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Selecting process
piping materials
These guidelines and referenced
codes and articles aid selection of
piping for most HPI processes
R.B. Setterlund, (OHPHQW Houston
SELECTION OF PIPING MATERIALS for refinery
and petrochemical plants requires collaboration between the
corrosion piping and process engineers, and usually involves
more than determining if a material is compatible with a given
environment. Many questions must be answered before a pipe
and valve specification can be written. Is the alloy available in
the size and thickness required? Is it the most economical
choice? Should it be specified as seamless or welded? Is it
suitable for the maximum anticipated operating temperature or
will long-term exposure to these temperatures cause its
mechanical properties to deteriorate? Will it require special
welding or heat treatment requirements?
It should be noted at the outset that the best approach
to corrosion control may not involve the use of corrosionresistant alloy materials. Often adequate life can be obtained
in corrosion services with carbon steel piping in conjunction
with control of process and operating variables. In other cases,
in particular those piping systems handling corrosive fluids at
elevated temperatures, there is no alternative to corrosion-resistant materials. Also, low or elevated temperature service
conditions can dictate the use of special materials.
General guidelines. Corrosion can be classified into three
general forms based on the type of damage that results. Some
types of damage can be tolerated, others cannot and it is
important to be aware of these distinctions. The three general
forms are: 1. uniform corrosion, 2. localized corrosion and 3.
stress corrosion cracking.
Uniform corrosion, in which metal is removed more
or less uniformly, is the most common form of corrosion and
the least dangerous. It is generally agreed that the maximum
acceptable loss of metal due to uniform corrosion is
approximately 20 mils per year (mpy).1 This rate of corrosion
is not usually desirable since high corrosion rates not only
reduce the thickness of piping but also can lead to plugging of
heat exchanger bundles and reactor screens by corrosion
deposits. Iron sulfide scale occupies a volume about seven
times the volume of metal that is removed, thus a ten in. pipe
corroding at 20 mpy would produce about three cubic feet of
loose scale per year per 100 feet of length.
Except where equipment becomes plugged,
contamination of process streams by corrosion products is not
usually as serious a problem in hydrocarbon processing plants
as in most chemical plants. One exception is equipment lube
and seal oil lines which must be kept absolutely free from
Environment
Caustic solutions at
Temperatures over 120F
To over 108F depending
On concentration1
Control of hardness or
selection of more
resistant alloys2
(Control of materials)
Austenitic stainless
steels with
susceptibility decreasing
with the more highly
alloyed grades4
Flushing, neutralizing,
avoidance of crevices,
coating
Chloride solution at
temperatures over 110F
to 180F depending on
chloride concentration
and alloy susceptibility
(Control of environment)
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Fig. 2Valve stem that failed from
sulfide stress cracking.
C C
4
Corrosion allowance (4 indicates
minimum corrosion allowance in
1/32s or 1/8-in. min)
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by- products formed from breakdown of these impurities.
Also, chemicals added to hydrocarbons during processing,
such as NaOH and H2SO4, may require the use of special
metals and/or certain precautions.5
The piping and valve specifications for general
hydrocarbon service are most often written around ASTM A
53 Grade B or A 106 Grade B seamless pipe, more familiar to
pipefitters as "black iron" pipe. The basic specification for
petroleum refinery service will require that valves have cast
steel bodies with stainless steel trim, usually 12% chromium
stainless steel.
Specifications for less severe service may allow cast
iron flanged valves under the limits for ductile cast iron and
for gray cast iron shown in ASME B 31.3, "Chemical Plant
and Petroleum Refinery Piping Code." Standard A 53 Grade B
pipe is widely available and low in cost, can be bent hot and
cold, and cut and welded using simple methods and minimal
precautions. Carbon steel pipe has relatively high strength and
ductility, adequate toughness for most applications, and fair
resistance to corrosion in a wide range of environments.
Changes from basic pipe specifications should be carefully
considered since any material substitution made to obtain an
improvement in either strength, toughness or corrosion
resistance, will usually involve increased cost and decreased
availability. Some hydrocarbon services, however, require
alternative materials. One example is piping to handle hydrocarbon at temperatures below ambient.
Low temperature service. The fracture toughness of
carbon steel and ferritic alloys decreases with decreasing
metal temperature.6 This phenomenon is the basis for the
20F minimum temperature limit in Appendix A of the
ANSI B 31.3 piping code. Some ferritic materials such as
structural grade steels without chemistry limits and ductile and
malleable iron cannot be used below this temperature, but
most ferritic steels can be used to a lower temperature
provided they are stress relieved and qualified by impact
testing.
The B 31.3 code has an important exclusion to the
impact test requirement based on the fact that brittle fracture
initiation is related to the level of applied stress. Impact testing
is not required for temperatures between -20F and -50F
provided the actual stress is less than 25% of the allowable
stress above -20F. This exclusion should be applied with care
and post weld stress relief is advised as a precautionary
measure even though it is not mandated by the B 31.3 code.
Austenitic grades of stainless steel, provided they are
in the solution treated condition and contain less than 0.10%
carbon, can be used to temperatures down to -325F without
being impact tested. Liquefied natural gas as well as other
refrigerated hydrocarbons are often handled in austenitic
stainless steel pipe. Since austenitic stainless steel can be
taken "off the shelf" and applied directly to low temperature
service without special tests, there is a temptation to employ it
automatically for temperatures under -20F. This may lead to
unexpected problems, as illustrated by chloride stresscorrosion cracking failures which recently occurred shortly
after the startup of a chemical plant. Three similar plants had
been constructed using A 53 B pipe to handle solutions
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Standard A 53 Grade B pipe has no silicon requirements
and can be furnished with or without silicon which resulted in
a 1986 failure having tragic consequences. A short section of
standard weight NPS 4 ASTM A 53 Grade B pipe was added
in the field to correct an interference problem. The added pipe
had only 0.016% silicon while the remaining shop spooled
pipe had 0.17% silicon or higher. The line carried hydrocarbon
with 0.06% sulfur at a temperature of 610F. A large number
of wall thickness readings had shown adequate wall thickness,
however, no thickness readings had been made on the fieldadded splice section. After many years of operation the short
section was thinned (Fig. 4), and failed due to fluid pressure
resulting in a fire with fatalities.
The workhorse alloy in petroleum refining is one
containing 5% chromium and 0.5% molybdenum. This alloy,
often called simply "5 chrome," has a sulfidation rate of about
one-third that of carbon steel, allowing it to be used in the
important 525F to 675F temperature range. Alloy steels.
with lower chromium contents such as 1-1/4 Cr-0.5 Mo and 21/4 Cr-l Mo steels are seldom employed for their corrosion
resistance in hydrocarbon plus sulfur environments. These
alloys are primarily used either for very high temperature,
noncorrosive services or for service in high temperature, high
pressure hydrogen environments, as discussed later.
In applications where corrosion rates are too severe for 5
Cr-0.5 Mo steel, either 7 Cr-0.5 Mo or 9 Cr-1 Mo alloy steels
may be used. At present 7 chrome steel is rarely produced and,
when it is used either 9 chrome (A 217 Grade C12) or 12
chrome (A 217 Grade CA15) castings must be specified for
valve bodies.
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Hydrocarbon-hydrogen. Hydrogen at high temperature
and high pressure can permeate steel, and when the conditions
are severe enough, react with metal carbides in the
microstructure. Two types of damage are possible: 1. surface
decarburization, which may not be serious, and 2. subsurface
decarburization, which results in internal fissures that make
the steel unsuitable for safe operation.
Alloy steels containing chromium and/or molybdenum
contain carbides more resistant to reduction by hydrogen. The
limits for various alloys in terms of metal temperature and
hydrogen partial pressure are contained in API Publication
941, "Steels for Hydrogen Service at Elevated Temperatures
and Pressures in Petroleum Refineries and Petrochemical
Plants." The operating limit chart contained in API Publication
941, referred to as the Nelson curve, was developed over the
past 30 years and finds application not only in petroleum
refinery units but also in plants that manufacture ammonia,
methanol, edible oils and higher alcohols.
The Nelson curve is based on the partial pressure of
hydrogen in the vapor phase and the maximum anticipated
metal temperature. The user should ensure that the correct
process information and the latest revision are used. The
carbon-l/2% molybdenum limit was lowered in 1977 and
because of subsequent problems at temperatures below this
limit, the current revision contains a warning against the use of
carbon-l/2% molybdenum steel in high temperature re-former
units. 15
When alloy steels are required by API 941 it is not only
necessary to specify chromium-molybdenum alloy pipe but
also to ensure that all components and welds are of the correct
composition. In the example shown in Fig. 6, a section of
carbon steel pipe had been welded into a 2-1/4 Cr-l Mo steel
line. The carbon steel failed by high temperature hydrogen
attack after 10 years.
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have excellent ductility and toughness even after long-term
service. Austenitic stainless steels are susceptible to stress
corrosion cracking when exposed to chloride environments
and Appendix F of the 831.3 code contains a precautionary
warning against their use when chlorides are known to be
present.
Hydrocrackers and heavy gas oil desulfurizers
present a more limited choice of piping materials than naphtha
desulfurizers, as shown by the dashed lines in Fig. 7. Nine
chrome steel is not acceptable and while 12 chrome stainless
steel has an acceptably low corrosion rate, its low code stress
values make it less attractive than austenitic grades of stainless
steel. Also, its low toughness becomes more significant as the
thickness of the pipe increases.
For hydrocrackers, where costs may exceed several
thou- sand dollars per linear foot of pipe, a more economical
alternative to extruded heavy wall type 321 stainless steel pipe
is centrifugally cast " HF modified" piping. Type HF modified
is a casting alloy developed for this application.17 It contains
more carbon than wrought 18-8 grades of austenitic stainless
steel which makes the metal more fluid at casting temperatures
and improves quality. Also, it is chemically balanced to
produce a two-phase ferritic-austenitic microstructure which
ensures the production of sound, crack-free castings. The high
chromium content gives the alloy very high resistance to high
temperature sulfide corrosion, however, it causes the alloy to
lose toughness after elevated temperature service. The loss of
toughness is kept to within acceptable levels by controlling the
ferrite level to under 15%. The usual composition of HF
modified is:
Chromium
Nickel
Carbon
Ferrite
21% to 25%
6.5% to 11%
0.15% to 0.20%
5% to 15%
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in carbon steel. (Maximum rather than average conditions
should always be used in conjunction with the API 941
hydrogen curves.)
4. The piping carrying liquid out of the bottom of the
hot high pressure separator is carbon steel because of the
lowered hydrogen content. The pressure letdown valve in this
line as well as downstream piping are specified to be stainless
steel to guard against corrosion/erosion by hot flashing H2S
liquids. Sulfide corrosion is velocity dependent and the use of
carbon or low alloy steel is questionable. In this example, the
letdown valve would be located to minimize the footage of
expensive stainless steel piping.
5. The mixture of sulfides, ammonia compounds and
water in the downstream piping can produce serious
corrosion.17 In this case, it was determined that carbon steel
with a high corrosion allowance could be employed provided
the fluid velocity was limited. In addition, injection facilities
were installed for wash water and for inhibitors to control
fouling and corrosion.
6. The hydrogen partial pressure in the recycle gas was
under 700 psig and the use of alloys was not required at the
maximum operating temperature of the recycle gas piping. To
prevent hydrogen attack resulting from the recycle gas being
further heated, the break point between carbon and stainless
steel was specified to be located well back from the mixing
point.
Precautions. It is hoped that the information in this brief
paper will aid the engineer concerned with the selection and
specification of piping for refinery and petrochemical service.
The charts and examples in this article have been simplified
and are intended only to illustrate concepts. Engineers
involved in specifying materials should refer to the data
contained in the original articles and standards before actually
selecting material for process piping.
LITERATURE CITED
1.
Corrosion Data Surry, 5th edition. National Association of Corrosion
Engineers, Houston, Texas, 1974
2.
"Sulfide Stress Cracking Resistant Metallic Material for Oil Field
Equipment," NACE Standard MR0175-90, National Association of
Corrosion Engineers, Houston, Texas, 1990.
3.
Fraser, J P and Treseder, R S.. "Cracking of High Strength Steels in
Hydrogen Sulfide Solutions," Corrosion, Vol. 8, 1952
4.
Couper, A. S. and McConomy, H. F., "Stress Corrosion Cracking of
Austenitic Stainless Steels in Refineries," Proceedings of API Division
of Refining, 1966
5.
Gutzeit, J., "Corrosion in Petroleum Refineries," Process Industries
Corrosion, NACE, 1988
6.
Metals Handbook, Volume I, Ninth Edition, American Society for
Metals, Metals Park, Ohio,1978.
7.
"'High Temperature Crude Oil Corrosivity Studies," API Publication
943, American Petroleum Institute, Washington, D.C., 1974.
8.
Humphries, M. J. and Sorel, G., "Corrosion Control in Crude Oil
Distillation Units," Materials Performance, Vol. 15, No.2, 1976.
9.
Minutes of the Refining Industry Corrosion Group Committee T-8,
National Association of Corrosion Engineers, 22nd Annual Conference,
April 20, 1966.
10. Gutzeit, J., "High Temperature Sulfide Corrosion of Steels," Process
Industries Corrosion, NACE, 1988.
11. McConomy, H F., "High Temperature Sulfidic Corrosion in HydrogenFree Environment," Proceedings of API Division of Refining, May 1963