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Introduction to:
Types of corrosion which may occur in downhole environments
Methods to prevent corrosion
Methods to find corrosion
Provide enough background knowledge to allow you to question Corrosion
Decisions in an intelligent manner.
Contents
Applicable Applications
Corrosion Engineers)
MR 0175
of
NACE
(National
Association
of
Electrochemical cell
beaker of concentrated hydrochloric acid. Within a few minutes, the zinc metal
dissolves, and significant amounts of hydrogen gas are liberated.
The reaction has some of the characteristic features of oxidation-reduction
reactions.
It is exothermic, in this case giving off 153.89 kilojoules per mole of zinc
consumed.
The equilibrium constant for the reaction is very large (Kc = 6 x 1025), and
chemists often write the equation for this reaction as if essentially all of
the reactants were converted to products.
Zn(s) + 2 H+(aq)
Zn2+(aq) + H2(g)
Oxidation:
Reduction:
Zn
Zn2+ + 2 e2 H+ + 2 eH2
By separating the two half-reactions, the energy given off by this reaction
can be used to do work.
Zn2+ + 2 e-
Zn
The electrons given off in this half-reaction flow through the circuit and
eventually accumulate on the platinum wire to give this wire a net negative
charge. The H+ ions from the hydrochloric acid are attracted to this negative
charge and migrate toward the platinum wire. When the H + ions touch the
platinum wire, they pick up electrons to form hydrogen atoms, which
immediately combine to form H2 molecules.
Reduction:
2 H+ + 2 e-
H2
The oxidation of zinc metal releases Zn 2+ ions into the Zn/Zn2+ half-cell.
This half-cell therefore picks up a positive charge that interferes with the transfer
of more electrons. The reduction of H+ ions in the H2/H+ half-cell leads to a net
negative charge as these H+ ions are removed from the solution. This negative
charge also interferes with the transfer of more electrons.
To overcome this problem, we complete the circuit by adding a U-tube
filled with a saturated solution of a soluble salt such as KCl. Negatively charged
Cl- ions flow out of one end of the U-tube to balance the positive charge on the
Zn2+ ions created in one half-cell. Positively charged K + ions flow out of the other
end of the tube to replace the H + ions consumed in the other half cell. The Utube is called a salt bridge, because it contains a solution of a salt that literally
serves as a bridge to complete the electric circuit.
Electrochemical in nature:
Involves the transfer of electrons
Requires electron path and ionic path
Requires two half reactions:
Production of electrons
Fe
Fe2+ + 2e Allows consumption of electrons 2H+ + 2e- H2
Must consider two aspects:
Thermodynamics willingness to corrode
Measured using potential difference (voltage)
Kinetics rate of corrosion
Indicated by electrical current flow
Increases with concentration / temperature / fluid velocity
Thermodynamics
Pourbaix diagrams
For particular conditions these demonstrate the stability of metals
They suggest different methods of mitigating corrosion
Lower potential
Raise pH
Raise potential
They do not say anything about the kinetics or rate of corrosion
* Figure 2 shows the Pourbaix diagram for iron and shows that iron exhibits two
separate regions of corrosion, a region of passivity, and at the bottom, a region
of immunity. The 'Passive' region indicates that corrosion (though possible) is
less likely than the formation of a protective oxide layer on the metal surface.
The 'Immune' region implies that no corrosion will occur (this is the region
sought for cathodic protection of iron). Finally, the two 'Corrosion' regions signify
the release of iron ions into solution.
Galvanic Series
The most Noble, metal lower in the Galvanic Series, will be the cathode while the
less noble, higher in the Galvanic Series, will act as an anode and it will
corrode.
The seawater galvanic series is used also to approximate the probable galvanic
effects in other environments for which there are no data.
However galvanic corrosion is a function of several different factors that needs
to be carefully evaluated when assessing the likelihood to have galvanic
corrosion.
6
We suggest you to have a look also at our Galvanic Corrosion page and also
at Galvanic Corrosion Documents
The table below reports the Corrosion potentials or Galvanic Series of metals in
flowing sea water at ambient temperature.
The unshaded symbols show ranges exhibited by stainless steels in acidic water
such as may exist in crevices or in stagnant or low velocity or poorly aerated
water where Stainless Steel become active, while the shaded areas show the
potentials of Stainless Steel when is in passive state.
Electrochemical Measurements
Electrochemical measurement whether done in the lab or in the field, requires
three electrodes.
Sample
References
Auxilliary
They are used to determine:
Corrosion rates
Current required for Cathodic Protection
Polarization behaviour
Types of Corrosion
Ring-worm corrosion
Localized corrosion around box end
Wireline attack (also in coated tubing)
Internal scratches along the tubular corrode rapidly
Caliper track corrosion
Similar to wireline attack but caused by the feelers of the caliper
tools
Sucker rod failure
Often caused by pitting, then fatigue
Tong damage
May lead to localized corrosion
Geometry
There are usually concentric strings of casing
8
Aggressive species
Water plus
O2
CO2
H 2S
ClOthers
Pressure
Temperature
Flowrate
pH
Bicarbonate
Bacteria
Galvanic couples
Differential concentration
Dew point
Inhibitor
Coating / lining
Figure 8
Sweet Corrosion
CO2 + Fe + H2O FeCO3 + H2
Half reactions:
CO2 + H2O 2H+ + CO32 Fe
Fe2+ + 2eSour Corrosion
H2S + Fe
FeS + H2
Half reactions:
H 2S
2H+ + S2- 2H+ + 2e- H2
Disassociation in water
Fe
Fe2+ + 2e-
10
Sweet
General corrosion (calculated using Shell Hydrocor, or Petronas
Corrosion Analyzer)
Pitting leaks, grooves
Scaling
Sour
Hydrogen Induced Cracks
Sulphide Stress Cracking (especially < 80C)
Blistering
Chloride
Pitting
Stress corrosion cracking of corrosion resistant alloys (especially
above 80C)
Mitigation Methods
Engineering
Permanent solution particularly for corrosion which can cause rapid /
sudden failure
Increases CAPEX
Operating
Adds to OPEX
Requires confidence in operations and commitment
Operations
Remove the corrosive species
Downhole dehydration?
Injection of chemicals to prevent or remove H 2S
Inhibit
Continuous
Batch
Cathodic Protection (for casing)
Impressed (continuous or pulsed for casing protection)
Sacrificial
Inhibitor Application: Batch
Tubing displacement and squeeze treatments
Inhibitor flowed through tubing
For displacement, the tubular is filled and the well shut-in. With
squeeze, the inhibitor is injected through the tubular into the
reservoir.
Typically shut-in for a day
Inhibitor residuals monitored at wellhead
Another treatment is necessary when ppm falls below a predetermined level
May require one treatment every 3 or 4 months
Squeeze protects below the packer
11
Figure 10
Weighted inhibitors
Intended to fall to rat hole and slowly release
Encapsulation
Inhibitors encapsulated in polymer gel are introduced into the well,
either in a basket or in the rat hole.
Figure 11
Inhibitor Application: Continuous
Through the production annulus
Into the casing through a valve positioned in a side pocket
Its possible to inject into specific region of the string
Can simply fill the annulus with inhibitor and inject through a gas lift valve,
but lacks control.
Doesnt protect below the packer
Figure 12
Protective coatings
Chemical inhibitors
Plastic or cement liners
Use of special alloys
Removal of corrosive gases
Dehydration
Multilateral Wells
FIGURE 13
Completions and Multilateral Team
Advanced completion design
Multilateral well technology
Casing exiting using milling / explosives
Novel multilateral junction designs
Expandable systems, monobore completions, slim wells
Materials selection / new materials / preparation of standards
Materials advice
Testing procedures / Industry standards
New Coiled-tubing technology
Amorphous bonding
Use of CRA with orbital TIG ?????
ML database / newsletter / website
Dissemination of latest completions technology
Http://swwrij.siep.shell.com/cc/dw/cmlt/home.htm
Kinetics
Evans diagram and related Potential/Current graphs
Illustrates the speed of a reaction
Illustrates how exposure to different environments can create a galvanic
cell
Can be used to demonstrate how changes in the environment may affect
the corrosion rate
Can be determined for simulated conditions and used in the materials
selection process
Illustrates a way to measure corrosion instantaneously in the field.
FIGURE 14
E log I for Cathodic Protection Equipment
Well casings may need cathodic protection
Obtaining E lg I data is an accepted method of determining current
requirements
Instant off reading should be used
The reference electrode should be remote from the wellhead
Note the similarity between this wet up and that shown earlier regarding
determination of corrosion rate and V-I graphs.
13
FIGURE 15
FIGURE 17
*Kinley mechanical caliper tool (www.kinley.com)
FIGURE 18
*Kinley caliper Fingers
14
FIGURE 19
*Kapuni caliper corrosion
FIGURE 20
*Kapuni caliper corrosion
The UCI takes 180 highly focused measurements during each revolution
of the ultrasonic sensors.
It has up to 5 rotations every inch of travel inside the casing and can
measure pits and other anomalies down to diameters of approximately 8
mm on either the inside and outside surfaces.
17
Sour corrosion
Hydrogen Induced Cracking
Sulphide
Stress
Cracking
Step-wise cracking
Blistering
Hydrogen-assisted
ductile failure
FeS dust can also block gas
line filters
Susceptibility increases with:
Increase pp(H2S)
Increasing hardness/strength
Decreasing pH/temperature
Increasing stress (residual or
applied)
Sweet corrosion
Dehydration
Corrosion resistant materials
13 Cr or better
Non-metallic
Use inhibitor
Prefer
continuous
application
Batching is possible
Require
test
to
determine
most
effective
Need to ensure it gets
to correct location
Coat / line
Insert
line
into
new/existing
line
(particularly for water
disposal)
Coat with GRE/FBE/PE
(sometimes used ofr
downhole equipment)
Sour corrosion
Dehydration
Resistant materials
SSC NACE qualified
materials bear in
mind the potential for
other kinds of failures
Request qualification:
slow strain and ripple
strain tests now used
Apply inhibitor
Coat/line
(isolate
from
environment)
Remove hydrogen sulphide
(use NACE criteria)
FIGURE 27
18
19