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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 Corrosion validates the universal law of entropy; Corrosion has brought down bridges, downed
Bruce MacKay everything trends toward a state of greater chaos aircraft, leveled chemical plants, parted drill-
Sugar Land, Texas, USA and disorder. The flecks of rust on an iron bar or pipe and ruptured pipelines. Given sufficient
the green patina on a copper fixture are evidence of time, this adversary has the potential to degrade
ystein Birketveit the insidious effects of corrosion. These examples any material. In certain environments, the
Marko Stipanicev may be regarded as an annoyance, but taken to the unchecked effects of corrosion can come swiftly,
Bergen, Norway
extreme, the results of corrosion can lead to cata- and the consequences of failure to manage corro-
strophic outcomes. sion can be costly.
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
34 Oilfield Review
According to the US Federal Highway Admin-
N
TA C H I N A
istration, the approximate annual direct cost of S
KI NEP
corrosion for the US in 2015 was an estimated PA AL
US$500 billion, representing around 3.1% of New Delhi
the nations gross domestic product.1 This figure BANGLADESH
amounts to six times the average annual cost of
weather-related disasters for the US, which was I N D I A
about US$87 billion in 2011.2 Unlike weather
events, corrosion can be controlled or at least Mumbai
May 2016 35
Iron can also react with CO2 to form iron carbon-
ate [FeCO3] and with H2S to form iron sulfides
Anodic reaction Cathodic reaction [FexSx]. In the absence of O2 but the presence of
Fe0 Fe2+ + 2e H2O + 2e 0.5 O2 + 2OH
CO2 and H2S, the cathodic reaction can generate
Fe2+ + 2OH Fe(OH) 2
hydrogen gas.
These reactions can occur rapidly, but if the
reaction rate can be reduced, the overall corro-
OH Water OH
sion rate will also be reduced. Many factors influ-
OH ence the reaction rate. These include the type
and quality of metal, electrolyte compositions,
Fe 2+ Fe(OH) 2
Fe(OH) 2 pH, temperature, pressure, presence of dissolved
gases, liquid velocity, water salinity, applica-
Fe0 Anode Fe 0 Cathode tion of cathodic protection and the presence of
Electron flow microbes.11 To manage corrosion and corrosion
rate, knowledge of the metallurgy of the mate-
Fe0 Fe 0 rials to be used and the environments in which
Steel they will operate is important.
If CO2 comes into contact with water in the
producing or transportation system of an oil and
Figure 3. Corrosion cell. When steel in water rusts, several reactions take gas operation, areas typically affected include
place simultaneously. At the anode, steel [Fe0] goes readily into solution to
well internals, gathering lines and pipelines. In
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 CO2 corrosion of iron, the products of reaction
form oxygen [O2] and hydroxyl [OH] ions. The OH ions combine with the are carbonic acid, iron carbonate [FeCO3] and
solubilized Fe2+ to form iron hydroxide [Fe(OH)2]. 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,
prevention and control averaged about 8% of Some forms of metal corrosion are related operators commonly use organic films that act as
the total capital expenditure for its projects. to stability; for example, galvanic corrosion is barriers and inhibitors that neutralize the acidity
On the UK Continental Shelf, 25% to 30% of BPs an electrochemical process associated with the of the carbonic acid generated in the corrosion
operating costs were related to the control and movement of electrons between areas that have process. Operators may also use corrosion resis-
management of corrosion. Costs associated with different electrochemical potentials. The corro- tant alloys (CRAs), which are resistant to general
replacing corroded equipment, lost production sion cell schematically describes oxidizing corro- and localized corrosion, in environments that are
and corrosion-related contamination contributed sion, which is analogous to a battery in which two corrosive to carbon and low-alloy steels.
to overall expenditures. In addition to the direct dissimilar metals are connected by an electrolyte Hydrogen sulfide is often found in produced
costs, the company found that corrosion had a (Figure 3).9 A metal that has a higher corrosion fluids or as a result of MIC.13 Although H2S is not
significant indirect cost on health, safety and ratemore unstablerepresents the negative corrosive, it becomes corrosive in the presence
environmental concerns. part of the cell and acts as the anode; a second of water.14 Sour corrosion from H2S can affect
This article focuses on descriptions of cor- metal that has a lower corrosion ratemore any part of the producing system, including well
rosion, management techniques and advances stableacts as the positive part of the cell, internals and oil and gas gathering lines. Oilfield
in corrosion abatement technologies. Field thecathode.10 fluids are considered sour if the produced gas con-
examples from Gabon, deepwater Nigeria andReviewDuring the galvanic corrosion process, metal
Oilfield tains more than 5.7mg of H2S per m3 [4parts per
the North Sea illustrate the ongoing battle waged
MAY 16 oxides are formed as electrons flow from the million (ppm)] of natural gas or produced water
Corrosion Fig
against corrosion by oil and gas operators. 3 to the cathode through the electrolyte
anode has greater than 5ppm H2S.15 At the anode, the
ORMAY 16 theCRSSN
fluid3in contact with the anode and cathode. H2S reacts with the iron to form several vari-
The Corrosion Process A simplified version of iron oxidation can be used ants of iron sulfide [FexS] such as mackinawite
Scientists and engineers today have a better to illustrate the galvanic corrosion processthe [(Fe,Ni)(1 + x)S], pyrrhotite [Fe(1 - x)S] and troilite
understanding of corrosion processes than did actual process is more complex. The presence of [FeS].16 These iron sulfide species precipitate and
the ancient Romans and Chinese. Fighting cor- water [H2O] on the surface of the iron [Fe or Fe0] can form localized microgalvanic corrosion cells.
rosion requires an understanding of the principal releases electrons to form ferrous iron [Fe+2] and The corrosion cells formed during sour corro-
elements that cause and contribute to the corro- ferric iron [Fe+3] ions, which act as the anode in sion cause pitting, sulfide stress cracking (SSC)
sion. There are several categories of corrosion; for our battery analogy. The liberated electrons flow and hydrogen embrittlement.17 Stress corrosion
the oil and gas industry, common types include to the cathode, where, in the presence of oxygen cracking is a result of tensile stress combined
exposure to carbon dioxide [CO2, sweet corro- [O2], ferrous oxide [FeO] and ferric oxide [Fe2O3] with a wet environment and often causes shal-
sion], hydrogen sulfide [H2S, sour corrosion], form as scales of rust or precipitates. A byproduct low, round pits that have etched bottoms accom-
oxygen [O2] and corrosion causing microbes, of the reaction at the cathode is hydroxyl ions panied by branching cracks that can lead to rapid
referred to as microbiologically influenced cor- [OH] from the reduction of oxygenated water. failure. Hydrogen embrittlement occurs when
rosion (MIC).8 H2S and H2 diffuse into metal, recombine with
36 Oilfield Review
other molecules and create pressure within the 30
metal matrix; byproducts of cathodic protection,
galvanic corrosion and other mechanisms may
lead to hydrogen embrittlement.
25
The failure mode during hydrogen embrittle-
ment depends on the steel type; for example,
low-strength steels exhibit blistering. The failure
mode of high-strength steels can be catastrophic
May 2016 37
Water
Flow
Anode
Steel Cathode
Water
Steel Force
Stress
Pitting Intergranular 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, cor- the potential for rapid growth. Localized corro- aged by cleaning internal piping surfaces, for
rosion usually falls into one or more of the fol- sion, of which even CRAs such as stainless steels example, with the use of pipeline pigs.
lowing categories: general or uniform, localized, are susceptible, can be subdivided into pitting, Galvanic corrosion can be a problem when
galvanic, erosion or flow induced, crevice, pitting, crevice and under deposit corrosion. Pitting ulti- two dissimilar metals are in contact. The metal
under deposit, cavitation, intergranular, stress mately can cause holes in metal components and that has the least resistance to corrosion acts as
cracking and corrosion fatigue (Figure5). Other is one of the primary causes of failure in oilfield the anode and the more resistant metal serves as
types of corrosion include environmental, top-of- hardware, including tubing, casing, sucker rods the cathode. The anode typically corrodes pref-
line and microbial. Based on the observed char- and surface equipment. erentially. This form of corrosion is frequently
acteristics of the corrosion, engineers can adopt Crevice corrosion occurs in constricted areas, observed in offshore platforms and pipelines.
appropriate preventive and mitigationmeasures. wherein the metal at the crevice becomes anodic The galvanic series, which orders metals accord-
Uniform corrosion is typical of low-alloy and the rest of the metal serves as the cathode. ing to their anodic or cathodic tendencies, is a
steels and may be observed over an entire The crevice can form where two dissimilar metals good predictor of corrosion severity (Figure 6).
exposed area. Initial evidence of uniform corro- come into contact or be created by microgalvanic Galvanic corrosion is controlled and mitigated by
sion is surface roughness. The metal becomes cells that may occur in certain steel alloys. use of the following:
thinner as the corrosion progresses, and it will Pitting corrosion rates are often much higher good engineering designto ensure that cor-
eventually fail from internal pressure or external than those of other types of corrosion. Inhibitors rosively active components present larger sur-
forces. Because this type of corrosion is linked to may be applied Oilfield
to theReview
surface to prevent initia- face area than do less active components
MAY 16
surface exposure, it may be prevented by prop- tion, but once Corrosion
a pit has formed
Fig 5 the inhibitors are material selectionto avoid metals far apart
erly protecting the surface. Uniform corrosion often unable toORMAY
slow its16
growth.
CRSSN 5 in the galvanic series
may occur in equipment used for oilfield opera- Under deposit corrosion occurs when sand, isolationto provide pipelines coming from the
tions such as hydraulic stimulation andacidizing. corrosives or porous solids adhere to the metal sea with sacrificial anodes and protect those
Localized corrosion occurs at specific sites surface. Although the area underneath the going into land with impressed current systems
rather than over a generalized area and may be deposit is resistant to inhibitors and can corrode inhibitors and coatingsto control initiation
more dangerous than some other types of cor- quickly, this type of corrosion can often be man- of corrosion, although this method may be inef-
rosion because of its unpredictable nature and fective once corrosion forms.
38 Oilfield Review
Flow-induced corrosion occurs when liquid
Pipe
flow accelerates corrosion. Wellheads and pumps
are susceptible to this form of corrosion, which
may occur as erosion or cavitation. Erosion cor-
rosion results when fluid flow removes the pro-
tective film that forms naturally or has been
applied externally. Because of their abrasive
properties, suspended solids will accelerate the
process. Damage can be seen as grooves in the Wet gas
piping that correspond to the flow direction.
Proper engineering design that allows for suf-
ficient pipe diameter and removing solids from
flow streams can minimize this type of corrosion.
Inhibitors may be applied to replace protective
films stripped away by the flowing fluids. Condensate
Monoethylene glycol
Anodic
Magnesium
Zinc Figure 7. Top-of-line pipeline corrosion. Top-of-line corrosion can
Cadmium result from the stratified multiphase flow of wet gas in horizontal
Aluminum pipelines. Liquidsincluding condensate and inhibitors such as
monoethylene glycolsettle to the bottom of the pipe. Wet gas fills
Steel
the pipe above the liquid line. If either CO2 or H2S are present in the
Chromium steel gas, along with water, corrosive byproducts form at the top of the
Stainless steel pipe and may not be controlled if the inhibitor remains at the bottom
Lead of the pipe.
Tin
Nickel
Inconel
Cavitation is caused by collapsing bubbles hydrogen embrittlementhydrogen enters
Hastelloy
that occur when the pressure changes rapidly in the metal matrix and weakens it
Brasses
flowing liquids. Over time, cavitation may cause stress corrosion crackingcracks form after
Copper
deep pits to form in areas of turbulent flow, espe- corrosion has attacked a surface
Bronzes
Monel
cially in pump impellers. Low-carbon steels are sulfide stress crackinga failure of the metal
Chromium steel
susceptible; stainless steels are more resilient.22 caused by H2S.
Silver Intergranular corrosion results from cor- Material selectionopting for materials that are
Titanium rosive attacks at metal grain boundaries in the resistant to hydrogen embrittlement and sulfide
Graphite form of cracks. The grain boundaries can become crackingis the primary avoidance technique.
Gold anodic with reference to the cathodic surround- Low-stress design practices and stress relief by
Platinum ing surface, typically due to formation of chro- heat treatment are also commonly used, and pre-
mium carbides or nitrides. Metal impurities can venting corrosion in components subject to stress
Cathodic
increase the effect, as can precipitates in the is another method.
metal that form during heat treatments. When Pipelines are subject to top-of-line corrosion
Oilfield Review
chromium combines with nitrogen orMAY carbon,
16 (Figure 7). Water condenses at the top of the
less free chrome is available locally for corro- pipe
Corrosion Fig 7 as the fluid inside cools. The corrosion rate
sion protection, and cracks can form alongORMAY 16 CRSSN 7 the condensation rate and concen-
the depends on
grain boundaries. Quenchingthe rapid cool- tration of organic acids. Generally, this type of
ing after heat treatmentsmay be effective in corrosion is controlled with inhibitors and pipe-
Figure 6. Galvanic series. Metals (not all shown) reducing or eliminating intergranular corrosion. line insulation that reduces condensation.
can be described by their anodic or cathodic Material selectionavoiding metals that are
tendencies arranged in a galvanic series. When 22. Port RD: Flow Accelerated Corrosion, paper NACE721,
susceptible to this conditionis the most reli- presented at the NACE Corrosion 98 Annual Conference,
dissimilar metals are connected electrically San Diego, California, USA, March 2227, 1998.
and submerged in an electrolyte, the anodic able method to preclude intergranular corrosion.
metal, rather than the cathodic metal, will Tests such as ASTM A262 can be used to evaluate 23. ASTM International: Standard Practices for Detecting
Susceptibility to Intergranular Attack in Austenitic
preferentially corrode. The rate of corrosion is susceptibility of materials to this mechanism.23 Stainless Steels, West Conshohocken, Pennsylvania,
a function of the separation between the paired USA: ASTM International A262-15, 2015.
Environmental cracking occurs when cor
metals in the galvanic series. The series shown
here is for seawater; the order may change rosion coincides with tensile stress. It may be
based on the electrolyte. manifested as the following:
40 Oilfield Review
Although materials selection is a major part
of the corrosion control process, once the equip-
ment is deployed, oilfield operations generally
follow three methodologies to battle corrosion. Galvanic DC current
nails occurred when copper claddingused to anode and the cathode, and, over time, the 29. von Baeckmann W: The History of Corrosion
Protection, in von Baeckmann W, Schwenk W and
prevent biofoulingwas applied to the outside sacrificial anode rather than the protected Prinz W (eds): Handbook of Cathodic Corrosion
ProtectionTheory and Practice of Electrochemical
of vessels. Davy found that sacrificial anodes structure experiences metal loss. Appropriate Protection Processes, 3rd ed. Houston: Gulf Professional
protected the iron nails. The actual processes placement and distribution of the anodes is cru- Publishing (1997): 126.
were not well understood at that time, but it is cial 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,
recognized today that the contact of dissimilar sufficiently protected.30 paper SPE 175337, presented at the SPE Kuwait Oil
metalsthe copper cladding and the iron of the and Gas Show and Conference, Mishref, Kuwait,
October 1114, 2015.
May 2016 41
Reactive inhibition operates at the cathode
Water Water
level for the corrosion cell. The cations of the
inhibitor react with the cathodic anions to form
Oil Oil insoluble films, which adhere to the surface
CH 3 of the metals and prevent O2 from coming into
contact with the metal. These films also prevent
the evolution of H2, a byproduct of the corrosion
Alkyl cell. Examples are forms of calcium carbonate,
chain
CnH 2n magnesium carbonate and iron oxides. Reactive
inhibitors can also serve as poisons to the corro-
N+
Polar head sion cell process by interfering with the forma-
group
tion of H2 and reducing the reaction rates at both
Metal surface the cathode and anode.
Vapor phase inhibitors are primarily used for
Figure 11. Film formers. Although they vary in composition and avenue of combating CO2 corrosion. These inhibitors neu-
protection, film formers create barriers between corrosive elements (water tralize CO2 and block the formation of carbonic
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 acid [H2CO3]. They are transported via vapor
metal (polar head group, bottom). When molecules of the polar head group phase in wet gas lines. To protect against future
of film formers attach to the surface of the metal, a portion of the molecule corrosion, they may also be used during hydro-
extends into the fluid. This usually oil-soluble tail is hydrophobic, repelling static testing of components with water, espe-
water away from the metal surface.
cially when the components are to be stored after
fitness testing. Examples of these types of inhibi-
tors include morpholine and ethylenediamine.
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 Film Formers
increased the potential applications of impressed and the liquids in and around the equipment. Film formers are the most widely used corrosion
cathodicprotection. Inhibitors can be a flexible and cost-effective inhibitors in the oil and gas industry. They cre-
In the impressed CP technique, current of method of fighting corrosion, and the inhibi- ate a continuous layer between the metal and the
several amps from a low-voltage rectifier passes, tor application can be altered when conditions reactive fluids, thus reducing the attack of corro-
or is impressed, from an inert anode (for exam- change. Although acquiring and delivering the sive elements (Figure 11). They may also attach
ple, graphite or iron) to the structure being pro- inhibitor incur an ongoing cost, the lower costs to the surface of corroded metal, altering it and
tected, which acts as the cathode. The anode associated with using less corrosion resistant reducing the corrosion rate. Although they are
is attached to the positive terminal of the DC low-carbon steels usually more than make up effective in reducing CO2 and H2S corrosion, film
source, and the cathode is attached to the nega- thedifference. formers are not effective against O2 corrosion.
tive terminal. The anode and cathode are often Inhibitors fall into four main categories: scav- Film formers are available in oil-soluble,
some distance from each other, separated by engers, reactive agents, vapor phase and film water-soluble and oil solublewater dispersible
anelectrolyte. formers. Oxygen scavengers are frequently used forms. Oil-soluble inhibitors are used to treat oil-
To counteract corrosion, sufficient current in operations in which oxygen poses a corrosive and gas-producing wells. Water-soluble inhibi-
density must be supplied to all parts of the pro- threat. These agents not only reduce oxidizing tors are used in high water-cut flow streams,
tected structure and the current density must corrosion, but also control the growth of microbes including those found in producing wells, trans-
always exceed what would be the measured cor- that require oxygen to thrive. Examples of oxygen mission lines and separators. Oil solublewater
rosion rate under the same conditions.Oilfield scavengers used in the oil and gas industry are
If theReview dispersible inhibitors are used in oil and gas
corrosion rate increases, the impressed MAY 16 sodium sulfite, sulfur dioxide, sodium bisulfite,
current wells that are also producing water.
density must be increased.31 Although the Corrosion
initial Fig 11 metabisulfite and ammonium bisulfite.
sodium Film-forming inhibitors take various chemical
equipment cost may be higher for impressed ORMAY CP 16Ammonium
CRSSN 11 bisulfite and sodium bisulfite are forms but are typically composed of long carbon
than it is for sacrificial protection, this technique commonly used in seawater injection systems. To chains with nitrogen, phosphate esters or anhy-
may be less expensive over the long term because speed reaction rates, a catalyst may be included drides. Inhibitors may adhere to or be adsorbed
sacrificial anodes do not need to be replaced. in the chemical. on the metal surface, which prevents the corro-
Impressed CP also has the advantage of provid- Hydrogen sulfide scavengers reduce the sives from attacking the metal. The most effec-
ing information to the operator about the extent level of H2S in the flow stream. Examples of H2S tive film-forming inhibitors create a molecular
of corrosion over time. scavengers are amines, aldehydes and zinc car- bond at the metal surface in a process of charge
boxylates. Common forms of amines are mono- sharing or charge transfer. For effective inhibi-
Corrosion Inhibitors ethanolamine (MEA) and monomethylamine tion, the surface of the metal being protected
Another line of defense against corrosion is (MMA) triazine. In some situations, operators must be fully covered; injection of the proper
inhibitors, of which there are a variety of types may be able to regenerate MEA and MMA for concentrations of the inhibitor are crucial. After
and applications. The primary goal of inhibitors reinjection and reuse. they interact with the corrosive elements, some
42 Oilfield Review
inhibitors are gradually removed from the metal
Use of corrosion
surface and must be continuously replenished inhibitor recommended
with new inhibitor.
In the petroleum industry, organic inhibitors
are frequently used because they can form protec-
tive layers even in the presence of hydrocarbons. Predict corrosion rate
from field data
Amides and imidazolines are examples of organic
film-forming inhibitors that are effective over
a wide range of conditions, especially in sweet
(CO2) and sour (H2S) gas corrosion environments.
Develop and execute
They can be water or oil soluble. Amines, which testing program
are also organic inhibitors, are effective for sweet
and sour corrosion but may exhibit biologic toxic-
ity and are thus not as environmentally friendly
as are amides.
Quaternary ammonium salt, or quaternary
amine, inhibitors are effective against sour corro-
sion.32 The corrosive element formed by sour gas
is iron sulfide on the metal surface. Quaternary
ammonium cations, or quats, are positively
charged, and when they are adsorbed on the
Rotating Cylinder Kettle Test Autoclave Test
surface of the material to be protected, they dis- Electrode Test
rupt the normal corrosion cell charge. However,
at least one study indicated that quaternary
Recommend and
ammonium inhibitors may actually increase the implement corrosion
corrosion rate of sweet corrosion in the presence inhibitor addition
of brine.33 The biocide properties of quaternary
ammonium salts may also preventMIC.
Many additional film formers are used in the
oil and gas industry, including phosphate esters, Conduct field trial
ester quats, dimer and trimer acids and alkyl pyr-
idine quaternary compounds. Most film-forming
applications include multiple inhibitors; labora- Sidestream Test
tory testing is used to establish optimum concen- Analyze field
trations, fluid tolerances, stability, effectiveness trial results
Inhibitor Selection Figure 12. Laboratory testing of corrosion inhibitors. Operators usually
Laboratory evaluation is the key to developing develop corrosion control plans and then test inhibitors using conditions
an effective program in inhibitor selection for expected from the field. This flowchart follows a testing sequence. Three
common testing methods are the rotating cylinder electrode, kettle and
corrosion control. Technicians begin the process
autoclave tests (middle). Even after laboratory testing, field trials should be
using fluid samples that replicate field condi- conducted to validate the effectiveness of the program. A sidestream test
tionsactual produced fluids are best if avail- (lower left ) acquires samples for analysis. If the proposed method provides
able. Simulated and synthetic fluids are used acceptable results, the method is adopted, although the corrosion inhibition
program must be reevaluated during the life of the well.
when produced fluids cannot be obtained. From
laboratory tests, corrosion rates can be mea-
sured and predictions can be made for large-
scale operations (Figure 12). Methods for test- 31. Schweitzer PA: Corrosion of Linings and Coatings: Carbon Steel under Water and Its Inhibition by a
ing corrosion inhibitors include the following Cathodic and Inhibitor Protection and Corrosion Quaternary Ammonium Salt, paper NACE 05307,
Monitoring. Boca Raton, Florida: CRC Press, 2006. presented at the NACE Corrosion 2005 Conference and
tests: wheel, kettle (also called linear polariza- 32. Binks BP, Fletcher PDI, Hicks JT, Durnie WH and Exhibition, Houston, April 37, 2005.
tion resistance (LPR) tests), rotating cylinder Horsup DI: Comparison of the Effects of Air, Carbon 33. Binks et al, reference 32.
Dioxide and Hydrogen Sulphide on CorrosionOilfield Review
of a Low
MAY 16
Corrosion Fig 12
ORMAY 16 CRSSN 12
May 2016 43
electrode, autoclave, jet impingement and flow
Rack
loop (Figure 13). The most common are the
wheel and kettle tests.34
The wheel test measures the loss of metal
during a specified period of exposure to corro-
sive liquids. Corrosives include produced fluids,
brines and refined oils. The test fixture includes
a rotating wheel inside a sealed box that keeps
the specimen, usually strips of metal or coupons,
in constant motion. Temperature can be main-
tained at a constant value or varied to simulate
Metal coupon container field conditions. The samples are tested with and
without inhibitor and the results are compared.
High-temperature autoclave
The kettle test, or LPR test, measures corro-
Pressure source sion rates electrochemically. Metal electrodes
(hydraulic pump) are placed in the test vessel, which is heated
while the corrosive fluid is continously agitated.
Agitation attempts to replicate field conditions
mild agitation is similar to flow of two distinct
Figure 13. Autoclave corrosion testing. A high-temperature autoclave is sources, and high agitation replicates turbulent
used to test the effectiveness of corrosion inhibitors on metal coupons
(inset). Hydrostatic pressure and temperature can be applied to simulate fluid flow that has dispersed hydrocarbons. To
downhole conditions. simulate the presence of gases, CO2 and H2S can
be bubbled through the liquid in the vessel in a
process referred to assparging.35
To establish a control corrosion rate, the test
is run with the electrodes exposed to the fluids
in aqueous phase without an inhibitor and then
followed by a series of tests on solutions that have
Thermometer
increased inhibitor volumes. Linear polarization
is performed by controlling the voltage potential
Gas sparge
and measuring the current then controlling the
Voltage potential, mV
Voltage
Corrosion rate
Steel electrode Current
Stir bar
Figure 14. Kettle test. To perform kettle tests, or linear polarization resistance and measuring the current then controlling the current and measuring
tests, technicians use a test fixture (left) and control the pressure and the voltage. The electrolyte can be agitated using the stir bar. Gas can be
temperature. They submerge electrodes inside the fixture into the fluids injected into the test fixture, a process referred to as sparging. From the
expected downhole and then measure electrical properties of the slope of the polarization resistance curve (right ), the corrosion rate can
electrodes. The tests are performed by controlling the voltage potential becomputed.
44 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 stations
Cathodic protection station
powered by two solar cells
Input temperature
~ 60 C
Rabi Field
Cathodic protection station
Figure 15. Corrosion in a pipeline from the Rabi field to Cape Lopez. A of the protective outer covering of the pipeline. Engineers concluded
three-section, 18-in. pipeline carries oil from the inland Rabi field in Gabon that corrosion observed in Section 1 resulted from a combination of the
to Cape Lopez on the coast. Cathodic protection stations are located along disbonding of the protective covering and ineffective cathodic protection.
the pipeline. Because the incoming oil is hot (around 60C), Section 1 of the Although the pipelines safety was not compromised, the operator
pipeline (red and dark blue) is exposed to a higher temperature than is the implemented new procedures to prevent the corrosion from recurring.
remainder of the pipeline. The elevated temperature led to the disbondment
current and measuring the voltage potential. thermal stability 100km [62mi] and then Section3 from Tchengu
The data are plotted, and the slope of the line emulsification tendency to Cape Lopez, 29km [18mi] (Figure15).
is the polarization resistance, which is inversely foaming tendency The inlet pressure at Rabi was about 40bar
proportional to the corrosion rate (Figure 14). metal compatibility [580psi], and the flowing temperature was 60C
This technique provides corrosion rate evalua- elastomer compatibility [140F] at the inlet. Beyond the inlet, the line oper-
tion from external measurements, whereas other compatibility with other chemicals used in the ates at about 35C [95F]. Impressed cathodic pro-
methods require technicians to physically mea- same stream. tection is used for the pipeline, which has sections
sure and evaluate corrosion. Application methods should be evaluated as well. that have solar cells to provide current. The pipeline
The effectiveness of inhibitors is dependent Injection may be continuous, batch or squeeze. was coated with three-layer polyethylene; each joint
on fluid velocity. For fluids containing little or The rate of film removal is a key concern when was brush cleaned and wrapped with heat-shrink
no solid particles, high flow rates can lead to determining the optimal application mode.
34. NACE Task Group T-1D-34 on Laboratory Corrosion
flow-accelerated corrosion. If the flow stream Inhibitor Test Parameters: Laboratory Test Methods for
contains solid particles, the accelerated corro- Corrosion in the Oil Field Evaluating Oilfield Corrosion Inhibitors, Houston, NACE
International, NACE Publication 1D196, December 1996.
sion is termed erosion corrosion. Several test A recent example of pipeline corrosion from 35. NACE Task Group T-1D-34 on Laboratory Corrosion
methods have been developed to model corrosion Gabon illustrates the need for thorough testing Inhibitor Test Parameters, reference 34.
in high-flow conditions and determine a films and understanding of the corrosion process.37 A 36. Efird KD: Jet Impingement Testing for Flow Accelerated
Corrosion, paper NACE 00052, presented at NACE
persistence, especially where turbulent flow is pipeline transports oil from the Rabi field to Cape Corrosion 2000 Conference and Exhibition, Orlando,
present.36 Test methods include jet impingement, Lopeza distance of approximately 234km Florida, March 2631, 2000.
37. Melot D, Paugam G and Roche M: Disbondments of
rotating cylinder electrodes and flow looptesting. [145mi]. The 18-in. pipeline comprises three Pipeline Coatings and Their Effects on Corrosion Risks,
The testing of inhibitors should determine sections: Section1 from Rabi to Batanga, 105km Journal of Protective Coatings and Linings 26, no. 9
(September 2009): 6776.
the following: [65mi]; Section2 from Batanga to Tchengu,
May 2016 45
may have prevented cathodic current from reaching
and protecting the surface of the exposed steel.
Although engineers discovered corrosion as a result
of disbonding of coatings, based on ASME standards,
the degree of corrosion was deemed not mechani-
cally dangerous. They also concluded that as long as
coatings remain bonded to the steel and cathodic
protection is correctly applied, monitored and main-
tained, no corrosion risk existed for this pipeline.
GABON
Gulf of Guinea
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
stability, performance and properties. Thorough Inhibitor Dose Rate, ppm Uninhibited Inhibited Protection, %
testing of the inhibitors is required to ensure Corrosion Rate, mpy Corrosion Rate, mpy
corrosion controlling properties are maintained,
DS-1617 inhibitor 10 173.01 4.18 97.58
that the injected chemicals remain stable and
DS-1617 inhibitor 20 156.43 0.98 99.37
that the inhibitors can be reliably delivered via
the umbilicals into the flow stream. Inhibitor Dose Rate, ppm Corrosion Rate, mpy Protection, %
Another risk in deepwater production is the
None 71.04
formation of hydratesice-like solids of water
and gas that form above the normal freezing point DS-1617 inhibitor 20 1.16 98.37
of waterthat can plug flowlines. To ensure cor- Figure 18. Corrosion testing of the DS-1617 inhibitor. Technicians conducted kettle tests with fluids
rosion controlling properties are maintained, representative of field conditions to evaluate the effectiveness of the DS-1617 inhibitor (top). They
inhibitors must be thoroughly tested to confirm also performed autoclave testing at high temperature (bottom). The corrosion rate is in milli-inches of
penetration/year (mpy).
that the injected chemicals remain stable and
that the inhibitors can be reliably delivered via
umbilicals into the flow stream. Engineers developed the DS-1617 deepwater and to pressurized CO2 heated to 120C [248F].
These conditions were faced by an operator corrosion inhibitor to meet the challenges of The results indicated a 98% reduction in the
of a deepwater production platform in Nigeria. thisfacility. corrosion rate.41 The 20ppm concentration
The platform served nine wells drilled in water To qualify this inhibitor, they tested the yielded corrosion rates of about 0.00016in./year
depth of 1,030m [3,380ft]. The operator used chemicals in accordance with the API TR 17TR6 [0.004mm/year]. For corrosion rate, the stan-
subsea completions that included five manifolds standard, which requires replicating the temper- dard industry units are milli-inches/year, or mpy.
and eight production flowlines and risers. The atures and pressures experienced by the inhibitor For this test, the corrosion rate was equivalent to
flowlines were connected to a floating produc- during deployment through the umbilicals.40 The 0.16mpy. Test technicians reported no foaming
tion, storage, and offloading (FPSO) vessel that evaluation included high-pressure flow-loop sta- problems associated with the inhibitor.
had 320,000m3 [2million bbl] of onsite storage bility tests. The engineers conducted additional The operator adopted the use of the DS-1617
capacity. Produced oil flowed to the FPSO for tests to look at resistance to hydrate formation, inhibitor and monitored corrosion at six loca-
transfer to tankers. Produced gas was directed to thermal aging and compatibility with seawater. tions on the FPSO. No corrosion monitoring
shore via pipelines. Because the operator was concerned about foam- was installed on the deepwater flowlines. The
The pipelines used to transport the oil and ing in the glycol regeneration unit, the inhibitor DS-1617 inhibitor was injected at a 100-ppm
gas were constructed of carbon steel. The flow- was tested for foamingtendency. rate, which is a lower rate than the initial inhibi-
ing pressure from the wells averaged 80bar Laboratory technicians performed kettle tor that was deemed insufficient. Criteria for
[1,160psi], and the average temperature was tests using the DS-1617 inhibitor at 20 ppm, corrosion protection established by the opera-
85C [185F]. The water cut was 45% and the which is a relatively low dosage; the corrosion tor was a rate below 0.05mpy [0.0013mm/year].
natural gas contained about 1.4% CO2. The com- rate was reduced by 99% (Figure 18). They also Testing at all six locations indicated corrosion
bination of produced water (brine) and CO2 performed high-temperature autoclave testing rates below the target rate (Figure 19). Based on
presented a high corrosion-rate potential for on carbon steel coupons. The samples were sub- the testing, the operator implemented the use of
the low-carbon steel. In wet gas pipelines such jected to test fluids that had corrosion inhibitor the DS-1617 inhibitor.
as these, produced water has a tendency to con-
6.0
dense at the top of the pipe, allowing top-of-line Low-pressure separator A
corrosion; the presence of both water and CO2 Low-pressure separator B
5.0
accelerates corrosion. Bulk oil treater
Engineers installed chemical umbilicals of Target corrosion rate
4.0
1to 20km [0.6 to 12.4mi] to inject corrosion
Corrosion rate, mpy
May 2016 47
Anode Water Depth, m Weight Loss, %
New Developments in Corrosion Control
Controlling corrosion has been an ongoing
1 13 13
battle between humans and nature for millen-
2 73 31 nia. Since scientists such as Sir Humphry Davy
3 116 25 and Michael Faraday discovered some of the
4 116 39 underlying physics that explained corrosion,
various methodologies have been adopted and
Figure 20. Anode corrosion after eight years of service in the North Sea. adapted. Modern scientific understanding and
new technologies are combining to improve
the tools available to fight the unending battle
with corrosion.
North Sea Cathodic Protection determined changes in physical dimensions and One area of emerging materials science is
North Sea production platforms routinely use measured electrical properties. Four anodes nanoparticles and nanostructures.43 Having sur-
cathodic protection. On one platform, the opera- were analyzed for the study. The reduction of face thickness of 1 to 100 nm, these coating mate-
tor installed 10 sacrificial anodes below the sur- anodes that had been placed in deeper water was rials have unique properties that may make them
face of the water and left them in place for eight greater than that of those placed in shallower almost impervious to corrosion. Nanoparticles
years. The anodes were composed of zinc, silver water. Some of the anodes were so corroded that and nanostructures may be deposited on metal
and silver chloride and were located at various visual inspection was difficult (Figure 21). surfaces as films, similar to film-forming tech-
depths and locations on the plaform.42 The system The original 20-year design projected that at niques, but because of nanoparticles greater
was designed to protect the structure for a mini- eight years, the anodes should be reduced by 40%; persistence, reapplying them is unnecessary. The
mum of 20 years. Engineers monitored the output however, the average weight loss of the anodes surfaces also become super-slickexhibiting
current from three of the anodes over the period. was only 24%. The engineers concluded that the low friction coefficientswhich reduces wear
The anodes were removed and inspected at the original design, although conservative, would and increases durability. Such surfaces are also
end of eight years. protect the structure for at least 20 years. Based less likely to experience biofouling.44
After retrieval, the sacrificial anodes were on the results of the study, a model was estab- The battle against corrosion will never
cleaned and weighed (Figure 20). Technicians lished for periodic inspections to be performed. be won; entropy will eventually win the war.
Humans will, however, continue to search for
effective means to combat this nemesis. The
costs of ignoring the problem are too great and
the consequences of failure can be potentially
catastrophic. At least in the oil field, operators
are armed with knowledge, science and effective
tools that allow them to actively manage or miti-
gate the effects of corrosion. DEA/TS
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.
42. Roche M: Offshore Cathodic Protection: The Lessons of 44. Tesler AB, Kim P, Kolle S, Howell C, Ahanotu O and
Long-Term Experience, paper OMC-2005-020, presented Aizenberg J: Extremely Durable Biofouling-Resistant
at the 7th Offshore Mediterranean Conference and Surfaces Based on Electrodeposited Nanoporous
Exhibition, Ravenna, Italy, March 1618, 2005. Tungstite Films on Steel, Nature Communications 6,
43. El-Meligi AA: Nanostructure of Materials and Corrosion no. 8649 (October 20, 2015).
Resistance, in Aliofkhazraei M (ed): Developments in
Corrosion Protection. Rijeka, Croatia: InTech (2014): 323.
48 Oilfield Review
Contributors
Nausha Asrar is the Manager for Materials Support Bruce MacKay is Client Support Manager for the Marko Stipanicev is Corrosion Discipline Lead for
and Failure Analysis at the Schlumberger Houston Schlumberger North America fracturing and cement- Schlumberger Production Technologies in Bergen,
Pressure and Sampling and Formation Evaluation ing operations in Sugar Land, Texas. He has worked Norway. Upon graduation from the University of
Centers in Sugar Land, Texas, USA. He began his as a chemical problem solver in various capacities Zagreb, Croatia, he worked as an external consultant
career with Schlumberger in 2005 as a senior materi- for Schlumberger for 10 years, spanning the R&D on industry related projects at the Faculty of Chemical
als scientist. He previously worked for Shell Global spectrum from research to product development to Engineering and Technology, in Croatia. Beginning in
Solutions in the US, the Saudi Basic Industries technology implementation. He has authored 12 peer- 2010, he worked as a research engineer for Det Norske
Corporation Technology Center and Saline Water reviewed scientific journal articles and five SPE papers Veritas in Bergen, investigating corrosion-based failures
Conversion Corporation, both in Saudi Arabia, and and has been granted several patents on chemical and performing root cause analysis studies. He joined
as principal corrosion engineer at the Research and technologies related to oilfield applications. He has M-ISWACO in 2013 as a corrosion specialist, working
Development Center for Iron and Steel for the Steel been a speaker on the importance of chemistry in oil- in Bergen, and in 2015, he was named the corrosion
Authority of India, Ltd. A NACE certified material field development to a variety of audiences, including discipline lead. Marko is responsible for Schlumberger
selection and design specialist, Nausha is a member the US National Academy of Sciences, the American corrosion products, which include inhibitors, biocides,
of NACE, ASM and SPE as well as a life member of the Chemical Society and the National Aeronautics and scavengers and nutrients. He has authored and coau-
Indian Institute of Metals; he is the author of more Space Administration Jet Propulsion Laboratory. thored numerous papers and publications related to
than 60 technical papers and reviews on corrosion, Bruce was a Natural Sciences and Engineering corrosion and corrosion management. He holds an MSc
phase diagrams, composite materials and failure cases. Research Council of Canada postdoctoral research degree in chemical engineering and technology from
He received an MS degree in chemistry from Aligarh scholar at the California Institute of Technology, the University of Zagreb and a PhD degree in environ-
Muslim University, Uttar Pradesh, India, and a PhD Pasadena, USA. He earned a BS degree in chemistry mental process and biocorrosion management from the
degree in materials science and engineering from the and a PhD degree in inorganic chemistry from the Universit de Toulouse, France.
Moscow State University. University of British Columbia, Vancouver, Canada. Jean Vittonato, is Head of the Total E&P Technology
ystein Birketveit is Technical Manager for Production Denis Mlot is a Nonmetallic Materials Expert with Division corrosion department in Pau, France. He
Technologies for M-I SWACO, a Schlumberger company, the technology department of Total Upstream, in Paris. is responsible for the headquarters corrosion team
in Bergen, Norway. For the past 18 years, he has Using his foundation of studies in polymer science, and provides technical assistance to projects and
specialized in the field of corrosion. Prior to joining his focus is on nonmetallic materials and corrosion. operating subsidiaries worldwide. He started work in
M-ISWACO, ystein worked for Statoil and for Det Prior to beginning work with Total in 2003, he was a 1999 focusing on cathodic protection with COREXCO,
Norske Veritas. He earned his MSc degree in materials researcher in the R&D department of Elf Atochem, an engineering cathodic protection company, where
and electrochemistry from the Norwegian University of which is now Arkema, in Serquigny, France. He then he was in charge of designing cathodic protection
Science and Technology, Trondheim. spent six years as the technical manager for pipe systems for both onshore and offshore and for installa-
Joshua E. Jackson is the CEO of G2MT LLC as well as coating products with the company. Denis chaired tion, monitoring and maintenance follow-up. In 2006,
the cofounder of G2MT Laboratories, LLC in Houston. the ISO 12736 working group on wet thermal insula- he joined Total as a corrosion specialist and was in
G2MT Labs is a metallurgical consulting and analysis tion systems, was a member of pipeline coatings work charge of cathodic protection activities. He provided
company that performs nondestructive materials char- group ISO 21809 and holds certifications from the support for projects for both Total E&P and operating
acterization to evaluate residual stress mechanical Association pour la Certification et la Qualification subsidiaries and was in charge of research projects
properties and other critical parameters including the en Peinture Anticorrosion and Faglig Rd for related to cathodic protection. He spent three years
effects of corrosion. His scientific focus areas include Opplring og Sertifisering av Inspektrer innen in Republic of the Congo as the head of the Total cor-
corrosion analysis, high-temperature materials, hydro- Overflatebehandling . He holds numerous patents in rosion department, where he supervised all projects
gen absorption effects, failure analysis and statistics. his field and has coauthored several papers on the related to corrosion. Jean is a certified Cathodic
Joshua is the coauthor of numerous papers in the field subject of coatings and corrosion. Denis has a degree Protection Specialist with the National Association
of materials science covering subjects including non- in materials science from the cole Universitaire of Corrosion Engineers and with the Centre Franais
destructive testing, metallurgy, welding, corrosion and DIngnieurs de Lille, France, and received his PhD de la Protection Cathodique and is chair of the
hydrogen. He obtained BS degrees in both mathemat- degree in polymer science from Universit de Lille. ISOTC67SC2GW11 working group on cathodic
ics and physics from the Massachusetts Institute of Jan Scheie is a Project Leader and Account Manager protection of pipelines. He obtained an engineer-
Technology, Cambridge, USA, and MS and PhD degrees for Production Technologies (PT) in Schlumberger ing degree from Institut National Polytechnique de
in metallurgical and materials engineering from the Norge A/S in Stavanger, where he serves customers in Grenoble, France.
Colorado School of Mines, Golden, USA. Scandinavia. He has also been an account manager
Alyn Jenkins, based in Aberdeen, serves as the Global for production technologies, an international sales
Asset Integrity Manager for Schlumberger Production manager and an area manager for production chemi-
Technologies. He manages asset integrity product cals in Stavanger. He has worked for M-I SWACO in
lines that include corrosion inhibitors, biocides, H2S market development for the eastern hemisphere, as
scavengers and oxygen scavengers and is responsible technical manager in the Middle East and CIS, as sales
for research and development projects related to manager in South Asia and as principal engineer for
corrosion. He began his career in 1998 with Clariant developing sales strategy in mainland Europe. He is a
Oil Services in Aberdeen and then worked for Baker member of TEKNA, the Norwegian Society of Graduate
Hughes in Liverpool, England. Alyn joined M-I SWACO Technical and Scientific Professionals, the SPE and
in 2005 as a corrosion specialist in Stavanger and then the National Association of Corrosion Engineers. He
served as lead integrity management specialist. Alyn received an MSc degree in chemical engineering from
holds BS and MS degrees, both in chemistry, from the the Norwegian University of Science and Technology,
University of Wales, Bangor. Trondheim, Norway, and an MBA degree from
Thunderbird School of Global Management, Glendale,
Arizona, USA.
May 2016 49