Corrosion

• Corrosion is the deterioration that

occurs when a metal reacts with its
environment.
• It is impractical to eliminate corrosion
• Effective engineering is to control
corrosion rather than to prevent
corrosion
• All metals and alloys are susceptible
to corrosion
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 Consequences of Corrosion
• Safety : Sudden failure may cause fire, explosion,
release of toxic products, construction collapse
• Health : Pollution due to escaping or corrosion
products.
• Shut down
• Loss of efficiency
• Loss of valuable product

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 CDU overhead Corrosion
• Major reason - Presence of acidic species in crude
• Acids commonly encountered
. Hydrochloric acid
. Hydrogen sulphide
. Carbonic acid
. Organic acids
. Acids derived from Sulphur Oxides viz. Sulphuric
& Sulphurous acids

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 Corrosion due to HCl

• Comes from incomplete desalting

• Calcium & Magnesium chlorides not removed get

hydrolyzed to form HCl in presence of heat and water
especially at temperature higher than 122 deg C

• HCl , a strong acid lowers the pH of water by several

units leading to severe corrosion

• In the presence of H2S corrosion of iron due to HCl

increases substantially
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 Chemical Reactions of corrosion

• Primary Corrosion
Fe + 2HCl -------- FeCl2 + H2

• Regeneration of HCl
FeCl2 + H2S ------- 2 HCl + FeS

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 Overhead corrosion due to HCl can be
reduced by

• Proper salt removal in the desalting operation

• Addition of caustic to the crude charge

• Injecting Ammonia or neutralizing amines & Filming

amines in the overhead system

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 Corrosion due to H2S

• H2S itself is present in the crude and gets generated

due to decomposition of organic sulphur compounds

• In presence of H2S corrosion potential due to HCl

increases substantially

• Corrosion potential due to H2S is minimum in the pH

range of 5.5 to 6.5

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 Mechanism of H2S Corrosion

• The reaction representing the corrosion mechanism

is :
H2S <—> (H+) + (HS-)
(Fe++) <—> FeSH+

• The FeSH+ further reacts to form a complex

sulphide scale.

• The dissociation of H2S is minimum at a pH of 5.0.

As pH increases towards neutral region, the
bisulphide ion concentration increases.

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• An increase in corrosion rate is the result of faster
reduction of bisulphide ion from scale lattice and
solution.

• As the scales lattice is altered, FeS is released,

exposing the unreacted Fe.

• This FeS thus released enters into the water phase.

• This phenomena in CDU is referred as “Black Water”

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 Corrosion due to Carbonic acid

• Carbon Dioxide is released from crudes with high

content of Naphthenic acid.

• Carbon Dioxide is a weakly acidic gas and becomes

corrosive when it dissolves in water to form Carbonic
Acid.

• The primary cause corrosion is the formation of

HCO3- which acts as a buffer for H2CO3 corrosion,
the source of FeCO3 precipitation(insoluble corrosion
product) and product of cathodic protection.
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 Mechanism of Carbonic Acid Corrosion

• The reactions can be represented as following

CO2(g) + H2O == H+ + HCO3-
Fe + 2HCO3- == FeCO3 + H2O + CO2

• The FeCO3 formed is an insoluble corrosion product

which forms a film on the carbon steel surface. This
helps in inhibiting corrosion.

• Conditions favoring the formation of the FeCO3 film

are elevated temperature, increased pH and lack of
turbulence.

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• In areas of high velocity, the corrosion rates are
increased as high turbulence prevents the formation
of the preventive FeCO3 film.

• This further exposes fresh surface for further

corrosion attack.

• The corrosion is generally localized in nature.

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 Can be reduced by

• pH control with caustic soda.

• Continuous injection of corrosion inhibitors in the

overhead system.

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 Corrosion due to Organic acids
1

• Organic acids - acetic acid, propanic acid, butyric

acid etc.

• Organic acids change pH in the CDU overhead

system

• Increase demand of neutralizer

------2

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 Corrosion due to Naphthenic acids
2

• Naphthenic acid attack often occurs in the parts

operating over 230 deg C such as heater tubes,
transfer lines, column flash zones and pumps.

• In sour crude units a crude TAN (Total Acid Number)

of 1.0 is sufficient to be concerned about Naphthenic
acid corrosion, in sweet units TAN of 0.5 may be high
enough to cause corrosion

• Naphthenic acid corrosion results in sharp edged,

smooth grooves, gouges or holes with no corrosion
scales or deposits
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• Isolated deep pits in partially filmed areas and
impingement type attack in film free areas are typical
type of Naphthenic Acid Corrosion attack.

• SS316 or SS 317H has good resistance for Naphthenic

acid corrosion with TAN no. greater than 0.5.

• Above 288°C and low Naphthenic acid content 5 Cr or

12 Cr cladding are recommended.

• When H2S is evolved an alloy with 9 Cr is preferred.

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Factors affecting Naphthenic Acid Corrosion

• Naphthenic acid chemistry – Crude oils with TAN no.

higher than 0.5 and cuts with TAN no. higher 1.5 are
considered corrosive between 230 °C and 400 °C.

• Sulphur Compounds – A level of 0.2% and above is

considered corrosive between 230 °C and 455 °C

• Temperature – Occurs primarily in the range of 220 °C

and 400 °C. Above 400 °C, no corrosion is observed
because of decomposition of Naphthenic acids.

• Velocity – High velocity results in higher corrosion rates.

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 Mitigation measures to be adopted

• Blending to reduce the Naphthenic acid content of the

feed by diluting a high TAN crude with a low one.

• Injection of corrosion inhibitors.

• Process control changes to provide adequate corrosion

control if there is a possibility to reduce charge rate and
temperature.

• Upgrading the material of construction to higher chrome

and/or molybdenum alloy.

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 Areas prone to Naphthenic Acid attack

Furnace Tubes and Transfer Lines

• Accelerated corrosion due to velocity and two-phase flow.
• Factors affecting this are temperature, velocity and
degree of vaporization.
• High temperature activates even small amount of
Naphthenic acid in oil thereby increasing corrosion
significantly.

Vacuum Column
• Preferential vaporization and condensation of Naphthenic
acids increase TAN of the condensates.
• Velocity has little effect.

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• Naphthenic acids are most active at their boiling point
but the severe corrosion occurs on condensation.
• Corrosion mechanism is mainly a condensate corrosion
and related to content, molecular wt and boiling point of
the Naphthenic acid.

Side Cut Piping

• Factors affecting corrosion are medium fluid velocity,
low vaporization and Naphthenic acid and H2S content.
• Increase in velocity increases the corrosion rate upto
the point where the impingement starts and then
corrosion is further accelerated.

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 CDU overhead Corrosion Control
Methods
• Blending

• Proper desalting

• Caustic Injection

• Ammonia injection

• Neutralizing & Filming amine injection

• Water washing
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 CDU overhead Corrosion Control
Methods

• Blending
Most commonly used technique
Blending of problem crudes with non-problem crudes
Sometimes the flexibility may not exist or blending
may not provide enough reduction of the problem

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 CDU overhead Corrosion Control
Methods
• Desalting
• Crude oil contains varying degrees of impurities like
naturally occurring salts, water, solids etc.
• The total salt (NaCl, MgCl2 and CaCl2) content in
crude varies from 3 to 300 ptb
• Wash water is employed to wash out these impurities
• Desalter removes the added water and most of the
the inorganic salts

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 Desalter operating conditions

• Addition of wash water - 3 to 10 % on total crude

charge
• Residence time ~ 2 hrs.
• Temperature - 120 to 150 deg C
• Mixing valve delta P - 10 to 20 psi

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 Caustic Injection
• Addition of small amount of dilute caustic (NaOH) to
the desalted crude is often an effective way to reduce
the amount of HCl released in the preheater
• Caustic converts the HCl to thermally stable NaCl,
thus reducing the amount of free HCl
• Disadvantages of caustic
Crude preheat train fouling
Stress Corrosion cracking
Catalyst contamination problems In d/s units
Furnace coking problems

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 Ammonia injection in overhead system

• To control pH of the overhead accumulator water

(pH range 5.5 to 6.5)
Disadvantages
• Inability to reliably control pH within the water dew
point range
• Its salt, NH4Cl causes fouling and under deposit
corrosion

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 Neutralizing Amines

• Neutralizing amines are nitrogen containing organic

compounds which are weak bases

• Morpholine, Ethylene diamine (EDA),

Monoethanolamine (MEA), Methoxypropylamine
(MOPA)

• Propietary formulations of amines by vendors

• All of the neutralizer salts are water soluble

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 Filming Amines

• Filming amine provides a barrier between the metal

surface and the corrosive aqueous environment by
providing micro-molecular film.
• For effectiveness proper pH control is necessary
• Effectiveness of the filmer gets diminished as pH of
the overhead system drops
• Typical injection rate is 3 - 5 ppmv during normal
operation
• Typically naphtha dilution is provided

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 Water washing

• Products of the neutralization reactions, amine

chlorides or ammonium chlorides can be highly
corrosive and fouling

• Stripped sour water, water condensate or overhead

receiver water recirculation to overhead vapour line

• Water containing dissolved oxygen should be

avoided as it can accelerate corrosion

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 Engineering of Water injection system

• Too little water can add to the acid making process

and too much can cause grooving of overhead line
• A proper spray nozzle is necessary to prevent
impingement corrosion of the pipe d/s of injection
point
• Good distribution system to ensure evenly divide flow
among the different banks of the condensers
• Ideal water injection rate - 5 - 10 % of the overhead
stream

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 Corrosion Monitoring

• Water analyses - Overhead receiver water

• Hydrocarbon analyses

• Corrosion rate measurement

• On stream non-destructive examination

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 Overhead receiver Water analyses
• pH - System pH can change from acceptable pH to aggressively
corrosive pH in matter of minutes so the pH should be measured
as frequently as possible
• Metals - Fe, Cu, Zn are typically measured but depends on
material of construction
• Chlorides - Aqueous corrosion is always related to the
quantity of HCl or chloride salts. Measurement of chlorides
confirm when the event of corrosion began and how long it
sustained. Regular measurement helps in optimizing caustic
addition or blending of crudes which result in minimum corrosivity
• Hardness - Hardness detected means leak in cooling water
exchanger. If recycled water wash in use, it means oxygenated
water wash I.e. increased corrosion so adjustments in corrosion
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 Hydrocarbon Analyses

• Inhibitor residual - To detect the presence of

inhibitor (Filmer)

• Metals - The only tool for naphthanic acid corrosion

measurement is metal analyses of oils. For this
historical data is useful as a check on current
conditions.

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 Corrosion rate Measurement
1

• Weight Loss Coupons - Calculated corrosion

rate based on initial surface area and weight.
Visual examination
Can be replaced on stream
Commonly used in overhead systems
• ER Probes - Change in x’ section of measuring
element is measured in terms of change in its
electrical resistance
On stream measurement
can be retracted also
Used in tower overhead systems ---------2
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 Corrosion rate Measurement
2

• Linear Polarization (LPR) Probes -

Instantaneous corrosion rate based on
measurement of corrosion current of the probe
element
- Works only in conductive medium
- Used in cooling water systems, application in
overhead receiver water is feasible but limited
- On stream measurement
- Can be retracted also

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 On stream non-destructive examination

• Ultrasonic (UT) & Radiography (RT)

• NDE normally not used for extensive routine

corrosion monitoring because of its cost

• Often used as inspection tool

• Used on exception basis for corrosion monitoring

when there is a confirmed or suspected problem
which is being watched closely
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