(Topics in Chemical Engineering) Lanny D. Schmidt - The Engineering of Chemical Reactions (2004, Oxford University Press, USA)

Corrosion & Integrity Management
October 30, 2013

Agenda
 HSE
 Corrosion Mechanisms
 Corrosion Mechanism Identification
 Corrosion Field Assessments
 Multi-Chem Product Applications
 Corrosion Monitoring
 Microcor® ER Probe
 Questions?
© 2012 HALLIBURTON. ALL RIGHTS RESERVED. 2

HSE
Safety Moment
 Daytime Running Lights

– Reduced daytime crashes between 6-11%
– Reduced left-hand turn crashes by 34%-37%
– Reduced crashes involving pedestrians by 28%
– When crashes did occur, the severity of the crashes was lower on
vehicles with daytime running lights (slower speeds)
– When travelling in US, remember that vehicles don’t have daytime
lights. Turn your lights on manually!
 Hazard
– You have no taillights when using running lights when used at night
– Repair shops shut off automatic lights when working on vehicle, be
sure to turn them back on if the shut your off

Corrosion Mechanisms
Corrosion Basics

Corrosion Basics
Definition:
(From: National Association of
Corrosion Engineers, NACE)
Corrosion is the deterioration of a

substance, (usually a metal) of its
properties because of a reaction with
its environment.

Electrochemistry
Electrochemistry deals with relation

of electricity to chemical changes
and interconversion of chemical and
electrical energy.

What is Required For a Corrosion Cell
Anode Cathode
Metallic
Electrolyte
conductor

Corrosion Cell

Do we have corrosive agents in
oil and gas production?

Liquid Water
No Water  No Corrosion
Example:
Alaska North Slope
All gas produced is
dehydrated and reinjected
to pressure the reservoir.
Many millions of cubic feet
of gas are injected each day
for 15 + years.
No corrosion problems have
occurred in the injection
system.
Water In A Producing Well
Where there is liquid water,

corrosion is likely to occur.
In general, experience tells us,

when the water cut in a crude oil is
> 30 %, expect corrosion in steel.

Water In Accumulation in a Pipeline

Corrosion Discussion
 There are a whole host of conditions in a production and
gathering system that can contribute to corrosion
 Many of these conditions will interact with one another to
aggravate corrosion rates and all must be taken into
consideration when developing a corrosion control program
– Gas Composition
– Water Composition
– Bacteria Presence
– Operating Conditions
– Flow Regime
– Pigging Practices
– Oxygen Content
– Methanol Consumption

Gas Composition
 Acid gas components in the produced gas contribute
significantly to corrosion as their presence in water lowers
the pH making the water more acidic. These include:
– carbon dioxide (CO2)
– hydrogen sulfide (H2S)
 Of interest are their partial pressures (mole % in gas
analysis multiplied by system pressure) and temperature
within the system, as these both factor into how much of the
gases are dissolved in produced water and thus can be
correlated to potential corrosion rates.
 Higher temperatures and higher partial pressures of acid
gases will greatly increase potential corrosion rates.

Water Composition
 Several components of a water analysis must be considered in
assessing corrosion potential
– Total dissolved solids (TDS) content indicates the ability of the water to
carry electrical current associated with corrosion reactions on the steel
surface – higher TDS values result in greater potential corrosion rates.
Chloride content is sometimes used interchangeably with TDS when
assessing corrosion affects
– Chloride ion levels have been shown to be related to pitting attacks through
the creation of concentration cells. The pitting potential increases as the
chloride ion count increases. Although waters with low levels of chlorides
(condensed waters) can become acidic and corrosive when mixed with CO2
– pH of the water affects solubility of iron, CO2 concentration, and chemical
reaction rates and can influence corrosion rates significantly
– Carbonate/bicarbonate levels work in conjunction with pH and CO2
concentration, since they affect buffering and pH associated with pressure
changes in the system
– Organic acid content (e.g. formic acid, acetic acid, propionic acid) in a
sweet gathering system can significantly increase corrosion rates. This
effect does not occur in a sour system

Bacteria Presence
 Microbiologically influenced corrosion is the degradation of
materials, as a result of the metabolic by-products of
microorganisms, such as bacteria
 Free-floating (planktonic) bacteria attach themselves to
surfaces, proliferate and grow into a biofilm (sessile)
population
 Planktonic (sessile) bacteria are fairly benign until they
attach themselves and develop into a biofilm
 Two main types:
– Sulfate reducing bacteria (SRB)
– Acid-producing bacteria (APB)

Operating Conditions - Pressure
 Henry’s Law
In a two phase system, liquid and

gas, as the pressure increases
the amount of gas dissolved in
the liquid increases.
(Soda bottle example)

Operating Conditions - Temperature
Rule of Thumb
Chemical reaction rates double with
10ºC rise in temperature.
Metal in presence of corrosive gas in
open container CR ↓ as temp ↑ (solubility
of a gas decreases as temp increases).
In a closed system with corrosive gas
CR↑ as temp ↑.

Flow Regime
 Information on pipeline diameter, operating pressure
and temperature, and gas rate is used to determine the
superficial gas velocity. This allows us to characterize
the flow regime for each unique section of pipeline into
the following three general categories:
– Stratified Flow
– Annular/Slug Flow
– Mist Flow

Effect of Velocity on Corrosion
Duncan, Materials Performance, Vol. 19, No.7, 1980

Pigging Practices – Water/Solids Removal
 Stagnant liquids and solids will have an adverse impact on
pipeline corrosion
– Stagnant liquids allow concentration cells to develop anodic
areas on pipe walls and allow solids/sand to settle out
– Solids and sand can allow for under deposit corrosion (pitting)
to occur
 Sand (formation fines) can cause severe erosion at elbows,
valves, chokes, areas where changes in diameter occur
 In any gathering system, one of the best forms of internal
corrosion control is frequent pigging
– Keeping liquids moving, removing solids, removing
environments favorable for bacterial growth, and creating
clean surfaces for inhibitor films to establish themselves upon
will have a huge benefit from a corrosion control perspective

Oxygen Content
 Introduction of oxygen into a system usually occurs
through methanol consumption, but may also be a
result of the introduction of:
– Untreated surface water in an injection system
– Trucking
– Tanks without vapor recovery systems
– Leaks in wellhead packing at rod pumped wells
– A various number of other ways

Corrosion Rate - Oxygen in Open/Closed Systems
Speller, Corrosion Causes and Prevention, McGraw-Hill, 1951

Oxygen Content

Methanol Consumption
 Methanol can affect inhibitor films

 The high solubility of oxygen in methanol results in
the introduction of oxygen into the gathering
system
 Methanol can also destabilize protective iron
sulfide films

Corrosion Mechanism Identification
Types of Corrosion

Forms of Corrosion

Forms of Corrosion

General Corrosion
General Thinning of the Metal Surface

Localized Corrosion (pitting)
Localized
Attack
TI-CHE
UL
M
M
PRODUCTION CHEMICALS
A Division of
Multi-Chem Group, LLC

Forms of Corrosion

Crevice Corrosion

Galvanic Corrosion
Copper to Stainless Steel

Forms of Corrosion (environmental cracking)

Stress Corrosion
Stress Corrosion Cracking

Corrosion Fatigue in a Sucker Rod

Hydrogen Damage - Embrittlement

Hydrogen Damage - Blistering

Flow Induced Corrosion

Flow Induced Corrosion – Mesa Attack

Flow Induced Corrosion – Erosion (Sand/Solids)

CO2 Rule of Thumb (API 1958)
Mole % CO2 x total pressure = partial
pressure of CO2
Partial pressure CO2 >30 psi

Corrosive
Partial pressure CO2> 7 < 30 psi
Moderately Corrosive
Partial pressure CO2> 7 psi
Non-corrosive (except in the presence of
organic acids)

Corrosion Due to CO2 – Honeycomb Pattern
Honeycomb Pattern Honeycomb Pattern Honeycomb Pattern

on Flange on Choke Body

Corrosion Due to CO2 – Mesa Attack

Corrosion Due to CO2 – Wormhole Attack

Corrosion Due to CO2 – Wormhole Attack

Corrosion Due to CO2 – High Flow Rate

Corrosion Due to H2S

Corrosion Due to H2S

Oxygen Corrosion
Of the last three corrosion mechanisms…
CO2, H2S and O2…
O2 is by far the most

corrosive!!

Relative Corrosion Rates (H2S, CO2 & O2)
L. Jones, Corrosion and Water Technology,pg.15, OGCI,1992

Allowable O2 Levels
For pressure maintenance in a water flood:
O2 level should be
<10 ppb in water to prevent O2
attack

O2 Corrosion
Why the threads?

O2 Corrosion

Solubility of O2 in Water
ºC ppm
0 14.6
10 11.3
20 9.2
25 8.4
30 7.6
40 6.6
50 5.6

Microbial Induced Corrosion (MIC) – Biofilm
Formation
Extra cellular polymeric substances
(EPS) cause bacteria to stick to metal
surfaces.
Result:
Colonization of the surface to form
biofilms at the metal/solution
interface.

Microbial Induced Corrosion (MIC)
Biofilm Formation

Biofilms
The environment at the bio-film metal

interface is radically different in terms
of pH, dissolved O2, organic and
inorganic species than the bulk
medium.

Important Oil Field Bacteria
Acid producing bacteria (APB) –
metabolize complex hydrocarbons to
organic acids.
Sulfate-reducing bacteria (SRB) –

reduce sulfate to H2S.
Slime-forming bacteria – create sticky

masses which trap nutrients.
Microbial Induced Corrosion (MIC) – Stair Step Pit

Microbial Induced Corrosion (MIC) – Stair Step Pit

Microbial Induced Corrosion (MIC) – Bacteria
Monitoring
Bacteria Medium Indicator
APB Phenol red Red (neutral) to

yellow (acid)
SRB Postgate (API) Clear to black
Monitoring sulfate-reducing bacteria:
comparison of enumeration media
API Recommended Practice RP-38
See, NACE Recommended Practice, TMO 194-2004

Microbial Induced Corrosion (MIC) – Testing for
Bacteria

Planktonic Bacteria
Serial Dilution method
# Bottles with growth # Bacteria / mL
0 <1
1 1-10
2 10 - 100
3 100 - 1000
4 1000 - 10000
5 10000 - 100000
6 100000 - 1000000
Planktonic vs Sessile Bacteria
Planktonic (free swimming bacteria)
do not correlate with number of
bacteria on pipe walls (sessile
bacteria).
Sessile bacteria attached to pipe

walls are ones causing corrosion by
generating metabolic products:
Organic Acids, S—2 CO2

Planktonic Bacteria
Planktonic - free floating bacteria
Determine the number of bacteria

using bottle testing on the produced
fluids

Corrosion Field Assessment
Problem Solving and Support – Multi-Chem
Approach
1) Take the time to understand the system and risks
– Gather production data, pipeline pressures and

temperatures, and fluid analyses (gas, water)
– Culture for APB/SRB bacteria
– Use our in-house programs to calculate/determine
other information necessary to assess the system
• Flow regimes and velocities
• De Waard-Milliams corrosion rates
– Prepare a risk assessment

De Waard - Williams

Problem Solving and Support
2) Develop a Comprehensive Corrosion

Mitigation Strategy
– Batch and/or continuous inhibitor application

• Emulsion/foaming tendencies verified
• Work with client to optimize/coordinate
pigging and application schedules

Problem Solving and Support
3) Monitor Program and Optimize
– Corrosion inhibitor residuals

– Fe/Mn counts
– Review of coupon data
– ER probes available
– Attend integrity team meetings and be present
on location when doing inspections, etc.

Multi-Chem Product Applications
Corrosion Inhibitor Applications
Downhole
Flowlines
Pipelines
• Separators
Surface • Dehydration equipment
Equipment • Storage tanks

Corrosion Inhibitor Applications
 Batch Application – Annulus (Anillo)
 Batch Application – Tubing (Tubería)
 Continuous Application – Annulus (neat) (Sólo Anillo)
 Continuous Application – Annulus (via slip stream) (Anillo a través

de fujo de deslizamiento)
 Continuous Application – Annulus (capillary string) (Hilo capilar)
 Squeeze Application (Aplicación de compresión)

Batch Application

Continuous Application

Continuous Application – Slip Stream
Flow T
Flowline Check Valve
Production Flow
Chemical + Flush down

Annulus
Chemical Injection Side Stream Application

Continuous Application – Slip Stream
Flow T
Sample Valve
Flowline Check Valve
Side Stream
Flow Production Flow
Casing Gas
Check Valve
Chemical + Flush down

Annulus (Anillo)
Chemical Side Stream Application

Injection

Batch Application

Batch Application – Batch & Circulate
Pump batch of CI into annulus with

treating truck and close tubing valve
and circulate to build a good CI film
on the production tubing, then return
well to production.

Batch Application – Batch & Park
Pump large batch of CI into annulus

with treating truck, close tubing valve
and circulate to build a good CI film on
the production tubing.
Return well to production, leaving a

high concentration of CI in the
annulus, which feeds into the
produced fluids, as the volume in the
annulus rises and falls.

Continuous Application – Capillary String
Pump CI in small bore tubing ¼ in to

bottom of well.
Use a filter at the pump to prevent

plugging of injection line.

Continuous Application – Neat

Batch Application – Tubing Displacement

Batch Application – Tubing Displacement
Pump a tubing volume of the CI

mixture into the production tubing.
Use where well is completed with a

packer.

Batch Application – Squeeze
Pump a tubing volume plus one

day production of the CI mixture
into the production tubing.
Use where well is completed with a
packer.

Corrosion Monitoring
Monitoring Note – Please Remember
All monitoring techniques are like puzzle pieces
Alone they do not tell you much
When put together, the picture becomes more
clear
Therefore,
Monitoring tools should be used in a synergistic
approach such that one technique is augmented
by the strengths of another
This is very important when considering the
application of a corrosion monitoring program
Implement at least two forms of monitoring

Problem Solving and Support – Monitoring
3) Monitor Program and Optimize
– Corrosion inhibitor residuals
– Fe/Mn counts
– Review of coupon data
– CID tests
– ER probes available
– Attend integrity team meetings and be present
on location when doing dig-outs, inspections,
etc.

Corrosion Inhibitor Residuals
What
A measure of the corrosion inhibitor concentration in
the produced water (quaternary amine)
Why
Provides information regarding the migration of the
corrosion inhibitor through the gathering system
How
Used as a monitoring tool to establish trends in the
ability of the corrosion inhibitor to migrate with the produced
water through the gathering system and can also be used to
help optimize chemical treatment programs

LIMITATIONS OF CORROSION INHIBITOR
RESIDUALS
Where the corrosion is occurring and what

is causing it
The type of corrosion that is occurring

(pitting or general)
Production slugs
water hold-up higher concentration of inhibitor
residual
higher/lower residuals than is really happening
can’t account for any inhibitor that sticks to steel
surfaces and sands/solids/debris

LIMITATIONS OF CORROSION INHIBITOR

RESIDUALS
Trends require numerous data points to be

meaningful
Can provide information of the migration of the

corrosion inhibitor throughout a gathering system,
but residual value can’t be tied to successful
corrosion mitigation
Residuals themselves are not predictive of

performance

Iron and Manganese Counts
What
A measure of the dissolved iron (Fe) and
manganese (Mn) concentration in the produced water
Why
Provides qualitative information regarding the
corrosivity of the system
How
Used as a monitoring tool to establish trends in
the corrosivity of the system and to help optimize
chemical treatment programs

LIMITATIONS OF IRON AND MANGANESE COUNTS
Where the corrosion is occurring and what is causing

it
The type of corrosion that is occurring (pitting or

general)
Doesn’t provide accurate system corrosion rates

assumes uniform/general corrosion
can’t differentiate from naturally produced iron
from reservoirs with high content of iron-based
minerals, primarily siderite

LIMITATIONS OF IRON AND MANGANESE COUNTS
Trends require numerous data points to be

meaningful
Naturally occurring iron in producing formations can

skew results (there are some, but not very may
formations that produce manganese)
Manganese is usually only found in the making of

steel. Therefore, the manganese results in most
cases are more accurate

SAMPLING TECHNIQUE IS CRITICAL!!
Equipment needed:
glass or plastic bottle with cap
nitric acid
tape
pipette
paint pen

SAMPLING TECHNIQUE IS
CRITICAL!!
Add 3 drops of HNO3 to sample bottle
Flush stagnant water and deposits
from tubing/valves
Collect sample in controlled manner,
minimizing oxygen and hydrocarbon
contamination
Always attempt to collect samples
from moving fluid
Tape off cap and label bottles (sample
point, date)
Send off for ICP analysis ASAP
Sampling frequency, why does it matter?
Ferric's Folly 3 - Wellhead Sample

180
Iron Concentration (ppm)
160
140
120
100
80
60
40
20
0
Fe ppm Batch Treatment

Is there a good or bad Fe and Mn count?

This depends on whether or not there is naturally occurring iron or manganese
present in the producing formation. If so, the results you get back will be skewed.
Higher results do usually indicate corrosion is taking place somewhere in the
system.
Are Mn counts more accurate than Fe counts in the
presence of H2S?
Not necessarily, iron will react with the sulfide ion to create iron sulfides (black
powder). Manganese will also react with sulfide ion, just not as readily as the iron
and therefore results can be misleading in both cases
What should the ratio of Fe to Mn be in the produced
water?
~100 to 1, this ratio is from the alloy and can vary based on metallurgy and
connate iron
Is there a standard for Fe and Mn counts?
Yes, NACE RP0192-98

Inline Corrosion Coupons
What
A physical corrosion measurement of corrosion
on a steel coupon placed into the gathering system
Why
Provides physical information regarding the
corrosivity of the system
How
Used as a monitoring tool to establish trends in
the corrosivity of the system and to help optimize
chemical treatment programs

Various shapes, sizes and

metallurgy
Frequently used with retractable
holders
Simple, no sophisticated
instrumentation
Direct, a direct measurement is
obtained
Relatively inexpensive

User friendly and durable

Visual confirmation of pitting attack
Does not provide instantaneous
feedback
Industry Standards:
ASTM G1-03: Preparing, Cleaning, and Evaluating
Corrosion Test Specimens
NACE recommended practice RP-0775

HANDLE WITH CARE!!
Prior to insertion:
Clean with solvent
Write down date and time
Do not touch with hands (even with any type of gloves
on)
Upon removal:
Photograph
Rinse in Methanol, IPA, acetone
Blot dry
Wrap tightly in paper towel and bag
• we want to preserve corrosion product or mineral
scales
• prevents further atmospheric corrosion
Do not scrape with knives or metal brushes
Do not touch with hands (even with any type of gloves
on)

Try to avoid:
High oil to water ratios
Partial immersion
Contact with pipeline
weld-o-let installation point

stratified flow
gas/water

COUPON ORIENTATION IS IMPORTANT!!
Coupon orientation is important:

Increased corrosion risk due to turbulence when flow changes directions

COUPON ORIENTATION IS IMPORTANT!!
Coupon orientation is important :

Increased surface area exposed to direct fluid impingement

Corrosion Coupons - Analysis
Corrosion rates calculated based on weight loss

W .L.  (3.45 10^ 6) W.L. = weight loss (g),
mpy  density (g/cm3)
(density  area  time) exposed area (cm2),
exposure time (hrs)
Pitting attack is not accounted for in the general corrosion

rate calculation

Corrosion Coupons - Analysis
The presence of pitting attack is confirmed through visual

analysis
Pit depth can be measured based on focal position or dial

depth gauges

Micorcor® ER Probe
Electrochemical Monitoring
What
A measure of the “real time” metal loss that is
occurring on the probe element to calculate the
corrosion rate over a specific time frame
Why
Provides qualitative “real time” information regarding
the corrosivity of the system
How
Used as a monitoring tool to establish program
effectiveness, corrosion trends and the corrosivity of the
system. Can also be used to help optimize chemical
treatment programs

Micorcor® ER Probe
 Great tool for “real time”
corrosion measurement
– Proving slip stream
downhole applications
– Proving corrosion
programs
– Incumbent vs. Multi-
Chem programs
 Installed incorrectly
– Week long test = no
measurements
 Battery issues
– 2 separate occasions
no measurements

Micorcor® ER Probe
 Pricing
– ER Probes
• ~$500 to $700
CAD
– Transmitter
• ~$4,200 CAD
– Data Logger
• ~$3,000 CAD
– Microcor Software
• ~$600 CAD
– Checkmate Handheld
• ~$4,600 CAD
Electrochemical Monitoring
 LPR probe measures the electrical conductivity that can

relate its corrosiveness
 Needs a liquid water phase to work
 Commonly used in laboratory testing

Microcor® Electrical Resistance (ER) Probe
Microcor® ER probe measures

metal loss from an element
Can work in a gas or liquid
environment
Can produce corrosion rate
results in less than 72 hours M4700 Flush Mount probe and M4500 cylindrical
Can be installed under probe
pressure with the use of the Model 60 retractor
Model 60 retractor
NACE papers on use of ER
probe in sour environment
NACE International Publication 3T199

Microcor® Electrical Resistance (ER) Probe
Rohrback confirms that the

Microcor® ER probe is suitable
for use in a H₂S environment
The Microcor® ER probe was
used as a tool to test and prove
Multi-Chem’s sour gas
corrosion inhibitors against
competitor products
We were able to show results
fairly quickly to our customer
on chemical performance and
gain their trust Microcor Transmitter and Retractable Probe
(Field Installation)

Monitoring using Microcor® ER Probe






Thank you!
Questions?

(Topics in Chemical Engineering) Lanny D. Schmidt - The Engineering of Chemical Reactions (2004, Oxford University Press, USA)

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Corrosion & Integrity Management

October 30, 2013

 Corrosion Mechanism Identification

 Corrosion Field Assessments

 Multi-Chem Product Applications

© 2012 HALLIBURTON. ALL RIGHTS RESERVED. 2

 Daytime Running Lights

© 2012 HALLIBURTON. ALL RIGHTS RESERVED. 4

© 2012 HALLIBURTON. ALL RIGHTS RESERVED. 6

Corrosion is the deterioration of a

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Electrochemistry deals with relation

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Where there is liquid water,

In general, experience tells us,

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In a two phase system, liquid and

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Duncan, Materials Performance, Vol. 19, No.7, 1980

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Speller, Corrosion Causes and Prevention, McGraw-Hill, 1951

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 Methanol can affect inhibitor films

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General Thinning of the Metal Surface

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Copper to Stainless Steel

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Stress Corrosion Cracking

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Partial pressure CO2 >30 psi

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Honeycomb Pattern Honeycomb Pattern Honeycomb Pattern

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