Amine

corrosion
Zhaugashty
Aidana
Amine corrosion
Amines are organic compounds that contain a lone pair
nitrogen atom. They are derived from ammonia by
substituting of one or more hydrogen atoms by organic
groups like an alkyl or aryl group. So amines are
derivatives of ammonia.

Amine causes corrosion known as amine corrosion. It

refers to a type of localized corrosion that happens
primarily on carbon steel in amine-treating processes.
Amine itself is not the cause of corrosion. This corrosion
has originated from dissolved gases (like CO2 and H2S),
amine degradation products, Heat stable amine salts
(HSAS) and other contaminants.
Amine Corrosion-Overview
H2S and CO2 from feed gases are absorbed into the
amine solvent by chemical reaction

• Amines with dissolved CO2 and H2S from the

contactor are called Rich Amines

• Corrosion in Rich Amine circuits is caused due to

dissolved acid gases and presence of impurities

• Acid gases are removed from amines in regenerators at

high temperature or low pressure

• Amine from regenerator contains low dissolved acid

gases and is called Lean Amine
Corrosion factors
Amine corrosion depends on many things like:

● Design and operating practices

● The type of amine
● Amine concentration
● Contaminants
● Temperature and velocity

Corrosion rates and temperature are directly proportional,

specially in rich amine services. High temperatures result in acid
gas flashing and severe localized corrosion when pressure drop is
also high. Though amine corrosion is usually uniform, high
velocities and turbulence will causes losses of localized thickness.

Many of the causes of amine plant corrosion have been identified and reported earlier, see Nielson et al for a comprehensive literature
review up to 19942. Among those factors identified are choice of amine, acid gas, acid gas ratio, contaminants and operating conditions.
While mention of good design practice for corrosion control has been made by a number of authors, for example see Kohl and Nielson3,
conflicts arise when normal design practice is applied from other engineering specialties.
HSAS in Amine System
Heat stable salts are formed when amines react with acidic
components other than H2S and C02 in the inlet process stream
to the amine absorber. Typical acidic components include acids
that form salts of chloride, sulfate, formate, acetate, oxalate,
cyanide, thiocyanide and thiosulfate. In addition, oxygen absorbed
into the amine solution creates amine oxidation products that
include formate and oxalate.

They are undesirable because they cannot be effectively removed in

the normal pressure/temperature swing in the absorption and
desorption cycle of amine sweetening. In actuality, their stability is
determined by the species of the anion (acidic) and cation (basic)
activity which make up the salt.
When do heat stable salts cause problems?
● The trouble can occur when the salt stability
decreases to the point where some disassociation
takes place in a site-specific location in the unit.
Corrosion occurs when that disassociation creates
a corrosion cell with metal in the system. Other
problems are caused by the chelating effect of
some of the organic acids, which are formed.
They can hold the iron in solution, rather than
allowing it to form a protective film on the metal,
resulting in areas of fresh metal where corrosion is
more likely.
● Corrosion and erosion of metal components are
accelerated by the increase in ionic strength of the
solution and by precipitation of salts or corrosion
end products.Increased foaming and reduced
mass transfer rates are caused by changes in the
surface-active character and the increased viscosity
of the solution. Reduced acid gas carrying
capacity is the result of less amine present in a
usable absorptive state.
Neutralization or ion-exchange cleaning
● HSAS will increase the corrosion of the amine system. To
control the corrosion, more and more refineries switch to
neutralization and corrosion inhibition.
● Neutralization is cheap, but the drawback is that the
amine system gets polluted with high levels of Sodium or
Potassium. At too high levels these components will
salt-out (precipitate) with the organic or inorganic acids,
resulting in severe fouling, Refineries have also experienced
that too much neutralization has significant side effects.
● Besides fouling by precipitation of salts, it leads to a very
high lean HS load, which will result in a severely off-spec
product in the absorber. A too high injection or presence
of a strong base (KOH, NaOH, K2C03 or Na2C03) will
transform an amine system in a system that is very difficult
to regenerate. It is therefore very important that there is
never an excess of a strong base in the amine system.
● Realizing the limits and drawbacks of
neutralization, refineries are nowadays regularly
cleaning there amine systems. One of the popular
methods is ion-exchange cleaning.
● This can be done by mobile or fixed units. A
mobile unit has in most cases the possibility to
remove the acids (anions) and the strong base
(cations) which will clean the system completely.
The fixed units that are sold in the industry have
only the possibility to remove the acids (anions),
because once they are installed there is no need to
inject a strong base to neutralize the acids.
Mechanism

Amines are compounds formed by replacing hydrogen atoms

of ammonia, NH3 by organic radicals. The chemistry of acid
gas removal by amine solutions is relatively complex, but the
simplified reactions (exothermic) are:

H2S + R2NH ←→ R2NH2+ + HS-

CO2 + R2NH ←→ R2NH2+ + R2NCOO-

Types of Amines used include primary amines (NH2R) such

as Methanolamine (MEA) and diglycolamine (DGA), and
secondary (NHR2) and tertiary amines (NR3) such as
diethanolamine (DEA), diisopropanolamine (DIPA) and
methyldiethanolamine (MDEA).
50% of corrosion incidents occur in...
● There are, frequently, several factors contributing to failure by
corrosion. Statistics show that almost 50% of corrosion incidents
occur in the hottest part of the plant: the reboiler and bottom of
the amine regenerator. In amine plants, most corrosion is related
to H2S or CO2 breakout and the subsequent attack of the metal
surfaces, usually at areas of elevated temperature and high
pressure drop.
● More potential corrosion mechanisms exist in amine columns.
In the lower section of a regenerator, for example, carbon steel
surfaces not wetted by the amine solution may be attacked by
water vapor and the formation of carbonic acid. Acid gas ratio,
choice of amine (DEA, MEA, MDEA, DGA, AGR, etc.),
contaminants, two-phase flow, flashing, high velocities, vessel
design, and insulation are all factors at play. Pitting, crevice
corrosion, flow enhanced corrosion and general corrosion loss
are frequent problems.
Typical Amine Process Flow Diagram
● Figure 1 gives a generalized overview of an amine plant.Acid gas is removed from the gas stream or light hydrocarbon liquid stream by counter
current reactive absorption with an acid gas lean (lean) aqueous amine solution in a multistage (trayed or packed) absorber tower, operated at
the pressure of the feed gas/ liquid stream
● Since hydrocarbons and other non-reactive gases also dissolve in the aqueous amine solution, many process designs recover these by pressure
reduction in a flash tank, which is configured so gases are separated from liquids and, if needed, hydrocarbon liquids can be skimmed from the
aqueous phase.
● Some acid gas may also flash with the recoverable gases. Amine solution chemistry permits acid gas removal from the rich amine solution at
elevated temperatures. The process is facilitated by counter current steam stripping in a multistage (trayed or packed) regenerator tower,
operated at low pressure
● Stripping steam, which is used for heating and acid gas dilution, is usually generated in a reboiler that takes its feed from the regenerator tower
below steam stripping section. Condensing water from the effluent water/ acid gas stream from the top of the regenerator helps minimize water
usage. Acid gas separation from the condensed water is done in the reflux accumulator. Specific plant design determines point of water return,
e.g. top 4 trays of the absorber or regenerator to conserve amine losses. Energy is conserved by preheating the rich solution prior to entering the
regenerator with the hot lean solution from the regenerator in the lean/ rich heat exchanger (L/R HEX). Low pressure booster pumps are
sometimes used to pump the hot lean solution from the reboiler/ basin of the regenerator tower through the L/R HEX and lean amine cooler
to a surge tank in front of the high pressure amine pumps. Depending on pressure and volume requirements, positive displacement or
multistage centrifugal pumps are used to pump the lean solution to the top of the absorber tower.
Thank you for
your attention