Cameron Tree Selection Guide - Corrosion at The Wellhead PDF

CHAPTER XII CORROSION AT THE WELLHEAD
Burning at Both Ends
You can learn a great deal about any one of our 50 states by examining the various
symbols that a state selects to represent itself. Texans are justly proud of their state tree -
the pecan, the state flower - the blue bonnet, the state bird – the mockingbird, the state
large mammal – the longhorn, and the state small mammal – the ubiquitous (at least on
highways) armadillo. Why did the armadillo cross the road? No one knows – none have
ever survived the journey to tell us about it. Most Texans are familiar with these well known
symbols of their culture, but only a diehard, native Texan with roots going back to the
Republic may be aware of some of the lesser known, state sanctioned symbols. For
example, the Texas state fossil is petrified palmwood. The state vegetable is the 1015
onion (developed by Texas A&M). The culinary symbols of Texas though not well known
are especially revealing for what they tell us about Texans. The state pepper is the
jalapeño. The state dish is chili. And finally, the official state snack food is salsa and tortilla
chips. Note the predilection for hot, spicy food. Texasphiles will say this fiery fare reflects
the Texans’ zest for life, while detractors say that it explains why Texans are prone to
flatulence. It may take awhile for non-natives to become accustomed to these Texas
gastronomical delights. Native Texans, whose insides have already been heavily
cauterized by years of eating the hot stuff, are relatively immune to any ill effects of even
the hottest pepper – one that would melt the lips off the first time imbiber. The newcomer to
the state would be wise to exercise moderation when first indulging in Texas cuisine. Start
with chili or salsa prepared with peppers low on the Scoville scale (after Wilbur Scoville
who, in 1912, developed a method of measuring the capsaicin content of a pepper –
capsaicin is the radioactive ingredient in peppers that causes the burning sensation) and
then slowly work up to more potent types. As a guide to the perplexed, here is an
abbreviated listing of peppers with their associated Scoville units:
Bell peppers – 0
Ancho – 1,000-1,500
Jalapeño – 3,000-5,000
Tobasco – 40,000
Cayenne – 40,000
Thai – 50,000-100,000
Haberño – 100,000-300,000
If you’re not a native Texan or a long time resident of the state, you would do well to
memorize this list. It may save your life. Note that bell pepper has no capcaisin and
consequently has 0 Scoville units. At the other end of the scale, the haberño is the
Chernobyl of the pepper world. The etymology of “haberño” is uncertain. Some linguists
think it comes from the Spanish word for “the lingering death of a thousand agonies that
comes from foolishly drinking molten lava”. Others think it is derived from the primal scream
of the first person to try one: “I burn…….ooooooOOOOOOh!!!!!” This utterance of course
was said through smoldering, fused lips so was not clearly heard by those who witnessed
the pyrotechnic display. While experts may disagree on its origins, they are unanimous as
to its effects. To all but the most jalepeño hardened, native Texan, the haberño pepper will
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scorch the lips, the tongue, the esophagus, the stomach lining, and then the lower regions
of the digestive tract. Once in the basement, it will corrode away the intestinal lining and
produce copious amounts of a highly acidified, highly toxic gas. Eventually, of course, the
pressure of this noxious gas will overcome all the valiant efforts of the haberño user to
contain it. It will then be vented through the user’s derriére, blistering all parts of the
anatomy and disintegrating any clothing that it contacts as it seeks daylight. The end effect
on the user and any surrounding bystanders can only be described as devastating. Heaven
forbid that it should happen near an open flame or in a confined area such as a crowded
elevator or a car pool where multiple casualties are likely. The haberño thus burns going in
and burns coming out. There is a lesson to be learned here about selecting materials for
wellhead equipment in the Oil Patch. You too can get burned both by what goes into a well
and by what comes out. There may be serious corrosion issues not only with the various
produced fluids, but with the myriad chemicals that are intentionally added while
completing, servicing, or operating the well. In this chapter we are going to examine the
role that both play in the corrosion of our equipment.
What Comes Out of a Production Well
If the geologists and petroleum engineers working for an oil company did their
homework right, the produced fluid coming out of a new well should be mostly crude oil
and/or natural gas. Both crude oil and natural gas consist of various hydrocarbon
molecules that are useful as an energy source or as feedstock for the manufacture of
plastics, lubricants, pharmaceuticals, and many other chemicals. Unfortunately crude oil
and natural gas are not the only things that can come out of a well. A well may also spew
out water, sand, mercury, other types of gasses, and a variety of organic and inorganic
compounds. The hydrocarbons that make up crude oil and natural gas are not corrosive to
any of our materials: it’s the other stuff that comes out with them that causes the corrosion.
Yet the types and amounts of hydrocarbons that are produced can have a profound effect
on the type and amount of corrosion that occurs. We’ll first look at the nature of the
substances that come out of the well and later on look at how they influence corrosion.
1. Crude Oil & Natural Gas
A hydrocarbon is a molecule consisting primarily of carbon and hydrogen. Carbon

forms the “backbone” of the molecule. Carbon is rather unique amongst the elements in
that a carbon atom can form a strong bond with two other carbon atoms and still be able to
form a strong bond with other elements. This allows long chain-like molecules to form.
Hydrocarbons can be divided into two main classes depending on their structure: aliphatics
and aromatics. The aliphatics can be further subdivided into four families, or series:
alkanes, alkenes, alkynes, and cyclic aliphatics. The different types of molecules in a given
series have a similar structure that differs by the number of carbon atoms that each
molecule contains. The chemical and physical properties of a given molecule in a series
are directly related to the number of carbon atoms in the molecule. The more carbon atoms
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there are in a molecule, the higher the melting point, boiling point, and specific gravity.
Don’t panic - we won’t dive too deeply into organic chemistry here, but we’ll a least stick our
big toe into the water.
The alkanes have the general formula CnH2n+2. The carbon atoms are saturated with
hydrogen. The various types of alkanes, or paraffins as they are sometimes called, are
distinguished by the number of carbon atoms in the molecule. Here is a list of the first 10:
Table 1
Alkanes
Number of
Carbon Atoms Formula Name
1 CH4 Methane
2 C2H6 Ethane
3 C3H8 Propane
4 C4H10 Butane
5 C5H12 Pentane
6 C6H14 Hexane
7 C7H16 Heptane
8 C8H18 Octane
9 C9H20 Nonane
10 C10H22 Decane
The first four alkanes on the list should look familiar to you – they’re gasses at room
temperature and pressure, and are the main constituents of natural gas. The composition
of natural gas varies from field to field, but is predominately methane (typically 85-95%),
ethane (typically around 5-10%), and small amounts of propane and butane. The gas you
use to heat your house is essentially all methane. The term LPG refers to Liquified
Petroleum Gas and is mostly propane. Propane bottles are a familiar site in Houston
backyards attached to gas fired barbeque grills. The bond strength of the alkanes is high so
this makes them relatively unreactive except at high temperature where they will combine
(burn) with oxygen producing CO2 and water. Alkanes (or paraffins as they are often called
in the Oil Patch) having 16 or more carbon atoms in their chain are classified as waxes.
Alkenes have the general formula CnH2n. Their distinguishing feature is a double
bond between some of the carbon atoms. This double bond is less stable than single bonds
making the alkenes more chemically reactive than alkanes. Alkenes are sometimes
referred to as unsaturated hydrocarbons or olefins. The physical properties of an alkene
are similar to the those of the corresponding alkane with the same number of carbon
atoms. The prefixes used in naming the alkenes are the same as for the alkanes in Table 1.
The first alkene (C2H4) is thus ethene, the second is propene, etc. The first two are often
commonly referred to ethylene and propylene.
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Alkynes have the general formula CnH2n-2. They are characterized by a triple bond
between two of the carbon atoms. This triple bond is not very stable so the alkynes are
chemically reactive much like the alkenes. The physical properties of the alkynes are
similar to those of the corresponding alkenes and alkanes with the same number of carbon
atoms. They are also referred to using the same prefixes in Table 1 followed by “yne”:
ethyne, propyne, butyne, etc. The first, ethyne, is more commonly referred to as acetylene
– an important gas used in welding and other applications requiring a high heat output.
Cyclic aliphatics differ in structure from the other three groups of aliphatics. The
carbon atoms in alkane, alkene, and alkyne molecules attach to each other and form
chains. In the cyclic aliphatics, as the name suggests, they form rings. One group of cyclic
aliphatics is the cycloalkanes. The general formula for these is CnH2n. Does this look
familiar? It should – it’s identical to that of the alkenes, but because of the ring structure
formed by the carbon atoms, the chemical and physical properties of the cycloalkanes are
much different. In the Oil Patch cycloalkanes are more commonly referred to as
naphthenes. Naphthenes are saturated, that is they consists of single bonds between the
atoms. Napthenes are named by putting the prefix “cyclo” in front of the alkane having the
same number of carbon atoms hence cyclopropane, cyclobutane, etc. (note there is no
cyclomethane or cycloethane – we need at least 3 carbon atoms to make a ring!). The
physical properties of naphthenes vary proportionately with the number of carbon atoms,
but the chemical reactivity of individual naphthenes vary widely.
The other class of hydrocarbons besides the aliphatics is the aromatics. These have
the general formula CnH2n-6.These compounds often have a pleasant odor and hence the
name, but don’t get hooked on them! They are toxic and many are carcinogenic. Benzene
is the best known. You may remember from high school chemistry class what a benzene
ring looks like – a hexagon with a carbon atom at each corner with a hydrogen atom
attached to each carbon atom. Benzene is the basis for many of the aromatic compounds.
The bonds in the very stable benzene ring apparently differ from the typical covalent
bonding (where atoms share valence or outer shell electrons) in the aliphatics. This gives
benzene and the other aromatics (toluene, xylene, etc.) significantly different properties and
is the reason they are in a separate class. A crude oil rich in aromatics will produce the
highest octane gasoline when it is refined.
Resins and asphaltenes are organic compounds consisting primarily of carbon and
hydrogen. The molecules are very large (40 or more carbon atoms). In addition to carbon
and hydrogen, the molecules contain one to three atoms of oxygen, nitrogen or sulfur. Their
structure is complex consisting of three or more rings, usually aromatic, in each molecule.
Resin molecules dissolve in crude oil while asphaltenes do not. Asphaltenes will be
dispersed throughout the crude in in very small particles (a colloid). At a refinery where
crude oil is distilled into its different components (fractions), the various resins will end up in
the different fractions depending on their volatility. The asphaltenes will be the leftover gunk
at the bottom, the residuum. Pure resins are heavy, sticky liquids with varying volatility.
Pure asphaltenes are nonvolatile solids. Crude oils get their dark colors from the resins and
asphaltenes.
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There are many other organic compounds found in crude oil besides the ones we
just discussed: a typical crude oil may have well over a hundred different ones. The
composition of your “average” crude oil is roughly 85% carbon, 13% hydrogen, and the
balance being small amounts of oxygen, nitrogen, and sulfur. The predominant molecules
in crude oil in descending order of occurrence are the naphthenes (these make up about
half the weight of crude oil), paraffins (around 30%), aromatics (around 15%), and resins
and asphaltenes (around 5%).
Crude oils can be characterized by their density or API (American Petroleum

Institute) gravity in degrees according to the following formula:
o
API Gravity = 141.5 - 131.5
Specific Gravity at 60o F
Where specific gravity is the ratio of the mass of the crude oil to the mass of an equal
volume of water.
The API gravity of crude oil varies from 5 o to 55 o. Light oils have a range of 34 o-45 o.
Heavy oils are those below 25 o. A typical crude oil may be 25 o -35 o. As a reference point,
fresh water has an API gravity of 10 o. The heavier the crude, the more viscous it is.
Crude oils can also be characterized by their pour point. This is a measure of the
amount of wax that the crude oil contains. Waxes are liquids at high reservoir
temperatures, but may solidify at the lower temperatures at the wellhead and beyond. Solid
wax buildup may interfere with the production flow. The pour point is the lowest
temperature at which a heated crude oil sample will still pour before it solidifies as it is
cooled. The higher the pour point, the greater the wax content. Pour points of crude oils
can vary from -75oF to 104oF.
2. HIJKLMNO
No, I’m not nuts. Just seeing who is still awake after the last section. If you’re a
survivor and your brain has not atrophied, then I’m sure you have figured out what this
section is about. It’s obviously about water – the liquid phase of H20 (H to O for you
sleepers!). Water is necessary for corrosion to occur during production at the wellhead. No
water, no corrosion. It’s that simple. When water is present (which is almost always the
case), then things can get much more complex. Water is a powerful solvent because it is a
highly polar molecule. The water that comes out of a formation is consequently loaded with
many different ions. The types and amounts of ions play a very important role in
determining the corrosivity of the produced fluid. The ions carry a charge and thus improve
the electrical conductivity of the water. This enhances the effectiveness of the water as an
electrolyte in an electrochemical cell. The chloride ion (Cl-) is one of the main ionic
constituents in produced water. As the chloride ion content increases, so does the
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corrosivity of the water. To put things in perspective, sea water contains around 20,000
ppm Cl-. Formation water from a well will run anywhere from 3,000 ppm to over 200,000
ppm Cl- with typical values running 20,000-50,000 ppm.
Chloride ions do not act in isolation, but in conjunction with other corrosive agents
dissolved in the water. Among the more important of these are H2S and CO2. When these
gasses are present in a well, they can dissolve in formation water and form acids that will
lower the pH of the water. The more acidic the water, the greater its corrosivity. For some
alloys, the pH will also determine their propensity for environmental cracking. There is a
multiplicative effect between chloride ions and H2S and CO2. The corrosion that takes place
when all three are present is greater than what would be predicted from adding up their
individual contributions. More on H2S and CO2 corrosion later. One gas that is thankfully
not present in formation water is oxygen. If free oxygen were present then corrosion rates
of carbon and low alloy steels would be unacceptably high. Fortunately oxygen is
chemically very reactive and thus any oxygen downhole is tied up in the form of stable
compounds or oxides.
There are many other ions present in formation water besides chlorides. Their total
amount will help determine the conductivity of the water. Carbonate and bicarbonate ions
will act as buffers in formation water. Buffers are dissolved substances that help the water
to resist changes in pH when an acid or alkali is added. Water with a high
carbonate/bicarbonate ion content will have a higher pH when exposed to H2S and CO2
than water with a low content of these ions and thus be less corrosive. Under certain
conditions, some ions may deposit out of solution and form a protective scale on metal
surfaces. This may be desirable from a corrosion prevention standpoint, but may be
detrimental to production if the scale deposit is extensive enough to constrict the flow inside
the bores of the equipment.
Many wells start off with little or no water production, but with very few exceptions
the vast majority of wells will eventually produce some water with the amount of produced
water generally increasing over the life of the well. Water production is generally measured
in barrels per day. Alternatively it may be expressed in a volume percentage of the
produced fluid – this is also known as the water cut.
Depending on temperature and pressure, the H2O that is present in a natural gas
formation may be in a gaseous phase. When the gas is produced a drop in pressure and
temperature occurs. The water vapor may then condense into liquid water. This water is
typically referred to on well analyses as condensate water. Condensate water has a very
low chloride and mineral content and is thus not as corrosive as liquid formation water.
3. Hydrogen Sulfide - H2S
H2S is a troublesome gas found in many wells. It is troublesome because it is a very

deadly gas that has killed many oilfield workers. It is troublesome because it can wreak
havoc on our equipment unless we take it into account when we select materials. H2S is a
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source of hydrogen. It can react on the surface of a steel part, for example, to produce
monatomic hydrogen in the reaction Fe + H2S → FeS + 2H. The hydrogen can then diffuse
into the part and cause embrittlement. This form of stress corrosion cracking is known as
sulfide stress cracking or SSC. The presence of sulfur on the surface tends to accelerate
the absorption of the hydrogen. In addition to causing SSC, H2S may accelerate general
corrosion because it will lower the pH as it dissolves in water.
A well fluid that contains enough H2S to make SSC a concern is termed sour. When
selecting materials for use in sour service, it is very important to use only those materials
known to have low susceptibility to SSC. A given alloy’s susceptibility to SSC may depend
on a number of parameters including hardness/strength, heat treat condition, product form,
the specific environment involved, how highly loaded it is, etc. The most widely use
standard that governs the use of metallic materials in sour service is NACE MR0175/ISO
15156 (hereafter referred to just as “NACE”). This course is not the place to delve deeply
into this standard – it warrants a separate course of its own, but we will refer to many of its
provisions. For our purposes, we will define sour service (based upon the criteria given in
NACE) as any well environment containing an H2S partial pressure of 0.05 psi or more.
What is partial pressure? It is that portion of the total pressure that is contributed by a
specific gas in a mixture of gasses.
It is important that you become familiar with the concept of partial pressure and how
to calculate the partial pressure of gasses when given a well analysis containing a gaseous
phase. Partial pressure calculations are greatly simplified if we assume the gaseous phase
consists of various ideal gasses. Let’s take a step backward in time to the much dreaded
high school chemistry class. You may remember the billiard ball model of a gas in a sealed
box that was used to explain gas pressure. The pressure was related to the number of
collisions of the billiard balls (representing the gas atoms or molecules) against the sides of
the box. An ideal gas is one that behaves like this billiard ball model: all collisions are
completely elastic and there are no intermolecular attractive forces. If you further sweep out
the cobwebs that have accumulated in your memory, you may remember that you once
learned about something called the ideal gas law. This states that pV=nRT where p is
pressure, V is volume, n is the number of gas molecules (expressed in moles), R is a
constant, and T is temperature. Look familiar? For a given temperature and pressure, the
volume that a gas occupies will be directly proportional to the number of molecules of gas
that are present. In our billiard ball model there is no difference between the different
gasses that may be present – each type of gas is represented by a billiard ball. The overall
volume of a gas mixture at a given pressure and temperature will be equal to the sum of
the volumes of each individual gas. The number of total gas molecules will be equal to the
sum of the molecules of each individual gas. Thus the volume fraction of a specific gas in a
mixture of different gasses is the same as the mole fraction of that particular gas. In reality
H2S is not an ideal gas, but for our purposes it’s close enough!
The amount of H2S in a well is typically reported as a mole% (often shortened to

mol%) or volume% (they’re the same for an ideal gas), or in ppm (parts per million). If we
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know the shut-in pressure of the well, we can calculate the partial pressure of H2S. Let’s do
a few sample calculations.
Example #1
A well has a shut-in pressure of 8,000 psi. H2S content is reported as 0.18 mol%. Is
this well sour?
H2S partial pressure = 0.18 X 8,000 psi = 14.4 psi ≥ 0.05 psi so well is sour
100
Example #2
A well has a shut-in pressure of 12,000 psi. H2S content is reported as 5 ppm. Is this
well sour?
H2S partial pressure = 5 X 12,000 psi = 0.06 psi ≥ 0.05 psi so well is sour
1,000,000
Both wells in our examples are sour so any materials that we select for wetted parts
must comply with the requirements of NACE. These requirements may include a maximum
allowed hardness, acceptable heat treated conditions, and additional environmental
restrictions (temperature, chloride content, pH, etc.). NACE also will impose process and
fabrication limits on metals that will be used in sour service. We have a whole flock of
gators headed our way so watch out! Just because a given material meets all the
requirements in NACE does not mean it can be used in any sour service! NACE does not
cover all failure modes. It does not take into account how highly loaded a part is or if a part
contains a defect. A steel part, for example, that is loaded at or above yield is highly
susceptible to SSC even if it meets the 22HRC maximum hardness imposed by NACE on
carbon and low alloy steels in sour service. A defect in a highly loaded part may result in a
KI value well over the KIssc of the material even though the material complies with NACE.
Just because a well analysis has less than 0.05 psi partial pressure H2S does not mean
you can use just any material and not have to worry about SSC. High strength low alloy
and martensitic stainless steels with yield strengths ≥ 105ksi are highly susceptible to SSC
at H2S partial pressures well below 0.05 psi particularly if they are used in highly loaded
parts such as hangers. This particular gator has taken a good size junk out of more than
one Cameron engineer’s behind. It is always prudent to impose NACE requirements on any
well if there is more than a trace of H2S present!
You will see a lot of inquiries come in from customers for fields with no reported H2S,
yet the customer will ask us to quote equipment in compliance with NACE. How come?
There are several reasons for this. Sometimes a customer wants to have the flexibility to
eventually move the equipment to other locations that may be sour. The most common
reason, however, is that some fields that initially contain no H2S may eventually turn sour.
This typically occurs where water injection is employed as an enhanced recovery method.
The bottom hole pressure drops over the life of a well. This may cause the production rate
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to drop off to the point where it is no longer economical to operate the well. To prolong a
given field’s life, water injection wells may be installed around the periphery of the field so
that water can be injected into the formation in order to boost the pressure and maintain an
economical production rate. The problem that may occur is that this injected water may
introduce bacteria into the formation along with the nutrients they need to grow. As we
learned from the section on Bacteria And Corrosion in the last chapter, H2S is a byproduct
of some bacteria’s metabolism. An individual bacterium is a pretty small critter and the
amount of H2S it produces is insignificant. A formation infested with a gazillion bacteria,
however, may eventually accumulate enough H2S to become sour.
4. Carbon Dioxide – CO2
Carbon dioxide is found in most wells containing a gaseous phase. It can combine
with water to form carbonic acid in the reaction CO2 + H2O → H2CO3 .Although relatively
weak as far as acids go, carbonic acid can lead to severe pitting problems in many steels.
CO2 corrosion is characterized by numerous broad, shallow pits. Whether or not CO2
corrosion is going to be a problem depends on a number of factors. Among the more
important is the partial pressure of the CO2. API 6A has established the following
guidelines for CO2 corrosion:
Partial Pressure
CO2 Relative Corrosivity
< 7 psi Non-corrosive
7 to 30 psi Slightly corrosive
> 30 psi Moderately to highly corrosive
In general carbon and low alloy steels are suitable when the CO2 partial pressure is
less than 7 psi. Although API 6A rates less than 7 psi as “noncorrosive”, in reality there will
be some minor corrosion that in most cases will be insignificant over the design life of API
6A equipment. It may not be insignificant for other components such as thin wall pipe. In
these cases it may be necessary to add a corrosion allowance to the wall thickness. For
partial pressures from 7 to 30 psi, carbon and low alloy steels may be suitable for body
components that can tolerate some pitting, but CRA’s (corrosion resistant alloys) or
stainless steels are required for parts with sealing surfaces. For partial pressures over 30
psi, CRA’s and stainless steels are required for all wetted parts. It should be emphasized
that these are only guidelines and that there are many exceptions depending on
circumstances. For example, severe CO2 corrosion of low alloy steels may occur at partial
pressures as low as 1 or 2 psi in wells that are producing fluids with abrasive particles such
as sand. On the other end of the spectrum, low alloy steels may undergo very little
corrosion in wells with very high CO2 contents if the conditions are such that a stable,
protective scale forms, or if conditions are such that any H20 is present is not in liquid form
or is present in very small amounts. There are many useful equations that have been
developed for predicting corrosion rates for carbon/low alloy steels in CO2 service. CO2
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does not act in isolation, but in concert with other corrodents. The synergistic effect must be
considered in these calculations. Check with the Metallurgy Department for further details.
5. Helium – He
Helium is sometimes found in gas wells. It’s an inert gas that doesn’t corrode
anything - ‘nuff said.
6. Mercury – Hg
Unfortunately mercury is sometimes found in gas wells. It is a hazardous chemical

that requires special handling and disposal. Mercury will not have any significant
detrimental effects on the materials that Cameron uses in our equipment. Liquid mercury
may accumulate downstream of the wellhead in heat exchangers. Often these heat
exchangers use aluminum tubes. Aluminum is highly prone to liquid metal embrittlement
when exposed to mercury. Very little mercury will diffuse into low alloy steel components at
the wellhead, but mercury may combine with corrosion products on the surface of the steel.
We have had valve bodies in returned from a field in Canada for repair that had small
droplets of mercury all over the interior, wetted surfaces. We sent them back to the
customer for clean-up. Mercury contamination is a major headache that is best left to the
customer to deal with!
7. Organic Acids
Some well fluids may contain various organic acids. Acetic acid is one example.
These acids even at very low concentrations (hundreds of ppm’s) may increase corrosion.
They are relatively weak as far as acids go, but the increase in corrosivity must be taken
into account when selecting a trim particularly when dealing with our standard low alloy or
stainless steel trims. 410 stainless steel normally has excellent resistance to CO2 corrosion.
It performs marginally, however, in wells also containing a significant amount of acetic acid.
F6NM with its added molybdenum content and duplex stainless steels will offer superior
performance.
8. Free Sulfur
Unfortunately some wells will produce free sulfur. “Free” here doesn’t mean that it
won’t cost you anything. Quite the contrary – it may cost you a bundle. “Free” means that
the sulfur is elemental, that is, not tied up as a compound. Free sulfur is very detrimental to
many alloys’ resistance to sulfide stress cracking. Its presence may preclude the use of
many standard CRA’s that are normally very SSC resistant. Contact Metallurgy for trim
recommendations when free sulfur rears its ugly head.
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9. Sand
Sand is something that operators don’t want to see coming out their wells. It can be
entrained in the production fluid and cause severe erosion or corrosion-erosion of metal
surfaces. Internal surfaces where there is turbulence (change in direction of fluid flow,
abrupt changes in surface profiles, etc.) are likely to see the greatest damage. If a sand
problem is anticipated, the operator can install a gravel pack or screens to trap the sand
before it enters the production tubing and causes havoc. If a well is producing some sand
and erosion is a problem, then special trims are required. Contact Metallurgy for
recommendations.
Putting It All Together
OK, we’re done looking at the stuff that can come out of a well – the good, the bad,
and the ugly. We examined what some of the issues are with each constituent of the well
fluid. These constituents don’t come out of the well in discrete packets, but as a mixture
whose composition will change over the life of the well. It is important that we understand
the interactions that can occur between these constituents and how these influence
corrosion. Predicting corrosion in a multiphase system (gas, crude oil, water) is very
complex and is not for the faint of heart. We’ll only look at general trends here in order to
keep things as simple as possible.
Corrosion will occur in a production well only if there is liquid water present and the
water can come into contact with the surface of the metal equipment. As we previously
discussed, hydrocarbons are not corrosive to our materials. But the vast majority of wells
will eventually produce some water and typically the amount of produced water will
increase over the life of the well. At what point are we going to get into trouble? It depends
on the following factors:
• the nature, types, and amounts of the hydrocarbons present

• water chemistry (including chloride content, pH, etc)
• water cut
• gas-to-oil ratio (GOR)
• CO2 content
• H2S content
• temperature
• fluid velocity
• presence of particulate matter (sand)
Let’s start with an example of a well initially producing nothing but crude oil. At some
point in time water will start to appear in the production fluid. A small quantity of water won’t
hurt anything because the oil will still be the continuous phase: the water droplets will be
entrained in the flowing crude oil. Metal surfaces in contact with the production fluid will be
wetted only by the crude oil. As the water cut increases during the life of the well,
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eventually a point may be reached where the water can wet the metal surfaces and begin
the corrosion process. The maximum water cut that carbon/low alloy steels can tolerate in
our well before the onset of corrosion will be dependent on the nature of the crude oil and
the velocity of the production fluid going through the equipment. Crude oils consist of many
organic compounds, some of which may be highly polar (the center of positive charges
does not coincide with the center of negative charges). Crude oils with a high polar
compound content will leave a persistent oil film on the surface of the steel. This film will act
as an effective barrier that keeps water from contacting the surface and permit the use of
carbon/low alloy steels at much higher water cuts. In general, the heavier the crude (the
lower the API gravity number), the better the inhibiting effect of the oil film. A persistent oil
film may provide protection against corrosion at water cuts up to 40 or 50%. A light crude
oil with few polar compounds may get you in trouble at a water cut of 5% or lower.
The velocity of the produced fluid is important in determining its corrosivity for many
different reasons. Increasing velocity may increase or decrease corrosion depending on
circumstances. Produced water has a different density than crude oil. If the velocity is too
slow, then the oil and water will tend to stratify out from each other. A portion of the wetted
surface could then be exposed continuously to water. Depending on the nature of the crude
oil, a velocity of a meter per second may be sufficient to entrain water cuts up to
approximately 30% as discrete droplets in the crude oil and thus prevent corrosion. Shut-in
periods when there is no production flow may actually be a worst case from a corrosion
standpoint because it allows time for the water to separate out and form a continuous
phase. The velocity of the well fluid will impact the kinetics of the corrosion reactions
through several different mechanisms. The rate of corrosion at a metal’s surface is
dependent on the quantity of the corroding agent that is delivered to the surface. As a
corrosion reaction takes place, the corroding agent will be used up unless it is constantly
replenished. The agent may have to diffuse across a thin, stagnant film of fluid known as a
boundary layer to reach the surface of the metal. This could be the rate controlling step in a
corrosion process. The greater the velocity of the well fluid, the quicker the corroding
agents can be replenished and the thinner the boundary layer across which they must
diffuse to attack the metal. Velocity has a large effect on concentration cells that may form
in dead zones in crevices, pits, etc. The greater the velocity, the less likely these
concentration cells will form. Pitting is thus typically greater in a stagnant or low velocity
fluid than in a high velocity fluid that can sweep a beginning pit clean. A high velocity fluid
may prevent an accumulation of corrosion products at the metal’s surface and thus prevent
polarization.
Corrosion-erosion is highly dependent on velocity: the higher the velocity, the more
severe the damage. There are several reason for this. The amount of mechanical abrasion
or cutting action that takes as the moving fluid with any entrained particles impinges on the
surface of the metal will obviously increase with velocity. Protective films, corrosion
products, or scales are likely to be removed so that fresh metal is always exposed to
attack. Corrodants are rapidly replenished. There may be little or no boundary layer due to
the mechanical action of the moving fluid. Forget about using the API 6A guidelines for CO2
corrosion when selecting materials for a high velocity well or a well that’s producing some
XII - 12
sand. Severe corrosion-erosion of carbon and low alloy steels may occur even at very low
partial pressures of CO2.
Water chemistry is important for the reasons we previously discussed. The pH of the
water is dependent on the type and amounts of dissolved minerals as well as the presence
of CO2 and H2S. In general, the higher the partial pressure of the CO2 and H2S, the lower
the pH and the more corrosive the water. Whether or not a stable, protective film will form is
highly dependent on pH of the water and on temperature. The chlorides, CO2, and H2S
dissolved in water act synergistically so that their net effect on corrosion is worse than the
sum of their individual contributions. Don’t consider them independently from each other!
The API 6A guidelines for CO2 for example may not be valid for wells that also contain high
chlorides in the water and also have a high H2S content.
Now let’s look at a more complex case where a well is producing mixed phase flow –
water, gas, and crude oil. If the crude oil is the predominant phase, then our discussion
about our initial example still holds true. But at what point does the amount of produced gas
have to be taken into consideration? There is no absolute value here. What is important is
the amount of gas produced relative to the amount of crude oil that is produced. The gas-
to-oil ratio, or GOR, of a producing well will determine if the effects of gas or the effects of
the oil will predominate. In general, at GOR values < 5,000 standard cubic feet of gas/barrel
of oil, the effects of oil predominate and our initial example discussion is applicable.
Standard cubic feet (or SCF) is the volume of gas in cubic feet at a pressure of 14.65 psi
and a temperature of 60oF. A barrel in the Oil patch is 42 U.S. gallons. A GOR of 5,000
SCF/bbl equates to 890 m3/m3 in metric.
Let’s assume we have a GOR of 100,000 SCF/bbl in a well. This obviously is within
the area where the effects of gas will predominate. Hydrocarbon gasses aren’t corrosive,
but they will not leave a protective film on metal surfaces as does crude oil. If water is
present, then corrosion can take place. The water must be in liquid form for it to be a
problem. Let’s further assume that our gas well is producing a substantial amount of water.
If the operating temperature is greater than the dew point of the well environment, then the
water will be in vapor form and corrosion will be minimal. The dew point is that temperature
at which a given environment is completely saturated with water vapor. If you reduce the
temperature below the dew point, water will begin to condense into liquid form and then
corrosion may become a problem. Thus corrosion may not be an issue in a gas well that is
operating above the dew point, but may be an issue during an extended shut-in where the
equipment and lading can cool down below the dew point. One last assumption - let’s
assume our gas well is operating in the condensing range at the wellhead (the wellhead
temperature is below the dew point) so liquid water will be present. Will corrosion be a
problem? Depends on the amount of water being produced relative to the amount of gas. If
the water-to-gas ratio is less than 2 bbl/MSCF then corrosion will be minimal. MSCF stands
for millions of standard cubic feet. In metric 2 bbl/MSCF becomes 11.3 m3/Mm3.
XII - 13
What Goes into a Production Well
There are many thousands of different chemicals that may be used in a production
well to control the pressure, enhance production, modify the fluid characteristics, prevent
deposits, to remove scale, inhibit corrosion, prevent hydrates, kill bacteria, etc. We’ll only
look at a few of the most important ones, but you should be aware that our customers can
pump a real witches’ brew of chemicals into a well with the best of intentions that may
cause problems with our materials.
1. Acidizing
The leading candidate for Public Enemy #1 as far as damage to our equipment
resulting from end user abuse is acidizing. Acidizing is a stimulation process used to
increase production in limestone, silicate rich, or carbonate bearing sandstone. A mixture of
one or more acids is pumped down the production tubing and into the formation. The acid
mixture will react with the formation and increase its permeability by enlarging/unplugging
pores, fissures, etc. There are a number of different acids that are used, but hydrochloric
acid (HCl) by itself or in conjunction with another acid is by far the most common. A 15%
HCl solution is frequently used. A mixture of 12% HCl and 1.5% HF (hydrofluoric acid) is
also a popular choice. One or two “flushes” (acid injections) may be required on a given
formation. Different acid mixtures may be used for each flush. Live acidizing mixtures can
be highly corrosive to metals, however, the exposure time during injection is very brief so
corrosion is minimal. In addition, acidizing mixtures usually contain corrosion inhibitors that
will reduce the rate of attack.
After the acid has done its job and the treatment is complete, the “spent” acid must
be flushed out of the formation and the production equipment. This “after flush” is typically
done by injecting EGMBE (ethylene glycol monobutyl ether) or methanol into the well and
then allowing it to flow back. The composition of the spent acid coming back out of the well
is of course quite a bit different than what went in because of its mineral content. Even
though the pH will become higher as the acid dissolves the minerals in the formation, the
spent acid is still strongly acidic. It will contain a great deal of silt. The spent acid will have
a high concentration of chloride ions from the HCl. The spent acid is thus still very
corrosive. The pH of the produced fluid coming out of a well that has been acidized may be
lowered from its normal value for up to a year after the acidizing treatment.
Corrosion damage due to acidizing is generally the result of the spent acid rather
than the live acid. The after flush operation may take six or more hours so the exposure
time to the spent acid is considerably longer. There are “dead zones” within wellhead
equipment (seat pockets in gate valves, for example) that are very difficult to flush clean so
spent acid may become trapped there. Naturally these areas will suffer the worst corrosion.
The types of corrosion damage that may result from acidizing include severe weight loss,
heavy pitting or crevice corrosion, and chloride stress corrosion cracking. Susceptibility of
some metals to sulfide stress corrosion cracking may increase due to the lowered pH of the
well fluid. Although corrosion inhibitors are generally used in the acidizing mixture
XII - 14
formulation, they may not be effective for all materials and may afford protection only for a
limited time. The amount of inhibitors is kept low to avoid damaging the formation.
A common variant of acidizing is acid frac’ing. Frac’ing (short for fracturing) consists
of using big truck mounted, reciprocating pumps to pump a frac fluid downhole under very
high pressure to create new, to unplug, or to enlarge fissures (cracks) in the formation. This
increases the flow of the hydrocarbons out of the formation into the production tubing. The
viscous frac fluid will contain proppants – sand or other particles – that are forced into the
fissures and will prop them open after the frac job is complete and normal production
pressure resumes. Acid frac’ing, as the name implies, uses one or more acids as the main
constituent of the frac fluid. Proppants aren’t used in acid frac’ing because the acid
enlarges the fissures to the point where particles aren’t necessary to keep them propped
open.
Stainless steels (especially 410) and carbon/low alloy steels are readily attacked by
HCl. Stainless steels are depassivated as the hydrochloric acid strips off the protective
oxide layer. Duplex stainless steels can be severely attacked because once the protective
oxide film is removed, there are countless galvanic cells set up between the ferrite and
austenite grains. The austenite grains are richer in alloying elements and are hence more
noble than the ferrite grains. Bottom line is that a lot of damage can be done to our
wellhead equipment during acidizing unless good practice is followed.
We frequently get inquiries from our customers asking whether or not it’s safe to
acidize through our equipment. The answer is a definite maybe. All of the materials we use
in our wellhead can survive the rigors of acidizing if it is done properly. All of the materials
we use in our wellhead equipment can be damaged if it is not. The safest thing to do for
surface equipment is use a Tree Saver®. This is essentially a hollow mandrel inserted
through the top of the tree on the wellhead and down through the connecting spools. The
acidizing/frac fluid is then pumped down hole through the Tree Saver® which acts as a
protective liner taking the full pressure and preventing the fluid from contacting the tree
components.
If a Tree Saver® can’t be utilized, then the following steps should be taken to
prevent damage to the equipment during acidizing:
• Before acidizing, grease all valves and then open and close them several times to
distribute the grease. This will leave a protective film inside the valve.
• Utilize an acidizing mixture that is no stronger than necessary. Use an acidizing
mixture with inhibitors appropriate for the wellhead equipment materials of
construction.
• Minimize the dwell time of the acid downhole.
• Do a thorough job of flushing.
• After acidizing, again grease all valves and then open and close several times. This
will help displace any trapped acid/sludge.
XII - 15
2. Packer/Workover/Completion Fluids
A packer fluid is a weighted fluid put in the annulus of a well (the area between the
ID of the casing and the OD of the production tubing) on top of the packer to help
counterbalance the pressure from the produced fluid. A packer is essentially an expandable
plug used to isolate certain sections of the well. A workover fluid is a weighted fluid used to
maintain control of a producing well during temporary workover operations. During a
workover, the production tubing is pulled and sand that may have accumulated at the
bottom of the well is flushed out in an effort to increase or restore production. A completion
fluid is a weighted fluid used to control well pressure during the completion of a new well.
Drilling muds, inverted emulsions, and clear brines have all been used in the past as the
weighted fluid. Clear brines are rapidly becoming the packer/workover/completion fluid of
choice because they are easily handled and, unlike the other two, they do not have
particulate matter that can settle out and cause operational problems. A clear, heavy brine
may be made up of one or more salts including KCl, KBr, NaCl, CaCl2, and ZnBr2.
At normal wellhead temperatures oxygen-free heavy brines are generally not very
corrosive. But at high temperatures or when contaminated with CO2, H2S, or oxygen,
corrosion can be severe. Down hole temperatures typically are much higher than at the
wellhead so, as expected, corrosion down hole is more of a concern. Many alloys that are
normally resistant to oxygen-free brine solutions are readily attacked at the temperatures at
the bottom of a well. Corrosion by heavy brines may include rapid general corrosion, pitting
or crevice corrosion, or catastrophic failure due to stress corrosion cracking. Inhibitors are
generally added to weighted fluids, but may not be effective at high temperatures or may
lose their effectiveness over a period of time.
Past experience is the best guide for selecting materials that are compatible with a
given packer/workover/completion fluid at a given temperature. If this information is not
available, then corrosion testing becomes mandatory. Testing should examine both the
potential for weight loss corrosion and for stress corrosion cracking.
3. Methanol
Methanol is a type of alcohol with the chemical formula CH3OH. It is often used in
subsea wells where it is injected into the well fluid to prevent hydrate formation. A hydrate
is a crystalline compound of water (H2O) and methane (CH4). The water freezes at a low
temperature and forms an ice lattice that traps molecules of natural gas. Hydrates have a
slushy, sludge-like consistency. Hydrate formation is bad news to an operator because it
may restrict or even stop the production fluid flow by plugging up the lines, or may prevent
the operation of mechanical equipment such as valves. At bottom hole pressures and
temperatures, hydrate formation is typically not a problem. But as the production fluid works
its way to the wellhead, temperatures and pressures begin to drop and may eventually
reach a point where hydrate formation is a possibility. The problem is especially acute
subsea where production fluid may have to go through miles of piping that is exposed to
the cooling effects of the surrounding seawater. If the fluid temperature is high enough at
the wellhead, it may be possible to insulate the piping and equipment downstream to
XII - 16
prevent the fluid temperature from dropping below the hydrate formation point. Even with
insulation, hydrates may form during shut-in periods when the temperatures drop. As a
consequence many subsea production systems are designed with injection lines so that
methanol can be injected into the fluid to prevent hydrate formation where it acts essentially
as an antifreeze.
Methanol itself is not corrosive to any of our commonly used wellhead materials.
Corrosion in closed loop methanol systems where the methanol is extracted from the
produced fluid and then reinjected may, however, be quite severe. The recycled methanol
may pick up water, H2S, and other contaminants that may increase its corrosivity. Typically
we’ll use 22Cr duplex stainless steel piping for methanol systems. For closed loop systems,
a customer may require a more corrosion resistant alloy.
4. Seawater
Subsea production equipment may be exposed to seawater during installation,

during hydrotesting of the completed subsea system, during the “parking” period before
production actually begins, and during retrieval. Seawater is an excellent electrolyte and
will cause rapid corrosion of unprotected carbon and low alloy steels. Even a few days
exposure may result in unacceptable pitting on seal surfaces. As a consequence, we must
always plan on inlaying seal surfaces (ring grooves, seat pockets, and stem packing areas
in gate valves, for example) on carbon, low alloy, and martensitic stainless steel equipment
that will be used subsea no matter what the production fluid actually is. Systems may be
parked for many months before the start of production. This extended exposure to
seawater may cause severe corrosion of bare steel interior surfaces unless protective
measures are taken. In confined spaces where there is no influx of fresh seawater, the
oxygen content will be used up as corrosion takes place. The corrosion rate will decrease
as the oxygen becomes depleted. Oxygen scavengers can be used in confined areas to
preferentially react with the oxygen thus tying it up so it is unavailable for corrosion
reactions. Often merely a good coat of grease is sufficient to provide temporary protection
on internal surfaces against seawater. Sometimes partial systems are installed and parked
subsea. Until the rest of the system is installed and production begins, temporary end caps
can be used to prevent the influx of fresh, oxygenated seawater. Where end caps aren’t
practical and the influx of seawater cannot be prevented, it may be necessary to use a
material inherently corrosion resistant to seawater or to coat the internal surfaces.
Trim Selection for Production Wells
There is perhaps no other subject in oilfield metallurgy that is as difficult or as

emotional as the selection of materials for a corrosive environment. A trim that is too
conservative can add a great deal to the overall cost of the equipment. A trim not
conservative enough may cost a great deal more in the long run due to down time,
equipment repair, and safety and environmental problems. The ideal material is cheap,
readily available in the optimum product form, easy to machine, has good strength and
toughness, is easily welded, can be weld repaired any number of times, has good erosion
XII - 17
resistance, never galls, and is immune to corrosion. The ideal material, of course, doesn’t
exist. Some of our customers don’t realize this and ask for the impossible. Trim selection is
a minefield that can be safely navigated only by those brave souls who have a thorough
knowledge of the well environment, the available materials, the engineering design
requirements for the equipment, and the customer requirements. Trim selection is not for
the faint of heart. It is not for most sales people. We are not fools so we are not going to
rush into the topic of trim selection. We are going to carefully tip toe through it to avoid
being atomized by a mine. Don’t look for an idiot proof table here that takes all the thinking
out of trim selection – you won’t find it. Just as the instruction booklet that comes with your
new lawnmover or electric toaster contains page after page of safety warnings before it
gets to the page or two that tells you how use the darn thing, we must first look at the safety
warnings that apply to trim selection.
Obviously there are a multitude of factors that must be considered in trim selection.
Appendix E in this book lists some of the more common ones. Each of these factors must
be evaluated and prioritized for a given application in a given environment. Trade-offs must
be made. For example, corrosion resistance in steels can be enhanced by the addition Cr,
Mo, Ni, and other alloying elements. These same alloying elements can make the steel
more difficult to weld, prone to galling, and certainly will increase cost. Does the enhanced
corrosion resistance outweigh the disadvantages? Depends on the circumstances. A
customer with a land well with a 7 year design life may be willing to settle for a less
corrosive resistant (hence less expensive) trim than a customer with a subsea well with a
30 year design life even though the fluid analyses for both wells are identical. Give a dozen
corrosion experts the same well fluid analysis and ask them for a trim recommendation and
you’re likely to get twelve different answers. They may all be correct – each based upon
that expert’s past experience, conservatism, and how each factor is weighed in importance.
Both API 6A and NACE MR0175/ISO15156 state that it is the end user’s
responsibility to decide whether or not a given material is suitable for a particular
environment. There is good reason for assigning this responsibility to the end user.
Obviously the end user is footing the bill for the equipment. The end user will suffer the
immediate consequences of equipment failure or downtime. The end user has the best
knowledge of the intended environment or a change in the environment. The end user has
control of how the equipment is used (or abused!). The end user controls what will be put
down into the well in the future. The end user has the first hand experience of how a given
trim has worked/not worked in a given field. Cameron is frequently asked by an end user to
recommend a trim for a given well analysis. No, it’s not a case of an oil company shirking
its responsibility and foisting it off on us. The smaller oil companies may have limited
resources in metallurgy/corrosion engineering. Sometimes even with the large oil
companies, production people in the field with limited knowledge of trims may be the ones
ordering the equipment. Sometimes a large oil company will ask Cameron to propose a trim
on a large project just to get a second opinion. Ideally an end user will specify a minimum
API 6A trim and ask Cameron to propose specific materials (that meet our engineering and
manufacturing requirements) for their approval. Bottom line is that while we’ll be happy to
XII - 18
suggest candidate materials/trims for a given application, it is still the end user’s
responsibility to insure that the proposed materials are suitable for the intended service.
There is a growing tendency for oil companies in RFQ’s (request for quotations) for
subsea projects to list not only environmental and well conditions, but also list several
pages of all the chemicals and workover, packer, completion, and acidizing fluids that they
plan on using in the wells. The RFQ will typically have a requirement that the manufacturer
(us!) must be able to prove to their satisfaction that our proposed materials of construction
are compatible with all these fluids. This is a 20’ long, ornery alligator waiting to bite us in
the butt so be very careful how you respond in our quotation to this requirement! We will
typically propose materials that we have used in the past for other projects and thus may
be able to provide some field history showing compatibility with some of the more
commonly used chemicals and fluids. It is highly unlikely that we can provide field
experience or lab data that will show compatibility to all the fluids. If the RFQ becomes an
order, then the customer may insist that we perform some very expensive and lengthy
corrosion tests for those material/chemical or fluid combinations for which we have no
compatibility data. Some customers have used this requirement to launch an R&D study at
Cameron’s expense. The proper way to muzzle this ‘gator and deprive him of lunch (us) is
to armor plate our backsides with a statement in our quotation similar to the following:
“Cameron will endeavor to provide materials with known compatibility with all the chemicals
and fluids listed in the RFQ based upon field experience, laboratory testing, or published
data whenever possible. Where this information is unavailable or incomplete to the
customer’s satisfaction, Cameron may propose that laboratory testing be performed. The
test parameters and acceptance criteria must be mutually agreed upon. Cameron will
submit a quotation to the customer for the additional cost of this testing along with the
impact on the delivery schedule of the equipment.”
Are we ready to select a trim yet? No. We must first gather some information. We
need to know the temperature and pressure rating of the equipment. We need a detailed
analysis of the well fluid showing the types and amounts of hydrocarbons, the amount of
CO2, the amount of H2S, the expected water cut over the life of the well, the in situ pH of
the fluid, the water chemistry, produced sand, and anything else that may be present in the
fluid. We need to know what fluids and chemicals the customer will be using to complete
and maintain the well. We need to know the design life of the equipment. We need to know
the external environment – offshore, subsea, etc. Will cathodic protection be employed on
subsea equipment? Will inhibitors be used? Any special impact or other mechanical
property requirements? Any special material testing requirements? What is the material
and strength of the production tubing? For fields with existing equipment in service, what is
the current trim being used? Any problems with it? What standards must the materials
meet?
OK. Here it is. The moment you all have been waiting for. Trim selection charts. Use
them with care and remember all the caveats, disclaimers, and consumer warnings that
we’ve discussed. Don’t use them if there is sand or free sulfur present or if
XII - 19
the service temperature is above 250°F (contact Metallurgy)! The recommendations in
these Tables are just that: other trims may be possible depending on circumstances and
field experience. Special Engineering and customer requirements may require alternate
trims.
XII - 20
Trim Selection for Components
Wetted by Production Fluid
250°F Maximum Service
Table 1
Sweet Service
(H2S < 0.05 psi)
Materials
Partial Chloride (Cl-)

Pressure Content API 6A
No. CO2 (psi) (ppm) M/C Bodies Stems VBSM1 Hangers
1 <7 < 50,000 AA LAS LAS LAS LAS2
2 <7 50,000-100,000 BB-MOD LAS3 SS SS SS2
3 <7 > 100,000 HH CRA CRA CRA CRA
4 7-30 < 50,000 BB LAS SS SS SS2
5 7-30 50,000-100,000 BB-MOD LAS3 SS SS SS2
6 7-30 > 100,000 HH CRA CRA CRA CRA
7 > 30 < 50,000 CC SS SS SS SS2
8 > 30 50,000-100,000 CC SS SS SS SS2
9 > 30 > 100,000 HH CRA CRA CRA CRA
Where:
LAS = Carbon/low alloy steel (non-NACE), e.g. 4130, F22, 4140

SS = Stainless steel (non-NACE), e.g. 410, F6NM, 22Cr duplex
CRA = Corrosion Resistant Alloy (NACE compliant), e.g. 925, 718
Notes:
1. LAS gates and seats may be nitrided. SS and CRA gates and seats should be
hardfaced with tungsten carbide or Stellite® 6. Solid Stellite® 3 seats are also
acceptable for all services.
2. For hangers over 80 ksi SMYS, use FF or HH trim if there is any H2S present.
3. Weld clad seal areas (seat pockets, ring grooves, stem packing area, etc.) with nickel
alloy 625 or use SS bodies.
XII - 21
Table 2
Mild Sour Service

(0.05-1.5 psi H2S, pH > 3.5)
Materials

1 <7 < 50,000 DD LAS LAS LAS LAS2
2 <7 50,000-100,000 EE-MOD LAS3 SS SS SS2
4 7-30 < 50,000 EE LAS SS SS SS2
5 7-30 50,000-100,000 EE-MOD LAS3 SS SS SS2
7 > 30 < 50,000 FF SS SS SS SS2
8 > 30 50,000-100,000 FF-MOD SS SS SS SS2
Where:
LAS = Carbon/low alloy steel (NACE compliant), e.g. 4130, F22, 4140
SS = Stainless steel (NACE compliant), e.g. 410, F6NM, 22Cr duplex
Notes:
1. LAS gates and seats may be nitrided. SS and CRA gates and seats should be
hardfaced with tungsten carbide or Stellite® 6. Solid Stellite® 3 seats are also
acceptable for all services.
2. For hangers over 80 ksi SMYS, use FF or HH trim if there is any H2S present.
3. Weld clad seal areas (seat pockets, ring grooves, stem packing area, etc.) with
nickel alloy 625 or use SS bodies.
XII - 22
Table 3
Intermediate Sour Service

(>1.5-10 psi H2S, pH > 3.5)
Materials

2 <7 50,000-100,000 EE-MOD LAS3 CRA SS CRA
4 7-30 < 50,000 EE-MOD LAS CRA SS CRA
5 7-30 50,000-100,000 EE-MOD LAS3 CRA SS CRA
7 > 30 < 50,000 FF SS CRA SS CRA
8 > 30 50,000-100,000 FF SS CRA SS CRA
Where:
SS = Stainless steel (NACE compliant), e.g. 410, F6NM
Notes:
1. LAS gates and seats may be nitrided. SS or CRA gates and seats should be hardfaced
with tungsten carbide or Stellite® 6. Solid Stellite® 3 seats are also acceptable for all
services.
2. For hangers over 80 ksi SMYS, use HH trim.
nickel alloy 625 or use SS bodies.
XII - 23
Table 4
Severe Sour Service

(H2S >10 psi, pH > 3.5)
Materials

2 <7 50,000-100,000 EE-MOD LAS3 CRA SS CRA
4 7-30 < 50,000 EE-MOD LAS CRA SS CRA
5 7-30 50,000-100,000 EE-MOD LAS3 CRA SS CRA
7 > 30 < 50,000 HH CRA CRA CRA CRA
8 > 30 50,000-100,000 HH CRA CRA CRA CRA
Where:
SS = Stainless steel (NACE compliant), e.g. 410, F6NM
Notes:
1. LAS gates and seats may be nitrided. SS or CRA gates and seats should be hardfaced
with tungsten carbide or Stellite® 6. Solid Stellite® 3 seats are also acceptable for all
services.
2. For hangers over 80 ksi SMYS, use HH trim.
nickel alloy 625 or use HH bodies.
XII - 24
Table 5
Extreme Sour Service

(H2S >10 psi, Any pH)
Materials

1 Any Any HH CRA CRA CRA CRA
Where:
Notes:
1. CRA gates and seats should be hardfaced with tungsten carbide or Stellite® 6. Solid
Stellite® 3 seats are also acceptable for all services.
XII - 25
Trim Selection for Water Injection Wells
Most wells are not terribly efficient in terms of extracting all the oil out of a
formation. Typically only about a third of the oil in a given formation is produced before it is
no longer economical to operate the well. There are a number of reasons for this, but chief
amongst them is the drop in pressure that occurs over the life of the well. Oil doesn’t lie in
vast pools below the surface of the earth. It is, rather, found in rock formations that are
permeable – rocks with interconnecting pores or fissures. A fluid will flow from a high
pressure area to a low pressure area. The weight of the overlying rock exerts tremendous
pressure on the oil and will cause it to flow upward where the pressure is less. The
continued upward flow of oil will cease when the oil encounters an impervious layer of rock
that effectively seals off the formation. The oil will then collect in a reservoir just under this
cap. We’ll pierce through this cap when we drill our well. Our well will be a vent for the
reservoir allowing access to the surface where pressures are much lower. Natural pressure
in the reservoir will drive the oil and gas in the reservoir to our well and then up to the
surface.
There are several mechanisms that may drive the hydrocarbons through the
formation into our well. Dissolved gas drive occurs when nearly all the hydrocarbons in a
reservoir are in a liquid state or dissolved in the well fluid due to the high pressure. A well
drilled into the reservoir creates an area of low pressure that allows the lighter
hydrocarbons to become gaseous. These gasses will then expand and force the remaining
liquid hydrocarbons (the oil!) into the well. We can illustrate dissolved gas drive by doing a
simple, yet elegant experiment. Take a can of Coke and shake it vigorously. Now walk over
to your neighbor’s cubicle (best not to do it in yours) and explain that you are about to
illustrate an important mechanism of reservoir drive. Tell your neighbor to watch closely. Tilt
the top of the can slightly towards your neighbor to offer an unobstructed view. Now pop
the top open. Voilà!!! Dissolved gas drive occurs as the CO2 comes out of solution and
spews the liquid out of the can. ”It’s a gusher!” you triumphantly pronounce. Beat a hasty
retreat back to your cubicle so that your neighbor is left in solitude to contemplate what has
just occurred. The lesson will soak in and will not soon be forgotten.
Gas cap drive occurs when reservoir conditions are such that not all the gas is
dissolved in the oil. The gas, being much lighter, forms a blanket or cap on top of the oil.
When the well is drilled, the gas cap expands and drives the oil into the well and then up to
the surface. Water drive occurs when the oil in a formation lies on top of a large amount of
formation water. When the well is drilled, the water will rise and drive the oil into the well
and then up to the surface. Most wells have a water drive in combination with dissolved gas
and/or gas cap drive.
The problem most well operators will face sooner or later is that the reservoir
pressure will drop to the point where it is no longer sufficient to drive the oil into the well
and up to the surface. There is a substantial amount of oil left in the formation (typically
over twice the amount already produced), but the formation pressure has been depleted to
the point where it just doesn’t have the oomph any more to push the oil up the tubing string.
XII - 26
All is not lost, however, and we’re not ready to abandon our well yet. There are a variety of
EOR (enhanced oil recovery) techniques that we may employ to squeeze out some
additional oil from our deflated formation. The one that will focus our attention on in this
section is water injection.
Water injection, as the name implies, involves drilling one or more wells around the
periphery of the formation and then using high pressure pumps to force water into the
formation. This restores some of the formation pressure and the injected water will drive the
oil to into the well and up to the surface. The operator may use an external source of water
or re-inject formation water. Offshore operators may use seawater. The water to be injected
may be treated with a variety of chemicals for various reasons. These may include oxygen
scavengers, corrosion inhibitors, scale inhibitors, biocides, etc. Sometimes unwanted
gasses that have been separated out from the production fluid may disposed of by injecting
them back into the formation along with the injection water. In some fields (SACROC in
West Texas, for example), a water-alternating-gas process (WAG service) may be used to
enhance recovery. In WAG service, CO2 is first injected into the formation. The CO2
dissolves into the oil and forms a miscible liquid with a lower viscosity. This makes it easier
to drive the fluid through the fissures in the formation to the well. Water is then injected
through the same tree and wellhead into the formation to act as a drive fluid. The process is
then repeated with CO2 injection alternating with water injection.
Water injection has some unique issues associated with it that make the trim
selection process different than for production wells. There have traditionally been two
diametrically opposite approaches to trim selection for water injection equipment. Some
customers want the cheapest trim possible and are willing to tolerate less than optimum
reliability and shorter life. The other camp goes for longer life with highest reliability despite
the higher price tag. Which approach a customer utilizes depends to a large extent on
whether the injection will be on land or offshore, and whether or not the water is treated
before injection. A corrosion failure of equipment used for just water injection is typically not
a catastrophic event. Usually it will manifest itself long before the pressure integrity of the
equipment is compromised. Shutting down the injection well and replacing the corroded
equipment has far fewer consequences for land operations than for those offshore on a
platform or subsea.
Whether or not a customers plans on having an oxygen control program for the
injection water has a profound impact on trim selection. The corrosion rate of carbon and
low alloy steels in fully de-oxygenated water is very low. It is typically easier and cheaper
for a customer to use oxygen scavengers to tie-up the oxygen in the injection water and
thus allow the use of carbon and low alloy steels than it is to leave the water untreated and
be forced into using coated/cladded steel or inherently corrosion resistant materials. What
constitutes “fully de-oxygenated” water? There is essentially no corrosion of carbon/low
alloy steels at oxygen levels below 10 ppb (parts per billion). From a practical standpoint,
as long as the oxygen content is controlled to 50 ppb or less, the corrosion rate of carbon
and low alloy steels in water will be minimal permitting the use of these materials. There
has been a growing tendency for some offshore platform operators to inject chlorinated,
XII - 27
raw (not de-oxygenated) seawater. They are willing to forgo the benefits of de-aeration in
favor of simplified platform operation and reduced weight (no de-aerating equipment). This,
of course, requires the use of inherently corrosion resistant (and expensive!) materials such
as super duplex stainless steel. The chlorine, added as a biocide, will greatly increase the
corrosivity of the seawater for many alloys.
Some customers may want their injection equipment to be NACE compliant. There
may be several reasons for this. They may plan on disposing H2S (separated out from the
production hydrocarbon gasses) by re-injecting them into the formation along with the
injection water. Some customers may want NACE compliance in case of accidental
flowback of sour production fluid into the injection well. And finally some customers may
order NACE compliant injection trim so that they have the flexibility of using the same
equipment for production purposes.
There are many possible water injection trims. Which one is the best choice for a
particular set of circumstances depends on what the customer is injecting, any chemical
treatments, what the design life of the injection well is, the degree of reliability that the
customer wants, what the customer is willing to pay for the equipment, whether or not
NACE compliance is required, and whether or not the equipment also needs to be trimmed
for the production fluids.
Tables 6-10 show possible trims for five different water injection scenarios. These
suggested trims are based on injected fluids only and not on possible flowback of
production fluids. Special Engineering and customer requirements may require alternate
trims. The different possible trims are listed in order from the least expensive (and least
reliable!) to the most expensive (and most reliable). I have indicated what our preferred
standard trims should be, assuming no special customer or engineering requirements.
Note that our preferred standard trims for de-oxygenated water still involve weld cladding
seal areas of low alloy steel bodies with 625 and the use of stainless steel or CRA
internals. Even though corrosion of low alloy steel is negligible in fully de-oxygenated
water, seal areas must be protected during down times when the injection system is being
worked on and air may get into the system. There may also be occasional oxygen “spikes”
during operation due to problems with the de-aerating equipment, oxygen scavenger
injection, etc.
XII - 28
Trim Selection for Water
Injection Components
Table 6
Land Service – Water Injection Only

Water De-Oxygenated to
50 ppb Maximum
Materials
Cost
And API 6A
Option Reliability M/C2 Bodies Stems VBSM3 Hangers
1 Lowest AA-MOD LAS LAS-ENP LAS-ENP4 LAS
2 Low AA-MOD LAS-C LAS-ENP LAS-ENP4 LAS
3 Low AA-MOD LAS-ENP LAS-ENP LAS-ENP4 LAS
4 Medium1 BB-MOD LAS-PWI CRA/SS CRA/SS4 CRA
5 High CC SS/DSS CRA/SDSS CRA/SS CRA
6 High CC SDSS CRA/SDSS CRA/SS CRA
7 Highest HH LAS-FWC SDSS/CRA+ SDSS/CRA CRA
Where:
LAS = Carbon/low alloy steel, e.g. 4130, F22, etc.

LAS-ENP = Carbon/low alloy steel with wetted surfaces plated with electroless
nickel
LAS-C = Carbon/low alloy steel with wetted surfaces coated
LAS-PWI = Carbon/low alloy steel partially weld inlaid with 625 (seal areas only – seat
pockets, ring grooves, stem packing area, etc.)
LAS-FWC = Carbon/low alloy steel fully weld cladded with 625 on wetted surfaces
CRA = Corrosion resistant alloy, e.g. 925, 718, 825, etc.
CRA+ = Corrosion resistant alloy with 6% Mo minimum, e.g. 725, 625+
SS = 316, duplex, super duplex stainless steel
DSS = 22Cr duplex stainless steel
SDSS = 25Cr super duplex stainless steel with PREN > 40
Notes:
1. Recommended standard trim
2. For water injection with H2S disposal use corresponding sour service M/C (e.g. AA→DD,
BB→EE, CC→FF)
®
3. Solid Stellite 3 seats are also acceptable for all services. CRA and SS gates and seats must
®
be hardfaced with Stellite 6 or tungsten carbide.
4. 410 or F6NM gates with tungsten carbide hardfacing may be used as alternates.
XII - 29
Table 7

Water Not De-Oxygenated
Materials
Cost
And API 6A
1 Low BB-MOD LAS-C LAS-ENP LAS-ENP CRA
2 Low BB-MOD LAS-ENP LAS-ENP LAS-ENP CRA
3 Low BB-MOD LAS-ENP SDSS/CRA SDSS/CRA CRA
4 High1 CC SDSS SDSS/CRA+ SDSS/CRA CRA
5 High1 HH LAS-FWC SDSS/CRA+ SDSS/CRA CRA
Where:

LAS-ENP = Carbon/low alloy steel with wetted surfaces plated with electroless
nickel
LAS-C = Carbon/low alloy steel with wetted surfaces coated
Notes:
2. For water injection with H2S disposal use corresponding sour service M/C (e.g. BB→EE,
CC→FF)
®
®
XII - 30
Table 8
Offshore Service – Water Injection Only

50 ppb Maximum
Materials
Cost
And API 6A
1
1 Medium BB-MOD LAS-PWI CRA/SS CRA/SS CRA
2 High CC SS/DSS CRA/SDSS CRA/SS CRA
3 High CC SDSS CRA/SDSS CRA/SS CRA
4 Highest HH LAS-FWC SDSS/CRA+ SDSS/CRA CRA
Where:

Notes:
2. For water injection with H2S disposal use corresponding sour service M/C (e.g. BB→EE,
CC→FF)
®
®
XII - 31
Table 9

Water Not De-Oxygenated
Water Chlorinated
Materials
Cost
And API 6A
1 High1 CC SDSS SDSS/CRA+ SDSS/CRA+ CRA+
2 High1 HH LAS-FWC SDSS/CRA+ SDSS/CRA+ CRA+
Where:

Notes:
2. For water injection with H2S disposal use corresponding sour service M/C (e.g. CC→FF)
®
3. Solid Stellite 3 seats are also acceptable for all services. CRA and SDSS gates and seats
®
must be hardfaced with Stellite 6 or tungsten carbide.
XII - 32
Table 10
WAG Service
50 ppb Maximum
Materials
Cost
And API 6A
1 High1 CC NiAlBr 316 SS 316 SS 17-4SS
17-4 SS 17-4 SS
NiAlBr NiAlBr
2 High1 CC 316 SS 316 SS 316 SS 17-4SS
DSS 17-4 SS 17-4 SS
NiAlBr NiAlBr
3 Highest CC SDSS SDSS/CRA SDSS/CRA CRA
4 Highest HH LAS-FWC SDSS/CRA SDSS/CRA CRA
Where:

NiAlBr = Nickel aluminum bronze
Notes:
2. For water injection with H2S disposal use corresponding sour service M/C (e.g. CC→FF)
®
®
XII - 33
INHIBITION
Corrosion inhibitors are substances that are added to a corrosive environment to

reduce the rate of attack on metals exposed to the environment. The exact mechanism
by which inhibitors protect equipment from corrosion in oil and gas wells is not clearly
understood, but it is apparent that the inhibitors combine with corrosion products on the
surface of a metal to form a protective film that isolates the metal from the environment.
An effective inhibition program may permit the use of carbon and low alloy steels in
hostile well fluids that would otherwise require the use of costly corrosion resistant
alloys.
There are many types of inhibitors used in the Oil Patch. Most are based on
organic molecules containing various combinations of nitrogen, sulfur, and phosphorus
that form an oily, water repellent film on the surface of the metal to be protected. This
film is easily damaged by the moving well bore fluid consequently a small, residual
amount of inhibitor must always be present in the system to repair the film. Inhibitor
selection is a very complex topic. Selection must be based upon the type of metal being
protected, the well fluid composition, temperature, pH, pressure, the expected corrosion
products, the velocity of the well bore fluid, the method of introducing the inhibitor into
the well, etc.
Inhibitors are typically liquids. They are typically diluted in a solvent such as
water, kerosene, field crude, etc. to an appropriate concentration before being injected
into the well. The solvent acts as a bulk carrier of the inhibitor and makes it easier to
transport and distribute the inhibitor in the well. There are many techniques used to get
the inhibitor into the well. Let’s examine a few of the more common ones.
Batch treatment, as the name implies, involves injecting a discrete volume of

inhibitor into the well. In the tubing displacement batch method, the desired amount of
inhibitor solution is displaced through the production tubing by pumping a liquid (often
produced fluid) behind it thus forcing it to the bottom of the well. The well is then shut-in
for several hours. The tubing displacement method is also known as the “kiss squeeze
method.” Standard batch treatment consists of putting the desired amount of inhibitor
solution in the annulus and then by-passing production at the top of well into the
annulus so it displaces the inhibitor solution to the bottom of the well. Extended batch
treatment is a variation that involves placing a large amount of inhibitor solution in the
annulus and allowing the production fluid to circulate. The inhibitor is displaced down
the annulus, up the tubing, and then into annulus again. The well is then put back into
production. As the annular fluid level fluctuates, inhibitor solution will be transported in
the oil into the production tubing.
Continuous treatment injects inhibitor solutions on a continuous basis. Injection

may be through a small tube extending to the bottom of the well. Wells with multiple,
concentric tubing strings can be continuously treated by injecting down one of the tubing
strings. Wells with a single tubing string and with a packer are sometimes continuously
XII - 34
inhibited through a downhole injection valve near the bottom of the string. The annulus
is filled with inhibitor solution. Continued pumping of the inhibitor solution into the
annulus creates a back-pressure sufficient to open the downhole valve and allow
inhibitor solution into the tubing string.
The squeeze treatment involves displacing a large amount of inhibitor solution

down the tubing string and forcing it into the formation. When the well is returned to
production, small amounts of inhibitor will be entrained in the production fluid as it
enters the tubing string. Given the right circumstances, squeeze treating may provide up
to 18 months protection.
Weighted liquid inhibitor solutions have a higher specific gravity then the
production fluid. Placed in a well, they will sink to the bottom. Inhibitors are then
released into the production fluid and carried into the production tubing. Weighted
capsules (an inhibitor pill, if you will) work on the same principle. When placed in a well
they will sink to the bottom where the capsules slowly dissolve and thus release
inhibitors. Solid inhibitors (often in the form of sticks) that sink to the bottom of a well are
another variant. Weighted inhibitors are the simplest to use, but are only effective under
some circumstances.
XII - 35
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NOTES:
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XII - 37

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CHAPTER XII CORROSION AT THE WELLHEAD

Burning at Both Ends

What Comes Out of a Production Well

1. Crude Oil & Natural Gas

A hydrocarbon is a molecule consisting primarily of carbon and hydrogen. Carbon

Crude oils can be characterized by their density or API (American Petroleum

3. Hydrogen Sulfide - H2S

H2S is a troublesome gas found in many wells. It is troublesome because it is a very

The amount of H2S in a well is typically reported as a mole% (often shortened to

4. Carbon Dioxide – CO2

Unfortunately mercury is sometimes found in gas wells. It is a hazardous chemical

Putting It All Together

• the nature, types, and amounts of the hydrocarbons present

Subsea production equipment may be exposed to seawater during installation,

Trim Selection for Production Wells

There is perhaps no other subject in oilfield metallurgy that is as difficult or as

Partial Chloride (Cl-)

LAS = Carbon/low alloy steel (non-NACE), e.g. 4130, F22, 4140

Mild Sour Service

Partial Chloride (Cl-)

Intermediate Sour Service

Partial Chloride (Cl-)

2. For hangers over 80 ksi SMYS, use HH trim.

Severe Sour Service

Partial Chloride (Cl-)

2. For hangers over 80 ksi SMYS, use HH trim.

Extreme Sour Service

Partial Chloride (Cl-)

CRA = Corrosion Resistant Alloy (NACE compliant), e.g. 925, 718

Land Service – Water Injection Only

LAS = Carbon/low alloy steel, e.g. 4130, F22, etc.

1. Recommended standard trim

Land Service – Water Injection Only

LAS = Carbon/low alloy steel, e.g. 4130, F22, etc.

1. Recommended standard trim

Offshore Service – Water Injection Only

LAS = Carbon/low alloy steel, e.g. 4130, F22, etc.

1. Recommended standard trim

Land Service – Water Injection Only

LAS = Carbon/low alloy steel, e.g. 4130, F22, etc.

1. Recommended standard trim

LAS = Carbon/low alloy steel, e.g. 4130, F22, etc.

1. Recommended standard trim

Corrosion inhibitors are substances that are added to a corrosive environment to

Batch treatment, as the name implies, involves injecting a discrete volume of

Continuous treatment injects inhibitor solutions on a continuous basis. Injection

The squeeze treatment involves displacing a large amount of inhibitor solution

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