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DNP-08-00-8009 Corrosion Inhibitor / Emulsifier Stabilizer / Primary soya amine + 9 moles (EO)
Dispersing Agent
DNP-08-00-8015 Corrosion Inhibitor / Emulsifier Stabilizer / Primary soya amine + 15 moles (EO)
Dispersing Agent
DNP-08-00-8080 Corrosion Inhibitor Intermediate Dimethyl benzyl ammonium chloride quaternary
DNP-08-00-8081 Corrosion Inhibitor Intermediate Alkyl pyridine quaternary ammonium chloride
DNP-08-00-8100 Corrosion Inhibitor Intermediate Cyclic amine salt
DNP-08-00-8105 Corrosion Inhibitor Intermediate Cyclic amine salt
DNP-08-00-8115 Corrosion Inhibitor Intermediate Refined tall oil imidazoline
DNP-08-00-8120 Corrosion Inhibitor Intermediate Poly amido amine
DNP-08-00-8140 Corrosion Inhibitor Intermediate Oil soluble organic phosphate ester amine
Introduction
Corrosion is the destruction of metal by a chemical or electrochemical action as seen in the rusting of
iron. This is not to be confused with erosion, which is the destruction of metal by mechanical means
or for example, the filing of iron into dust.
Essentially, atmospheric corrosion is the reverse process of that involved in refining metals from their
ores. Iron is usually found in nature as iron oxide or iron hydroxide. Copper occurs as the sulfide or
basic sulfate. When copper tarnishes, it reverts to the sulfide and, in certain atmospheres, to the basic
sulfate. Because the refining of metal from ore requires an expenditure of energy, the metal is at a
higher energy level than the ore, and it is natural that it would try to revert to the form in which it is
found in nature. Since iron need only combine with oxygen to form iron oxide, or with oxygen and
Two chemical reactions occur during corrosion. The first, termed oxidation, occurs at the anode,
where metal changes from a solid, neutral material into a positively charged ion. The other reaction,
termed reduction, occurs at the cathode, where a material in solution changes to a less positively
charged material. An example of corrosion of iron, when coupled with copper in salt-water solution
containing oxygen, will serve to illustrate these reactions. At the anode (iron), the oxidation reaction
will occur and may be written as follows:
Fe Fe2+ + 2e-
(A neutral material going into solution as a positively charged iron and leaving behind two negatively
charged particles or electrons).
Electrons travel through the metal to the more noble cathode (copper), where they enter into the
reduction reaction. In this particular case, the reduction occurring at the cathode may be written as
follows:
e- + 2H2O + O2 4OH-
(A case of two neutral materials combining with electrons to become negatively charged ions).
If these same two metals were connected in an acidic solution, the reaction occurring at the cathode
would be written as follows:
(Positively charged hydrogen ions receive electrons and become a neutral or uncharged material).
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The copper is said to be more noble than the iron, and is also cathodic in relation to iron. The iron
has a greater tendency to give up two of its electrons and enter the solution than does copper.
When iron is coupled to aluminum, the iron would be the cathode and aluminum the anode.
It is not necessary for two different metals be coupled together in order to have anodic and cathodic
areas. Corrosion occurring on a single piece of metal is electrochemical in nature and that anodes,
cathodes, and current flow are present. A common example is of iron and its oxide.
Iron oxide is cathodic to the bare metal. Steel with mill scale present will corrode rapidly if the mill
scale is removed from a small area and a large area of the steel is left covered with scale.
Solutions can be an electrolyte for the current to flow through, the earth can also act as an
The amount of corrosion occurring (amount of metal that is being converted to ionic form) is directly
proportional to the amount of current that flows between the anode and cathode.
When a reaction occurring at the cathode yields an insoluble product, the product will tend to keep
chemicals from reaching the surface of the metal to accept the electrons. As a result, the corrosion
process will be slowed. If chemicals are present which immediately react with the metal as it goes
into solution at the anode producing an insoluble product, this will stifle the corrosion. If the anodic
reaction yields a soluble product and chemical is present to act as electron acceptors (hydrogen
ions in acid solution), and if no insoluble product is formed at the cathode, the corrosion process will
continue.
Organic Inhibitors
Inhibitors of the organic type are compounds containing sulfur, oxygen, or nitrogen. Such organic
inhibitors usually consist of a polar group (which is the end of the molecule containing either
nitrogen, sulfur, or oxygen) attached to a long chain of saturated hydrocarbons.
Organic semi-polar compounds are adsorbed at the cathodic areas. Organic inhibitors cannot be
electrically discharged as hydrogen. They remain adsorbed and prevent hydrogen ions from
discharging at the cathodes, thus inhibiting corrosion by cathodic polarization.
Another theory of organic inhibitors is that adsorption takes place generally, rather than specifically,
at either anodic or cathodic areas. One explanation is that, like the theory mentioned on inorganic
inhibitors, the surface of the metal has some valence forces that must be satisfied.
Thus, it may be the binding forces responsible for the strong attraction of these inhibitors, is the
formation of a dative bond between the metal and the organic molecule. Bonds can be formed
through sharing a pair of electrons between the organic inhibitor and the metal.
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Iron Determination
The use of iron in solution in the produced water is a very useful tool to determine the protection being
afforded by inhibitor treatment, especially in sweet oil wells or sweet gas-condensate wells.
The use of iron in water in gas-condensate wells is especially meaningful, since most of the iron in a
true condensate water is iron that has been removed from the well equipment as fluid is being
produced.
If a well is making bottom-hole water, then the measure of the iron in solution is not necessarily a
Even in this case, the iron determination is useful, especially if it is performed before inhibitor
treatment and after inhibitor treatment.
In this way, if a reduction in iron content is obtained, it can be reasonably assumed that the reduction
is due to a reduction in corrosion.
While the actual figure of the parts per million of iron in solution may not be particularly valuable, the
amount that it is reduced after inhibitor treatment is very useful.
For example, the well might contain 300 ppm iron in the water before inhibitor treatment and, after
inhibitor treatment, contain only 100 ppm iron in solution.
This would mean that the corrosion had almost stopped and that the water being produced from the
formation contained about 100 ppm iron.
This cannot definitely be established without obtaining bottom-hole samples, but the fact that the iron
content has been reduced by 200 ppm can be converted into a certain number of points of iron being
saved from the well equipment.
The exact amount would depend on the volume of water being produced. This amount can be
calculated by the following equation:
Pounds Iron = 3.494x10-4 x bbls Water x ppm (with consistent units of time)
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Specifically any corrosion inhibitor for group presented will work in any system, with
exception of the rust inhibitors. The corrosion chemical must be placed to area it is
needed in sufficient quantity to form a film.
Corrosion inhibitor must have a sufficient film life to remain on potentially corroded
areas or must be available continuously to repair, abraded or eroded films, or films
solubilized by the fluids.
A corrosion inhibitor which is insoluble in the fluid in which it sees in its environment is
Fluids:
Nitrogen
Air
Natural gas
Compressed gas liquids
Oils
Refined oils
Water
Sea water
Brines
Carbon dioxide
Hydrogen sulfide
Oxygen
Membrane nitrogen
Is it water soluble-what type of water: water is fresh, common to heavy oil production;
water is acidic like vinegar, or carbonated beverages (carbonic acid) common to gas
condensate production. Some reservoirs produce waters much more concentrated than sea
water (about 18 to 20,000 chlorides), with these connate waters reaching solids content
up to 35% of chlorides, calcium, and sulfates.
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At high temperatures these can react from the salt to an amide. This changes the solubility but
they are still inhibiting. Also in the high temperature and high-pressure systems, carbonic acid
and hydrogen sulfide will react with the corrosion inhibitor altering its character. However FTIR
analysis, fingerprints show chemical changes but they are still inhibiting solutions. The effect is
change of solubility.
Sometimes the question is do the chemicals polymerize. There are some, which do, but more
real is they are extracted or separated to mixed to components with the heavier ends becoming
The additives which are the surfactants included to disperse or non-emulsify may exceed their
cloud point (loses solubility in water or brine at some temperature), especially around the boiling
point of water, 100C or even lower. DNP-08-00-82901 or 8091 contains a dispersant which clouds
about 45C and if a mutual solvent is not added to the chemical mixture, the solution separates
at into phases. If the corrosion inhibitor is dispersed, then the solubility changes and it becomes
less soluble in one of the phases. The solubility is changes anyway as the chemical bonds and
fractionates in the fluids.
A tragic evaluation technique used by many evaluates the corrosion inhibitor at very low
dosages to indicate their performance, regardless of application. These concentrations maybe 5,
10, 25, 50, 100 ppm. Many systems require minimum concentrations of 500 to 2000 ppm to form
uniform films, which will persist. In some cases these concentrations must be maintained in
multifluids. In water floods, concentrations of use with water-soluble corrosion, particularly
concentrated (highly active), will work at treatment dosages of 1, 3, 5, 10 ppm, added
continuously or squeezed into the formation with feedback.
How to treat:
CCT capillary coil tubing, internal through tubing with no flow valve hanging on Bottom or
external through mandrel/valve provides excellent method of controlling Chemical addition and
getting to where needed. Other methods are being studied.
Solubility varies with concentration. Higher concentrations are typically more soluble in fluids.
Some inverse solubility can occur at low concentrations.
Corrosion inhibitors highly favored and describes as alkly pyridine benzyl quaternary ammonium
chloride fractions to hydrocarbons (minor) and to various salinity of brines. The active component
nears some its components at >9.0 # gal, density of 1.08 grams/cc.
Why do we use methanol in so called water soluble corrosion inhibitors for other than
winterizing. These corrosion inhibitors are not completely soluble in water and methanol is used
as a coupler or mutual solvent. Methanol will make a film thinner but it does not changes its
character as do other solvents, including water.
Why would I use a water-soluble corrosion inhibitor in an oil system containing only small amounts of
water?
The corrosion inhibitor follows its solubility to water the area of corrosion in an electrochemical
cell ; the corrosion inhibitor is very film resistant to the oil phase. We are not considering galvanic
cells.
Water 10 ft/sec
Above the limiting velocity the metallurgy must be considered, especially if solids as sand are
present which can significantly lower the above numbers.
At high velocities, the DNP-08-00-82901 (APQ), DNP-08-00-8613 (heavy oil precipitating film), and
DNP-07-00-76521 (organic phosphate). These are best suited for batch to form heavy films.
However they can be supplemented with same inhibitor by continuous injection or with others.
The DNP-08-00-82901 and the DNP-08-00-82461 have been found very resistant to shear stress.
Continuous injection through CCT should include a filter on pump discharge before check valve on
the line. It sometimes contains a little sediment (residual catalyst).
What effect does the density of the corrosion inhibitor have on treating if expected to fall through a
column of fluid it should be heavier than the fluid column or its extractable components (anhydrous)
should be.
Otherwise a displacement method is required. It is significant when trying to treat below pump
suction.
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The dispersibility of CI must be tested in the fluids depending if selected to treat continuous or
batch, what diluent, or flush.
An emulsion test must run in the associated fluids at expected dosages instantaneous.
Tenacious films.
The emulsion test is run with fluids and shaken by hand with concentrations of chemical of
1000 to 10,000 ppm for continuous and up to 100,000 ppm for batch.
No persistent emulsions lasting longer than 15 minutes for all systems except rod pump wells
which can be slower.
Fluids must develop 2 distinct phases. Where highly film persistent CI, a tacky ring will occur
at the interface and maybe on the bottle.
The treatment for corrosion in gas, oil, and water pipelines and wells is based on applying a
corrosion inhibitor film in areas where corrosion and erosion occurs or is apt to occur.
The basic premise is corrosion occurs at the vapor-liquid interface and at the water wet
surface, saturated with gases, or impingement areas.
Density of brine.
Published by the Oil and Gas Journal, series by Marshall E. Parker, Corrosion of Subsurface
Equipment in Producing he-states [application of a similar technique to a producing well involves at
least two additional difficulties: first, the well is accessible at one end only, and there may or may not
be a path through which the chemical can be injected].
Industry uses thicknesses of 1 to 4 mils active for a film which is not easily eroded.
Film requirements may increase to 10 mils or higher velocity abraded or erosive areas.
The films are best obtained by a slug-batch treatment followed by a continuous treatment.
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Film thickness
Inhibitor activity
Surface area
- Actual treatment surface area
Most important in successful mitigation program is applying at the most favorable point
of application by estimating treatment rate.
3 gallons/diameter inch/mile
For 4 mils active with a corrosion inhibitor that is 25% active, well depth is 10,000 and tubing
is 2 ID, then:
Pipeline Treatment
The batch treatment for pipelines is much same on thickness as for wells.
For pipelines it is preferred to place the CI then fill the pipeline with 200 to 1000 feet with fluid,
as crude oil, diesel, methanol, glycol, or water.
Add daily and continuous @ 0.2286 pints/ 1000 ft2 /day = 0.0458 mils
Surface Area
SA = ft2
Per foot
Per mile
2
= 1382 ft x diameter-inch x mile
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Volume
= 0.083333 ft3
1 mil
Oil lines carrying low volumes of water are treated with 3 to 12 ppm based on total fluid.
@ 1.0% BS&W this represents 300 to 1200 ppm in the water/etc.
Batch treat pumping wells with 12 to 36 ppm based on total fluid for the treating period.
Concentrates being 2 to 4 normal strength are used through truck or big pumps @ to
volumes
@ production of 100 BPD ( 80 BWPD and 20 BOPD) if treat weekly then 700 BFW would
require only 1.05 gal @ 36 ppm.
Some aggressive CO2/H2S gas systems may require 800 to 1500 ppm in the water
phase, heavy brines.
Lab test data of 25-50 ppm is inadequate, when considering surface area and total
volume.
Continuous-wellheads/flow lines/pipelines
Gas lift valves via pump into annular or flowline through atomizers
Batch-rod pumps/tubing/pipelines
Treating trucks-weekly/biweekly/monthly
During Fracturing
The assumption is made that the chemical with diluent or flush fluid is stable enough to
get to point where production or transported fluids or gas are encountered
The annular area, the internal of tubing plus surface of the rods, must coat.
The annular area above the operating valve, then the internal tubing for gas wells.
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1 MMSCF = 42,000 lb
CI about 8 #/gal
Saturated gas of 20# water, 2 #(1 quart) would equal 2/20, 10% chemical in water.
Recommended minimums:
Transport through aqueous medium to metal interfaces that are intermittently water
wet.
Films are not eroded by oil, unless velocities are extremely high.
Gas or Oil/Water Gathering lines horizontal flow, gas drag or acceleration <<<-
Gas Transmission lines-horizontal flow: Spray, slug, or three phase. Slug batch preceding.
Pumping Wells
Treatments may be down between the casing and tubing continuously or in batch stages.
Batch Treatment
The premise of batch treatment or slug treatment is to implant a large dose at once.
Typical 6 to 36 ppm based on total fluid production per weekly production can be applied.
Example if the production is 100 BPD (20 BOPD and 80 BWPD) then 7 times or 700 barrels of
production.
Since 1 gallon/1000 barrels is 24 ppm the treatment would be 0.7 gallon per week, on near 1 gallon per
week
Surface area calculations can be done and treat as other treatments for about 3-mil initially and 1-mil for
maintenance.
The surface area for the internal of tubing plus surface of the rods should be considered.
Typically 1 gallon/ 5000 ft2 may be used. Thicknesses of 1-3 mils down to 0.01 to 0.3 mils are used.
Increasing the time interval will increase the dose per treatment.
Assume the treatment will fall at a rate of 4000 feet per hour down the casing assisted by water flush.
So the chemical amount of 1 gallon seeing the metal coming up the hole, upon dilution with well fluids,
at 100 barrels per day, for 1 hour or 100/24 or 4.17 barrels in 1 hour.
1 gallon per 4.17 barrels for 1 hour or 1 gallon per 100 barrels = 240 ppm.
1 gallon per 1.042 barrels for 15 minutes or 4 gallons per 100 barrels = 960 ppm
If a superior product is used the product will film over itself, or actually build film.
Do not under film as the deficient areas are anodic and promote pitting.
THE ASSUMPTION IS MADE THAT THE CHEMICAL WITH DILUENT OR FLUSH FLUID IS STABLE
ENOUGH TO GET TO POINT WHERE PRODUCTION WELL FLUIDS ARE ENCOUNTERED.
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The biggest concern is low spots where solids or bacteria can cause under deposit corrosion.
A rate as low as 2.5 ppm can be used; however, inhibitor residual should be maintained at 250 ppm in
the water phase.
To treat these lines with an adequate batch prefers a fill of 200 feet (minimum for pigging or non
pigging) to 1000 feet of line volume as a slug.
This slug can be added and displaced with pigs with one frontal and those following.
In some cases a pig is run prior to treatment to displace the fluids lying in the pipeline from liquid hold-
up.
Pipe-size (inch) volume barrels/ 1000 feet gallons per 1000 feet
2 3.89 163
3 8.74 367
4 15.54 653
6 34.97 1469
8 62.17 2611
Batch treating or treating continuously with corrosion inhibitor diluted in or flush with methanol and
glycols is preferred.
well depth
well type completion
well point of treatment possible
flowline treatment point(s)
gas line treatment point(s)
water injection treatment point(s)
System Diagram
Run dispersibility in oil (condensate) and water (brine) at about 1000 ppm to 1% in each.
Run emulsion test in 6 ounce script bottle @ 50/50 each with 100, 1000, and 10,000 ppm chemical.
After shaking 100 times record break, after 1 minute, 3 minutes, 5 minutes, noting condition of fluids
and interface.
Origin:
Based on surface area, amount of inhibitor injected, and inhibitor activity, calculated
targeted film thickness was 3.1-mils.
Based on case histories, it appears that treatment rate developed from early field testing
of inhibitors clearly described by the surface-area treatment principle.
Some chemicals experience auto solubility when the fluid is absorbed by the chemical
and an invert solution is created.
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Objective:
To maximize penetration, use a solution of 10% APQ in methanol. To pretest the performance, use
the following procedure.
Expected Results:
Acidic PO4 ester will form a well dispersed solution without oiling out. The THPS will begin to oil out
which will look like a film on the inside of the bottle. Addition of Soya Lecithin will immediately cause
precipitation resulting in a top clear solution.
Note:
Variations of this procedure should be tried. The initial water is the pad. The 10% APQ is the
treatment. The second water is the second pad. The final anion is a hold-up technique. This is the
chemical classic, do not add cations and anions together. Contrary to chemical techniques, the
original premise is antagonistic precipitation, ATGPP.
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The following information provides some basic information on corrosion inhibitors for CO2 and H2S
corrosion and also for erosion especially from sand. Treatment with Alkyl Pyridine Salts or Quaternary
and sulfur modified Imidazoline salts are especially efficient against sand.
Alkyl Pyridine Salts are alkyl pyridine benzyl quaternary ammonium chloride or organic amine salts or
In dilute solutions, Alkyl Pyridine Salts form thin films for use in pipelines and is used more for
continuous applications. Dilution in methanol or glycols (especially TEG) produces these thin films,
typical @ 15 to 30% concentration.
In more concentrated solutions of Alkyl Pyridine Salts, films are formed that are very thick, heavy,
strong and highly velocity resistant, as CST 8701 or 8901.
In acid with dispersants, Alkyl Pyridine Salts act as an electron, a hydrogen acceptor (nascent
hydrogen). These are then excellent in HIGH H2S systems.
In systems with low H2S and high CO2, corrosion attack is acid Alkyl Pyridine Salts are good for
brines. H2S is not required by Alkyl Pyridine Salts to form stable films.
For heavy films, the concentrates of Alkyl Pyridine Salts can be made with anionic surfactants to
precipitate an antagonistic film of various thicknesses. For pipeline treating where vapor corrosion
may occur, the pH is usually buffered to pH=8.3. The backbone of Alkyl Pyridine Salts are flexible and
do not accelerate corrosion if under treated.
Alkyl Pyridine Salts are ideal when their solution pH is alkaline for vapor corrosion.
Alkyl Pyridine Salts are ideal when their solution pH is acidic for under deposit corrosion.
For Downhole applications, use Alkyl Pyridine Salts neat and flush with water or dilute in methanol or
glycols. Diluting Alkyl Pyridine Salts only makes the film thinner. Water Flush precipitates the film.
Acidic Alkyl Pyridine Salts disperse or are soluble in brines (water) and acid.
Sulfur modified Imidazoline and Fatty Acids such as, CST 8461, 82431 modified, and 8675 improve
corrosion treating for CO2 and low levels of H2S including solid, as sand.
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DNP-08-00-8462