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Address International Community in Awareness Program on Corrosion & Metallurgical

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.

Corrosion depends on Geographical conditions.


Steel structures that last for decades in dry parts of inland
China fail within months in humid and salty coastal areas of
southeast Asia.
Protective polymer coatings that work for years at northern latitudes can
degrade in weeks near the Equator, where heat and greater doses of
ultraviolet radiation break chemical bonds more quickly .
Inferring general corrosion knowledge such as how particular steels
are affected by humidity, salt or air pollution requires combining
studies from many diverse environments.
With global trade increasing, the oil and gas, construction, car,
electronics and other industries have called for corrosion data to be
shared between countries to ensure the quality and safety of their
products.

Crude Oil
&
its Corrosivity to
refinery equipment

Crude oil in itself is


n't corrosive, but
the
impurities
commonly found in
it make it corrosive.

1.Brackish Water (Chlorides)


MgCl2, CaCl2 and NaCl in the range 3 to 300 ppb drawn from crude oil
wells along with hydrocarbons. In heavy crude oils this value tends to
be higher.
heating of crude 120C , these chloride except NaCl ( most stable)
break down to HCl by Hydrolysis. At 380 C
MgCl2 + H2O
CaCl2 + H2O
CaCl2 + H2O
HCl + Fe
FeCl2 + H2S

= MgO + 2 HCl
= CaO + 2 HCl
= CaO + 2 HCl
= FeCl2 + H2
= FeS + 2 HCl (Catalyst)

Presence of Sour Crude bearing "sour acid" (H2S) aggravate the


corrosion wherein HCl acts as a catalyst & hence once generated
result continuous corrosion of steel below dew point.
Mitigation: 1. Removal of chloride after de-salter by caustic dosing

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

The chemical formula of naphthenic acid is R(CH2)nCOOH,


where R is one or more cyclopentane rings and n is more
than 12. Their atomic mass unit is between 120 and 700.
Following reaction shows the interaction between
naphthenic acids and steel. The product of this reaction is
hydrogen and a complex of iron-organic acid (Iron
naphthenate, which is soluble in crude oil.
Fe + 2 RCOOH = Fe (RCOO)2 + H2
In the presence of sulfides in crude oil, Fe (RCOO)2 reacts
with H2S to create FeS : Fe (RCOO)2+ H2S = FeS + 2
RCOOH
FeS is insoluble in water and oil and can form a protective
layer on steel at low shear stress of fluid, therefore
protecting it from further corrosion. As a result, the presence

Characteristic Features of NAC


NAC is considered to be a localized corrosion and is seen in areas where fluid
velocity is high and organic acid vapours are present.
The lack of corrosion product in the corroded area is another feature of NAC.
Many high-resistance steels that are resistant to sulfur corrosion, including high
chromium and even high molybdenum steels, could be susceptible to this kind of
corrosion

The concentration of naphthenic acids in crude oil is shown by the


Total Acid Number (TAN) which is defined as the amount of potassium hydroxide
(in milligrams) needed to neutralize one gram of oil.

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.

In the presence of H2 gas most of the organic


sulphides - which are categorized into inactive
sulphides - decompose to H2S, an active sulfur that
can lead to sulfidation.
Sulfidation becomes more severe in the presence of
hydrogen gas as in hydrocracker& and hydrofinishing units in oil refineries.
Sulfidation happens at temperatures higher than
230C) and its rate accelerates when the
temperature is raised to 480C.
At
temperatures
higher
than
370C,
H2S
decomposes into elemental sulfur, which is the most

Sulfidation Mechanism & Control

During sulfidation, a protective iron sulfide scale is


formed on the surface of a substrate and reduces the
corrosion rate. This scale is known as a diffusion barrier
layer and its growth follows parabolic kinetics (d=kt).
Factors affecting Sulfidation
high velocity of fluids, which can keep this protective
scale separate from the metallic surface.
Presence of naphthenic acids in crude oil. As mentioned
above, these acids can react with FeS to create soluble
compounds.
Hydrogen, which can penetrate into sulfide scale and
create a porous iron sulfide scale

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

The other drawback of McConomy curves is that the effects of fluid


velocity and the presence of H2 gas have not been considered in
McConomy curves. Therefore, the NACE T-8 committee on Refining
Industry Corrosion has introduced the "Couper-Gorman" curves
based on a series of experimental surveys.

According to Couper-Gorman curves, iron sulfide is not


thermodynamically stable and no sulfidation occurs at very low
levels of H2S and temperatures above 315C.

It should be noted that estimates achieved from either the


McConomy or the Couper-Gorman curves are uniform corrosion
rates or thickness loss, while the localized corrosion that usually
happens and might occur at a higher rate is not considered when
estimating the first leak or corrosion allowance.

Effect of Silicon On sulfidation in


Carbon
steel

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.

A mil is 1/1000 inch

Process and Design Modifications to explore TAR


extensions
Broadly,
there are 6 types of Process and Design changes
that influence unit TAR extensions;
Metallurgical changes upgrades to higher alloys to
improved corrosion resistance
Tighter Integrity Operating Windows lesser swings of
process variable deviations by improving control /
automation techniques
Implementing on-line cleanings, backwashes, flushing,
filter changes, de-coking, etc. this minimizes the impact of
process related factors and allows extended run lengths.
(i.e., fouling, plugging, coke build up, etc.)
Equipment protection changes can reduce impact of
corrosion (i.e., lining / coatings on pipes, tanks, vessels)
Removal of catalyst poisons and de-activation agents
(contaminants removal by improved QA / QC, installation of

Tighter Integrity Operating Windows Application of


McConomycurves to evaluate TAR extensions Carbon

Why Sulfidation / NAC are


Unpredictable causing
Sulfidation fatalities
corrosion ?has caused
severe fires and fatalities in the
refining industry, primarily because
it causes Corrosion
resulting
thinning over a relatively large area,
so failures tend to involve ruptures

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

Metallurgy for Processing Sour Crude / Naphthenic


Acid Crude below Dew point
Corrosion Phenomenon

Locations

Metallurgy Selection

Over head Corrosion


due to cyclic
regeneration of HCl

Column top section ( up to 4th


tray)

CS with Monel cladding + Monel


Trays & valves

Column O/H lines

Dry section - CS
Wet Section CS+ Neutralizers &
Vap. CI

Condensers

Shell: CS, Tube: CS + vap.CI, or


tube: Duplex

Equipment handling wet HS


Environment

CS NACE GRADE
CS-HIC Resistant
CS- Clean Quality
100 % PWHT & RT

Wet H2S corrosion


(Blistering, HIC,SOHIC,SSCC

Metallurgy for Processing Sour Crude above dew point


Below 230C

Low high temperature


sulphur attack

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

CS+3mm SS 410 cladding or


9Cr 1 Mo alloy steel

300 to 400C

High Temperature
Sulphur Attack

Column/ Vessel/Piping

CS+3mm SS 410 cladding or


9Cr 1 Mo alloy steel

6. Bacteria Causing Microbiologically influenced


corrosion also known as biological corrosion &
microbial corrosion.
Metal deterioration as a result of the metabolic activity of various
microorganisms caused by microorganisms, typically chemo autotrophs.
Applies to non-metallic objects as well as metals.
wide range of bacteria in water known to provoke MIC in Stainless steel, Carbon steel, Copper &
Aluminium alloys
Such bacteria can be both aerobic and anaerobic. For instance, sulfate reducing bacteria (SRB) is considered to be
accountable of hastened corrosion to offshore steel as well as ships, although it only exists in stagnant, deep water.
In surface sea water, other specific types of micro-organisms are responsible for catalyzing the reduction of oxygen in
the biofilm, leading to the formation of hydrogen peroxide. These are typically related to accelerated corrosion pitting
attacks involving stainless steel.

Mitigation
Periodic mechanical cleaning
Chemical treatment using biocides to prevent bacteria population
Dry storage and total drainage
Flushing of equipment at regular interval.

High Temperature Corrosion-Oxidation


High temperature Dry corrosion oxidation occur
above environmental dew point 204 C. Metal reacts
with oxygen at high temperature and get oxidized
and form scale.
M = M+ + n eOxidation
At the same time , oxygen is reduced at the scale
surface as under
O2 + 2e- =
O-2
Reduction
The overall corrosion reaction
M + O2 = MO (Scale)

Maximum scaling temperature : alloys used in


Refinery
Alloy
Temperature (C)

Carbon Steel / Carbon MO

1 1/4 Cr-1/2 MO

2 Cr-1 MO

5 Cr 1/2 MO

9 Cr 1/2 MO

Stainless Steel Type 410

SS Type 304,316,317,321 & 347

SS Type 309

SS Type 310

Inconel 625 & 825

Monel

Hastelloy B-2

Hastelloy C-4 & C-276

565
593
635
648
816
816
871
1093
1149
1093
538
760
982

Save Earth
Only
Known
Inhabited
Planet in
Universe

In the midst of Professional


& Technical endeavors
for Operational
Excellence or Business
Excellence, One should
never forget the service
of humanity as a whole &
considering its future
impacton environment.

Solution Provider
Mahendra Kumar
Rastogi