Beruflich Dokumente
Kultur Dokumente
DNP-08-00-8015
DNP-08-00-8080
DNP-08-00-8081
DNP-08-00-8100
DNP-08-00-8105
DNP-08-00-8115
DNP-08-00-8120
DNP-08-00-8140
DNP-08-00-8185
DNP-08-00-8205
DNP-08-00-8310
DNP-08-00-8340
DNP-08-00-8431
Corrosion Inhibitor
DNP-08-00-8451
DNP-08-00-8461
DNP-08-00-8462
DNP-08-00-8510
(Not Available)
DNP-08-00-8571
DNP-08-00-8601
DNP-08-00-8612
DNP-08-00-8613
DNP-08-00-8651
DNP-08-00-8653
DNP-08-00-8701
DNP-08-00-8702
Corrosion Inhibitor
DNP-08-00-8875
DNP-08-00-8895
DNP-08-00-8901
DNP-08-00-8911
DNP-08-00- CD
Coco diamine
DNP-08-00-MAS
DNP-08-00-TD
Tallow diamine
DNP-08-00-8009
Introduction
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
water to form the hydroxide, it is a wonder that we can use iron at all when it is exposed to air. The
main reason it does not destroy itself more quickly than it does, is that rust as it forms on the metal,
acts as a barrier between the metal and the air thus slowing down the corrosion process.
Electrochemical Theory of Corrosion
Corrosion is electrochemical in nature. An electrochemical reaction is a chemical change and a flow
of electric current. Corrosion current can be measured. It is possible to establish the existence and
direction of a current, in even if cannot measure.
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:
2e- + 2H+ 2H0 H2
(Positively charged hydrogen ions receive electrons and become a neutral or uncharged material).
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.
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.
Solutions can be an electrolyte for the current to flow through, the earth can also act as an
electrolyte.
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.
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.
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.
If a well is making bottom-hole water, then the measure of the iron in solution is not necessarily a
measure of the iron being remove from the well equipment, sine the formation water can contain iron
as it is produced.
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.
calculated by the following equation:
Pounds Iron = 3.494x10-4 x bbls Water x ppm (with consistent units of time)
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.
A corrosion inhibitor which is insoluble in the fluid in which it sees in its environment is
normally very resistant to removal by the fluid. If it is thick enough it is impermeable to
corrosion if penetration by corrodents as carbon dioxide, hydrogen sulfide, and oxygen
does not occur.
Fluids:
Nitrogen
Air
Natural gas
Compressed gas liquids
Oils
Refined oils
Water
Sea water
Brines
Carbon dioxide
Hydrogen sulfide
Oxygen
Membrane nitrogen
Commonly asked questions or comments:
Is it oil soluble or water dispersible? This is a misnomer. By conventional cooking or
food preparation, if it is soluble in oil and then dispersible in water, the emulsion like
mayonnaise is likely to form. Salad dressing oil does not mix with vinegar except
temporarily and if allowed to sit it separates to 2 layers: top is oil and bottom is water and
acetic acid (a corrodent). Formation of stable emulsions is oil internal in water and the
corrosion inhibitor loses its ability to form persistent and uniform films.
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.
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.
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
insoluble just like paraffin wax or asphalt or Asphaltenes.
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.
Do corrosion inhibitors form emulsions?
Yes, as we showed earlier. Corrosion inhibitors are surface-active materials by nature and
definition. Also many surfactants are added to them.
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.
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.
What effects does velocity have on corrosion inhibition?
90 ft/sec
Hydrocarbons (oil)
14 17 ft/sec
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.
Jet impingement and RCE studies are used in these evaluations.
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.
The DNP-08-00-82091 can be used batch or continuous.
The DNP-08-00-82461 is for continuous injection.
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.
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.
A critical point when testing is to identify that a CI will film at high dose and not remove itself
due to its surfactancy.
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].
Recommended Methods for Treatment Amounts
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.
Film thickness
Inhibitor activity
Surface area
- Actual treatment surface area
- Area exposed in corrosion process
Most important in successful mitigation program is applying at the most favorable point
of application by estimating treatment rate.
3 gallons/diameter inch/mile
Gatlin and EnDean
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.
Surface Area
SA = (
SA = ft2
Per foot
Per mile
= 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.
Volume
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.
Treating Methods
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.
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.
Transport through aqueous medium to metal interfaces that are intermittently water
wet.
Films are not eroded by oil, unless velocities are extremely high.
Treating rate is function of velocity ranging from 1000 to 1 ppm active(0-60 ft/sec).
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.
or
or
or
Typical 6 to 36 ppm based on total fluid production per weekly production can be applied.
The biggest concern is low spots where solids or bacteria can cause under deposit corrosion.
Part of a maintenance program includes pigging, if possible.
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 holdup.
This assumes the pipelines are not running full.
The length-volume of 1000 feet represents 0.19 miles.
Pipe-size (inch)
2
3
4
6
8
Batch treating or treating continuously with corrosion inhibitor diluted in or flush with methanol and
glycols is preferred.
Pretreatment with micro biocides or water clarifier is preferred.
Type of Production
Production Volumes
Gas ______ MMSCFPD
Oil _______BOPD
Water ____BWPD
Water Injection ____BWPD
Area to Treat
Where does the water go?
CO2_____%
H2S_____PPM or _____%
O2 ______PPM
organic ______PPM or ____%
Acids
pH ______
System Diagram
Treatment Type to Consider
Batch slug via pump
Batch slug via treating truck
Continuous via pump
Continuous via capillary coil tubing
Squeeze
Tubing Displacement
Fracture
Screening Selection: Sample Fluid
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.
Stable emulsions must not be formed.
well depth
well type completion
well point of treatment possible
flowline treatment point(s)
gas line treatment point(s)
water injection treatment point(s)
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.
Procedure:
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
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.
To maximize penetration, use a solution of 10% APQ in methanol. To pretest the performance, use
the following procedure.
Alkyl Pyridine Salts are alkyl pyridine benzyl quaternary ammonium chloride or organic amine salts or
other type quaternary that are 10-90% active alcohol typically.
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.
Alkyl Pyridine Salts are not usually fully soluble in water.
Neutral Alkyl Pyridine Salts have very low solubility in oil or condensate.
Alkaline Alkyl Pyridine Salts disperse in gas, condensate (oil), and water.
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.
DNP-08-00-8462
DNP-08-00-8462