosion monitoring and inspection
Chemical treatments, coatings, linings
Repair and replacement
Determines the ultimate risk
The
Corrosion
Challenge
Photo: Dbert
Photo: Dbert
One material
One design environment
Many corrosion rates
Photo: Dbert
The corrosion challenge
Corrosion is a chaos mathematics problem.
Very small changes in conditions can lead to very large changes in outcome
Well below the detail level of design data
More akin to predicting the weather than conventional engineering
analysis
The corrosion challenge
Even under laboratory controlled conditions, corrosion rates show huge
variability
Out in the real world
Production streams vary
Process conditions and compositions are uncertain
Particularly in raw material production such as oil and gas, mining
Reservoir predictions, changes over time
even in many manufacturing processes
e.g. side reactions, variable feedstock, process upsets
Contaminants
Production data is uncertain
We dont operate to design conditions
External conditions are uncertain
Weather, seasonal variation, coatings
The corrosion challenge
Our aim:
To predict a reasonable conservative case
To show sensitivity to variation in conditions
To create a start point for corrosion design
Not:
To predict corrosion rates to 3 decimal places.
this is not a precision subject
Be wary of anyone who claims otherwise.
Corrosion
Basics
Photo: Axolotl Pty.
Corrosion basics
Corrosion occurs when metal is dissolved in an aqueous solution.
Slight differences in the crystal structure of metal form +ve and
ve sites.
Metal dissolves at the -ve site (anode) to release electrons
Water is split at the +ve site (cathode) to absorb electrons
The specific reactions vary according to the corrosion mechanism
M(s) -> Mn+(aq) + ne-
H2O + O2
-ve Anode
2OH+ve Cathode
ne-
Corrosion basics
Simple CO2 Corrosion
H2 (gas)
CO2(g)
Gas
CO2(g) + H2O HCO3-(aq)+ H+(aq)
Fe Fe2+(aq) + 2e-
2Fe2+(aq) + HCO3- FeCO3+ H+
Water
2H+ + 2e- H2
(gas)
Fe
2eSteel
A network of chemical reactions
Chemical Reactions
Fe Fe2+(aq) + 2e
CO2(g) + H2O HCO3-+ H+
2H+ + 2e- H2
Fe2+(aq) + HCO3- FeCO3+ H+
This is the simplest version.
Several different Iron Oxide / Iron Hydroxide / Iron Carbonate forms
Dozens of forms of Iron Sulphide
Other reactions between iron and contaminants
A network of physical mechanisms
Diffusion Processes
CO2 from gas to liquid
HCO3 from liquid to steel through the corrosion / debris layer
H2 from liquid to gas
Physical conditions
Flow and turbulence
Heat transfer and temperature
Contaminants
H2S, Organic Acids
A myriad of other competing reactions
All naturally occurring processes
Not engineered reactions
Little or no control
Corrosion Engineering is Backwards Chemical Engineering
Chemical Engineering
Trying to maximise a chosen reaction and minimise side reactions
Corrosion Engineering
Trying to predict or control a naturally occurring phenomena
Fighting the 3rd law of thermodynamics
Uncertainty is a fact of life. It is inherent in the corrosion process.
Predictive
Approaches
Three main types of predictive approaches
Corrosion databases
lists of materials, conditions, corrosion rates
Laboratory tests
Recreate the environment, insert a sample, measure the result
Theoretical or empirical models
Calculated predictions based upon process conditions
Corrosion databases
Pure, historical empirical data
Material + conditions corrosion rate
May be laboratory or inspection / experience based
Used for
Materials that are not carbon steel
Environments that are not:
Oil, gas
Water (seawater, boilers, produced water)
Unusual corrosives:
Other than CO2, H2S, oxygen, seawater
Basis of corrosion engineering for many industries
Mining and mining processing
Petrochemical and Pharmaceutical
Corrosion data sources
Corrosion societies
National Association of Corrosion Engineers (NACE Corrosion Data Survey)
European Federation of Corrosion (EFC)
Australasian Corrosion Association (ACA)
Academic papers and research
Industry bodies
Design Standards
DNV, ASME, API, Standards Australia, NORSOK
Corporate research units and experience
What have other plants done / experienced?
Government research units
CSIRO, US Navy, NASA, UK HSE, US DOT
Vendors and trade associations
Steel mills, ASSDA, NiDi (Caution! Vested interests!)
Corrosion databases
Advantages
Simple
Cheap and fast
Cover materials and conditions which do not have analytical models available
Corrosion databases
Disadvantages
Low resolution
Broad classes of material and conditions
Usually not quite the conditions you want
No knowledge of actual test / operating conditions
Flowrates, Contaminants, Operating methods
Little traceability
No idea of the accuracy / repeatability / sensitivity
Use with caution (last resort)
Corrosion databases
Pointers for success
Find out as much as you can about the test conditions
Read the paper, talk to the researchers
Examine track record: do they cover your industry or process?
Look for independent validation or a second source of data
Watch for cross quoting
Identical results => comes from the same experiment
Take only data close to your example
Worse conditions may not be worse.
More / higher is not always more corrosive
Consult the theory and chemistry
Use a large safety factor
Build your own
Inspection histories, own database of material performance
Share with peers / industry societies
Laboratory Studies
Photo: Asia Scientific Apparatus
Laboratory studies
Recreate the process conditions in the laboratory
Measure the resultant corrosion
Options
In house laboratories
Large operators only
Private / state run laboratories
CSIRO, IFE (Norway), TWI (UK)
Universities
Curtin, Ohio, Tulsa, Imperial College London, Heriot Watt Edinburgh
Chemical vendors
Caution! Vested interests!
Laboratory studies
Three types of lab study
Beaker (atmospheric batch test)
Simple, quickndirty screening
Limited accuracy
Autoclave (pressurised batch test)
Control the atmosphere and conditions
No flow
Can use rotation or jet impingement to simulate flow
Good accuracy if used properly
Appropriate corrosion types and conditions
Flow loop (pressurised, circulating test)
By far the most representative
Also the most time consuming and expensive
Typical Flow Loop
Image: Institutt For Energiteknikk (IFE) Norway
Laboratory studies
Advantages
Can precisely replicate your exact process conditions
Can control and tailor the test programme
Laboratory studies
Disadvantages
Expensive
Slow (months per test)
Small data set (unless in a JIP)
Still cannot cover every variable
Vendor labs can be biased
Best used for verification and validation of modelling / database
predictions
Laboratory studies
Pointers for success
Choose a lab with industry ties or experience in your industry
Use a progressive programme
Start with beaker tests for screening
Autoclave to determine final candidates
Flow loop if required for final validation
Do as many sensitivity variations as you can
Run the tests for as long as possible
Use real process fluids where possible
Use a private or in-house lab where possible
Discuss tests and process requirements with the lab operator
Buy in to JIPs early to share costs and data
Speculative membership testing takes a long time
Too late to start when you already have a problem or project
Corrosion Models
Photo: Bill Edwards
Corrosion models
Main varieties
CO2 corrosion (oil and gas)
With amendments for H2S, chlorides, organic acids
Seawater (marine, power generation, oil and gas)
Steam / boiler water (power generation)
Dissolved oxygen (power generation, petrochemical, oil and gas)
Other, specialised specific correlations
The deWaard family tree of
CO2 Corrosion Models
Shell
HYDROCOR
BP
CASSANDRA
de Waard , Lotz,
Milliams 1991
deWaard, Lotz, Dugstad 1995
Total / Elf
CORPLUS
Electronic Corrosion
Engineer (ECE)
Many others
de Waard and
Milliams 1975
Nyborg Olsen and Halvorsen
IFE Norway
University of Tulsa
SPPS CO2
NORSOK M506
Gusta et.al.
Nyborg et. al..
University of Ohio
MULTICORP
FE KSE
Nyborg and Dugstad
IFE Vapour Corrosion Model
Gusta et.al.
University of Ohio TOPCORP
deWaard Milliams 1975
Carbonic Acid Corrosion of Steel, Corrosion Vol. 31, No. 5, 1975 (NACE)
First usable general corrosion model for CO2 in oil and gas systems.
Modelled the effects of
Partial pressure of CO2
pH
Temperature
Surface condition
deWaard Milliams Nomograph
deWaard Milliams 1975
Simple, usable
Based on real design parameters
Generally adequately conservative for most oil and gas liquid systems
Limitations and weaknesses
Sour systems, organic acids
Vapour / condensing phase (TOL) systems
Many tweaks and fudge factors published to extend the usage
deWaard, Lotz, Milliams 1991
Predictive Model for CO2 Corrosion Engineering in Wet Natural Gas Pipelines,
Paper 577, Corrosion 1991, National Association of Corrosion Engineers
Probably the most widely used and practical model available.
Improvements to 1975 model:
Non ideal gas behaviour
Corrosion product correction
Measured pH Correction
Condensation rate / saturation correction
Effect of Oil, Glycol
Effect of corrosion inhibitors
deWaard, Lotz, Milliams 1991
The deWaard Lotz, Milliams Equation
Vcorr
= Base corrosion rate (mm/yr)
Correction factors (0 1)
Fscale = Corrosion product correction
FpH
Fcond
1710
0.68 log( f CO2 )
T
T = Temperature (K)
fCO2 = Fugacity of CO2 (bara)
log(Vcor ) 5.8
= pH correction
pHsat = Saturation pH
pHact = Actual pH
= Condensation correction (TOLC)
log( Fscale )
2400
0.6 log( f CO2 ) 6.7
T
log( FpH ) 0.32( pH sat pH act )
pH sat 3.71 0.00417(T 273) 0.5 log( f CO2 )
C
Fcond
0.25
C = Condensation Rate (g/m2s)
Fgly 1.6(log(W ) 2)
Fgly
= Glycol correction
W = Water content of Glycol Mixture (weight%)
deWaard, Lotz, Milliams 1991
Strengths
Usable
Easy to understand
Based on real empirical data
Uses real design parameters
Easy to put into a spreadsheet
Generally conservative in sweet, liquid systems
deWaard, Lotz, Milliams 1991
Weaknesses
Very poor at vapour phase corrosion
Too simplistic, linear
Does not cover important corrosion modifiers
H2S, Organic Acids, Flow
Not always conservative
Powerful but blunt tool
Often abused for purposes beyond intent
deWaard, Lotz, Milliams 1991
Usage
Liquid phase only
Sweet (no H2S, low organic acids) only
Quick and dirty estimate
Order of magnitude results
Validate or extrapolate other methods
E.g. lab results
Use with caution
Beware of multi-digit accuracy predictions
Be cautious, use uncertainty factors
Validate by laboratory tests / similar operations
deWaard, Lotz, Dugstad 1995
Influence of Liquid Flow Velocity on CO2 Corrosion: a semi empirical model, Paper
128, Corrosion 1995, National Association of Corrosion Engineers
Evolution of the 1991model
to include the effect of liquid flow
Based upon extensive empirical data
combined with theoretical
mechanisms
deWaard, Lotz, Dugstad 1995
More accurate and realistic than 1991 model
Inclusion of flow and transport of corrosives
Usually conservative
Somewhat less usable than 1991
Flow parameters more complex than those often readily available to designers
Usually require a simulation or flow assurance study
Basis of many commercial corrosion prediction packages
Hydrocor
Electronic Corrosion Engineer
BP Cassandra (discontinued)
OLGA Corrosion Module (CORR1 Liquid Model)
and many more
deWaard, Lotz, Dugstad 1995
Weaknesses
Still unable to model corrosion in the vapour phase with any accuracy
Simplistic multiplier
No account for H2S, organic acids
Limitations of applicability not clearly defined
Often abused beyond the scope
Limitations of accuracy not discussed
Order of magnitude estimate only
Common to see reports quoting thousandths of mm per year
Seductively simple
Easy for inexperienced people to use
Needs an experienced eye to interpret the results into a reliable design
NORSOK M506
Developed by Statoil, IFE and Norsk Hydro JIP
Adopted by Norwegian Standards (NORSOK)
Similar scope to deWaard 1995
Basic liquid phase CO2 corrosion model
Includes flow effects
Based on more readily available parameters
Simple software freely available from NORSOK
NORSOK M506
Strengths
Usable
Based upon empirical data
reasonably accurate / conservative
Uses real design parameters
Software freely available
Contains clear limitations on method applicability
Temperature, pressure, CO2 maxima
NORSOK M506
Weaknesses
Same as deWaard 1995
No H2S or organic acids
Not applicable to vapour phase
Usage
Liquid phase, sweet (no H2S)
Mild conditions (no high temperature or pressure)
Order of magnitude estimates
Verification / sense check
Hydrocor
Proprietary software from Shell Global Solutions
Until recently, only available within Shell associated operators
Or used by SGS on contract
Advanced development of deWaard family of models
Hydrocor
Strengths
Comprehensive pipeline model
Liquid and vapour phase
Internal heat transfer model and for vapour phase
Accounts for H2S and organic acids
Simplified models
Comprehensive range of outputs
Automates production profiles and sensitivity
New versions very usable
Hydrocor
Weaknesses
Proprietary
Expensive, limited availability outside Shell
Simplified flow regime model
Often better to turn off
Black box method detail not available
Questionable reliability in vapour phase
Several examples of non-conservative design causing failure
Multicorp
Mechanistic liquid phase model developed by University of Ohio JIP
Only available to members
Anyone can join
For a price
Multicorp
Strengths
Comprehensive mechanistic model
Attempts to model most of the processes in the corrosion reaction
Physical and chemical
Incorporates H2S, organic acids, flow effects
JIP membership allows influence of test regime / model basis
Open method no black box
Multicorp
Weaknesses
Requires JIP membership (medium expensive)
Can be accessed via consultants like WGIM
Academic model less practical / usable than Hydrocor etc.
Less usable software (large spreadsheet)
Liquid only
Topcorp available for vapour
Work in progress
Topcorp
Mechanistic vapour phase model developed by University of Ohio JIP
Requires separate JIP membership to use software
Open to all for a price
Can commission studies from Praecipium
University of Ohio consulting arm
Topcorp
Strengths
Probably the most sophisticated and comprehensive vapour phase corrosion
model available at this time
Open availability and method
Topcorp
Weaknesses
Expensive
Not very user friendly
Work in progress
Does not have a long track record
Method weaknesses not known
Practical Corrosion Prediction
Photo: Axolotl Pty.
Practical corrosion prediction in oil and gas projects
Technique and resolution of the predicitons develops as a design matures
Concept Select
FEED
Detailed Design
Concept Select
Initial Screening
Inlet and outlet conditions only
Liquid only (simple vapour estimate)
Simplified parameters / estimates
Detail not available yet
Feasibility of carbon steel
Requirement for inhibitor / corrosion resistant materials
Methods
Simple deWaard 1991, 1995 or NORSOK spreadsheet
Corrosion Database
Feasibility laboratory tests (beaker)
Concept Select
FEED
First detailed model
Liquid and vapour modelling
Cooling condensation vapour modelling only
Initial Laboratory studies (autoclave)
Detailed feasibility check
Identify further studies (e.g. corrosion inhibitor testing)
Justify more detailed tests
Longitudinal temperature profile (e.g. pipeline)
Single production condition or simplified production profile
Simple sensitivity assessments
Material selection
Carbon steel corrosion allowance
Identify areas requiring corrosion resistant alloys
Identify candidate corrosion resistant alloys
FEED
Single OLGA or Hydrocor profile
Detailed Design
Full detail corrosion model
Mature flow assurance simulation
Multiple temperature profiles (changes along the process)
Detailed production profile (process changes over time)
Full detail liquid and vapour modelling
Cooling condensation corrosion
Hungry water
Mixing condensation
Detailed sensitivity assessments
Aggregate through life corrosion model
3-400 individual models
Detailed, extensive laboratory testing
Flow loop to validate corrosion modelling
Selection of corrosion inhibitor or chemical treatment
Detailed Design
Multiple OLGA or Hydrocor Profiles
Prediction progression as the design matures
Greater detail
More confidence
Less uncertainty
Less conservatism
The art of
Corrosion Engineering
Photo: Colin Winterbottom Elegant Corrosion
The art of corrosion engineering
You will have noticed
Fundamentals of corrosion processes are unstable
Small changes in conditions can mean big changes in outcome
Data we use is inaccurate
Models all have accuracy and applicability caveats
The art of corrosion engineering
deWaard / Hydrocor
Conservative
Non-Conservative
Nesic and Vrhovac, A neural network model for CO2
Corrosion of Carbon Steel, Journal of Corrosion Science and
Engineering, Vol 1. Paper 6, March 1999
IFE / NORSOK
Conservative
Non-Conservative
The art of corrosion engineering
Experience in the vagaries of corrosion behaviour is ESSENTIAL to
interpret the results of a corrosion prediction into a safe and reliable
design.
The model result is only the beginning
The most important document in your materials and corrosion design is
the CV of your corrosion engineer.
The only true wisdom is knowing that you know nothing - Socrates
Thank you for
your attention.
Photo: Colin Winterbottom Elegant Corrosion