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METALLURGY TRAINING MODULE 5

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Introduction
Wellhead corrosion is a complex subject. A thorough knowledge of the various
corrosion processes that may come into play on wellhead equipment is necessary in
order to select the most appropriate materials of construction or trim. Some of the
most hostile, corrosive environments on earth are found in the Oil Patch. Of course we
want to select the trim that will provide adequate corrosion resistance over the design
life of our equipment. Well error on the side of conservatism better safe than sorry,
but we have to be careful of being too conservative. Over-specifying a high end trim can
entail a great deal of extra cost that may make our quotes non-competitive. Corrosion
resistant alloys (CRAs) are expensive both in terms of cost per pound and in the
difficulty in machining, welding, and fabricating them. Lead times are typically longer
than low alloy steels.
Most API specifications as well as NACE give the ultimate responsibility for trim
selection to the end user. The end user will suffer the immediate and greatest
consequences if the wrong trim is selected. The end user often has firsthand data
showing what has worked or not worked in a particular field. The manufacturer of the
equipment has no control over where and how the equipment is utilized in the field. The
manufacturer has no control over the accuracy of the well data used in selecting the
appropriate trim. The manufacturer has no control over what chemicals the equipment
may be exposed to in service. These are all good reasons for giving the end user
primary responsibility for trim selection. Yet the manufacturer must also bear some of
the responsibility. Manufacturers must ensure that materials have not only the
necessary corrosion resistance, but also meet all the engineering requirements
(strength, toughness, hardenability, galling resistance, weldability, etc.) as well as
comply with any applicable standards and codes. Often manufacturers will be asked to
recommend a trim by end users with limited corrosion expertise.
Corrosion at the wellhead may stem from three separate sources: from produced fluids,
from the external environment, and from various chemicals that the end user may inject
into the well to enhance production or use for well control. Produced fluids will include
the good (hydrocarbons such as oil and natural gas), the bad (formation water, CO 2),
and the ugly (H2S, sand, free sulfur). The external environment may lead to severe
corrosion especially offshore where seawater serves as an excellent electrolyte. There
are literally thousands of different chemicals used to enhance production or to control
wells. They include some very nasty customers such as hydrochloric/ hydrofluoric acid
mixtures used during acidizing, and heavy brines used as packer, workover, or
completion fluids. The engineer making a trim selection must be fully versed in the
effects that each of these potential sources of corrosion has on the materials he
selects.
Trim selection must take corrosion resistance, engineering needs, cost, availability,
weldability, machinability, etc. all into account. It is clearly a complex business that must

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be done correctly. Theres no room for guesses or gut feelings here. Know what
youre doing or find someone who does!

Produced Hydrocarbons
Hydrocarbons are the good guys. They are the reason the well is drilled and completed
in the first place. The oil and natural gas that are produced are essential sources of
both energy and the raw materials for plastics, fertilizers, pharmaceuticals, lubricants,
etc. The hydrocarbons that constitute oil and natural gas are not themselves corrosive
to metals, but the specific types and relative amounts of hydrocarbons present in a
produced fluid may greatly influence the corrosion rate of steels and other metals used
to manufacture wellhead equipment. Clearly a familiarity with hydrocarbons is a must if
you are going to be doing trim selection.
A hydrocarbon is an organic molecule based primarily on carbon and hydrogen. Carbon
forms the spine or backbone of the molecule. Carbon based molecules are capable of
forming long chains because carbon has a valence of four. This means it has four
electrons in its outer shell that are available to be shared in up to four separate covalent
bonds. A carbon atom can thus link up between two other carbon atoms in a chain and
still be capable of forming two additional side bonds. Hydrocarbons are classified by
their structure and by the number of carbon atoms in their molecule. The two main
classes of hydrocarbons are the aliphatics and the aromatics. Aliphatic hydrocarbons
have chain molecules or non-aromatic rings while the aromatics have molecules based
upon the benzene ring (well go into the details of these shortly). The aliphatics can be
divided up into four series: alkanes, alkenes, alkynes, and cyclic aliphatics. The
physical properties of these molecules are very dependent on the number of carbon
atoms they contain. In general, the greater the number of carbon atoms, the higher the
melting point, boiling point, and specific gravity.
The alkanes, or paraffins as they are sometimes called, have the general formula of
CnH2n+2 where n is the number of carbon atoms in the molecule. They are classified by
the number of carbon atoms in their chain (see Table 1).The first four alkanes in Table
1 are gases at room temperature and pressure. They are the main constituents of
natural gas (typically 85-95% methane, 5-10% ethane, and small amounts of butane
and propane). The natural gas delivered to your house for heating is essentially 100%
methane. LPG refers to liquefied propane gas. Propane is a liquid at room
temperature and high pressure, but quickly vaporizes as the pressure is reduced to
ambient. This allows a great deal of propane to be compactly stored in tanks for heating
homes or for backyard barbecue grills. Alkanes have strong covalent bonds that make
them very stable up to high temperatures where they will eventually react with oxygen
(burn or combust) to form CO2 and water. Waxes are defined as alkanes having sixteen
or more carbon atoms in their chain.

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Table 1
Alkanes
Type
Methane
Ethane
Propane
Butane
Pentane
Hexane
Heptane
Octane
Nonane
Decane

Number of
Carbon Atoms
1
2
3
4
5
6
7
8
9
10

Formula
CH4
C2H6
C3H8
C4H10
C5H12
C6H14
C7H16
C8H18
C9H20
C10H22

Alkenes, or olefins as they are sometimes called, have a double bond between some of
the carbon atoms giving them the general formula of C nH2n. This double bond is not as
strong as a single bond so the alkenes are more reactive than the alkanes. Their
physical properties are similar to the alkanes with the same number of carbon atoms in
their molecules. The nomenclature of the alkenes uses the same prefixes as the
alkanes in Table 1: the first alkene is called ethene, the second propene, the third
butene, etc Ethene and propene are more commonly referred to as ethylene and
propylene.
Alkynes have a triple bond between two of the carbon atoms in their molecule making
them relatively unstable and more reactive. They have the general formula C nH2n+2.
Their physical properties are similar to the alkanes and alkenes with an equal number
of carbon atoms in their molecules. The nomenclature for alkynes also uses the same
prefixes as the alkanes in Table 1: the first alkyne is ethyne, the second propyne, the
third butyne, etc. Ethyne is more familiar to us as acetylene. Acetylene has a high heat
output when it combusts making it an important fuel gas for welding, oxyacetylene
cutting, etc.
The molecular structure of cyclic aliphatics differs significantly from the other aliphatics
weve discussed. Instead of forming long chains, the carbon atoms form rings. They
lack the two hydrogen atoms that appear on the ends of the straight chain molecules
thus creating two valence electrons that the terminal carbon atoms can share. Cyclic
alkanes consist of a ring of three or more carbon atoms all connected by single bonds.

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They have two less hydrogen atoms than their straight chain counterparts so their
general formula is CnH2n. There are several different ways of showing the structural
formula of a cyclic aliphatic. Heres an example:

Butane (C4H10) can be illustrated as shown at the right where


each straight line is a single chemical bond. A hydrogen atom
is assumed at the end of each open ended line.
Cyclobutane (C4H8) is the corresponding
cyclic aliphatic version of butane and can
be illustrated by any of the following.

Cyclic aliphatics are named after their corresponding straight chain counterparts having
the same number of carbon atoms with the prefix cyclo added (cyclopropane or
cyclobutane for example). Cyclic alkanes, as previously mentioned, are rings with all
single bonds. Cyclic alkenes are rings that contain a double carbon to carbon bond.
Cycloalkanes are commonly referred to as naphthenes in the Oil Patch. The physical
properties of the naphthenes vary with the number of carbon atoms in their molecules.
Their chemical reactivity depends on many different factors and can vary widely.
The other main class of hydrocarbons (besides the aliphatics) is the aromatics.
Aromatics have the general formula CnH2n-6. They all have a ring structure based upon
the benzene ring you might remember from high school chemistry (see below).

Some of the aromatics (notably benzene and toluene) have a pleasant odor hence the
name aromatics. They are toxic and carcinogenic. The bonds in a benzene ring are
very stable. Apparently the bonding in the aromatics differs from the covalent bonds in
the aliphatics giving them significantly different properties. Aromatics are important raw
materials for styrene, phenol, polyester and nylon. Aromatics are used to boost the
octane rating in gasoline. The higher the octane rating number, the more compression
the gasoline can withstand before detonating and the greater the efficiency.

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Resins and asphaltenes are components of crude oil consisting of very large (>40)
carbon chains. In addition to carbon and hydrogen, the molecules may contain one to
three atoms of oxygen, nitrogen, or sulfur. Each molecule consists of three or more
rings, usually aromatic. Resin molecules dissolve in crude oil while those of
asphaltenes do not. Asphaltenes are dispersed in the crude oil as very small particles
forming a colloid. During refining, the resins will end up in the different fractions
depending on their volatility while the nonvolatile asphaltenes will be the residue at the
bottom. Pure resins are heavy, sticky liquids. Asphaltenes are solids. Crude oil gets its
dark color from resins and asphaltenes. Tar sands are rich in asphaltenes.
Now lets look at some terminology that is commonly used in the oil Patch. An oil well,
not too surprisingly, produces mostly crude oil, but typically will have some gases
dissolved in it including natural gas. Natural gas is a mixture of hydrocarbon gases,
mostly methane, along with smaller amounts of CO 2, H2S, and N2 (see Table 2). Crude
oil is under a great deal of pressure in the formation. The hole that is drilled to access
the formation creates a low pressure path that allows the oil to flow to the surface. As it
does so the pressure is lowered and some of the gases will come out of solution and
either be recovered or burned (flared) off. A gas well produces mostly natural gas,
however, some of the heavier hydrocarbons such as pentane, hexane, and heptane
that are gaseous in formation due to the high temperature and pressure will condense
out as liquids near the surface where temperature and pressure are less. This liquid
mixture of hydrocarbons is referred to as condensate.

Table 2
Typical Natural Gas Composition
Gas
Methane
Ethane
Propane
Butane
Carbon dioxide
Oxygen
Nitrogen
Hydrogen Sulfide
Other

Formula
CH4
C2H6
C3H8
C4H10
CO2
O2
N2
H2S
(argon, helium, etc.)

Amount
70-90%
0-20%
0-8%
0-0.2%
0-5%
0-5%
trace

Crude oil composition varies by field, but the hydrocarbons are on average 30%
alkanes (or paraffins), 49% cycloalkanes (or naphthenes), 15% aromatics, and 6%
asphalts and resins by weight. There are over a hundred other organic compounds that

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can be found in crude oil in small amounts. The elements present in crude oil are found
in fairly narrow limits regardless of the molecular makeup as can be seen in Table 3.

Table 3
Elemental Makeup of Crude Oil
Element
Carbon
Hydrogen
Nitrogen
Oxygen
Sulfur
Metals (Fe, Cu, V, Ni, etc.)

Weight Percent
83-87
10-14
0.1-2
0.05-1.5
0.05-6
<0.1

Crude oils are characterized by their density or API (American Petroleum Institute)
gravity in degrees according to the following formula:
o

API Gravity =

141.5
- 131.5
o
Specific Gravity at 60 F

Where specific gravity is the ratio of the mass of the crude oil to that 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 heavy crudes will be more viscous
than light crudes.
Crude oils also contain waxes consisting mainly of paraffin hydrocarbons (C18 - C36) and
naphthenic hydrocarbons (C30 - C60). Waxes are liquids at high reservoir temperatures,
but may solidify at the lower surface temperatures at the wellhead. Deposition of the
waxes in the solid state can interfere with the production flow. The pour point of a crude
oil is a measure of its wax content. It is defined as 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 more wax the crude oil contains. Pour points of crude oils can vary from
-75oF to 104oF.
As mentioned in the introduction, none of the hydrocarbons weve just examined are
corrosive to the steels or other metals we use to manufacture wellhead equipment. The

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types and relative amounts of hydrocarbons can directly influence the rate of corrosion
through several different mechanisms. Before we examine why this is so, we must first
examine another produced fluid: water.

Produced Water

The crude oil in a formation will often have a gas cap on top of it consisting of the lighter
weight hydrocarbons. The crude oil itself often lies on top of a pool of water. Some of
this water will be drawn up the production tubing along with the crude. At the beginning
of production, the amount of water may be very small, but as the well ages the amount
of water being produced with the crude can rise significantly. The amount of this
produced water is generally given either as a percentage of the total volume of
produced fluids, also known as the water cut, or in barrels of produced water per day.
The water cut of a produced fluid is one of the major factors in determining the
corrosivity of a well. Gas wells typically have less produced water than oil wells.
Water (the liquid phase of H2O) is necessary for corrosion to occur. Water must come
into contact with the surface of a metal for a sufficient period of time to allow the various
corrosion mechanisms weve already discussed to occur. Water is a highly polar
molecule which makes it a powerful solvent. It thus contains many dissolved ions that
make it a very effective electrolyte. The chloride ion (Cl-) is one of the main ionic
constituents in produced water. As the chloride ion content increases, so does the
conductivity and corrosivity of the water. Chloride and other halide ions are very
detrimental to the protective oxide layers that make CRAs corrosion resistant.
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. Seawater, in comparison, has about
19,000 ppm.
There are many other types of ions in formation water besides chlorides. Their sum
total will determine the conductivity of the water. Carbonate and bicarbonate ions will
act as buffers in formation water 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 and thus be less corrosive. A protective scale
may deposit on a metals surface under certain conditions when ions come out of
solution. This may greatly reduce corrosion. Protective scales may allow the use of
carbon or allow steels in sweet service (high CO2, no H2S) under some conditions.
Water is necessary for acid gases such as H2S and CO2 to dissolve in and form acids
and thus lower the pH of the water. The more acidic the water, the greater is its
corrosivity. A low pH will increase the risk of environmental cracking in many alloys.
There is a synergistic effect between chloride ions and H2S and CO2. The corrosion that

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takes place when all three are present is greater than what would be predicted from
adding up their individual contributions.
There is very little or no free oxygen in produced water which is very fortuitous because,
as weve already learned, oxygen can greatly accelerate the corrosion of steel. Oxygen
is very reactive chemically and will quickly react with minerals and other substances
downhole at the high temperatures and pressures to form stable oxides. If its tied up as
a stable oxide, the oxygen is no longer available to react with our wellhead equipment in
a corrosion process.
The H2O that is present in a natural gas formation may be in a gaseous phase
depending on the pressure and temperature. As long as it remains in a gaseous state, it
presents no corrosion problems at the wellhead. Produced gas may contain large
amounts of H2O and CO2 as gases and still not be corrosive to carbon or low alloy
steels. However, as the produced gas heads to the surface its temperature and
pressure may drop sufficiently to let the H2O condense at the wellhead and form liquid
water. Now we have a corrosion issue. This condensate water, as it is called, has a very
low chloride and mineral content and is thus not as corrosive as liquid formation water.
Corrosion may still be severe because now acid gases can dissolve in the condensate
water to form acids.

Acid gases In Produced Fluids


Weve already discussed the fundamental corrosion mechanisms that may result from
the presence of acid gases such as H2S and CO2 in production fluids. Here well look at
the thresholds they must exceed in order to be considered a problem. Lets start with
CO2. CO2 will dissolve in water and form carbonic acid, H2CO3. Carbonic acid is a
relatively weak acid, but may cause serious corrosion issues with carbon and low alloy
steels over a period of time. Here again are the CO2 guidelines presented in API 6A:
Partial Pressure CO2

Relative Corrosivity

< 7 psi

Noncorrosive to carbon or low


alloy steels

7 to 30 psi

Slightly corrosive to carbon or


low alloy steels

> 30 psi

Moderately to highly corrosive to


carbon or low alloy steels

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Guidelines are just that guidelines and no guarantee that theyll work in every case.
You need to know when there are exceptions to the rule. At a CO 2 partial pressure of
< 7psi it is generally safe to use carbon and low alloy steels. All bets are off, however, if
there is particulate matter (sand, etc.) entrained in the produced fluid or for extremely
high production velocities were erosion may be a concern. The sand or high velocity
fluid will strip away protective scales and corrosion products exposing fresh metal to the
corrosive environment. Under these conditions CO2 partial pressures as low as 1 or 2
psi may become highly corrosive. Carbon and low alloy steels are then unsuitable and
stainless steel or better must be used. Stainless steels generally have excellent
resistance to CO2 corrosion, but their suitability for this service depends on the
maximum service temperature and what else is present in the produced fluid. Their
chromium content gives them good corrosion-erosion resistance.
Depending on the ion content of the produced water, there may be certain temperature
and pressure combinations where the CO2 will combine with ions to form a tenacious,
protective scale on metal surfaces. This is an extremely important consideration when
designing miles of pipelines where it is prohibitively expensive to use CRA instead of
carbon steel pipe. This is not something that we can make use at the wellhead,
however. Pipe has smooth curves with a minimum of flow disruptions that permit rapid
and even scale deposition. This is not true of wellhead equipment where scales may
have difficulty forming or can get damaged. Go with corrosion resistant alloys here.
For CO2 partial pressures between 7- 30 psi, API 6A says the environment will be
moderately corrosive. Carbon and low alloy steels can generally be used for the body
components (unless sand is present!) because under API 6A design rules, the wall
sections can tolerate some minor surface corrosion without going below the minimum
design thickness. Ring grooves, seat pockets, and stem packing areas in carbon/low
alloy steel bodies may need to be inlaid with stainless steel or CRA because they have
sealing surfaces that must hold gas tight. Valve bore sealing mechanisms (seats and
gates) and stems also have sealing surfaces that must hold gas tight so they must be
made out of stainless steel or CRA material.
For CO2 partial pressures over 30 psi, stainless steels or CRAs should be used for all
components. So which should you use? Depends on the temperature, pressure, and
what else is in the produced fluid. Not all stainless steels or nickel alloys have the same
corrosion resistance so care must be exercised in selecting the right one appropriate for
the service conditions.
Note that these API 6A guidelines for CO2 corrosion should never be applied to pipe!
Piping and pipelines are designed to different standards and have different minimum
wall requirements. They are not as tolerant of corrosion as the heavy sectioned API 6A
bodies. The amount of expected corrosion over the design life of the pipe should be
estimated and a corrosion allowance added to the OD of the pipe. There are many
computer models available for predicting the amount of corrosion in a carbon steel

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pipeline. Most are based upon variants of the predicative model of DeWaard and
Milliams. These gentlemen developed equations that factor in the different variables
that influence CO2 corrosion. From these they constructed the DeWaard-Milliams
nomograph (see Figure 1) that can easily be used to estimate CO 2 corrosion on carbon
steels.

Figure 1
The DeWaard-Milliams Nomograph

To use the nomograph, draw a straight line between the applicable temperature and
CO2 partial pressure (note: 1 bar = 14.5psi). Where the line crosses the Corrosion Rate
axis will be the expected corrosion rate in mm per year. If the line also crosses through
the Scale factor axis, then you must multiply the corrosion rate value by the scale factor
to get the expected corrosion rate. In the example shown, the corrosion rate at 120C
and CO2 partial pressure of 0.2 bar (29 psi) is equal to 10mm/year X a scale factor of
0.7 for an expected corrosion rate of 7mm/year.

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Will wells containing over 30 psi CO2 partial pressure always be highly corrosive to
carbon and low alloy steels? No! It depends on what the other constituents of the
produced fluid are. For CO2 to be corrosive, water (liquid H2O) must be present in
sufficient quantity so that it can come into contact with the surface of the metal. Oil
wells with small water cuts, for example, may have all the water entrained in the flowing
oil so it does not contact the metal surface. The oil may leave a persistent, protective
film on the metal surface. The corrosion rate under these circumstances may be very
low regardless of the CO2 partial pressure. Well try to quantify this later.
Lets move on now to the other acid gas, H2S. H2S is found in many wells and can
serious problems both from a general corrosion standpoint and from a stress corrosion
cracking standpoint. H2S is an acid gas and so will cause the pH to drop and thus
increase general corrosion, although under some circumstances it may actually
decrease corrosion by forming a protective scale. More importantly it can combine with
iron in the reaction Fe + H2S FeS + 2H to produce hydrogen atoms that can diffuse
into the metal and cause a form of hydrogen damage known as sulfide stress cracking
or SSC. The sulfur apparently facilitates the diffusion of the hydrogen into the steel.
NACE MR0175/AISO 15156 (hereafter referred to as just NACE) is the standard most
often specified for the selection and use of metallic materials for production equipment
used in sour service. For the type of equipment produced by ARGUS Subsea, NACE
has established a partial pressure of 0.05 psi H2S as the threshold for sour service.
NACE is invoked by many other standards including all API specifications for production
and drilling equipment. Production equipment to be used for sour service in the state of
Texas (and all other states for that matter) is required to comply with NACE by state
law. Production equipment to be used offshore on the U.S. continental shelf by law
must comply with NACE if the service is sour under federal law. NACE has the effect of
law in many other places in the world as it is frequently cited in government regulations
for oil and gas production. If the service is sour, NACE is mandatory! You cannot by law
accept any deviations to its requirements.
NACE is a very complex document that has almost become unreadable and impossible
to use since it was made into an ISO specification. It is very user unfriendly and difficult
for a non-metallurgist to interpret. Were not going to go into all its intricacies here
there will be another Training Module dedicated just to this document. We will make a
few general comments here. NACE prescribes allowable materials, the conditions in
which they may be used, allowable processing parameters, and any restrictions for
materials in sour service. The requirements and/or restrictions for a given material may
change depending on the component it will be used for. Just because a material is
good for a pressure controlling gate, for example, does not mean its good for a
pressure containing body. NACE only addresses environmentally assisted cracking
(EAC) mechanisms from production fluids containing more than the threshold amount
of H2S. It does not address general corrosion nor does it address EAC from nonproduction fluids (seawater for example). Be sure you understand this - the safe limits

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in NACE are based on EAC resistance in production fluids only general corrosion or
EAC from external fluids such as seawater are not addressed!
If a given service has less than 0.05 psi partial pressure H 2S, it is classified as non-sour
or sweet service. Does this mean that we can use any material we want without worry
of SSC? No it does not. Some high strength metals or metals loaded closely to yield
may still fail by SSC even when exposed to H2S partial pressures less than 0.05 psi.
Conversely if a material is NACE compliant, can it always be safely used in sour service
within the prescribed NACE restrictions without worry of SSC? Again the answer is no.
There are always exceptions to rules and no one standard can cover all of them. EAC is
a tripod: one leg is susceptible material, one leg is an applied tensile stress, and the
last is a specific environment. NACE does not address the design aspects of the
equipment or regulate the allowable tensile stresses. The higher the strength of the
material, the higher its residual stresses and the more susceptible it becomes to SSC.
The higher the applied tensile load, the more susceptible a part becomes to SSC.
NACE compliant parts loaded at or above their yield strength may still crack in H 2S.
Bulk stresses may be low, but localized stresses may exceed yield in some designs and
this can lead to failure by SSC.
Most customers will order NACE compliant materials, especially for subsea equipment,
if there is any detectable H2S in their well analysis just to be conservative. Customers
who plan on eventually using water injection to boost production in the later stages of
the life of their well will always require NACE compliancy even if there is no reported
H2S in the initial well analysis. Water injected into the formation may introduce
anaerobic bacteria and the nutrients they need to thrive. This may cause the formation
to sour over a period of time. Many customers will routinely order NACE compliant
materials to give them the freedom to move the equipment around without worrying if
H2S is present or not.

Other Stuff in Produced Fluids


Weve addressed the major components of the fluids coming out of a well:
hydrocarbons, water, and acid gases. There are many other substances that can come
out of a well. Here are some you may come across listed in well analyses sheets.
1. Helium Helium is an inert gas that is sometimes associated with natural gas in gas
wells particularly in Texas and Oklahoma. Its non-reactive so nothing to worry about. It
takes up space.
2. Mercury Mercury can be found in trace amounts in some wells. The concern with
mercury, besides its toxicity, is that it can cause liquid metal embrittlement in some

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alloys. Mercury is not a problem for wellhead equipment made from steels or nickel
based CRAs either as a vapor or as a liquid. The small amounts of mercury present in
a produced fluid are entrained in the fluid and will not have any significant contact with
the metal surfaces for any appreciable length of time. Things are different, however,
downstream of the wellhead where temperatures cool down and the mercury can
condense and collect in low spots. This is especially a problem in downstream heat
exchangers using aluminum tubes. The aluminum can become embrittled and suffer
massive cracking because of the mercury.
3. Sand Nobody wants to produce sand because of its erosive effects. Gravel packs,
filters, etc. are used to keep sand in its place so it doesnt become entrained in the
production fluid. Occasionally wells can produce sand unexpectedly. This can have a
serious impact on the corrosivity of the production fluid. When dealing with a well
producing some sand, forget about general guidelines for trim selection: contact a
metallurgist for his or her recommendations.
4. Free Sulfur Free sulfur is elemental sulfur that has not formed a compound with
anything. Offshore wells in the Gulf of Mexico (South Texas, etc.) may contain trace
amounts of free sulfur. The presence of free sulfur in sour environments greatly
increases the likelihood of sulfide stress cracking (SSC) in many alloys. NACE has
separate ground rules for using alloys when free sulfur is present.
5. Organic Acids Organic acids (particularly acetic acid) can be found in many wells.
They are relatively weak acids, but can accelerate general and pitting corrosion over a
period of time because they lower the pH. F6NM or CRAs may have to be used in
place of 410 stainless steel in wells with significant acetic acid present.

Interactive Effects
Weve looked at the meat, the tortilla, the cheese, the beans, and the chili sauce of
produced fluids. Now its time to put them all together and look at the whole enchilada.
The effects of any one component of the produced fluid cannot be considered in
isolation to all the rest. The components that weve talked about do not come out of a
well in discrete packets, but in complex mixtures. Multiphase flow is the norm. The
following produced fluid attributes must be considered when determining the overall
corrosivity of a well:

The types and relative amounts of hydrocarbons


water cut over the life of the well
composition of produced water

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pH
shut-in pressure over the life of the well
gas-to-oil ratio (GOR)
CO2 content
H2S content
temperature
fluid velocity
presence of organic acids
presence of particulate matter (sand)

Water must be present for corrosion to occur. No water no corrosion regardless of


what else is in the well. Only a very few wells will never produce any water (there are
some fields in Wyoming that have remained water free for decades), the vast majority
will produce increasing amounts of water over their lifetime. In order for water to
corrode, it must be able to come into contact with the surface of a metal for a sufficient
period of time to allow the corrosive reactions to take place. Discrete droplets of water
that are entrained in a flowing crude oil present no problem, but at some point as the
water cut increases, sufficient water may come into contact with the metal surfaces and
corrosion can begin. When do we need to start worrying? It depends on many factors,
but the most important are the types and relative amounts of hydrocarbons that are
present and the velocity of the produced fluid.
Liquid hydrocarbons have corrosion inhibitive properties: they leave a persistent,
protective film on the surface of metal parts they flow through. The higher the API
gravity and the more polar the molecule, the more protective this hydrocarbon film will
be. Heavy oils will thus be more protective than light oils. Carbon and low alloy steels
used in heavy oil production can withstand higher water cuts than in light oil production.
A persistent, heavy oil film may provide protection against corrosion at water cuts up to
40 or 50%. A light crude oil with few polar compounds may afford protection only up to
5%.
Produced water has a different density than crude oil hence it will tend to separate out
in slowly moving or stagnant conditions. A production flow of at least 1 meter per
second is necessary to keep water (up to 30%) in suspension as discrete droplets in the
crude oil (this will vary somewhat with the type of oil). There will little corrosion during
production, but during shut-in periods the water may stratify out and cause corrosion
problems.
The velocity of the produced fluid will impact the kinetics of the corrosion reactions
.through several different mechanisms. The rate of corrosion at a metals surface is
dependent on the quantity of the corrodent that is delivered to the surface. The
corrodent is being used up as the corrosion reactions occur and corrosion will

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eventually cease if the corrodents are not continuously replaced. There is a thin,
stagnant fluid boundary layer at the surface of the metal through which the corrodent
will have to diffuse to reach the surface. The faster the fluid velocity, the thinner this
boundary layer will be and the faster the corrodents can be delivered to the surface.
Higher velocity also means there will always be a fresh supply of corrodents available to
replace those used up in corrosion.
High velocity increases corrosion-erosion. The amount of mechanical abrasion or
cutting action that takes place as the moving fluid with any entrained particles impinges
on the surface of the metal increases with velocity. Protective scales or surface
deposits of corrosion products are abraded away exposing fresh metal: cathodic areas
are depolarized.
High velocity can mitigate some types of corrosion. Pitting and crevice corrosion are the
result of concentration cells. High velocity production fluid can continuously sweep out
the insides of pits or crevices thus preventing concentration cells from forming
Weve already discussed the importance of water chemistry. The higher the dissolved
ion content, the more efficient electrolyte it becomes. The pH of the water is dependent
on the type and amounts of dissolved minerals as well as the presence of CO 2, organic
acids, and H2S. In general, the higher the partial pressure of the CO2 and H2S, the lower
the pH and the more corrosive the water. Acids increase the efficiency of water as an
electrolyte and are a source of hydrogen ions that will consume electrons at the
cathode that must be replaced by additional corrosion at the anode. Whether or not a
stable, protective film will form is highly dependent on pH of the water, its dissolved
mineral content, and on temperature. The chlorides, CO2, and H2S dissolved in water
act synergistically so that their net effect on corrosion can be worse than the sum of
their individual contributions. Dont 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.
Multiphase flow complicates corrosion considerations. Our discussion so far has
assumed that crude oil is the continuous phase, but what if its not? Gaseous
hydrocarbons dont have the inhibiting effect that heavy oils do. At what point do the
effects of hydrocarbon gas outweigh the effects of the crude oil? This is where the gasto-oil ratio (GOR) comes in. As a rule of thumb, if the GOR of a well is < 5,000 standard
cubic feet of gas per barrel of oil, then the oil effects will predominate. Standard cubic
feet (or SCF) is the volume of gas in cubic feet at a pressure of 14.65 psi and a
o
temperature of 60 F. A barrel in the Oil patch is 42 U.S. gallons. A GOR of 5,000
SCF/bbl converts to 890 m3/m3 in metric. (As an interesting side note, the abbreviation
bbl for barrel comes from the early oil producing days in Pennsylvania. There were
many different size barrels used for transporting oil. In the 1870's, the 42-gallon barrel
was adopted as the standard for oil trade. This was 2 gallons per barrel more than the
40-gallon standard whiskey barrel used by many other industries at the time. The extra

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2 gallons was to allow for evaporation and leakage from the wooden barrels during
transport - kind of like a bakers dozen. Standard Oil began manufacturing 42 gallon
barrels to be used for transporting petroleum. They were colored blue to distinguish
them as 42 gallon barrels instead of the commonly used 40 gallon ones. BBL is short
for blue barrel.)
Lets look at a case now where the GOR is well over 5,000 SCF/bbl and the effects of
the gaseous hydrocarbons will predominate. Gaseous hydrocarbons leave no protective
film. If the well is also producing water, then corrosion may become a problem. Note
that water must be in a liquid form for corrosion to take place. If the operating
temperature of the well is greater than the dew point of the well production fluid, then
there will be no liquid water (it will be in a vapor phase) and corrosion will not be issue.
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. Corrosion may become an issue during an extended shut-in
where the equipment and lading can cool down below the dew point. Suppose now we
assume that our gas well is operating below the dew point of the produced fluid. Liquid
water will be present. For corrosion to become a significant problem there must be a
sufficient quantity of water present relative to the amount of gas being produced.
Corrosion will be minimal if the water-to-gas ratio is less than 2 bbl/MSCF (11.3
m3/Mm3) where MSCF stands for million standard cubic feet.

Down the Hatch What Goes Into a Well


Production fluids arent the only things that can cause corrosion in our equipment.
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. Most of
these cause no problems, but there are a few troublemakers to look out for. Sometimes
a customer will include a 5 or 6 page long, single spaced list of chemicals he plans on
using in his well and ask for a guarantee that the proposed trim materials will be
compatible with them. This is not something that we can agree to do. Many of the
chemicals will be identified solely by trade names and are proprietary in nature. Many
we may be familiar with, but many will probably be unknown. The proper way to
address this issue is in the quotation stage by including a statement such as the
following in our quotation:
ARGUS Subsea will only use field proven materials or materials qualified through
rigorous laboratory testing in the equipment we produce. While our materials are
standard in the industry and have been used in conjunction with many of the different
types of chemicals typically injected into wells, we are not in a position to address or
guarantee compatibility with each specific chemical on your list. We will review the list

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and note any known chemicals of concern. The end user is responsible for trim
selection. We will work with the end user to address any chemical compatibility issues.
If laboratory testing is required, ARGUS Subsea must agree to a test protocol. The end
user shall bear the cost of all testing. Testing may have a significant impact on
delivery.
In this section well look at a few of the more common substances that end users put
into their wellhead equipment and discuss their impact on material selection.
1. Workover/Packer/Completion Fluids
A workover fluid is a heavy 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 packer fluid is a heavy 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 (an expandable plug used to isolate certain sections of the well) to
counterbalance the pressure from the produced fluid.. A completion fluid is a heavy fluid
used to control well pressure during the completion of a new well. Drilling muds,
inverted emulsions, and clear brines have all been formulated in the past as the heavy
fluid. Drilling muds and inverted emulsions have the disadvantage of particulate matter
settling out of suspension. Clear, heavy brines are made up of one or more salts
including KCl, KBr, NaCl, CaCl2, and ZnBr2 dissolved in water and do not have this
problem hence are finding increasing use. The heavy brines are the fluids of most
concern to us from a corrosion standpoint.
The salts used to formulate heavy brines produce a very efficient electrolyte that can be
highly corrosive. The concentrated halide ions may readily attack protective oxide films
on CRAs depending on temperature. Oxygen contamination during a workover can
result in very rapid corrosion in the presence of a heavy brine. Of greatest concern is
the increased risk of stress corrosion cracking (SCC). The high concentration of halide
ions, the high temperatures found downhole, and the disruption of the passive oxide
film all promote SCC in CRAs normally resistant at cooler wellhead temperatures.
Heavy brines typically contain corrosion inhibitors, but these may not be effective at
high temperatures found downhole or may breakdown over a period of time.
There is a lot of published data showing the compatibility of heavy brines with various
alloys, but be careful when using these. Make sure the formulations have the same
concentrations of salts, inhibitors, etc. and that the environmental conditions are the
same as your potential application. The service companies that formulate the heavy
brine fluids are another good source of information on their corrosivity. The best guide
for selecting materials to be used in conjunction with a heavy brine is past experience:
work closely with the end user to see what has worked or not worked for him in the
past. If a fluid formulation is new or if there is no information of its corrosivity with a

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particular alloy, then laboratory testing must be done. Laboratory testing must include
tests for weight loss types of corrosion as well as for stress corrosion cracking.
2. Acidizing Fluids
Acidizing is an enhanced oil recovery process used to stimulate 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 minerals in the formation thus enlarging or unplugging pores, fissures,
etc. This increases permeability allowing more oil to flow. There are a variety of different
acid mixtures that are used. Hydrochloric acid (HCl) by itself or used in conjunction with
second acid is the most common. A 15% HCl solution is often used, but higher
concentrations are not uncommon.. A mixture of 12% HCl and 1.5% HF (hydrofluoric
acid) is also a popular choice. Depending on the formation, one or two injections (called
flushes) may be required. Different acid mixtures may be used for each flush.
Acidizing mixtures can be highly corrosive to metals. Fortunately the exposure time
during the injection of the live acid mixture is very short. Acidizing mixtures usually
contain corrosion inhibitors that are effective in preventing corrosion during the injection
phase. The main corrosion problem occurs with the spent: acid as it flows back through
the wellhead equipment.
After the acid has been allowed to dissolve obstructions and open up channels, the
spent acid must be removed from the formation and the production equipment. This is
done by flushing - injecting either EGMBE (ethylene glycol monobutyl ether) or
methanol into the well and then allowing it to flow back. The returning fluid initially will
contain the flushing fluid, spent acid, and a lot of silt and particulate matter. The pH of
the returning fluid will be higher than that of the starting acid because of the neutralizing
effects of the dissolved minerals, but is still strongly acidic. The spent acid will have a
high concentration of chloride ions from the hydrochloric acid. 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. There are dead zones within wellhead equipment (seat pockets in gate
valves, for example) that are very difficult to flush clean. These areas may be exposed
to spent acid for long periods of time resulting in heavy corrosion damage. The heavy
influx of chloride ions from the hydrochloric acid may increase the likelihood of 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 mixtures, they may not be effective for all
materials and may have a limited service life. The amount of inhibitors is kept low to
avoid damaging the formation.

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Fracking (short for fracturing) is a means of enhancing oil production that utilizes large,
truck mounted, reciprocating pumps to pump a frac fluid downhole under very high
pressure. The pressure pulses exceed the strength of the rock in the formation and
create new fissures, enlarge old channels, or unplug existing channels. This increases
the flow of the hydrocarbons out of the formation into the production tubing. The various
frac fluids are mostly water with a variety of chemical additives. Frack jobs are typically
done in three or four stages with different fluids with each fluid serving a different
purpose. One of fluid also contain proppants sand or other particles that are forced
into the fissures and will prop them open after the frack job is complete and normal
production pressure resumes. Acidizing is often done in conjunction with each stage.
Metals can be severely damaged by acidizing treatments unless good acidizing practice
is followed. Stainless steels in particular are readily depassivated by the hydrochloric
acid which strips away the protective oxide film. Duplex stainless steels are problematic
in that they can be difficult to inhibit and, when stripped of their protective oxide film,
have innumerable galvanic cells established between the ferrite and austenite grains
with the ferrite being anodic.
The service company performing the acidizing job must be cognizant of the materials in
the wellhead they are going to acidize through. Acidizing fluids must be formulated with
inhibitors appropriate for these materials. Whenever possible for surface equipment a
tree saver should be used. 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 into the well 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 cant be used, then the following steps should be taken to mitigate or
prevent corrosion 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.

3. Descalers
Oil wells occasionally get plugged up by deposits, or scales, that form when dissolved
minerals in formation and/or injection water react with other components in the well fluid

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and then precipitate out. There are many different types of scales, but carbonates and
sulfates seem to be the most common. There are many proprietary chemical mixtures
that the well operator can inject into the well in order to dissolve away these deposits.
Hydrochloric acid is typically one of the key components. A specific descaler is selected
for the type of scale that needs to be removed. Descalers must be formulated with
corrosion inhibitors appropriate for the metals found in the well production equipment
and for the environmental conditions found in the well.
Descalers can be very aggressive towards metals. Depending on their concentration,
time in the well before flushing, and a number of other factors, descalers may cause
extensive corrosion damage to the production equipment. If a customer asks you if
ARGUS Subsea equipment is compatible with a certain descaler, the correct response
is to provide a list of alloys found in the equipment and tell the customer he must
confer with the service company doing the descaling for an answer. We cannot
guarantee that equipment will or will not be damaged.
4. Seawater
Subsea production equipment may be exposed to seawater during installation. It may
become filled with seawater that will remain inside of it until production begins and the
seawater is flushed out. This wet parking period is typically no more than a few
months, but occasionally may be a year or longer. Subsea production equipment may
be filled with seawater during hydrotest of the completed subsea system. Seawater is
an excellent electrolyte and will cause rapid corrosion of unprotected carbon and low
alloy steels. Depending on the exposure time and environmental conditions, weight loss
corrosion may or may not be a problem, but pitting on seal surfaces will always be a
concern.
API 17D requires ring grooves in carbon or low alloy steel end connections to always be
weld inlaid with a protective CRA weld metal, but remember that there are many other
critical seal areas besides ring grooves in our equipment. As a minimum the ring
grooves, seat pocket, and stem packing areas of carbon, low alloy, and martensitic
stainless steel subsea gate valves should always be weld inlaid with nickel alloy 625.
In small, confined spaces where there is no influx of fresh seawater, the available
oxygen in the trapped seawater will be quickly up as corrosion takes place. The
corrosion rate will decrease as the oxygen becomes depleted. In larger spaces where
sufficient oxygen may be trapped to cause damage, it may be possible to add corrosion
inhibitors containing oxygen scavengers preferentially react with the oxygen making it
unavailable for corrosion reactions. Sometimes a coat of grease is all that is necessary
to provide temporary protection on internal surfaces against seawater. Not all the
segments of a production system may be immediately connected after being 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.

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Where end caps arent 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.
5. Methanol
Hydrates are crystalline compounds of water and methane (CH4) that may form in gas
wells. The water freezes at a low temperature and forms an ice lattice that traps
molecules of natural gas. Hydrates can be solid or slushy in consistency: either way
they can restrict flow through pipe or make it difficult to operate valves, etc. Produced
fluid downhole is at a high temperature and pressure. As it moves towards the
wellhead, the pressure and temperature drop and hydrate formation becomes a
possibility. Problems are more common downstream where pressure is reduced and
the temperature of the produced fluid in the piping has been substantially reduced by
the surrounding cold seawater.
Customers will often require that production equipment be insulated if hydrate formation
is a concern. This may keep the production fluid above the hydrate formation point,
although hydrate formation may still be a concern during shut-in periods when the fluid
cools down.
Where the conditions exist for potential hydrate formation, most customers will require a
methanol injection system. Methanol (CH3OH) is a simple alcohol that is noncorrosive
to the types of metals used in our equipment. It acts essentially as an antifreeze when
injected in amounts approximately 50% of the weight of the produced water. It is very
expensive to continuously supply a production platform with fresh methanol so closed
loop systems were developed that recycle the methanol. The methanol is injected in the
production tubing or at the wellhead. At the production platform the gas will be
processed to remove and recycle the methanol. The water is removed from the gas so
it can be sent to shore often through miles of pipe without worrying about hydrates.
Unfortunately the recycled methanol can pick up H2S and other contaminants as it is
recovered. This makes it corrosive to carbon and low alloy steels. As a consequence,
duplex stainless steel piping is typically used for methanol injection lines.
6. Injected Water
Only about a third of the oil in a formation is typically recovered before the formation
pressure drops to the point where the oil is no longer economic to recover unless EOR
(enhanced oil recovery) techniques are employed. Chief amongst these for subsea
wells is water injection. A common misconception is that oil lies in vast pools below the
surface of the earth. It doesnt. It is found in rock formations that are permeable rocks
with interconnecting pores or fissures. The weight of the overlying rock exerts
tremendous pressure on the oil in the formation and will cause it to flow upward where

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the pressure is less. The flow of oil stops it encounters an impervious layer of rock that
effectively seals off the formation or caps. The oil will then collect in a reservoir just
under this cap. When a well is drilled through this cap, the reservoir fluids now have
access to the surface where pressures are much lower. Natural pressure in the
reservoir will drive the oil and gas in the reservoir up to the surface. The pressure in the
formation will drop over the life of the well.
Water injection utilizes one or more wells around the periphery of the formation.High
pressure pumps re used to force water into the formation to build the formation
pressure back up to an acceptable level. The operator may use an external source of
water such as seawater or re-inject formation water. 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. Contaminants removed
from productions fluids may be re-injected with the water. The water-alternating-gas
process (WAG service) may be used to enhance recovery. In WAG service, CO 2 is first
injected into the formation. The CO2 dissolves into the oil and forms a miscible liquid
with a lower viscosity making 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.
There are numerous corrosion issues associated with water injection depending on the
composition of the water, whether or not other substances are also being injected (acid
gas disposal for instance), and whether or not the water is being treated in anyway.
Injection water is often deaerated then treated with oxygen scavengers. There is no
corrosion of carbon/low alloy steels at oxygen levels below 10 ppb (parts per billion). A
practical limit of 50ppb of oxygen is often specified for treated water resulting in
corrosion rates so low that unprotected carbon or low alloy steels can be used for water
injection equipment and piping. If H2S is being injected with the water, then materials
must comply with NACE. WAG service in which carbon dioxide and water are
alternately injected generally requires 316 stainless steel or better. Aluminum bronze is
also sometimes used.
Offshore wells use seawater for injection. The seawater may be treated to reduce
oxygen to an acceptable level. It may be chlorinated to prevent marine growth or
microbiological induced corrosion (MIC). Other chemicals may be injected for corrosion
control and to prevent scale formation. Deaerating and injecting oxygen scavengers
requires a lot of equipment and maintenance on a platform. It is increasingly common to
inject raw, chlorinated seawater seawater that has not been de-aerated, but has been
chlorinated. While this saves a great deal of weight and space on a platform, the
chlorinated seawater will be highly corrosive to carbon, low alloy, and many low end
stainless steels. Super duplex stainless steels or nickel base alloys such as 625 are
typically used instead.

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As previously mentioned, injecting water into a formation with no reported H2S may
cause it to turn sour as the result of anaerobic bacteria and the nutrients they need also
being injected. Some operators will base trim selection for injector wells the same as for
the producing wells. This gives them the flexibility to use equipment in either production
or injection service. It also gives them some insurance against corrosion problems
occurring in case produced fluid flows back into the injection equipment during
maintenance, etc.

Production Well Trim Selection


Selecting the appropriate materials for a production well is complicated business. It is
not for the faint of heart. Here are just a few of the factors that must be considered:

General corrosion resistance


Susceptibility to environmentally assisted cracking
Weldability
Fabricability and machinability
Availability
Cost
Galling resistance
Hardenability
Strength
Toughness
Hardness
Compliance to standards and codes
Design life
Erosion resistance
Customer requirements

No one material is going to have all the desired attributes: we may have to select
different materials for different parts. No one material is going to satisfy all of our
desires for a given part so compromises must be made and taken into account. Often
the preliminary well analyses provided by a customer may be best guesses or not
contain all the information we need. Well conditions change over time. How the well will
be operated, what chemicals will be injected, what maintenance will be performed on
the well are often unknowns at the time of trim selection. It would be nice to have a
clear bulls eye to aim at, but often we wont.
The trim tables that follow give suggested materials for many of the well environments
and produced fluids that you are likely to encounter, however, it isnt possible to come
up with an all-encompassing list. If the well conditions you are selecting materials for

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dont fall within the parameters specified for a given table, dont use that table! Check
with a metallurgist. If free sulfur or sand is being produced in your well, dont use these
tables! Trims are given by material family (stainless steel, nickel base alloy, carbon
steel, etc.). Not all the alloys within a family may be appropriate for all parts. The
suggested materials are not the only alternatives, but are the ones typically used. There
are many other CRAs that could be used besides the ones listed. It is always possible
to upgrade a part to a higher API material class. For example Stellite 3 seats, a cobalt
based alloy and hence a CRA, may be used in low alloy or stainless steel trims
(API.M/C AA, BB, CC, DD, EE, and FF) besides in the CRA material class HH. The
suggested materials are listed in order of increasing cost (the least expensive listed
first).
The suggested materials will have adequate corrosion resistance for the environmental
parameters stated for the particular table. This does not mean, however, that minor
pitting or crevice corrosion will not occur. It may be necessary to use a corrosion
resistant coating on a part with seal surfaces (a 410 stainless steel gate has the seal
surfaces coated with LW45, for example, both for hardfacing and corrosion resistance).
Any NACE restrictions for a particular material that are more restrictive than the
environmental parameters given for the table are presented in the notes section of each
table. The tables cover service temperatures of -75F to 250F. For higher temperatures
check with a metallurgist for the appropriate trim recommendations. Some of the
suggested materials may have poor impact toughness at the low end of this range so
these are restricted to a higher minimum temperature.
NACE imposes a minimum pH on some materials to be used in sour service. This is the
in situ pH the pH in the well under production conditions. Unfortunately this value is
seldom reported on well analyses. The pH that is typically reported is the pH of the well
fluid at ambient pressure and temperature in the test lab. Its not the same! The in situ
pH can be estimated using the charts found in Appendix D of NACE MR0175/ISO
15156-2.
To use the trim tables, you must know the partial pressure of the H 2S and CO2, the
service temperature range, and the chloride ion content in ppm. All of these
environmental factors must fall within the stated ranges for the particular table. First
select the appropriate table for the H2S partial pressure. Table A is for sweet (non-sour)
service where the H2S is less than 0.05 psi. Note the caution about high strength low
alloy steels in wells having H2S below 0.05 psi! Technically these wells arent sour and
are outside of NACE, but SSC may still occur at these low partial pressures in very
susceptible materials. Table B is for H2S partial pressures from 0.05 to 10 psi. The 10
psi is an absolute limit dont round off partial pressures hoping to get away with a
cheaper trim!
After selecting the right table for the H2S, find the applicable CO2 partial pressure range
and then the applicable chloride ion range. The recommended material classes for the

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major components are given to the right where: LAS = Low Alloy Steel, SS = Stainless
Steel, DSS = Duplex Stainless Steel, and CRA = Corrosion Resistant Alloy. Note that a
LAS body that has all wetted surface clad with a nickel base alloy such as 625 is
considered a CRA. The API 6A material class listed may vary depending on the actual
materials selected.
Trim Table A for Production Equipment
Sweet Service
H2S < 0.05 psi
NACE Compliance Not Required
-75 to 250F
Cl(ppm)
< 50,000

Bodies

#1

CO2
(psi)
<7

LAS
4130
8630
F22

LAS
4130
4140
8630

LAS
4130
4140
8630

#2

<7

50,000
100,000

LAS1

SS

SS

Trim

Stems

VBSM

Hangers

API 6A
M/C
AA

LAS1
4130
41402
Suggested Materials
8630
4340
F22
Note 1: Do not use LAS hangers with a SMYS >85ksi if there is any H2S present. Use
NACE compliant material.
Note 2: 4140 hangers good down to -20F
SS4

BB-MOD

4130
4102
410
4103
Suggested Materials
8630
F6NM
F6NM
F6NM
17-4PH
F22
17-4PH
Note 1: 625 weld clad ring grooves, seat pockets, seal areas, & stem packing area.
Note 2: 410 stems good down to -20F.
Note 3: 410 hangers good down to 0F.
Note 4: Do not use 410 or F6NM for hangers with a SMYS > 85ksi if there is any H2S
present. Use NACE compliant material.

#3

<7

>100,000

Suggested Materials

DSS
22Cr

DSS/
CRA
22Cr

DSS

DSS/CRA

22Cr

25Cr

CC

METALLURGY TRAINING MODULE 5


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Selection

25Cr

25Cr
718
925

25Cr

REV. A01

Page 26 of 34

718
925

Trim Table A (Cont.) for Production Equipment


Sweet Service
H2S < 0.05 psi
NACE Compliance Not Required
-75 to 250F
Cl(ppm)
< 50,000

Bodies

#4

CO2
(psi)
7-30

#5

7-30

50,000
100,000

LAS1

Trim

Stems

VBSM

Hangers

API 6A
M/C
BB

LAS
SS
SS
SS
1
4130
410
410
4102,3
8630
F6NM
F6NM
F6NM3
Suggested Materials
F22
17-4PH
17-4PH
Note 1: 410 stems good down to -20F.
Note 2: 410 hangers good down to 0F
Note 3: Do not use 410 or F6NM for hangers with a SMYS > 85ksi if there any H2S
present. Use NACE compliant material.
SS

SS

SS

BB-MOD

4130
4102
410
4103,4
Suggested Materials
8630
F6NM
F6NM
F6NM4
F22
17-4PH
17-4PH
Note 1: 625 weld clad ring grooves, seat pockets, seal areas, & stem packing area.
Note 2: 410 stems good down to -20F.
Note 3: 410 hangers good down to 0F.
Note 4: Do not use 410 or F6NM for hangers with a SMYS > 85ksi if there any H2S
present. Use NACE compliant material.
#6

7-30

>100,000

Suggested Materials

DSS/
CRA
22Cr
25Cr
4130,

DSS/
CRA
22Cr
25Cr
718

DSS

DSS/CRA

22Cr
25Cr

25Cr
718
925

CC

METALLURGY TRAINING MODULE 5


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REV. A01

Page 27 of 34

8630 or
F22 clad
w/625
925

Trim Table A (Cont.) for Production Equipment


Sweet Service
H2S < 0.05 psi
NACE Compliance Not Required
-75 to 250F

Trim
#7

CO2
(psi)
>30

Cl(ppm)
80,000

Suggested Materials

Bodies

Stems

VBSM

Hangers

SS
410
F6NM

SS
4101
F6NM
17-4PH

SS
410
F6NM

SS
4102,3
F6NM3
17-4PH

API 6A
M/C
CC

Note 1: 410 stems good down to -20F.


Note 2: 410 hangers good down to 0F
Note 3: Do not use 410 or F6NM for hangers with a SMYS > 80ksi if there any H2S
present. Use NACE compliant material.
#8

>30

>80,000

Suggested Materials

SS/CRA
22Cr
25Cr
4130,
8630 or
F22 clad
w/625

SS/CRA
22Cr
25Cr
718
925

SS
22Cr
25Cr

SS/CRA
25Cr
718
925

CC

METALLURGY TRAINING MODULE 5


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REV. A01

Page 28 of 34

Trim Table B for Production Equipment


Sour Service - NACE Compliance Required
H2S (0.05- 10.0 psi)
-75 to 250F, pH 3.5
Trim

CO2
(psi)

Cl(ppm)

Bodies

Stems

VBSM

Hangers

API 6A
M/C

LAS1/SS/
DD
CRA
4130
4130
4130
4130
8630
4140
4140
41402
F22
8630
8630
8630
Suggested Materials
F22
17-4PH3
718
925
Note 1: Use LAS hangers for 85ksi SMYS. Use 17-4PH or CRA for higher SMYS.
Note 2: 4140 hangers good down to -20F
Note 3: 17-4PH is limited to 0.5 psi H2S maximum with a minimum pH of 4.5.
#1

<7

< 50,000

LAS

LAS

LAS

#2

<7

50,000
100,000

LAS1

SS/CRA

SS

4102,5
F6NM5
17-4PH4

410
F6NM

SS/CRA

EE-MOD

4103,5
F6NM5
Suggested Materials
17-4PH4
718
718
925
925
Note 1: 625 weld clad ring grooves, seat pockets, seal areas, & stem packing area.
Note 2: 410 stems good down to -20F.
Note 3: 410 hangers good down to 0F.
Note 4: 17-4PH is limited to 0.5psi H2S maximum with a minimum pH of 4.5.
Note 5: F6NM and 410 are limited to 1.5psi H2S maximum for hangers and stems.
4130
8630
F22

METALLURGY TRAINING MODULE 5


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REV. A01

Page 29 of 34

Trim Table B (Cont.) for Production Equipment


Sour Service- NACE Compliance Required
H2S (0.05- 10.0 psi)
-75 to 250F, pH 3.5

Trim

CO2
(psi)

Cl(ppm)

Bodies

Stems

DSS/
DSS/
CRA
CRA
1
22Cr
22Cr1
25Cr2
25Cr2
4130,
718
Suggested Materials
8630 or
F22 clad
925
w/625
Note 1: 22Cr is limited to 1.5 psi H2S.
Note 2: 25Cr is limited to 3.0 psi H2S maximum.
#3

#4

<7

7-30

>100,000

< 100,000

Suggested Materials

VBSM
DSS/CR
A
22Cr1
25Cr2
825

Hangers

API 6A
M/C

DSS/CRA

FF/HH

25Cr2
718
925

625

LAS
4130

SS
410,3,5

SS
410

SS
4102,3

8630

F6NM3

F6NM

F6NM3

F22

17-4PH4

17-4PH4

718

718

EE-MOD

925
925
Note 1: 625 weld clad ring grooves, seat pockets, seal areas, & stem packing area.
Note 2: 410 hangers good down to 0F
Note 3: F6NM and 410 are limited to 1.5psi H2S maximum for hangers and stems.
Note 4: 17-4PH is limited to 0.5psi H2S maximum with a minimum pH of 4.5.
Note 5: 410 stems good down to -20F

METALLURGY TRAINING MODULE 5


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Page 30 of 34

Trim Table B (Cont.) for Production Equipment


Sour Service- NACE Compliance Required
H2S (0.05- 10.0 psi)
-75 to 250F, pH 3.5
-

Trim

CO2
(psi)

Cl
(ppm)

#5

7-30

>100,000

Bodies

Stems

VBSM

Hangers

DSS/CRA
22Cr1

DSS/CRA
22Cr1

DSS
22Cr1

DSS/CRA
25Cr2

25Cr2
4130,
8630 or
F22 clad
w/625

25Cr2

25Cr2

718

718

825

925

925
Note 1: 22Cr is limited to 1.5 psi H2S maximum.
Note 2: 25Cr is limited to 3.0 psi H2S maximum.

625

Suggested Materials

#7

>30

80,000

SS/CRA
/DSS
410
F6NM

SS/CRA

SS/CRA

SS/CRA

4101,5

410

4102,5

F6NM5

F6NM

F6NM5

825

17-4PH

625

718

17-4PH
Suggested Materials

22Cr

3
6

718

API 6A
M/C
FF/HH

FF/HH

25Cr
925
925
4130,
8630 or
F22 clad
w/625
Note 1: 410 stems good down to -20F.
Note 2: 410 hangers good down to 0F
Note 3: 22Cr is limited to 1.5 psi H2S maximum.
Note 4: 17-4PH is limited to 0.5psi H2S maximum with a minimum pH of 4.5.
Note 5: 410 and F6NM stems and hangers are limited to 1.5 psi H2S maximum.
Note 6: 25Cr is limited to 3.0 psi H2S maximum.

METALLURGY TRAINING MODULE 5


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REV. A01

Page 31 of 34

Trim Table B (Cont.) for Production Equipment


Sour Service- NACE Compliance Required
H2S (0.05- 10.0 psi)
-75 to 250F, pH 3.5
Trim

CO2
(psi)

Cl(ppm)

#8

>30

>80,000

Bodies

Stems

VBSM

Hangers

DSS/CRA
1
22Cr

DSS/CRA
1
22Cr

DSS/ CRA
1
22Cr

DSS/CRA
2
25Cr

Suggested Materials

25Cr
4130 or
F22 clad
w/625

25Cr

25Cr

718

825

925

625

API 6A
M/C
FF/HH

718
925

Note 1: 22Cr is limited to 1.5 psi H2S.


Note 2: 25Cr is limited to 3.0 psi H2S.

Trim Table C for Production equipment


Sour Service- NACE Compliance Required
H2S (> 10.0 psi)
-75 to 250F

Trim

CO2
(psi)

Cl(ppm)

#1

Any

Any

Suggested Materials

Bodies

Stems

VBSM

Hangers

CRA
4130,
8630, or
F22 clad
w/625

CRA

CRA

CRA

718

825

718

925

625

925

API 6A
M/C

HH

METALLURGY TRAINING MODULE 5


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REV. A01

Page 32 of 34

Water Injection Well Trim Selection


Trim selection for water injection wells differs significantly from trim selection for
production wells. Besides the obvious differences in the fluids they are exposed to, the
two may differ in their criticality or required reliability. A field may have many injection
wells and the loss of one for maintenance may not be as significant as the loss of a
production well. This may not hold true for offshore injection wells. Depending on the
injection well location and the priorities of the customer, trims may range from dirt
cheap with a short life to long lasting and costing an arm and a leg. You get what you
pay for! Reliability may be critical and cost not an object for a subsea injection well or
an injection well on a platform. Cost may be the overriding factor in the selection of an
injection tree for a surface field in Saudi Arabia. A corrosion failure of water injection is
typically not a catastrophic event. It will generally happen within an expected timeframe.
Replacing the corroded equipment has far fewer consequences for land operations
than for those offshore on a platform or subsea.
Whether or not the injected water is treated to control oxygen is a critical factor in trim
selection. The corrosion rate of carbon and low alloy steels in fully deoxygenated water
is very low. It is generally much cheaper for a customer to use a treatment plan than it
is to make the injection equipment out of high alloyed stainless steel or CRAs. There is
virtually no corrosion of carbon/low alloy steels at oxygen levels below 10 ppb (parts per
billion). If 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.
Recently more offshore operators are dispensing with deaerating and oxygen treatment
and are injecting chlorinated, raw seawater. The higher cost of the equipment is offset
by eliminating a deareator on the platform, not requiring a constant supply of oxygen
scavenging chemicals, and simplifying injection operations
.There are many possible trims for water injection equipment. Which one is preferred is
dependent on the needs of the customer. There is no one right answer here. In the
following tables, the cheapest trims (and the least reliable!) are listed first. Note that
even the cheapest trims involving deaerated water injection still require 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 for those occasions when air can get into the
system (during maintenance, etc.). There may also be occasional oxygen spikes
during operation due to problems with the de-aerating equipment, oxygen scavenger
injection, etc. Often a customer will want injection equipment to be NACE compliant.
This may be due to fears that sour production fluid may backflow into the injection
wellhead. Sometimes a customer wants the flexibility to use the equipment either for

METALLURGY TRAINING MODULE 5


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Selection

REV. A01

Page 33 of 34

injection or production. Recommended materials are for standard service: if customer


wants NACE compliance or if H2S is being reinjected, materials must comply with
NACE.
Table D for Water
Injection Equipment
Water De-Oxygenated to
50 ppb Maximum
Ambient Temperature
Trim
#1

Bodies
LAS1

Stems
VBSM
Hangers
API 6A M/C
SS/DSS/CR
SS/DSS/CR
DSS/CRA BB-Mod
A
A
Suggested 4130, 8630, 316
316
22Cr
Materials
or F22
22Cr
22Cr
25Cr
25Cr
25Cr
728
718
825
925
926
625
Note 1: 625 weld clad seat pockets, stem packing area, seal areas, and ring grooves.
#2

SS/DSS

SS/DSS/CR
SS/DSS/CR
A
A
Suggested 3161
316
316
Materials
22Cr
22Cr
22Cr
25Cr
25Cr
718
825
925
625
Note 1: Suitable for low pressure only (SMYS 32ksi)

DSS/CRA

CC

#3
Suggested
Materials

DSS
25Cr

DSS/CRA
25Cr
718
925

DSS/CRA
22Cr
25Cr
825
625

DSS/CRA
25Cr
718
925

CC

#4

LAS1

CRA

DSS/CRA

HH

Suggested
Materials

4130, 8630, 718


or F22
925
725

SS/DSS/CR
A
825
625

925
725

22Cr
25Cr
718
925

718

METALLURGY TRAINING MODULE 5


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Selection

REV. A01

Page 34 of 34

Note 1: 625 weld clad seat pockets, stem packing area, seal areas, and ring grooves.

Table D (Cont.) for


Water Injection Equipment
Water Not De-Oxygenated
Water Chlorinated
Ambient Temperature

Trim

Bodies

Stems

VBSM

Hangers

API 6A M/C

#1
Suggested
Materials

DSS
25Cr

DSS/CRA
25Cr
718
925

DSS/CRA
25Cr
825
625

DSS/CRA
25Cr
728
925

CC

CRA
625

CRA
718

HH

.
#2
Suggested
Materials

CRA
CRA
4130. 8630, 718
or F22 clad
w/625
925
725

925
725

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