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March /April 2014 Volume 20, Issue 2

Since 1995, Inspectioneering Journal has provided the oil & gas
and chemical industries with information to help optimally manage
equipment risk and reliability, cradle to grave.
FEATURING:
IS YOUR KILLED CARBON STEEL
RESISTANT TO HIGH TEMPERATURE
SULFIDATION?
BY MARC MCCONNELL, DIRECTOR OF CORROSION TECHNOLOGY,
PINNACLEAIS
CONTRIBUTING AUTHORS: GERRIT M. BUCHHEIM, P.E., REFINING
METALLURGICAL AND CORROSION EXPERT, BECHT ENGINEERING
CO., INC. AND JOSH YOAKAM, INTEGRITY ENGINEER, HOLLY R&M
- TULSA, LLC.
18 | March/April 2014 | Inspectioneering Journal
FEATURE
Is Your Killed Carbon Steel Resistant
to High Temperature Sulfdation?
By: Marc McConnell, Director of Corrosion Technology, PinnacleAIS
Contributing Authors: Gerrit M. Buchheim, P.E., Refning Metallurgical and
Corrosion Expert, Becht Engineering Co., Inc. and Josh Yoakam, Integrity
Engineer, Holly R&M - Tulsa, LLC.
INTRODUCTION
High temperature sulfdation is probably the most well-
known corrosion mechanism in the oil refning industry
because it occurs in large sections of the refnery. Sulfda-
tion corrosion (also known as sulfdic corrosion) is a result of
naturally occurring sulfur (S) compounds found in crude oil.
In the absence of hydrogen, corrosion due to sulfur com-
pounds in the crude is thought to occur at temperatures
above 500oF (230oC). Up to that temperature, corrosion
rates due to sulfdation are relatively low, even for carbon
steels, unless there is naphthenic acid present in the crude.
The Modifed McConomy curves used for selecting materi-
als and also for predicting in-service resistance to sulfda-
tion corrosion have historically served the industry well.
There are many nuances in sulfdation corrosion related to
the exact types of sulfur compounds present in the stream.
Other nuances include additional corrosives such as naph-
thenic acid, shear stress, and, as has been shown over the
years, even the amount of residual silicon (Si) present in the
steel component.
The Chevron Richmond Refnery piping failure that oc-
curred on August 6, 2012 is just one of the latest incidents
that was partially attributed to a particular section of piping
with low silicon (Si < 0.10 wt %), where other piping sec-
tions contained higher Si contents in a hot sulfur containing
process stream. Although there were numerous CML’s on
the piping system, one section of pipe was not monitored
and thinned at a greater rate. Sulfdation corrosion can
take place in refnery units such as the crude unit, as well
as the catalytic cracking unit (FCCU), delayed coker (DCU)
and others.
API 939-C, Guidelines for Avoiding Sulfdation (Sulfdic)
Corrosion Failures in Oil Refneries was frst published in
2009 and highlights the low Si issue. A new edition is cur-
rently being drafted to strengthen this section of the docu-
ment since failures continue to occur. Si is believed to help
form a somewhat protective FeS scale. If the Si content of
the steel is below 0.10 wt % the corrosion rate can be quite
variable, and in some cases can range from 2-10 times
higher than surrounding steel components with greater
Si content. Therefore, materials should contain silicon in
quantities of greater than 0.10 wt % to provide adequate
(and more consistent) sulfdic corrosion resistance.
The Modifed McConomy Curves are the tool of choice for
predicting sulfdation in hydrogen-free streams. First data
was provided by a survey conducted by the American Pe-
troleum Institute (API) Subcommittee on Corrosion in 1961.
Data was presented as the original McConomy Curves [3].
These curves focused on heater tubes and lab data. Fur-
ther experience proved that the original McConomy Curves
should be decreased by factor 2.5 for the general equip-
ment components, and in 1986 the Modifed McConomy
Curves were reported [4] [5] [6]. While these curves have
historically served the industry well, there is not a lot of
available data to correlate the curves with the silicon level
in the steel. As found in the NACE 2010 Conference paper
number 10358, A Study of High Temperature Sulfdation
Under Actual Process Conditions, the authors concluded
that in actual practice, the Modifed McConomy Curves are
“effective in ranking risks to metallurgy… they may be used
as a directional tool at best”. A possible explanation to
these results could be the silicon content in the material of
construction.
Sulfdation corrosion results in the thinning of the pres-
sure containment envelope, affecting such components as
piping and pipe fttings, heater tubes, and pressure ves-
sels. Most industry incidents have occurred in piping, due
to lower nominal wall thicknesses as compared to other
equipment types. Sulfdation corrosion can be localized or
general in nature for a given component, though the ma-
jority of cases exhibit general thinning. When the damage
is general, and thinning occurs over a large area, ruptures
are possible and can lead to the potential release of large
quantities of hydrocarbon streams.
Recent industry experience indicates carbon steel compo-
nents (primarily pipe) and their respective welds with low-Si
content can corrode at an accelerated rate when exposed
to H2-free sulfdation corrosion conditions. In some pipe
systems, “regular” carbon steel appears to be adequate
based on measured corrosion rates until a failure occurs at
some previously unknown low-Si component (the lower-Si
content steel components corrode at a greater rate). Expe-
rience has shown that piping welds where the root passes
were made with low-Si containing fller metals, corroded
at a greater rate than the base metal components when
exposed to the same process conditions.
So what is low-Si carbon steel? In API 939-C, carbon steel
is called low-silicon when Si content is less than 0.1 wt%.
This includes carbon steel pipe systems where ASTM A53
or API 5LB piping was used. Prior to the introduction of
Inspectioneering Journal | March/April 2014 | 19
dual stamped pipe in 1985, A-53 and API 5L pipe had no
required minimum silicon content. A-106, the usual alter-
native to A53 and API 5L for carbon steel plant piping, has
always had a minimum required content of 0.1 wt % Si. In
view of the fact that inventories of older pipe could have
been used for several years after 1985, it would be prudent
to group all SA-53 and API 5L pipe installed before 1990
together as candidates that may contain low-silicon. By the
mid-eighties, most refneries called for ASTM A106 piping
(Si > 0.1 wt % minimum by specifcation). By then, even if
requirements did not specify A106, carbon steel piping was
often dual certifed (usually triple-stamped) as A106/A53/
API 5LB at that time and on through today. Incidents have
occurred where, during a maintenance operation, older
(non A106) pipe was reused and installed in A106 piping
systems.
DEOXIDATION IN STEEL
MANUFACTURE (KILLED STEEL)
Over the years, the demand for better mechanical proper-
ties has motivated steel
producers to improve
the cleanliness of their
fnal products, and
spawned more ad-
vanced manufacturing
methods. In order to
obtain the satisfactory
cleanliness of steel, it
is necessary to control
and improve a wide
range of operating
practices throughout
the steelmaking pro-
cess, like deoxidation
and alloy additions,
secondary metallurgy
treatments, and casting
procedures.
Deoxidation and secondary metallurgy treatments are im-
portant issues in modern steel making and relevant to this
article. Deoxidation is the removal of excess oxygen from
molten metal (commonly called killing). As shown in the
ASM Materials Engineering Dictionary:
Killed steel is steel treated with a strong deoxidizing
agent such as silicon or aluminum in order to reduce the
oxygen content to such a level that no reaction occurs
between carbon and oxygen during solidifcation.
Common deoxidizing agents include aluminum, ferro-
silicon and manganese or, in some cases, chromium, vana-
dium, titanium, zirconium, or boron have been used. The
deoxidizing agents react with the dissolved gas to form
a slag which is foated out during the melting process. If
oxygen remains in the steel in large amounts, it can form
oxide particles with iron and manganese. These oxide
particles impact steel cleanliness and can affect mechanical
properties. Major cleanliness problems involve entrained
slag (e.g. - aluminates) and non-metallic inclusions, such as
manganese sulfdes.
STEEL CLEANLINESS
Steel cleanliness is a factor of steel quality, and the demand
for cleaner steels increases every year. Clean steel is the
steel in which the content of impurity elements (phospho-
rus, sulfur, total oxygen, nitrogen, hydrogen (sometimes
includes carbon)) and the number of non-metallic inclu-
sions are very low. Non-metallic inclusions, such as oxides,
sulfdes, nitrides and phosphides, are undesirable compo-
nents of all steels and can adversely affect steel properties.
The improvement of steel cleanliness has therefore become
a subject in the development of ferrous metallurgical tech-
nology - an important task for steel producers.
Producing clean steel requires control of non-metallic in-
clusions and controlling their size distribution, morphology,
and composition. All steels contain non-metallic inclusions
to a greater or lesser extent. The term “clean” steel is rela-
tive. Usually, the amount of non-metallic inclusions in steel
is not higher than 0.1%. However, the number of inclu-
sions in metal is very high because of their extremely small
size and light weight.
Non-metallic inclusions
disrupt the homoge-
neity of the structure,
so their infuence on
the mechanical and
other properties can be
signifcant. Inclusions
generate defects and
many steel applications
restrict the maximum
size of inclusions. For
example, during forg-
ing and stamping,
non-metallic inclusions
can cause cracks and
fatigue failure in steel,
so the size distribution
of inclusions in steel
products is important.
SULFIDATION RESISTANCE
Corrosion resistance to sulfdation is not a matter of whether
the material is killed or non-killed, clean or dirty; the issue
is whether the material contains silicon or not. Older pipe
with low Si may corrode at rates 2 to 10 times faster than
surrounding higher Si piping [5].
LOW SILICON CARBON STEEL INSPECTION PROGRAM
Carbon steels with low-Si (< 0.10 wt. %) content can cor-
rode at an accelerated rate when exposed to sulfdation
corrosion conditions. Typically, fttings (elbows and tees)
are cast or forged, and therefore due to their manufactur-
ing technique, they inherently have higher silicon content.
Commonly used grades of carbon steel pipe fttings (A-234
and A-420) have a minimum silicon content of 0.1 wt %.
Older carbon steel (low alloy) pipe fttings could have been
manufactured before the silicon spec was established.
Most inspection programs will have Condition Monitoring
Locations (CML’s) established on fttings where the highest
20 | March/April 2014 | Inspectioneering Journal
IS YOUR KILLED CARBON STEEL RESISTANT TO HIGH TEMPERATURE SULFIDATION?
turbulence is expected, and therefore the greatest poten-
tial for corrosion is expected. In theory, the fttings should
be representative (or the extreme) of the corrosion rates in
the piping circuits. However, in instances where the fttings
contain high silicon and the piping has lower silicon, there
can be defnite discrepancies in the corrosion rates.
Armed with the knowledge that various segments of pipe
may experience elevated corrosion due to sulfdation,
many refners have instituted a specifc inspection program
aimed at identifying low silicon/elevated corrosion areas.
Such an approach may involve an initial risk assessment to
focus inspections on the circuits representing the highest
risk. Methods vary, but programs differ from stripping all
insulation to the use of radiographic methods or long range
guided wave UT methods to fnd all welds and selectively
strip insulation at the welds. This allows access to the pip-
ing on either side, as well as the weld.
When mill certifcates are available they can be used to
determine whether low-Si steels were procured. PMI of
carbon steel is a controversial issue at this time. New PMI
instruments are being marketed that claim to be able to
measure Si at these low concentrations accurately, but the
operating companies are still evaluating whether these
claims can be verifed. Rather than stripping insulation,
there are more practical ways to do the baseline thickness
checks. For example, one could use an X-ray imager to
fnd welds and then cut a cookie in the insulation to check
each piping segment. Once the cookie has been cut, thick-
ness checks can be done and PMI could be performed.
Generally, sulfdation corrosion is relatively uniform, so
straight beam UT thickness readings are suffcient. If the
piping is in service, a qualifed procedure specifying high-
temperature calibration and/or adjustment to the thickness
measured is needed. Until all components in a carbon
steel system have been checked for silicon content and/
or thickness, the Inspector should assume that low-Si steel
may be present in the system and may corrode at much
higher than predicted rates or higher than adjacent CML’s
located on higher Si piping components.
CONCLUSION
The Modifed McConomy Curves have been a reliable in-
strument used to predict sulfdation corrosion. However,
the curves are not as precise in predicting sulfdation corro-
sion in materials where the Si content is less than 0.1 wt %.
Older carbon steels that are not alloyed with silicon tend to
experience increased corrosion rates due to the high tem-
perature mechanism of sulfdation. Corrosion resistance to
sulfdation is not a matter of whether the material is killed,
non-killed, clean or dirty; the issue is whether the material
contains the minimum amount of silicon to resist sulfda-
tion. Killing steel with silicon does not guarantee that the
residual silicon level in the steel will meet the minimum
requirement of the specifcation.
Old carbon steel (low alloy) pipe could have been manu-
factured before the silicon specifcation was established.
Fittings have been manufactured by different methods
and therefore routinely will have increased levels of silicon.
Therefore, utilizing corrosion rates in fttings or an adjacent
straight section of piping for a corrosion rate may not ad-
equately refect the real corrosion rate in the system. As a
result, all pieces of material in a suspect circuit need to be
evaluated for thickness and/or silicon content.
REFERENCES
1. API RP 571 “Damage Mechanisms Affecting Fixed
Equipment in the Refning Industry,” Second Edition,
April 2011.
2. U.S. Chemical Safety and Hazard Investigation Board,
Regulatory Report. Chevron Richmond Refnery, Pipe
Rupture and Fire. Report No. 2012-03-I-CA, Decem-
ber 2013.
3. McConomy, H F., “High Temperature Sulfdic Corrosion
in Hydrogen-Free Environment,” Proceedings of API
Division of Refning, May 1963.
4. Gutzeit, J., “High Temperature Sulfde Corrosion of
Steels, “Process Industries Corrosion, NACE, 1988.
5. API RP 939-C “Guidelines for Avoiding Sulfdation
(sulfdic) Corrosion Failures in Oil Refneries” (page 16)
First Edition, May 2009.
6. NACE Technical Report 34103, “Overview of Sulfdic
Corrosion in Petroleum Refning (Houston, TX: NACE,
2004).
Marc has more than 30 years
of crude oil refning experience
as a maintenance/reliability
corrosion engineer, process
engineer, project engineer, project
manager, mechanical integrity
expert, and business manager. He
is an active member of several
industry groups, including the
American Society of Mechanical
Engineers, National Association
of Corrosion Engineers, and the American Petroleum
Institute, where he has stewarded key initiatives.
Marc teaches both NACE and API related courses
in the US and internationally, and is recognized
globally as an expert in asset integrity.
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