ENM205 Tutorial 2

a) There are a number of factors that enhance the risk of corrosion

occurring. Name 7.

Chlorides

Biofouling

Scaling

Galvanic effects

High velocity

High T, P

Flow type

b) What are the anodic and cathodic reactions occurring during the
corrosion of iron?
Anodic reaction:
Fe → Fe2+ + 2e
Cathodic reaction:
O2 + 2H2O + 4e → 4OH-

c) Under what conditions is the rate of corrosion affected?

Corrosion rate is enhanced by:
increased acidity
pH 7.0 or higher (significant corrosion unlikely)
pH 6.0 or less (significant corrosion)
increased temperature & pressure
high and very low fluid velocities
dissolved acid gases (CO2, H2S) and O2
high chloride ion content (pitting)
Corrosion rate can be reduced by scale or passive layers

d) What is the corrosion allowance?

Maximum thickness that can be lost during service life - the ‘Corrosion
Allowance’
The corrosion allowance is normally specified when purchasing steel,
typically 3mm, but can be 1mm or 6mm
Additional “corrosion allowance” can be gained by decreasing
pressure during service life
For piping or vessels the corrosion allowance is based on internal and not
external metal loss
It is normally assumed that the external metal surface is protected
against corrosion (e.g. by coating)
e) Name 8 types of corrosion and describe, with illustrations, 3 of
them.
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Uniform corrosion, pitting corrosion, crevice corrosion, erosion corrosion,

galvanic corrosion, stress corrosion, intergranular corrosion, selective
leaching – see slides 28-44 of L5 for examples and illustrations.

f) What is sweet corrosion? Describe the equations associated with

the presence of CO2.
CO2 is normally present in produced oil and gas and forms a weak acid
(carbonic acid) in water.
CO2 + H2O → H2CO3 → H+ + HCO3-
Fe + 2H+ → Fe2+ + H2
Fe + H2CO3 → FeCO3 + H2

CO2 corrosion often occurs as mesa-type corrosion

g) What are the key equations associated with sour corrosion?

H2S absorption:
𝐻2 𝑆 (𝑔) + 𝑂𝐻 − ↔ 𝐻2 𝑂 + 𝐻𝑆 −

Oxidation reaction:
𝐹𝑒𝑆𝑥 + 𝑥𝐻+ + 2𝑥𝑒 − ↔ 𝐹𝑒 + 𝑥𝐻𝑆 −

Reduction reaction: 𝐻 + + 𝑒 − ↔ 𝐻(𝑎𝑑𝑠)

𝐻 (𝑎𝑑𝑠) + 𝐻+ + 𝑒 − ↔ 𝐻2

h) What cracking mechanisms are induced with the presence of H 2S?

Describe 3 examples.
a. Hydrogen induced cracking (HIC)
atomic hydrogen absorbed at surface and diffuses into steel
atoms can combine at discontinuities in microstructure (such as
inclusions) to form hydrogen molecules and cause cracking
Mainly affects rolled low strength steels with high impurities
(sulphur, phosphorous)

b. Chloride stress corrosion cracking (SCC)

Austenitic and duplex stainless steels sensitive to Cl-SCC in
chloride containing environments
Concentration and temperature dependent:
AISI 316 >50ºC
22%Cr DSS >70ºC
25%Cr DSS >80ºC
Requires presence of oxygen under normal conditions but at high
temperatures and high Cl concentrations can occur in absence of
oxygen

c. Sulphide stress cracking (SSC)

ENM205 Tutorial 2

hydrogen atoms can cause embrittlement at crack tips or pits

partial pressure of H2S in gas is critical variable
mainly affects high strength steels and alloys
hardness is an important property
i) Hydrogen embrittlement is a problem associated with high-strength
steels, what is done to mitigate the risk of hydrogen
embrittlement?
Hydrogen embrittlement is a problem with high-strength steels, titanium,
Monel K-500 and 17-4PH, particularly in bolting materials
Control is by eliminating hydrogen from the environment, use of resistant
alloys (high strength cupro-nickels, high strength austenitic stainless
steels, nickel-based alloys), or control of hydrogen during processing

j) Corrosion control requires a lot of planning, describe the method of

cathodic protection.
Needs full immersion to be effective
Normally applied to subsea facilities, offshore pipelines and buried
onshore pipeline
Anodes are often used at the bottom of vessels and storage tanks with
high water cut
Can also be applied to piping (so-called RCP) but rare as it needs intense
monitoring and maintenance
k) The level of oxygen in seawater can present an ideal corrosive
environment. Discuss the methods applied to control this.
Seawater typically contains 8 - 9 ppm oxygen and is highly corrosive
Main risk for seawater injection systems
Can be removed by gas stripping, vacuum deaeration and/or oxygen
scavengers
Need to aim for oxygen content below 10ppb to reduce to a negligible
corrosivity
Difficult to achieve by chemical scavenging alone
Sodium sulphite and bisulphite
O2 + 2Na2SO3→2Na2SO4
Slow reaction
No hazard
Catalysed: Add Co, Ni, Cu catalyst (0.04 % Co)
Ammonium bisulphite (65% solution)
Supplied in liquid form
Popular world-wide
No catalyst needed

l) Describe three factors influencing corrosion inhibitor selection.

Performance (under representative shear conditions)
Solubility and Partitioning behaviour
Compatibility with materials (undiluted)
Neat inhibitors can be corrosive to carbon steel
Persistency
How long does the inhibitor film remain intact if the injection is interrupted?
ENM205 Tutorial 2

Foaming behaviour
Some inhibitors can cause significant foaming in downstream equipment
Emulsion tendency
Inhibitors are surfactants so will promote emulsion forming
Compatibility with other chemicals
Mixing with other chemicals such as methanol can cause “gunking”

Exam question example:

a) A seawater injection system has been constructed out of pipework

made from 316 stainless steel. The system has been shut down for
summertime maintenance for about a month. Since the shutdown
period was expected to be short, the system was left nearly full of
seawater. Do you consider this to be good practice? Explain your
reasoning. (5)

This is not good practice. Unless the seawater was filtered or had a biocide
added then it may contain bacteria and although 316 is considered to be
corrosion resistant these conditions are ideal for corrosion to occur. The
presence of bacteria in the sea water might lead to microbial induced corrosion
occurring. Another concern is the level of oxygen present in the seawater if an
oxygen scavenger had not been used prior to infilling the injection system with
the seawater. The level of oxygen is it is greater than 10 ppb oxygen then
corrosion may occur. As this was left for a period of time then these corrosion
events could occur unnoticed.

b) When the system was started up again, slight leakage was

observed from several pinholes which appear to be located about
2 cm from a circumferential field weld in the pipework. What could
have caused this? How could it have been avoided? (8)

When welding carbon steel it is possible to get a range of microstructures. Next

to molten weld pool there is area of parent metal which is influenced by the
heat from welding and is known as the heat affected zone (HAZ). Pitting
corrosion has occurred in the material because of the use of 316 and not
maintaining material composition with the weld filler used.

It could be avoided by using a lower carbon content material e.g. Reduce carbon
content ≤ 0.03% (304L, 316L) – most common approach. The formation of
chromium carbide formation could be induced by using strong carbide formers
(stabilisers) that “grab” the carbon preferentially e.g. Niobium or Columbium
(Nb, Cb) (e.g. 347SS), Tantalum (Ta) (usually with Nb) (e.g. 348SS), Titanium
(Ti) (e.g. 321SS). Another way to avoid this issue is to re-heat treat welded
piece followed by quench annealing or solution-quenching – dissolving the
carbides back into solid solution. This process is carried out by heating to
1060°C to 1120°C then water quench.

c) A well which has been completed with L-80 Type 1 tubing. As a

result of injecting filtered, but otherwise untreated, seawater into
a limestone reservoir to support production, the produced fluid
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now smells strongly of hydrogen sulphide. Production is slowing

and scale is forming in the production tubing. What potential
problems do you foresee and what would you recommend the
operator do about it? (12)
The increasing production of scale could lead to a blockage in the
production tubing, reducing capacity. Acidisation may be necessary to
clear the scale. Care needs to be taken with choice of acid used and
whether a corrosion inhibitor needs to be used with it.

May need to upgrade with if production becomes sour

Specify grade according to ISO 15156 to prevent H2S stress corrosion

Use Corrosion Resistant Alloy (CRA):

Where inhibition is not feasible or for highly corrosive environments

13Cr general purpose CRA for downhole

Often used offshore to avoid subsurface inhibitor application

Duplex 22Cr, 25Cr for highly corrosive environments

Non-metallic pipe option for water handling at low pressures