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Degradation (CMD)
Corrosion
A COMPLEX PROCESSES
Understanding
corrosion
&
predicting accurately how materials
will degrade in a given environment
Biggest Challenge
It requires full knowledge of all relevant
factors and their interactions.
Crude Oil
&
its Corrosivity to
refinery equipment
= MgO + 2 HCl
= CaO + 2 HCl
= CaO + 2 HCl
= FeCl2 + H2
= FeS + 2 HCl (Catalyst)
4. Organic Acids
Naphthenic acids are a sort of organic acids that can
be present in crude oil and cause severe corrosion in
certain circumstances.
This kind of corrosion, which is known as naphthenic
acid corrosion (NAC), usually occurs at temperatures
between 230C and 400C and in the presence of a
sufficient quantity of naphthenic acids in the crude oil.
NAC generally happens in refinery distillation units
such as furnace tubes, transfer lines, vacuum columns
and side cut piping.
NAC rarely happens in fluid catalytic units because the
temperature at these units is more than 400C, which
A normal TAN value in crude oils varies in the range of 0.1 to 3.5 mg/gr. Despite
that, higher values of TAN such as 10 mg/g have been reported in rare cases.
TAN is not a constant characteristic in an oilfield, and can change over a period of
time during the extraction of crude oil.
NAC occurs when TAN is more than 0.5 mg/g. However, in some cases NAC has
been reported for TAN values between 0.3-0.5 mg/g. According to investigations,
just 0.5 percent of the naphthenic acids present in crude oil are corrosive.
Mitigating NAC
By Blending
One of the most common ways to reduce NAC in crude oil refining systems is by
blending a high TAN crude oil with a crude oil having low TAN. In this condition,
the overall TAN value will be reduced to the immune range (less than 0.3 mg/g).
By Inhibitor
Injecting corrosion inhibitors into the crude oil stream is another method to
decrease the naphthenic acid corrosion rate.
In this case, economic issues and effects of inhibitors on downstream processes
should be considered.
Since NAC occurs at high temperatures and iron sulfide deposit are not formed on
the surface, traditional filming amine inhibitors are not suitable.
Phosphorous and non-phosphorous containing inhibitors are very effective
inhibitors to mitigate NAC.
Although the phosphorous containing inhibitors have more inhibition efficiency,
their effects on the poisoning of catalysts downstream have to be considered.
5. Sulfur Compounds
Crude oils usually contain sulphides that can cause corrosion
at high temperatures and termed as "sulfidation well known
in Refinery.
Amount of total sulfur in crude oil depends on the type of oil
field and varies from 0.05 - 14 percent.
Sulfur as low as 0.2 percent enough to create sulfidation
corrosion in CS & low alloy steels in refinery.
Sulfur in crude oil in form of organic molecules (such as
mercaptan, alkyd sulfide, sulfoxide and thiophene), and trace
amounts of them are elemental sulfur and hydrogen sulfide
(H2S).
All kinds of sulfur compounds are not corrosive; only a
fraction can react with metallic compounds.
Mitigation
Select suitable material that is resistant to sulfidation.
Modified McConomy" curves are used for selecting the
material resistant to sulfidation . Sulfidation corrosion rate
as a function of temperature and total sulfur content.
McConomy curves show that the steels containing more
chromium exhibit higher corrosion resistance against
sulfidation. Moreover, the corrosion rate increases by
increasing the sulfur content and temperature.
In the McConomy curves, the corrosion rate depends on the
total sulfur content. However, only active sulphides (such as
H2S) can cause sulfidation. In other words, McConomy
curves overestimate high corrosion rates. Therefore, the
corrosion rates in McConomy curves are decreased by a 2.5
CS piping with
silicon content less than 0.10 wt % corrode
16 times faster than piping with silicon higher than it.
Annex C of API RP 939-C.
API RP 939-C
for
predicting
sulfidation
corrosion
rates
versus
temperature for several
steel
alloys.
Higher
chromium steels are better
safeguard than carbon steel
because
sulfidation
CS corrodes approximately
corrosion
rates
are than
greatly
nine times
faster
9reduced.
Chrome
steel,
which
contains 9 % chromium,
and
CS
corrodes
approximately 120 times
faster than stainless steel, Modified McConomy Curves from
which contains 18 percent API RP 939-C
Locations
Metallurgy Selection
Dry section - CS
Wet Section CS+ Neutralizers &
Vap. CI
Condensers
CS NACE GRADE
CS-HIC Resistant
CS- Clean Quality
100 % PWHT & RT
Column / vessel/piping
CS + 3 mm Corrosion allowance
230 to 275C
High Temperature
Sulphur Attack
Column / Vessel/Piping
CS +3 mm SS 410s cladding or
5 Cr 1/2Mo Alloy steel
275 to 300C
High Temperature
Sulphur Attack
Column/ Vessel/Piping
300 to 400C
High Temperature
Sulphur Attack
Column/ Vessel/Piping
Mitigation
Periodic mechanical cleaning
Chemical treatment using biocides to prevent bacteria population
Dry storage and total drainage
Flushing of equipment at regular interval.
1 1/4 Cr-1/2 MO
2 Cr-1 MO
5 Cr 1/2 MO
9 Cr 1/2 MO
SS Type 309
SS Type 310
Monel
Hastelloy B-2
565
593
635
648
816
816
871
1093
1149
1093
538
760
982
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