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Electrochemical corrosion
The corrosion of a metal surface is an electrochemical process that can be
demonstrated by the corrosion cell diagram shown in Fig. 4. The cell contains:
1. Anodic area with a positive charge. The iron is oxidized at the anodic area.
2. Cathodic area with a negative charge. Electrons are present at the cathodic area.
These electrons may react with other chemicals in the system.
3. Metallic path that allows electron flow.
4. An electrolyte that covers the iron surface. In an oilfield environment this
electrolyte is water with dissolved salts.
Salt Solution
Fe ++
-Anode
Electron flow
Cathode
Iron Solid
Types of Corrosion
Corrosion in the oilfield is defined as deterioration of a metal by chemical or
electrochemical reaction with the environment. Low carbon steel is the most common
metal that is utilized in oil and gas production.
There is more than one type of corrosion encountered in the oilfield, so different
methods are used for corrosion protection.
1. Corrosion of exterior surfaces
Corrosion of exterior surfaces is a special problem that requires formulation of a
corrosion program by experienced corrosion engineers. Exterior surfaces are often
given a permanent coating that prevents contact with the external environment.
Cathodic protection is generally required to prevent corrosion of exposed metal
surfaces.
Secondly carbon dioxide dissolves in water to form H2CO3 which reacts directly with
iron to form Fe2CO3. The reaction is:
H2CO3 + Fe FeCO3 + H2
Predicting the corrosiveness of carbon dioxide is difficult. High temperatures may
reduce carbon dioxide solubility, but higher temperatures cause a higher corrosion
rate. Oilfield waters may naturally buffer dissolved carbon dioxide to prevent low pH.
Calcium carbonate and calcium sulfate scales may reduce corrosion, but these
scales must be tight, uniform and nonporous. A break in the scale surface may
increase corrosion below the scale. Carbon dioxide corrosion is characterized by the
presence of smooth edged pits that are closely grouped.
5. Velocity Corrosion
High velocity may cause erosion of a metal surface. These high velocity gases are
often found at the wellhead of high pressure gas wells. The high velocity gas may
prevent corrosion inhibitors from adhering to metal surfaces and strip protective
scales from the metal.
Low velocity may cause another type of corrosion. Low velocity areas may serve as
incubation sites for sulfate reducing bacteria. These sites may also tend to hold water
at low points in a flow line. Sites with excess water accumulation are more corrosive.
6. Wear Corrosion
Wear corrosion is caused by metals that rub together. This is perhaps most common
in cases where pumping rods rub against the tubing in rod pumped wells. This
causes a disruption of both protective scales and corrosion inhibitor films.
Solubility or Dispersability
It is important to formulate an inhibitor that works in the system phases. An inhibitor can
be made oil soluble, oil soluble/water dispersible or water dispersible. Any liquid phase
inhibitor can also be blended with volatile amines to inhibit gas phase corrosion.
In general, neutralization of the amine with a dimer trimer acid (DTA) will make it oil
soluble. Neutralization with acetic acid will make it water dispersible. Neutralization with
a combination of DTA and acetic acid will make it oil soluble/water dispersible.
In systems with 100% oil, it is best to neutralize the amine with 100% DTA. As we shall
see, there are certain treatment techniques that require an oil soluble inhibitor. Even
with small amounts of water present it may be best to make an oil soluble/water
dispersible inhibitor, or add a quaternary ammonium compound to the blend. When
there is a high percentage of water present, a water dispersible blend may be best.
Inhibitor Selection
An oil soluble inhibitor is normally best for squeeze treatments. Squeeze treatments are
made by forcing the inhibitor into the formation. As the well is produced, the corrosion
inhibitor slowly returns in the produced fluid to maintain a long period of corrosion
inhibition. In certain wells these treatments may cause formation damage because the
corrosion inhibitor will oil-wet the formation. The extent of the damage depends on the
concentration of inhibitor pumped, the type of inhibitor used, the characteristics of the
formation and the flush fluid. Core flow tests are recommended to test for formation
damage and prior histories in similar wells are sometimes a good indicator of potential
damage. A non-emulsifier may be added to prevent emulsion blocks.
In tubing displacement or yo-yo treatments the inhibitor is an oil soluble inhibitor along
with an oil-based diluent (diesel or condensate), that is used to fill about half of the
tubing volume. As the inhibitor climbs back to the well head during well production the
inhibitor leaves a deposit on the tubing. This deposit may inhibit down-hole corrosion for
a long period of time. The yo-yo treatment variation simply requires that the inhibitor
solution be allowed to reach the wellhead and fall several times. After reaching the
wellhead, the well is shut down to allow the inhibitor solution to fall back down the
tubing. This rise and fall of inhibitor suggests the yo-yo terminology and this treatment
variation will result in more deposition of the inhibitor in the down-hole tubing.
Batch treatments normally utilize an oil soluble inhibitor. The batch and flush treatments
are most often done with a shot truck. A shot truck typically injects a few gallons of
inhibitor followed by a few gallons of water into the annulus of the well. The shot truck
can quickly run to many wells to deliver this treatment. Batch and circulate treatments
require that a chemical pot be welded to the well. With batch and circulate methods, the
inhibitor is added to the pot and the produced fluids are diverted into the annulus to
circulate this slug of corrosion inhibitor throughout the well.
Pigging treatment requires an oil soluble inhibitor. With pipeline pigging, a slug of
inhibitor is run before a pig to coat the pipeline with a film persistent corrosion inhibitor.
It is best to run this slug between two pigs to obtain more complete coverage of the
internal surfaces of the pipeline. A complete coating of the pipeline will deposit inhibitor
in low spots where water accumulates and place inhibitor on the upper pipeline surfaces
where the gas phase corrosion is a problem. These pigging treatments may also
remove scale formations that harbor sulfate reducing bacteria.
Pipelines with both oil and water require an oil soluble/water dispersible inhibitor. Even
small quantities of water may collect in low spots, so the water dispersible inhibitor is an
absolute requirement. Quats such as Arquad DMCB-80 are also effective as corrosion
inhibitors in the water phase. Pipeline inhibition will be more fully discussed below.
Tubing string treatment requires that a string be placed in the bottom of the well. This
type of treatment may be required for wells that have packers in the annulus. The
corrosion inhibitor may be applied by batch or continuous injection. With batch injection,
an oil soluble inhibitor may be best. For continuous injection, an oil soluble/water
dispersible inhibitor is best. For wells with high bottom-hole temperatures, a high
temperature inhibitor must be selected.
When there is an excess of produced water in separators or water injection lines, a
water dispersible inhibitor may be required to supplement inhibitor from down-hole
injection treatments. Corrosive gas wells may require wellhead injection of a water
dispersible inhibitor to prevent corrosion in the water phase.
Unlined water injection lines and wells obviously require a water dispersible inhibitor.
Only oxygen free water can be inhibited. An inhibitor that does not plug the formation
must be selected.
Inhibition of the gas phase requires special inhibitors. Gas phase inhibitors can be
blended with liquid phase inhibitors offered by Akzo Nobel. Volatile amines such as
diethyl amine, diethanolamine bottoms, morpholine, and methoxypropyl amine are used
to control corrosion in the vapor phase. The gas from a water separator will contain
water vapor. The water vapor may be very corrosive. Volatile amines do not neutralize
all the acid gas in the system, but they will increase the pH of condensed water. Sour
gas systems often require alkyl pyridine quats to control this aggressive corrosion.
The above recommendations do not cover all situations in the oilfield but are presented
as a general guide for selection of corrosion inhibitors.
Special Considerations
The desired dispersion characteristics of the inhibitor will vary from field to field. When
testing the dispersion characteristics of a proposed blend, a sample of the field brine
should be used. Addition of surfactants such as Witconol NP-100 should result in a
more water dispersible blend. Ethoxylated amines, such as Ethomeen T/15, may
serve a dual role as both a surfactant and corrosion inhibitor. The surfactants also clean
the metal and allow the corrosion inhibitor to work its way to the metal surface. Though
cationic, Arquad DMCB-80 can penetrate scale and reduce corrosion of steel under
the scale.
Because corrosion inhibitors are designed to oil-wet metal surfaces, an undesirable
emulsion is often created during both batch and continuous treatments. Demulsifiers are
often blended with the corrosion inhibitor to prevent emulsions. The proper demulsifier
must be chosen by bottle testing of the oil and water from the field. Please contact Akzo
Nobel about our Witbreak demulsifier product line.
Corrosion inhibitors may cause foaming in oil/water separators and glycol dehydrators.
This foaming is more likely when high concentrations of inhibitor are injected. Glycol
and silicone defoamers are used to prevent foaming. Laboratory testing is recommend
and useful for defoamer selection.
Corrosion inhibitors may be formulated to perform dual functions. Mixing of paraffin
inhibitors or gas hydrate inhibitors, with corrosion inhibitors, may be practical. These
mixtures must be checked for potential compatibility problems. Problems with blend
stability and inhibitor performance must be considered.
There are both polymerized and maleated dimer trimer acids. These grades of dimer
trimer acids may be very efficient. Neutralization of some polyamines with these polyacids may cause a gelled solution.
The selection of a dimer trimer acid is not a simple task. Variations in dimer trimer acids,
differing fluid characteristics of the field and the intended method of application, make it
difficult to recommend a generic formula. All generic formulations in this bulletin should
be used as a guide, rather than a final recommendation. Lab testing is recommended
prior to taking a corrosion inhibitor formulation into the field.
Blend Stability
The finished formula must be a stable blend that does not separate or cloud under field
conditions. The blend should be subjected to freeze/thaw stability testing before field
use. Aromatic 150 or isopropanol may improve blend stability. Ethomeen T/15 is an
inhibitor/surfactant that may help in blend stability.
Though inhibitors do not normally degrade at temperatures below 400oF, the solubility
characteristics at bottom-hole temperatures must be considered when formulating a
corrosion inhibitor.
Imidazolines
Imidazolines are the most effective film forming amines. The imidazolines are normally
neutralized with organic acids to increase their effectiveness. The imidazolines may be
quaternerized for special applications.
Armohib 209
Armohib 209 is the most common amine for oilfield corrosion inhibition. Armohib 209
is sold as Armohib 219 in Europe. Armohib 209 is a high quality imidazoline that
serves as the starting point for formulating many corrosion inhibitors. Below are typical
properties for Armohib 209:
Form
Color
Amine Equivalent
Viscosity cps at 77oF
Pour Point oF
Density lbs/gal at 77oF
Flash Point (PMCC), oF
Liquid
Dark Amber
210
200
<30
7.8
>200
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Below are typical formulations. These formulas may be modified to fit the needs of
individual fields. Dimer trimer acid is abbreviated as DTA. Glacial Acetic Acid is
abbreviated as GAA.
Below is a typical oil soluble inhibitor formulation:
Armohib 209
DTA
Aromatic 150
Isopropanol
15%
10%
65%
10%
15%
7.5%
6.0%
61%
10.5%
20%
3%
20%
10%
47%
Armohib Al-42-12
Armohib AL-42-12 is an imidazoline with an alcohol group. This alcohol group gives
the imidazoline more water dispersability. This product is formulated in the same way as
Armohib 209.
Armohib 210
Armohib 210 is an amide that can be formulated in much the same way as
Armohib 209 and it can be an economical alternative product in many formulations.
Fatty Amines
Fatty amines form weaker films than Armohib 209, but fatty amines may be both
economical and useful in many oilfield applications. These products are often used in
pipeline inhibitor formulations.
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Primary amines, such as Armeen T and Armeen C, form a strong oil-wet film that
can be useful in many blends. For example, these products have been used in refinery
overhead corrosion inhibitor blends.
Duomeen T and Duomeen C are diamines that are used in oilfield corrosion inhibitor
formulations. They are formulated in much the same way as the primary amines. For
example, these diamines may be neutralized with acetic acid or benzoic acid, to make
effective flow line corrosion inhibitors.
The ethoxylated amines serve as both surfactants and corrosion inhibitors. Ethoxylated
tallow amines are popular as corrosion inhibitors. Tallow amine with 2, 5 and 15 moles of
ethylene oxide are commercially available. Ethomeen T/15 is tallow amine with 5 moles
of ethylene oxide. Ethomeen T/15 is probably the most effective product, because it is
hydrophilic enough to readily disperse in water while maintaining film persistency.
Ethoduomeen T/13 is a commonly used corrosion inhibitor.Ethoduomeen T/20I and
is also used in formulations when more water dispersability is required.
The quaternary ammonium salts are useful as water soluble corrosion inhibitors. The
most popular quat for oilfield use is benzyldimethylcocoalkylammonium chloride, Arquad
DMCB-80. This quat can be mixed with other corrosion inhibitors. Fatty amines can be
used in new and unexpected corrosion inhibitor applications. The formulator should
review these products and select amines that offer original methods to solve problems.
Mixed Polyamido-Imidazolines
Armohib CI-41
Armohib CI-101
Armohib CI-312
Armohib CI-471
The polyamido-imidazolines (PIs) are economical and efficient corrosion inhibitor
intermediates that may be formulated to work in the oil and water phases. These
inhibitors have the potential for a broad spectrum of applications, such as in producing
well, pipeline and water handling applications.
The PIs are complex imidazolines. Corrosion inhibitors, formulated with the
intermediates, display high film persistency against the attack of severely corrosive
fluids in sour (H2S) and sweet (CO2) environments. These inhibitors can be formulated
into oil-soluble, oil-soluble / water-dispersible and water-soluble products. Because
these inhibitors are effective in a wide range of chemical and physical environments, the
formulator has high versatility and low inventory requirements.
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Below are typical properties of the PIs. For more specific information please refer to the
product data sheet of the individual product. The color of these products ranges from
dark amber to black.
Product
Amine Value
Armohib CI-41
Armohib CI-101
Armohib CI-312
Armohib CI-471
Pour Point
223-258
190-205
370-410
390-420
<0C
5C
<0C
<0C
Viscosity @ 20C
3000 cps
1700 cps
1500 cps
1700 cps
Flash Point
>100C
>200C
>200C
>200C
14%
22%
59%
5%
When both oil and water are present it is best to make an oil soluble / water dispersible
product. Quaternary ammonium salts such as Arquad DMCB-80 are sometimes used
to boost inhibitor efficiency in the water phase. Below are two formulations. Note that
the first formula does not contain acetic acid.
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48%
10 %
10%
5.0 %
10%
17 %
When the system has a high percentage of water, a water dispersible inhibitor is best.
Arquad DMCB-80 is sometimes used in these formulations. Below is a formulation that
is water dispersible:
Water Dispersible
PI
Witconol NP-100
Isopropanol
Aromatic 150
GAA
20%
5%
10%
15%
50%
14
20%
10%
16%
54%
In the above systems Ethomeen T/15 and Arquad DMCB-80 may be required to
reduce corrosion in low spots where stagnant water tends to accumulate.
15%
10%
16%
59%
An example
15%
7.5%
6.0%
16%
55.5%
For three phase inhibition, quaternary ammonium salts, such as Arquad DMCB-80,
may be required to reduce corrosion, by partitioning in the low spots of lines that collect
stagnant water.
Ethomeen T/15 may also be added. Ethoxylated tallow amines can penetrate scaled
areas and reduce this localized corrosion.
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15%
10%
75%
It is important to remember that even traces of water can cause corrosion in low spots
of the pipeline. If water is present, some glacial acetic acid must be used in the blend.
15%
7.5%
6.0%
71.5%
As mentioned above, Ethomeen T/15 and Arquad DMCB-80 may be required for
these systems.
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Surfactants
Customer Service
For additional information, samples or assistance please contact your
Local sales representative or the Akzo Nobel Customer Service Department at:
www.surfactants.akzonobel.com
All information concerning these products and/or all suggestions for handling and use contained herein are offered in good faith
and believed to be reliable. Akzo Nobel Surface Chemistry LLC and its affiliates, however, make no warranty as to the accuracy
and/or sufficiency of such information and/or suggestions, as to the products merchantability or fitness for any particular
purpose, or that any suggested use will not infringe any patent. Nothing contained herein shall be construed as granting or
extending any license under any patent. Buyer must determine for himself, by preliminary tests or otherwise, the suitability of
these products for his purposes. The information contained herein supersedes all previously issued bulletins on the subject
matter covered. The user may forward, distribute and/or photocopy this document only if unaltered and complete, including all of
its headers and footers, and should refrain from any unauthorized use. You may not copy this document to a website.
2006 Akzo Nobel Surface Chemistry LLC, all rights reserved.
Publication S-06-17
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