Corrosion protection

Gas engineering CE -619

 Basics
• Corrosion is the destructive attack of a material by
reaction with its environment and a natural potential
hazard associated with oil and gas production and
transportation facilities.
• Almost any aqueous environment can promote
corrosion, which occurs under numerous complex
conditions in oil and gas production, processing, and
pipeline systems
• This process is composed of three elements: an anode, a
cathode, and an electrolyte. The anode is the site of the
corroding metal, the electrolyte is the corrosive medium
that enables the transfer of electrons from the anode to
the cathode, and the cathode forms the electrical
conductor in the cell that is not consumed in the
corrosion process
 Corrosion in gas wells
• Crude oil and natural gas can carry various high-impurity
products which are inherently corrosive.
• In the case of oil and gas wells and pipelines, such highly
corrosive media are carbon dioxide (CO2), hydrogen sulfide
(H2S), and free water
• Continual extraction of CO2, H2S, and free water through
oil and gas components can over time make the internal
surfaces of these components to suffer from corrosion
effects.
• The lines and the component fittings of the lines would
undergo material degradations with the varying conditions
of the well due to changes in fluid compositions, souring of
wells over the period, and changes in operating conditions
of the pressures and temperatures
• This material degradation results in the loss of
mechanical properties like strength, ductility, impact
strength, and so on.
• This leads to loss of materials, reduction in thickness,
and at times ultimate failure.
• A point will be reached where the component may
completely break down and the assembly will need to
be replaced while production is stopped.
• The serious consequences of the corrosion process
have become a problem of worldwide significance [1.
 Corrosion and industry
• Corrosion in the modern society is one of the
outstanding challenging problems in the
industry.
• Most industrial designs can never be made
without taking into consideration the effect of
corrosion on the life span of the equipment.
• Recent industrial catastrophes have it that
many industries have lost several billions of
dollars as a result of corrosion.
• Reports around the world have confirmed that some oil
companies had their pipeline ruptured due to corrosion
and that oil spillages are experienced which no doubt
created environmental pollution; in addition, resources are
lost in cleaning up this environmental mess, and finally,
large-scale ecological damage resulted from corrosion
effects.
• The possibility of occurrence of corrosion in an industrial
plant has been posing a lot of concern to petroleum,
chemical, and mechanical engineers and chemists.
• It is now known that corrosion can have some effects on
the chemistry of a chosen process, and the product of
corrosion can affect reaction and purity of the reaction
products.
 Corrosion and economics
• The total annual cost of corrosion in the oil and
gas production industry is estimated to be $1.372
billion, broken down into $589 million in surface
pipeline and facility costs, $463 million annually
in down hole tubing expenses, and another $320
million in capital expenditures related to
corrosion
• Corrosion costs the oil and gas industry tens of
billions of dollars in lost income and treatment
costs every year
• Corrosion costs US industries alone an estimated $170 billion
a year in which the oil and gas industry takes more than half
of these costs
• internal corrosion in wells and pipelines is influenced by
temperature, CO2 and H2S content, water chemistry, flow
velocity, and surface condition of the steel.
• Having a greatly reduced corrosion rate (mm/year) can
dramatically increase component life, which leads to much
greater benefits such as reduced maintenance costs.
• Currently, many components used for oil and gas extraction
are made from carbon steel-based alloys. Now, organizations
are looking to move away from these types of alloys to a
more corrosion-resistant alloy at a much higher cost. The
problem of corrosion is a challenge to the whole world and
must be greatly tackled.
Corrosion types and associated agents
in the oil and gas industry
• The most common form of corrosion in the oil
and gas industry occurs when steel comes in
contact with an aqueous environment and rusts
• When metal is exposed to a corrosive solution
(the electrolyte), the metal atoms at the anode
site lose electrons, and these electrons are then
absorbed by other metal atoms at the cathode
site.
• The cathode, in contact with the anode via the
electrolyte, conducts this exchange in an attempt
to balance their positive and negative charges.
 Reaction mechanism
• Positively charged ions are released into the
electrolyte capable of bonding with other
groups of atoms that are negatively charged.
This anodic reaction for iron and steel is

• After the metal atoms at the anode site

release electrons, there are four common
cathode reactions
• In the oil and gas industry, carbon dioxide
(CO2) and hydrogen sulfide (H2S) are
commonly present, and water is their catalyst
for corrosion.
• When water combines with CO2 and H2S, the
environments form the following reactions
• There may be a combination of the above two
reactions if both gases are present
• These resulting molecules either attach
themselves to the cathode or are released into
the electrolyte and the corrosion process
continues.
 Corrosion Classification
• It is a great challenge to classify the types of
corrosion in the oil and gas industry in a uniform
way
• One can divide the corrosion on the basis of
appearance of corrosion damage, mechanism of
attack, industry section, and preventive methods.
• There are many types and causes of corrosion.
• The mechanism present in a given piping system
varies according to the fluid composition, service
location, geometry, temperature, and so forth.
• In all cases of corrosion, the electrolyte must be present for
the reaction to occur.
• In the oil and gas production industries, the major forms of
corrosion include
1. Sweet corrosion,
2. Sour corrosion,
3. Oxygen corrosion,
4. Galvanic corrosion,
5. Crevice corrosion,
6. Erosion corrosion,
7. Microbiologically induced corrosion, and
8. Stress corrosion cracking.
 Sweet corrosion (CO2 corrosion)
• CO2 corrosion has been a recognized problem in
oil and gas production and transportation
facilities for many years
• CO2 is one of the main corroding agents in the oil
and gas production systems
• Dry CO2 gas is not itself corrosive at the
temperatures encountered within oil and gas
production systems but is so when dissolved in an
aqueous phase through which it can promote an
electrochemical reaction between steel and the
contacting aqueous phase
• CO2 will mix with the water, forming carbonic acid making the fluid
acidic.
• CO2 corrosion is influenced by temperature, increase in pH value,
composition of the aqueous stream, presence of non-aqueous
phases, flow condition, and metal characteristics and is by far the
most prevalent form of attack encountered in oil and gas
production.
• At elevated temperatures, iron carbide scale is formed on the oil
and gas pipe as a protective scale, and the metal starts to corrode
under these conditions.
• CO2 corrosion can appear in two principal forms:
1. Pitting (localized attack that results in rapid penetration and
removal of metal at a small discrete area)
2. Mesa attack (a form of localized CO2 corrosion under medium-
flow conditions
 Sour corrosion (H2S corrosion)
• The deterioration of metal due to contact with hydrogen sulfide
(H2S) and moisture is called sour corrosion which is the most
damaging to drill pipe.
• Although H2S is not corrosive by itself, it becomes a severely
corrosive agent in the presence of water leading to pipeline
embrittlement
• Hydrogen sulfide when dissolved in water is a weak acid, and
therefore, it is a source of hydrogen ions and is corrosive.
• The corrosion products are iron sulfides (FeSx) and hydrogen.
• Iron sulfide forms a scale that at low temperature can act as a
barrier to slow corrosion
• The forms of sour corrosion are uniform, pitting, and stepwise
cracking The general equation of sour corrosion can be expressed
as follows
 Oxygen corrosion
• Oxygen is a strong oxidant and reacts with the
metal very quickly.
• Oxygen dissolved in drilling fluids is a major
cause of drill pipe corrosion.
• Oxygen ingress takes place in the well fluids
through leaking pump seals, casing, and process
vents and open hatches
• As a depolarizer and electron acceptor in
cathodic reactions, oxygen accelerates the anodic
destruction of metal
• The high-velocity flow of drilling fluids over the
surfaces of a drill pipe continues to supply oxygen to
the metal and is destructive at concentrations as low as
5 ppb
• The presence of oxygen magnifies the corrosive effects
of the acid gases (H2S and CO2). The inhibition of
corrosion promoted by oxygen is difficult to achieve
and is not practical in the drilling fluid system.
• The forms of corrosion associated with oxygen are
mainly uniform corrosion and pitting-type corrosion.
 Galvanic corrosion
• This type of corrosion occurs when two metallic
materials with different nobilities (electrochemical
potential) are in contact and are exposed to an
electrolytic environment.
• In such situation, the metal with less or the most
negative potential becomes the anode and starts
corroding
• The anode loses metal ions to balance electron flow.
• Because metals are made up of crystals, many of such
cells are set up, causing inter granular corrosion.
• Problems are most acute when the ratio of the
cathode-to-anode area is large
 Crevice corrosion
• Crevice corrosion is normally a localized corrosion
taking place in the narrow clearances or crevices in the
metal and the fluid getting stagnant in the gap.
• This is caused by concentration differences of
corrodents over a metal surface
• Electrochemical potential differences result in selective
crevice or pitting corrosion attack.
• Oxygen dissolved in drilling fluid promotes crevice and
pitting attack of metal in the shielded areas of drill
string and is the common cause of washouts and
destruction under rubber pipe protectors.
 Microbiologically induced corrosion
• This type of corrosion is caused by bacterial activities. The
bacteria produce waste products like CO2, H2S, and organic
acids that corrode the pipes by increasing the toxicity of the
flowing fluid in the pipeline
• The microbes tend to form colonies in a hospitable
environment and allow enhanced corrosion under the
colony.
• The formation of these colonies is promoted by neutral
water especially when stagnant
• Numerous reports of the presence of microbes in reservoirs
had been published where scientists found abundant
microbial flora indigenous in oil field formation waters,
which included species of Bacillus, Pseudomonas,
Micrococcus, Mycobacterium, Clostridium, and
Escherichia.
• Bacteria that form slime (some form of
polysaccharides), such as Achromobacter sp.,
Flavobacterium sp., and Desulfuricans sp., will adhere
to each other, forming a large mass.
• They also adhere to the walls of the pores, causing
severe plugging problems at injection wells
• Microbiologically induced corrosion (MIC) is recognized
by the appearance of a black slimy waste material or
nodules on the pipe surface as well as pitting of the
pipe wall underneath these deposits.
Corrosion mitigation in the oil and gas
industry
• Oil field corrosion challenges are not static
phenomena.
• Fluid characteristics change over time, resulting
in systems becoming less responsive to
established corrosion mitigation programs
• Within the sphere of corrosion control and
prevention in the oil and gas industry, there are
technical options such as cathodic and anodic
protection, material selection, chemical dosing,
and the application of internal and external
coatings.
 Methods
• While many methods have been advised to arrest
these events, these methods can be broadly
classed as follows
1. Selection of appropriate materials
2. Use of inhibitors
3. Use of protective coatings
4. Adequate corrosion monitoring and inspection
5. Cathodic protection technique
 Selection of appropriate materials

• When it is observed that the existing materials of

construction are prone to corrosive attack, it is
normally decided to change the materials of
construction and select alternate materials to suit
the specific need
• Stainless steels cover a wide range of alloys, each
with a particular combination of corrosion
resistance and mechanical properties
• In oil and gas applications, many of these
stainless steel grades are used, depending on the
demands of the particular service environment
• Applicable corrosion-resistant alloys in the oil and
gas industry include
1. 13Cr,
2. Super 13Cr,
3. 22Cr duplex,
4. 25Cr duplex,
5. 28Cr stainless steel,
6. 825 nickel alloy,
7. 625 nickel alloy,
8. 2550 nickel alloy, and C276 nickel alloy
• some of the commonly used materials in the
hydrocarbon and oil and gas industries based
on a detailed study of process and operating
conditions are ,
 Use of inhibitors
• Inhibitors are chemicals that are used to protect the surface
of metals used in oil and gas industries to prevent
corrosion.
• They protect the surface of metals either by merging with
them or by reacting with the impurities in the environment
that may cause pollution
• A corrosion inhibitor may act in a number of ways:
1. It may restrict the rate of the anodic process or the
cathodic process by simply blocking active sites on the
metal surface.
2. Alternatively, it may act by increasing the potential of the
metal surface so that the metal enters the passivation
region where a natural oxide film forms.
• Factors to be considered before using a corrosion inhibitor
in the oil and gas industry include
1. toxicity,
2. environmental friendliness,
3. availability,
4. cost.
• Organic corrosion inhibitors are more effective than
inorganic compounds for protection of steels in acid media.
• A review of high-temperature acid corrosion inhibitors
revealed that the effective corrosion inhibitors for oil well
acidization include acetylene alcohols, quaternary
ammonium salts, aldehydes, amines, etc
• recommended inhibitors by previous
researchers and their places of applicability in
the oil and gas industries include
• Active ingredients of the inhibitors included long-chain
amines, fatty amides, imidazolines, fatty acids, and
their salts.
• concentration range of 50 to 200 ppm in the
electrolyte and electrolyte/hydrocarbon mixture in the
presence of CO2 and H2S in static and dynamic
conditions. These products provide a very high level of
protection for steel subjected to a broad range of
corrosive attack and flow restriction from moisture,
condensation, oxygen, carbon dioxide, hydrogen
sulfide, and other corrosive contaminants
 VpCI technology
• Unlike conventional methods, such as filming
amine-based corrosion inhibitors, an injection of
a volatile corrosion inhibitor (VpCI)-based
material into any part of the system will set the
VpCI to work immediately with a self-replenishing
mono-molecular protective layer
• VpCI technology is an environmentally safe and
cost effective option for corrosion protection.
• VpCIs form a physical bond on the metal surface
and create a barrier layer to protect against
aggressive ions.
• The barrier reheals and self-replenishes, and
can be combined with other functional
properties for added protective capabilities.
• It can be used in pipelines, oil and gas wells,
refinery units, and fuels.
• In addition, these VpCI-based anti-corrosion
additives have been designed to work well in
multiphase flow systems in conjunction with
different drag reducers.
 Use of protective coatings
• A protective layer or barrier on the material to
avoid the direct contact with the process media
will enhance the material and equipment life.
• The barrier layer can be paint, a coating or a
lining, or a metallic lining or metallic sheets.
• There are also non-metallic linings like fiber glass,
glass flake, epoxy, and rubber which are normally
carried out on the equipment like separators,
knock-out drums, and storage tanks.
• Nickel, zinc, and cadmium coatings are preferred at
times on certain components like flanges and bolting
• Fusion-bonded epoxy (FBE) and a three-layer polyolefin
(3LPO) (polyethylene or polypropylene (PP)) are
currently the most widely used external anti-corrosion
coating system
• Single-layer FBE has been more popular in North
America, Saudi Arabia, and the UK; dual-layer FBE is in
favor in Australia; and 3LPO coatings dominate the rest
of the world's pipe coating market
 Adequate corrosion monitoring and
inspection
• Corrosion monitoring is the practice of measuring the corrosivity of
process stream conditions by the use of probes
• A mechanical, electrical, or electrochemical devices which are
inserted into the process stream and continuously exposed to the
process stream condition.
• Corrosion monitoring techniques alone provide direct and online
measurement of metal loss/corrosion rate in oil and process
systems
• One of the methods is to carry out the on-stream inspection by
doing the wall thickness measurements periodically on fixed and
vulnerable locations on the equipment, piping, and pipelines to
assess the material conditions and corrosion rates
• corrosion is monitored by placing electronic
probes in the pipelines and by measuring the
change in the electric resistance in the probe coil.
• The cross-country pipelines are normally checked
with intelligent pigging operations like magnetic
flux or ultrasonic pigs
• These pigs will detect the internal conditions of
the pipeline and corrosion conditions on the pipe
wall thickness and also indicate the wall thickness
available on the pipe wall
Ultrasonic pigs
• Most of the equipment like separators, drums,
and heaters are checked for corrosion during
annual shutdown and turnaround operations.
• Other areas where corrosion monitoring and
inspection are necessary in the oil and gas
industry include drilling mud systems,
digesters, water wash systems, flow lines,
transport pipelines, desalters, sour water
strippers, crude overheads,