Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Locations that host oil and gas operations often provide ideal conditions for corrosion.
Ongoing research and advances in coatings, cathodic protection, nondestructive
testing, corrosion analysis and inhibitors allow operators to safely produce oil and
gas in these corrosive environments.
Nausha Asrar
Bruce MacKay
Sugar Land, Texas, USA
ystein Birketveit
Marko Stipanicev
Bergen, Norway
Joshua E. Jackson
G2MT Laboratories, LLC
Houston, Texas
Alyn Jenkins
Aberdeen, Scotland
Denis Mlot
Total
Paris, France
Jan Scheie
Stavanger, Norway
Jean Vittonato
Total
Pau, France
Oilfield Review 28, no. 2 (May 2016).
Copyright 2016 Schlumberger.
DS-1617 is mark of M-I LLC.
Hastelloy is a registered trademark of
Haynes International, Inc.
Inconel and Monel are trademarks of
Special Metals Corporation.
34
Oilfield Review
According to the US Federal Highway Administration, the approximate annual direct cost of
corrosion for the US in 2015 was an estimated
US$500 billion, representing around 3.1% of
the nations gross domestic product.1 This figure
amounts to six times the average annual cost of
weather-related disasters for the US, which was
about US$87 billion in 2011.2 Unlike weather
events, corrosion can be controlled or at least
managed; scientists estimate that 25% to 30% of
corrosion costs could be avoided if good corrosion
management practices and preventive strategies
were employed.3
Throughout the ages, and despite an early
lack of understanding concerning the fundamental mechanisms involved, humans have attempted
to control corrosion. In ancient times, corrosion
resistance was sometimes imparted to materials
as a matter of circumstance rather than design
(Figure 1).4 Early corrosion control methods
included the use of bitumen and lead-based
paints by the Romans in the first century. Around
500BCE, Chinese sword makers used copper
sulfide coatings to inhibit corrosion on bronze
swords. Centuries later, the copper sheathing
used on British sailing vessels to reduce biofoulingfouling of underwater surfaces by organisms
such as barnacles and algaeand increase speed
accelerated the corrosion of nails that held the
ships together.5
1. Koch GH, Brongers MPH, Thompson NG, Virmani YP and
Payer JH: Corrosion Costs and Preventive Strategies in
the United States, Washington, DC: US Department of
Transportation Federal Highway Administration,
Publication FHWA-RD-01-156, March 2002.
Jackson JE: Corrosion Will Cost the US Economy over
$1 Trillion in 2015, G2MT Laboratories, http://
www.g2mtlabs.com/corrosion/cost-of-corrosion/
(accessed January 6, 2016).
Papavinasam S: Corrosion Control in the Oil and Gas
Industry. Waltham, Massachusetts, USA: Gulf
Professional Publishing, 2014.
2. The US$ 87 billion cost of weather-related disasters in
2011 was the highest on record. The average annual cost
has been closer to US$ 10 billion in recent years. For
more on the cost of weather-related disasters: Smith AB
and Katz RW: U.S. Billion-Dollar Weather and Climate
Disasters: Data Sources, Trends, Accuracy and Biases,
Natural Hazards 67, no. 2 (June 2013): 387410.
3. Chillingar GV, Mourhatch R and Al-Qahtani GD: The
Fundamentals of Corrosion and Scaling for Petroleum
and Environmental Engineers. Houston: Gulf Publishing
Company, 2008.
4. Kumar AVR and Balasubramaniam R: Corrosion Product
Analysis of Corrosion Resistant Ancient Indian Iron,
Corrosion Science 40, no. 7 (July 1, 1998): 11691178.
Balasubramaniam R: Story of the Delhi Iron Pillar. Delhi,
India: Foundation Books Pvt. Ltd, Cambridge House, 2005.
5. Groysman A: Corrosion for Everybody. Dordrecht, The
Netherlands: Springer Science+Business Media, 2010.
6. Ahmad Z: Principles of Corrosion Engineering and
Control, 1st ed. Burlington, Massachusetts: ButterworthHeinemann, 2006.
7. Kermani MB and Harrop D: The Impact of Corrosion on
the Oil and Gas Industry, SPE Production & Facilities 11,
no. 3 (August 1996).
May 2016
PA
S
KI
TA
C H I N A
NEP
AL
New Delhi
BANGLADESH
I
Mumbai
0
0
km
500
miles
SRI LANKA
500
Figure 1. Delhi pillar. This iron pillar is located in the Qutub Complex in New Delhi, Delhi, India (inset).
It is about 9.1m [30ft] tall and weighs approximately 6,000kg [13,200lbm]. Erected in 400CE, the
pillar is essentially free of the typical rusting that would be expected to take place over 1,600years
of exposure. Reasons for the lack of corrosion include New Delhis low humidity but are primarily
attributed to the high concentration of phosphorus in the iron.
Michael Faraday was one of the most important contributors to the early understanding of
corrosion; in the early 1800s, he established a
quantitative relationship between the chemical action of corrosion and electric current.6
Although much more is known about the subject
today, scientists continue to study the mecha-
Oilfield Review
MAY 16
Refining
Corrosion
Fig 1 Distribution
3.7
ORMAY 16 CRSSN 1 5.0
Production
1.4
Storage
7.0
Tankers
2.7
Pipelines
7.0
35
Anodic reaction
Fe0 Fe2+ + 2e
Cathodic reaction
H2O + 2e 0.5 O2 + 2OH
Fe2+ + 2OH Fe(OH) 2
OH
OH
Water
OH
Fe 2+
Fe0
Fe(OH) 2
Anode
Fe(OH) 2
Fe 0
Cathode
Electron flow
Fe0
Fe 0
Steel
Figure 3. Corrosion cell. When steel in water rusts, several reactions take
place simultaneously. At the anode, steel [Fe0] goes readily into solution to
form ferrous iron [Fe2+] and ferric iron [Fe3+] (not shown) ions, and electrons
move to the cathode. Electrons at the cathode react with water [H2O] to
form oxygen [O2] and hydroxyl [OH] ions. The OH ions combine with the
solubilized Fe2+ to form iron hydroxide [Fe(OH)2].
36
Iron can also react with CO2 to form iron carbonate [FeCO3] and with H2S to form iron sulfides
[FexSx]. In the absence of O2 but the presence of
CO2 and H2S, the cathodic reaction can generate
hydrogen gas.
These reactions can occur rapidly, but if the
reaction rate can be reduced, the overall corrosion rate will also be reduced. Many factors influence the reaction rate. These include the type
and quality of metal, electrolyte compositions,
pH, temperature, pressure, presence of dissolved
gases, liquid velocity, water salinity, application of cathodic protection and the presence of
microbes.11 To manage corrosion and corrosion
rate, knowledge of the metallurgy of the materials to be used and the environments in which
they will operate is important.
If CO2 comes into contact with water in the
producing or transportation system of an oil and
gas operation, areas typically affected include
well internals, gathering lines and pipelines. In
CO2 corrosion of iron, the products of reaction
are carbonic acid, iron carbonate [FeCO3] and
hydrogen gas [H2].12 For CO2 corrosion to occur,
the partial pressure of the gas can be as low as
21kPa [3 psi]. To prevent this type of corrosion,
operators commonly use organic films that act as
barriers and inhibitors that neutralize the acidity
of the carbonic acid generated in the corrosion
process. Operators may also use corrosion resistant alloys (CRAs), which are resistant to general
and localized corrosion, in environments that are
corrosive to carbon and low-alloy steels.
Hydrogen sulfide is often found in produced
fluids or as a result of MIC.13 Although H2S is not
corrosive, it becomes corrosive in the presence
of water.14 Sour corrosion from H2S can affect
any part of the producing system, including well
internals and oil and gas gathering lines. Oilfield
fluids are considered sour if the produced gas contains more than 5.7mg of H2S per m3 [4parts per
million (ppm)] of natural gas or produced water
has greater than 5ppm H2S.15 At the anode, the
H2S reacts with the iron to form several variants of iron sulfide [FexS] such as mackinawite
[(Fe,Ni)(1 + x)S], pyrrhotite [Fe(1 - x)S] and troilite
[FeS].16 These iron sulfide species precipitate and
can form localized microgalvanic corrosion cells.
The corrosion cells formed during sour corrosion cause pitting, sulfide stress cracking (SSC)
and hydrogen embrittlement.17 Stress corrosion
cracking is a result of tensile stress combined
with a wet environment and often causes shallow, round pits that have etched bottoms accompanied by branching cracks that can lead to rapid
failure. Hydrogen embrittlement occurs when
H2S and H2 diffuse into metal, recombine with
Oilfield Review
May 2016
30
25
20
15
O2
CO2
10
H2S
50
100
150
200
100
200
300
400
250
300
350
400
450
500
600
700
800
900
Oxygen
Carbon dioxide
Hydrogen sulfide
Gas concentration in water phase, parts per million
Figure 4. Corrosion rates. The relative rates of corrosion in milli-inches/year (mpy) of carbon steel
show pronounced differences when the steel is exposed to varying concentrations of O2, CO2 and H2S.
At a concentration of 5ppm, O2 is almost three times more corrosive than is H2S and 30% more
corrosive than is CO2. Photographs near each curve show the effects of these corrosion agents on
metal surfaces.
37
Water
Flow
Anode
Cathode
Steel
General or Uniform
Galvanic
Crevice
Water
Steel
Force
Pitting
Intergranular
Stress
Corrosion Cracking
Corrosion Fatigue
Figure 5. Generalized categories of corrosion. Corrosion can be categorized by appearance and the
agent of causation. These eight corrosion types cover most of the observed corrosion mechanisms
for metals.
that caused it. Although not an exclusive list, corrosion usually falls into one or more of the following categories: general or uniform, localized,
galvanic, erosion or flow induced, crevice, pitting,
under deposit, cavitation, intergranular, stress
cracking and corrosion fatigue (Figure5). Other
types of corrosion include environmental, top-ofline and microbial. Based on the observed characteristics of the corrosion, engineers can adopt
appropriate preventive and mitigationmeasures.
Uniform corrosion is typical of low-alloy
steels and may be observed over an entire
exposed area. Initial evidence of uniform corrosion is surface roughness. The metal becomes
thinner as the corrosion progresses, and it will
eventually fail from internal pressure or external
forces. Because this type of corrosion is linked to
surface exposure, it may be prevented by properly protecting the surface. Uniform corrosion
may occur in equipment used for oilfield operations such as hydraulic stimulation andacidizing.
Localized corrosion occurs at specific sites
rather than over a generalized area and may be
more dangerous than some other types of corrosion because of its unpredictable nature and
38
the potential for rapid growth. Localized corrosion, of which even CRAs such as stainless steels
are susceptible, can be subdivided into pitting,
crevice and under deposit corrosion. Pitting ultimately can cause holes in metal components and
is one of the primary causes of failure in oilfield
hardware, including tubing, casing, sucker rods
and surface equipment.
Crevice corrosion occurs in constricted areas,
wherein the metal at the crevice becomes anodic
and the rest of the metal serves as the cathode.
The crevice can form where two dissimilar metals
come into contact or be created by microgalvanic
cells that may occur in certain steel alloys.
Pitting corrosion rates are often much higher
than those of other types of corrosion. Inhibitors
Oilfield
may be applied
to theReview
surface to prevent initiaMAY 16
tion, but once Corrosion
a pit has formed
Fig 5 the inhibitors are
often unable toORMAY
slow its16
growth.
CRSSN 5
Under deposit corrosion occurs when sand,
corrosives or porous solids adhere to the metal
surface. Although the area underneath the
deposit is resistant to inhibitors and can corrode
quickly, this type of corrosion can often be man-
Oilfield Review
Pipe
Wet gas
Condensate
Monoethylene glycol
Anodic
Magnesium
Zinc
Cadmium
Aluminum
Steel
Chromium steel
Stainless steel
Lead
Tin
Nickel
Inconel
Hastelloy
Brasses
Copper
Bronzes
Monel
Chromium steel
Silver
Titanium
Graphite
Gold
Platinum
Cathodic
May 2016
Oilfield Review
MAY 16
Corrosion Fig 6
39
Separator Tank
Sidestream
Emulsion
Water outlet
Oil outlet
Water
Oil layer
Corrosion
inhibitor film
Iron sulfide
particle
Oilfield Review
MAY 16
Corrosion Fig 9
ORMAY 16 CRSSN 9
40
Oilfield Review
May 2016
Galvanic DC current
milliamp
Electrolyte
Cathode
Anode
Backfill
nailsled to the corrosion. Davy and his assisBecause the direct current (DC) is extertant carried out a number of experiments on cor- nally applied, this type of corrosion managerosion prevention techniques; that assistant was ment is referred to as impressed cathodic
Michael Faraday, who would later establish the protection. It is most frequently used for cases
relationship between the chemical action of cor- in which the electrolyte resistance is high, such
rosion and electric current.
as in soil or freshwater, and where a constant
In the oil field, CP was first applied to land24. Stipanicev M: Improved Decision Support Within
based pipelines, and the first documented use
Biocorrosion Management for Oil and Gas Water
Injection Systems, PhD thesis, Institut National
was by Robert J. Kuhn in 1928.29 He established
Polytechnique de Toulouse, France (2013).
a negative 850 mV potential between the steel 25. Madigan MT, Martinko JM, Bender KS, Buckley DH,
Stahl DA and Brock T: Brock Biology of Microorganisms,
pipe of a pipeline and a copper-sulfate electrode.
14th ed. San Francisco: Benjamin Cummings, 2014.
This example became the foundation of modern
Oilfield Review
26. Sessile refers to fixed or immobile organisms.
CP technology, although for many years the
effecMAY
16 27. Lehmann JA: Cathodic Protection of Offshore
Structures, paper OTC 1041, presented at the
tiveness was met with scientific skepticism.
Corrosion Fig 10
First Annual
ORMAY
10 Offshore Technology Conference, Houston,
Today, CP uses sacrificial elements
made 16 CRSSN
May 1821, 1969.
from aluminum, zinc and magnesium to protect 28. Davy H: On the Corrosion of Copper Sheeting by Sea
Water, and on Methods of Preventing This Effect; And
the steel of large structures and piping. These
on Their Application to Ships of War and Other Ships,
dissimilar metals create the galvanic coupling
Philosophical Transactions of the Royal Society of
London 114 (January 1, 1824): 151158.
that establishes a current path between the
Baeckmann W: The History of Corrosion
anode and the cathode, and, over time, the 29. von
Protection, in von Baeckmann W, Schwenk W and
Prinz W (eds): Handbook of Cathodic Corrosion
sacrificial anode rather than the protected
ProtectionTheory and Practice of Electrochemical
structure experiences metal loss. Appropriate
Protection Processes, 3rd ed. Houston: Gulf Professional
Publishing (1997): 126.
placement and distribution of the anodes is crucial to ensure that all parts of the structure are 30. Amani M and Hjeij D: A Comprehensive Review of
Corrosion and Its Inhibition in the Oil and Gas Industry,
sufficiently protected.30
paper SPE 175337, presented at the SPE Kuwait Oil
and Gas Show and Conference, Mishref, Kuwait,
October 1114, 2015.
41
Water
Water
Oil
Oil
CH 3
Alkyl
chain
CnH 2n
N+
Polar head
group
Metal surface
Figure 11. Film formers. Although they vary in composition and avenue of
protection, film formers create barriers between corrosive elements (water
and oil, top) and metal surfaces. Inhibitors may be adsorbed on the surface
(alkyl chains, middle) or form a strong bond by sharing charges with the
metal (polar head group, bottom). When molecules of the polar head group
of film formers attach to the surface of the metal, a portion of the molecule
extends into the fluid. This usually oil-soluble tail is hydrophobic, repelling
water away from the metal surface.
source of current is readily available. The use is to interrupt the electrochemical process by
of solar panels in remote locations has greatly which the corrosion cell forms between the metal
increased the potential applications of impressed and the liquids in and around the equipment.
Inhibitors can be a flexible and cost-effective
cathodicprotection.
In the impressed CP technique, current of method of fighting corrosion, and the inhibiseveral amps from a low-voltage rectifier passes, tor application can be altered when conditions
or is impressed, from an inert anode (for exam- change. Although acquiring and delivering the
ple, graphite or iron) to the structure being pro- inhibitor incur an ongoing cost, the lower costs
tected, which acts as the cathode. The anode associated with using less corrosion resistant
is attached to the positive terminal of the DC low-carbon steels usually more than make up
source, and the cathode is attached to the nega- thedifference.
Inhibitors fall into four main categories: scavtive terminal. The anode and cathode are often
some distance from each other, separated by engers, reactive agents, vapor phase and film
formers. Oxygen scavengers are frequently used
anelectrolyte.
To counteract corrosion, sufficient current in operations in which oxygen poses a corrosive
density must be supplied to all parts of the pro- threat. These agents not only reduce oxidizing
tected structure and the current density must corrosion, but also control the growth of microbes
always exceed what would be the measured cor- that require oxygen to thrive. Examples of oxygen
scavengers used in the oil and gas industry are
rosion rate under the same conditions.Oilfield
If theReview
corrosion rate increases, the impressed MAY
current
16 sodium sulfite, sulfur dioxide, sodium bisulfite,
Corrosion
11 metabisulfite and ammonium bisulfite.
sodium
density must be increased.31 Although the
initial Fig
ORMAY
CRSSN 11 bisulfite and sodium bisulfite are
equipment cost may be higher for impressed
CP 16Ammonium
than it is for sacrificial protection, this technique commonly used in seawater injection systems. To
may be less expensive over the long term because speed reaction rates, a catalyst may be included
sacrificial anodes do not need to be replaced. in the chemical.
Hydrogen sulfide scavengers reduce the
Impressed CP also has the advantage of providing information to the operator about the extent level of H2S in the flow stream. Examples of H2S
of corrosion over time.
scavengers are amines, aldehydes and zinc carboxylates. Common forms of amines are monoCorrosion Inhibitors
ethanolamine (MEA) and monomethylamine
Another line of defense against corrosion is (MMA) triazine. In some situations, operators
inhibitors, of which there are a variety of types may be able to regenerate MEA and MMA for
and applications. The primary goal of inhibitors reinjection and reuse.
42
Oilfield Review
May 2016
Use of corrosion
inhibitor recommended
Rotating Cylinder
Electrode Test
Kettle Test
Autoclave Test
Recommend and
implement corrosion
inhibitor addition
Sidestream Test
Analyze field
trial results
Make final
recommendation
Review
MAY 16
Corrosion Fig 12
ORMAY 16 CRSSN 12
43
Rack
Thermometer
Voltage potential, mV
Gas sparge
Steel electrode
Heating mantel
Voltage
Corrosion rate
Current
Current, mA
Stir bar
Figure 14. Kettle test. To perform kettle tests, or linear polarization resistance
tests, technicians use a test fixture (left) and control the pressure and
temperature. They submerge electrodes inside the fixture into the fluids
expected downhole and then measure electrical properties of the
electrodes. The tests are performed by controlling the voltage potential
44
and measuring the current then controlling the current and measuring
the voltage. The electrolyte can be agitated using the stir bar. Gas can be
injected into the test fixture, a process referred to as sparging. From the
slope of the polarization resistance curve (right ), the corrosion rate can
becomputed.
Oilfield Review
Cape Lopez
Cathodic protection station
Section 1
Section 2
Section 3
Tchngue
Cathodic protection station
AT LA N T IC O CEAN
GABON
Batanga
Cathodic protection station
Figure 15. Corrosion in a pipeline from the Rabi field to Cape Lopez. A
three-section, 18-in. pipeline carries oil from the inland Rabi field in Gabon
to Cape Lopez on the coast. Cathodic protection stations are located along
the pipeline. Because the incoming oil is hot (around 60C), Section 1 of the
pipeline (red and dark blue) is exposed to a higher temperature than is the
remainder of the pipeline. The elevated temperature led to the disbondment
May 2016
thermal stability
emulsification tendency
foaming tendency
metal compatibility
elastomer compatibility
compatibility with other chemicals used in the
same stream.
Application methods should be evaluated as well.
Injection may be continuous, batch or squeeze.
The rate of film removal is a key concern when
determining the optimal application mode.
Corrosion in the Oil Field
A recent example of pipeline corrosion from
Gabon illustrates the need for thorough testing
and understanding of the corrosion process.37 A
pipeline transports oil from the Rabi field to Cape
Lopeza distance of approximately 234km
[145mi]. The 18-in. pipeline comprises three
sections: Section1 from Rabi to Batanga, 105km
[65mi]; Section2 from Batanga to Tchengu,
45
BURKINA FASO
BENIN
FPSO vessel
NIGERIA
COTE
GHANA
DIVOIRE
Niger Delta
field
Gulf of Guinea
CAMEROON
GABON
Subsea
wellheads
Flowlines and
umbilicals
Figure 17. Niger delta subsea operations and a floating production, storage, and offloading (FPSO) vessel. Production from subsea wellheads (yellow) at a
field in the Niger delta off the coast of Nigeria (inset) is sent to an FPSO. Oil is transferred to tankers, and natural gas is piped directly to the mainland.
46
Oilfield Review
May 2016
Inhibitor
Uninhibited
Corrosion Rate, mpy
Inhibited
Corrosion Rate, mpy
Protection, %
DS-1617 inhibitor
10
173.01
4.18
97.58
DS-1617 inhibitor
20
156.43
0.98
99.37
Inhibitor
Protection, %
None
71.04
DS-1617 inhibitor
20
1.16
98.37
Figure 18. Corrosion testing of the DS-1617 inhibitor. Technicians conducted kettle tests with fluids
representative of field conditions to evaluate the effectiveness of the DS-1617 inhibitor (top). They
also performed autoclave testing at high temperature (bottom). The corrosion rate is in milli-inches of
penetration/year (mpy).
6.0
Low-pressure separator A
Low-pressure separator B
5.0
4.0
3.0
2.0
1.0
0.0
0
0.5
1.0
1.5
2.0
2.5
3.0
Time, hr
3.5
4.0
4.5
5.0
6.0
Figure 19. Corrosion monitoring at a production facility. The operator injected DS-1617 inhibitor into
the flowlines of producing wells using underwater umbilicals. The corrosion rate of the flowlines was
monitored at the low-pressure separator A (blue), low-pressure separator B (red) and the bulk oil
treater (green) as well as at three other locations (not shown). The corrosion rate dropped below the
target level (black) established by the operator. Corrosion rates remained below the threshold at all
test sites for the duration of the testing period.
47
Anode
Water Depth, m
Weight Loss, %
13
13
73
31
116
25
116
39
Figure 20. Anode corrosion after eight years of service in the North Sea.
Figure 21. Cathodic protection on a North Sea platform. Anodes were recovered
after eight years of service from a North Sea platform. After the anodes were
cleaned and weighed, technicians were able to determine the effectiveness of
the anodes at protecting the structure.
48
Oilfield Review
Contributors
Nausha Asrar is the Manager for Materials Support
and Failure Analysis at the Schlumberger Houston
Pressure and Sampling and Formation Evaluation
Centers in Sugar Land, Texas, USA. He began his
career with Schlumberger in 2005 as a senior materials scientist. He previously worked for Shell Global
Solutions in the US, the Saudi Basic Industries
Corporation Technology Center and Saline Water
Conversion Corporation, both in Saudi Arabia, and
as principal corrosion engineer at the Research and
Development Center for Iron and Steel for the Steel
Authority of India, Ltd. A NACE certified material
selection and design specialist, Nausha is a member
of NACE, ASM and SPE as well as a life member of the
Indian Institute of Metals; he is the author of more
than 60 technical papers and reviews on corrosion,
phase diagrams, composite materials and failure cases.
He received an MS degree in chemistry from Aligarh
Muslim University, Uttar Pradesh, India, and a PhD
degree in materials science and engineering from the
Moscow State University.
May 2016
49