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