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What is Mercaptan?
for many oxygenated organic compounds, there are analogous derivatives in which sulfur
replaces the oxygen atom. The derivatives are called “thiocompounds” (e.g., thioalcohols,
thioethers, and thioaldehydes). Thiocompounds
corresponding to the alcohols (e.g., methanethiol) also are called “mercaptans” because
they easily form mercury salts and have been used to treat mercury poisoning.
Mercaptans tend to have strong, repugnant odors resembling skunk spray, rotten egg, or
rotten cabbage. Low-molecular weight varieties of the compounds are used to odorize
natural gas. Mercaptans are integral raw materials for many agricultural, pharmaceutical,
and industrial products (e.g., pesticides and jet fuel additives). They are supplied
primarily by companies such as OxyChem (NGO), ChevronPhillips, and Atofina, although
waste products in the form of mercaptan and sulfide byproducts have long been available
from pulp mills.
Methyl mercaptan (CH3SH) is toxic, as is hydrogen sulfide (H2S), but those of higher
molecular weight (e.g., ethanediols, etc.) are not. In the presence of moisture they can be
corrosive to various metals.
OTHER HAZARDS
H2S forms stable, explosive mixtures with air over a wide range of concentrations. It
explodes on contact with powerful oxidizing agents such as dichlorine oxide (Cl2O) and
chlorine trifluoride (ClF3). Methyl mercaptan should be very similar, and even its high-
molecular-weight derivatives are readily oxidizable and presumably combustible.
CORROSIVITY
Like H2S, methyl mercaptan should be noncorrosive in the anhydrous state but corrosive to
certain metals in the presence of moisture—possibly because of hydrolysis and the release
of sulfide ions.
ALUMINUM
These organic sulfides can be safely handled in aluminum storage tanks and piping.
STEEL
When anhydrous, mercaptans are noncorrosive to steel. The lower molecular- weight-
compounds, however, such as those encountered in petroleum production and used to
odorize natural gas, should be expected to cause sulfiderelated attack—sulfide stress
cracking or hydrogen-affected cracking in susceptible steels in the presence of water—but
this has not been observed in practical applications. High-molecular- weight mercaptans
probably are
substantially noncorrosive, given their minimal water solubility.
Carbon steel process equipment gives decades of service in the manufacture of
mercaptans and alkyl sulfides at up to 150°C. This is ascribed to the formation of a
protective metal mercaptide film. Only in plant areas using alkanolamine acid gas removal
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systems is there any significant attack. This is a phenomenon well-known in the chemical
processing industry.
STAINLESS STEELS
An austenitic stainless steel (SS) shows <2 mpy (51 µm/y) metal loss in 100% methyl
mercaptan at ambient temperatures. By analogy with H2S, they probably will withstand wet
mercaptans as well. Type 304L SS (UNS S30403) is used in equipment for
selective absorption of heavy water from H2O via H2S extraction in those areas where
steel is inadequate by virtue of physical removal of an otherwise protective iron sulfide
(FeS) film.
Austenitic SS, however, is not resistant to mercaptans in the simultaneous presence of
chlorides. Field tests in an 11-to-14% ammonium chloride (NH4Cl) brine at 90°C showed
pitting of type 304 SS (UNS S30400) (nominally <1 mpy [25.4 µm/y] metal loss) in
the presence of H2S and other mercaptans.
Type 316 SS (UNS S31600) did not experience attack under the same condition.
With mercaptans present in straight-run tower bottoms in the petroleum industry at ~185°C,
type 304 SS showed severe pitting and crevice corrosion although the overall metal loss
rate was only 0.5 mpy (12.7 µm/y). Severe pitting also was observed on type 316 SS—but
with only 0.2 mpy (5.1 µm/y) general corrosion.
One must remember that the threshold temperature for stress corrosion cracking of 18-8
SS (UNS S31600) in sulfide/chloride environments may be lowered to ambient
temperatures.
COPPER ALLOYS
Copper alloys typically are considered incompatible with mercaptans. It is probable,
however, that the corrosivity of the mercaptan will vary both with moisture content and the
particular alloy. It is common knowledge that “tarnishing” of copper hardware stems from
traces of H2S in the atmosphere.
In a humid atmosphere in the simultaneous presence of H2S, however, copper is severely
corroded—with the simultaneous formation of a thick, nonprotective copper sulfide
(CuS) film. Yellow brass, however, can form a tightly adherent quasi-protective film.
There apparently is no reason for mercaptans to produce different corrosion characteristics,
although published data 2 suggest rates of >50 mpy (1,270 µm/y) for copper, brass, and
cupronickel in 100% mercaptan at ambient temperature.
The data distinguish neither humidity nor molecular weight of the mercaptans.
It would seem that a more detailed study might be made in the future.
NICKEL ALLOYS
The data also indicate a >50 mpy corrosion rate for nickel alloy 200 (UNS N02200) and
Monel† alloy 400 (UNSN04400) in 100% mercaptans. It offers no data on higher alloys,
however with or without chromium. Of course,
sulfur contamination makes nickel alloys subject to liquid metal embrittlement by the Ni-S
eutectic if weld repairs are attempted without scrupulous cleaning.
MISCELLANEOUS METALS
Because divalent sulfur compounds like thiols (-SH) and sulfides (-S-) readily bond to
heavy metal ions (silver, mercury, lead, and cadmium) and to iron, molybdenum, zinc, and
copper, one should expect a potential for corrosion by mercaptans if moisture (e.g.,
relative humidity or aqueous phases) is present. Gold, platinum, and tantalum resist
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corrosion in such conditions.
Powerful oxidizing agents would convert these sulfides to sulfuric acid (H2SO4)-type
compounds of different corrosion characteristics.
Conclusions
Plastics and elastomers can be affected by the organic component in mercaptans. Such
complex interactions may be caused by the simultaneous presence of chlorides. The
corrosion data published for wet and dry H2S should be broadly useful for this closely
analogous environment (mercaptans)—at least for the lower-molecular-weight products.
However, H2S really is a separate consideration and extrapolation of its data would lead
to significant project costs because of overspecification of engineering requirements and
controls.
References
1. Lange’s Handbook of Chemistry (New York, NY: McGraw-Hill Corp.).
2. N.E. Hamner, ed., Corrosion Data Survey, 5th and 6th ed. (Houston, TX: NACE, 1975).
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