Oilfield Corrosion

Prepared by: DSc PhD Dževad Hadžihafizović (DEng)

Sarajevo 2024
Production Chemistry &
Corrosion Control
Surface Operations
• Significance of Corrosion
• Why and How Corrosion Occurs
• Manifestations of Corrosion
• Corrosion Control Techniques
• Corrosion Monitoring

Oilfield corrosion can be considered under the following headings:

Significance - what it costs.
Why it occurs - the mechanism.
What it looks like.
The last two items, “How to control it” and
“How to measure it” are covered in the next section
 Why is Corrosion Important

Significance
• Operating Costs
• Health & Safety
• Environmental Impact

All three of the above will appear in most asset goals.

Corrosion can prevent the attainment of these goals on one
or more of these criteria

The costs fall into three categories:

Financial
Risks to Health and Safety
Possible Environmental Problems

Each is important in today’s business and political environment.

 Operating Costs

• Direct (Money Spent) • Indirect (Money Not Saved)

• Replacement • Unplanned shutdowns
• Installation • Loss of product (oil or gas)
• Maintenance • Overdesign (“corrosion
• Clean up of spillages allowances”)
• Loss of efficiency (e.g.
thermal efficiency of
corroded heat exchangers)
• Bad publicity

Indirect costs are often considerably higher than

direct costs, BUT are difficult to quantify

Bad publicity can lose a company business. It is difficult to determine how much business is lost.
 Opportunity Costs

Shell
• Estimated costs of corrosion at $100MM in 1992
• Estimated 70% was avoidable

Another Major Oil Company

• Estimated costs of $320MM due to corrosion in a recent 3 year period
• Equivalent to 6.5% of net asset value/yr
• 67% Repairs, 33% Lost Production
 Health & Safety

• Leaks caused by corrosion • Mechanical failure caused by

• Can release corrosion
hydrocarbons/other • Can cause process upsets
chemicals • risk of injury from operating
• risk of injury from fire, outside normal envelope
explosion • Can occur catastrophically
• risk of exposure to • risk of injury
hazardous materials
• Can cause equipment
malfunction
• risk of injury to personnel
 Environmental Impact

• Pollution of environment from corrosion leaks

• Depletion of non-renewable resources

In most countries environmental concerns can no longer be ignored. This is especially

true for large multi-national companies like Shell, which must avoid upsetting the
‘neighbours’.

It is not just the cost of clean-up; often leaks lead to financial penalties from local and
national regulatory bodies.

Once the oil is spilled, it is usually not recoverable.

 Why and How Corrosion Occurs

A brief look at the mechanisms that lead to oilfield corrosion problems.

 What is meant by “Corrosion”?

Definition

• NACE International has defined “CORROSION” as:-

“… the deterioration of a substance (usually a metal) or

its properties because of a reaction with its
environment

NACE - the National Association of Corrosion Engineers.

Does this definition really help us? Let us analyse what it means in a practical sense.
 • All corrosion processes are chemical reactions

• Chemical reactions only occur spontaneously if there is

a net decrease in the energy of the system as a result

G must be negative

What is the main metal used for construction in the oil industry?
Carbon steel, otherwise known as mild-steel.
 • Metals of importance in engineering generally exist in
their “natural” state as compounds e.g. iron oxide

• Refining of metals consumes energy - “stored” in the

pure metal

• Refined metals are generally unstable and tend to

revert to a lower energy state, as a chemical
compound, by reacting with their environment, i.e.
they CORRODE

Iron oxide is heated (energy input) to convert it to pure iron, then a small amount of carbon is added
during the process to form mild-steel.
It is this stored energy that is the driving force for the metal to react with its environment (e.g.
oxygen in air) and revert to the more stable iron oxide.
 How Do Corrosion Reactions Occur?

• Oilfield corrosion is almost entirely electrochemical in

nature

• This means that an electrochemical cell is in operation

• flow of electrical current (electrons) Occur in
• chemical reaction conjunction
 Electrochemical Cell
• MUST have 5 components
• anode  cathode

• electrolyte (ionic conductor)

• metallic conductor
• cathode reactant (electron acceptor)

e-

Anode Cathode

We need electrical contact between the anode and cathode, in the presence of an electrolyte and cathode
reactant (which accepts the electrons from the anodic reaction).
 Electrochemical Cell
• In practice microscopic cells can be generated where 3 of the cell components
are provided by a single piece of metal

Water (electrolyte)

Water (electrolyte)
Metal loss
(corrosion)

Cathode
Anode Metal

Electron Flow (metallic conduction)

• In practice cells are often microscopic, they move location and often overlap
one another

Carbon steel has a crystalline structure consisting of iron (Fe) and iron carbide grains. The iron carbide acts as
the cathode and the iron grains as anodes. Since these grains are adjoining, there is electrical contact. Hence
the 3 components automatically present are the anode, cathode and metallic conductor.
 How Fast Will Corrosion Occur?

• Factors which can influence corrosion rates

• temperature
• pressure
• velocity
• pH
• dissolved solids
 Effect of Temperature
• Generally as T , corrosion rate 

• But not always

• as T  solubility of corrosive gases 
• as T  protective scales may form
Effect of Pressure
• Main effect is on solubility of corrosive gases

• As P  more gas goes into solution so corrosion rate 

Chemical reaction rates usually increase with increasing temperature and corrosion is a chemical reaction.

Increasing temperature will drive corrosive gases out of solution in the water, thus reducing the corrosion
rate. This may also lead to the deposition of mineral scales, that may partially protect against corrosion.
 Effect of Velocity

• Complex
• Usually as V , corrosion rate 
• improved mass transfer
• protective film of corrosion product removed
• erosion corrosion at very high velocity
• But sometimes as V  corrosion rate 
• suspended solids deposit on surfaces - “under deposit”
corrosion
• bacteria prefer “stagnant” conditions to colonise surfaces

Increased flow rate keeps the concentration of oxidising agent high at the corrosion site.
When solids are present, such as sand, scale, or corrosion by-products, a reduction in velocity
allows them to deposit on surfaces.
 Effect of pH

Corrosion
Rate

4 9 12 14
pH
Oilfield water systems are typically in the range of pH 4.0 to 8.3. Hence, the severe corrosion likely at lower pH is
only possible when excess mineral acids enter the system e.g. from well stimulation work.
 Effect of Dissolved Solids (Salts)
• Complex

• Usually as Concentration  corrosion rate 

• increased conductivity of electrolyte
• increased flow of current in basic electrochemical cell

• BUT sometimes as Concentration  corrosion rate 

• solubility and diffusivity of dissolved gases 
• precipitation of protective scales

The effect of increased conductivity and hence higher current flow in the electrochemical cell,
increases the speed (or rate) of the chemical reaction.
 • The solutes which cause most oilfield corrosion:

• Carbon dioxide (“sweet”)

• Hydrogen sulphide (“sour”) - may be of bacterial origin

• Oxygen (not normally present)

A solute is any material dissolved in a solvent, in this case water.

Carbon Dioxide is usually present in % levels, whereas hydrogen sulphide is only at ppm levels. However, there
some oilfield systems where H2S can reach 1-2%.
The presence of oxygen is normally due to leaky equipment and the most effective treatment is to find and repair
the leak.
• Oilfield corrosion can be divided into external and internal
(process side). The principles involved are the same for
both but emphasis here will tend to be on the internal
(process side) corrosion issues
 Electrochemical Attack

Manifestations
Fe Fe2+ + 2e-
• This process is called oxidation (electron donation) and
always occurs at the anode
To maintain the charge balance another reaction must occur:

O2 + 2H2O + 4e-  4OH-

• This is reduction (electron gain) and occurs at the
cathode
 Oxygen Corrosion

Appearance:
Large, shallow pitting.
O2 contamination due to air drawn in.
Fatigue cracks may initiate if enough metal removed
The above corrosion cell illustrates the electrochemical reactions taking place
at the anode and cathode under acidic conditions.

Fe - 2e- Fe2+ 2H+ + 2e- H2

ELECTROLYTE H2
2+
Fe icorr
H+ H+

icorr Cathodic Area

Anodic Area 2 e- (Reduction)
(Oxidation)
METAL
 Corrosion Mechanism
H2CO3 is carbonic acid. The higher the pressure, the more CO2 dissolves in the water and the stronger the
resultant carbonic acid.
Carbonic acid then gives rise to acid attack on mild steel structures.

The Carbon Dioxide cathodic reaction is associated with hydrogen ions:

H2O + CO2 H2CO3

H2CO3 H+ + HCO3-

2H+ + 2e- H2
 CO2 Corrosion

Appearance:
Round-bottomed pitting with sharp sides

This example is a section of sucker-rod from a reciprocating-rod pumped well.

 Corrosion Mechanism

Hydrogen Sulphide acts as a corrosion

rate accelerator

Fe2+ + H2S FeS + 2H+

There is much misunderstanding about H2S and its role in the corrosion process. While thermodynamically it is an
acid, its ionisation is dependent upon the pH of the solution. As a result, the rate of reaction in typical oilfield
waters is relatively slow in comparison to the corrosion rate due to carbon dioxide.
However, the reaction with iron ions (shown above) is extremely fast.
Pitting damage often occurs since FeS is cathodic to steel.
 H2S Corrosion

Appearance:
Small, steep-sloping pits
May contain fatigue cracks
H embrittlement also possible
 Manifestations
• Classification
• Uniform
• Pitting
• Crevice (under deposit)
• Galvanic
• Includes selective leaching
• Intergranular
• Erosion corrosion
• Includes:-
• cavitation
• Microbiologically Influenced (MIC)
• Environmental Cracking
• Stress corrosion cracking
• Hydrogen damage
• Corrosion fatigue

This is about what the corrosion looks like when it does occur and how it affects the corroded metal.
 General (Uniform) Corrosion

Manifestations
• Most common form of corrosion
• Electrochemical reactions proceed uniformly over the
entire exposed surface over a large area
• Represents the greatest destruction of metal on a tonnage
basis
• Life of equipment can be accurately estimated from
corrosion tests
Simply put, this is where the corrosion takes place evenly over the whole metal surface.

Design engineers take into account the expected general corrosion rate and determine the metal
thickness based on maintaining equipment integrity over the design life of the system.

System failures do not normally occur as a result of uniform corrosion.

 Pitting Corrosion

Manifestations
• More destructive than uniform attack - due to prediction
difficulties
• Alloys that rely on passive films are particularly susceptible
e.g. 13 Cr stainless pits rapidly in presence of chlorides and
oxygen
• Can be isolated or clustered giving appearance of uniform
attack
• Slower rate if more pits
• Changes in velocity can be both beneficial and detrimental
Pitting corrosion rates can be 10-50 times the general corrosion rate. Hence, holes in the metal
can appear within times much shorter than the system’s design life.
 Pitting/Crevice Attack

Pitting Corrosion

Crevice Corrosion

Pitting corrosion occurs when the corrosion reaction takes place in localised areas, leaving much of
the surface relatively corrosion free.
Since the corrosion reactions are concentrated at a few points, the metal loss is greater at those
locations. Hence, pits are formed.
 Crevice (Under Deposit) Corrosion

• Occurs in constricted areas where free access of the surrounding

environment is restricted

• Crevice corrosion caused by metal-to-metal or metal to non-metal

surfaces, e.g. gaskets, couplings and joints

• Under deposit corrosion - crevice formed from discontinuous deposit, can

be inert (e.g. sand) or electrochemically active (e.g. FeS)

• Under-deposit corrosion is often the cause of failures in oilfield

systems.
 How Corrosion Occurs
In the crevice between the edge of the deposit and the metal surface, a differential concentration
cell develops. Here the concentration of corroding species becomes less compared to the bulk fluid
covering the rest of the surface. This location then becomes anodic to the rest of the surface and
pitting corrosion results.

Deposit Cathode
H+ + 2e H2
Anode

Fe2+ - 2e Fe2+
Metal
 Galvanic Corrosion

• A potential difference usually exists between two dissimilar metals

• Corrosion of less resistant metal is increased and more resistant metal is reduced

• Less resistant metal is anodic and more resistant metal is cathodic

• To predict corrosion can use galvanic series

• Particular problem with threaded connections between dissimilar metals

• A number of simple guidelines exist concerning galvanic corrosion. Surface area differences
and the relative position in the Galvanic Series of the two adjoining metals, effect the
corrosion rate.
 Galvanic Series in Seawater

NOBLE Platinum
Gold
Graphite
Stainless Steel (passive)
Nickel
Monel
Bronze
Copper
Brasses
Tin
Lead
Stainless Steel (active)
Mild Steel
Aluminium
Zinc
Magnesium
ACTIVE
In simple terms, the Galvanic Series can be regarded as the decreasing order of the amount of energy required to
process the pure metal from its natural state. That is, the more active the metal the more energy is ‘stored’ in that
metal and the greater the driving force for it to revert to its natural low energy state.
 Galvanic Attack

N o b le
B a s e M e ta l
M e ta l

Such connections as these can lead to rapid and drastic failures.

 Factors Effecting the Rate of Galvanic Corrosion

• The degree of potential difference between the two metals

• Distance effect - greatest near the junction
• Area effect - better to have large anode, small cathode
• Corrosiveness of the environment

For example, if the more active metal surface area is smaller than that of the noble metal, the
corrosion rate is higher. Likewise, if active metal has a much larger surface area, the corrosion rate
will be lower.
Referring to the table in the next slide, the corrosion rate rate would be lower if copper and steel
were connected (the steel would corrode) compared to the corrosion of magnesium when
connected to copper.
 Intergranular Corrosion

• Localised attack of grain boundaries with relatively little corrosion of the grains

• Caused by more reactive grain boundaries

• The metal has a granular structure. In circumstances where the grain

boundaries become anodic with respect to the grains themselves, the
corrosion reaction will preferentially occur along the lines of those
boundaries. This will obviously affect the strength / integrity of the metal.
 Intergranular Attack - Weld Decay

Weld
HAZ

HAZ - heat affected zone.

When weld areas have not been (or poorly) stress relieved by annealing,
intergranular corrosion can occur in the HAZ. Often this appears as a corroded
groove / channel all the way round the internal circumference of the pipe.
 Velocity Phenomena

Erosion Cavitation
Bubbles
Flow

Erosion is due to the ‘wearing’ effect of high velocity fluid streams, usually containing solid particles.
This is NOT a corrosion effect.
Similarly, cavitation is the implosion of vapour bubbles (created by forced evaporation due to
pumping effects) as a higher pressure region is reached. The implosion on metal surfaces can
result in metal loss.
 Velocity Effect
• Velocity of the flow is sufficient to remove weakly adherent corrosion
products from metal’s surface
• Breakaway velocity determined by alloy and environment system
50

Film Free Surface

40
Corrosion Rate

30

20

Protective
10
film on Film Breakdown
Surface
0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Velocity

Erosion corrosion is a velocity effect that disrupts a partially protective corrosion product layer,
opening the metal surface to further corrosive attack.
 Erosion - Corrosion

• High velocity - film removal and corrosion

• Suspended solids assist
• Areas of turbulence susceptible
• section changes, elbows, etc.

• Damage follows flow direction

• Corrosion inhibitors can reduce damage

Continued stripping of the corrosion product layer leads to a higher overall corrosion
rate, but in a localised area.
The major difference between erosion and erosion corrosion is that corrosion inhibitors
can reduce the damaging effects of the latter, but not erosion.
 Erosion - Corrosion : Condenser Tube Wall

Water Flow

Corrosion Film Impingement/Pits

Metal Tube Wall

 Cavitation

• Also occurs during fluid flow

• Rapid changes in pressure
• Formation and collapse of gas bubbles
• Repeated action wears away metal
• Example : pump impellers
• Often design problem, but can inhibit
• Where the metal loss is mainly due to cavitation impact
removing the corrosion product layer, inhibition can reduce
the amount of damage.
 Bacteria in Oilfield Systems

• Section of pipe indicating bacterial growth

Pipe
Planktonic
wall
bacteria

Sessile
Biofilm bacteria

The next five slides are a brief introduction to oilfield microbiological problems, which is
covered in more detail immediately after this topic (Corrosion).
 Bacterial Corrosion

Certain types encountered:

 Sulphate reducing bacteria (SRB) cause most

problems

– Exist
in anaerobic conditions
– Metabolise by reducing inorganic sulphate to sulphide
2- 2-
– 4H2 + SO4 S + 4H2O

– FeS deposits associated with black bacterial slimes

– Pitting problems
– Anaerobic conditions - in the absence of oxygen
 Sulphate Reducing Bacteria

FeS

Fe2+ 8H
-
SO42- + 8H H2S + 2H2O + 2OH

SRB
CATHODE
ANODE

Pipe Wall
 Bacterial Corrosion
SRB

These sketches show the typical form of SRB induced pitting corrosion.

PLAN SIDE

Appearance:
Shallow pits within pits
 Bacterial Corrosion
SRB

This pit was in a section of a failed oil pipeline. Note the smoothness of the pit sides and the hole.
The remaining pipe surface was almost untouched by corrosion. The red-brown rust seen on the
remaining surface occurred after removal of the section from the pipeline (i.e. it was due to
atmospheric oxidation).
 Environmental Cracking

• Environmental cracking is the brittle failure of an

otherwise ductile material as a result of the combined
action of corrosion and tensile stress
• Stress Corrosion Cracking (SCC)
• Hydrogen Induced Cracking (HIC)
(and Hydrogen Blistering)
• Corrosion Fatigue
• Liquid Metal Embrittlement (LME)
 Stress Corrosion Cracking

• Stress Corrosion Cracking is the brittle failure in an

otherwise ductile metal from combined action of tensile
stress and specific corrosive environment

• Carbon steel : caustic

• Stainless steel : chlorides

• Copper alloys : ammonia

 Hydrogen Blistering
• Hydrogen blistering results from the penetration of atomic hydrogen into a metal
• More prevalent in softer metals, the harder metals usually suffer from hydrogen
embrittlement
• Blistering is the local deformation and in extreme cases complete destruction of
vessel wall + +
H H
Electrolyte
H H
H H2 H
H H

H H H H2 H
Void
H H2 H
Air

This effect usually happens only where high pressures, or high concentrations (% levels) of hydrogen sulphide, exist.
The hydrogen atom combination to form molecular hydrogen (H2), is an extremely rapid reaction. However, some hydrogen atoms
can enter the metal lattice before the reaction takes place. When H2 is then formed within voids in the metal, the molecule is too
large to exit the metal lattice. As the pressure of hydrogen builds in the void, the metal becomes distorted.
 Hydrogen Induced Cracking

• Hydrogen embrittlement results from the penetration of

atomic hydrogen into a metal
• Embrittlement results in a loss of ductility and tensile
strength
• Potentially more damaging than Hydrogen Blistering
• When hydrogen enters harder steels, the pressures
exerted cannot distort the metal and cracking tends to
be the result.
 Sulphide SCC

• Sulphide is a poison to the reaction of the formation of

molecular hydrogen from its atomic form
• Greater concentration of atomic hydrogen on the metal
surface
• Therefore accelerates Hydrogen Blistering or Embrittlement
• In the presence of sulphide films on the metal surface the
H-H combination reaction is slowed down to the extent that
far more hydrogen atoms can enter the metal lattice
structure.
 Corrosion Fatigue

• Metal fatigue
• Repeated cyclic stressing causes cracking failure
• Corrosion fatigue
• Fatigue life much reduced in corrosive environment
The shorter failure time is due to corrosion, where the resultant pits provide weak points in the metal.
80

70

60
In Air
50

40

30
In Corrosive Environment
20

10

0
1000 10000 100000 1000000 10000000 100000000 1000000000 10000000000
Cycles
 Typical Face of a Corrosion Fatigue
Break in a Sucker Rod Body

Crack Initiation Smooth Area

Fibrous Area

Half Moon
(Line Between
Stretched & Torn
Smooth &
Fibrous Areas) Steel At Final
Fracture

The corrosion pit causes the eventual failure.

• Where will corrosion occur?

• Almost anywhere where liquid water is present either continuously or intermittently

GAS
PROCESSING
PRODUCTION

WATER
DISPOSAL
OR
DEHYDRATION FLOOD
How fast will corrosion take place?

• Very difficult to predict accurately

• systems constantly changing
• mechanism complex and not well understood
 How fast will corrosion take place?

• Prediction of CO2 Corrosion

• DeWaard - Milliams relationship (1975)
log(C.R.) = 5.8 - 1710 + 0.67 log (PCO2)
273+t
• Since revised to account for:-
• corrosion product films
• pH
• systems pressure
• effect of methanol or glycol
• effect of crude oil
• effect of velocity

This equation was developed by these two Shell employees and is used world-wide for
system design. It is not a day-to-day practical tool.
 How Fast will Corrosion Take Place

• Prediction of H2S Corrosion

• no simple models

• Estimated corrosion rates in oil wells

Blank Rate = 1/25 [ (CO2 + 1/2 H2S) + (HCO3- + 1/2 H2S) ]

10

Where all concentrations are in ppm and where O2 = 0 ppm