Amines themselves are not inherently corrosive, the operating conditions and chemical interactions in these systems create

an environment conducive to corrosion. Sour gas (containing CO2 and H2S) is passed through an absorber column, where it
contacts an aqueous amine solution (e.g., monoethanolamine [MEA], diethanolamine [DEA], or methyldiethanolamine [MDEA]). The amine chemically reacts with the acidic gases, forming water-soluble amine salts, which are absorbed into the solution.
Causes of Amine Corrosion:
1. Dissolved Acid Gases (CO2 and H2S): Role in Corrosion: CO2 and H2S, when dissolved in the aqueous amine solution, create an acidic environment that promotes corrosion of carbon steel. These gases react with water to form weak acids: CO2 +
H2O H2CO3 (carbonic acid): Carbonic acid partially dissociates, lowering the pH and attacking the steel surface. H2S: In the presence of water, H2S can dissociate to form HS⁻ and S²⁻ ions, which are corrosive, especially in combination with other
factors. Mechanism: The acidic environment facilitates electrochemical corrosion, where the steel acts as an anode and cathode in a corrosion cell. At the anode, iron oxidizes (Fe Fe² + 2e ), and at the cathode, reactions like oxygen reduction or
hydrogen evolution occur, depending on the environment. Localized Effects: The presence of CO2 and H2S can lead to pitting corrosion, particularly in areas with high turbulence or stagnant flow, where protective oxide layers on the steel are disrupted.
2. Heat Stable Amine Salts (HSAS):Heat stable amine salts are formed when amines react with strong acids or contaminants in the process stream, such as formic acid, acetic acid, oxalic acid, or sulfur-containing compounds. Unlike the reversible
reactions between amines and CO2/H2S, HSAS do not decompose during the regeneration process (where the amine is heated to release absorbed acid gases). Examples of HSAS include amine salts of formate, acetate, oxalate, and thiocyanate.
Corrosion Contribution: Acidity: HSAS are acidic and lower the pH of the amine solution, increasing its corrosivity. Localized Attack: HSAS can concentrate in certain areas, such as low-flow zones or crevices, leading to localized corrosion. Examples:
Common HSAS include amine salts of formate, oxalate, acetate, and sulfate ions. Sources: Contaminants in the feed gas (e.g., oxygen, sulfur compounds). Degradation of the amine solution due to high temperatures or oxidation. Ingress of acidic
compounds from upstream processes.
3. Amine Degradation Products: What Are They?: Over time, amines degrade due to thermal stress, oxidation, or reactions with contaminants, forming byproducts that contribute to corrosion. Examples include: Bicine: A degradation product of MEA,
formed under high-temperature conditions. Oxalate and Formate Salts: Organic acids formed from amine breakdown or oxidation, which create HSAS. Other Compounds: Complex organic molecules like imidazoles or polymers that alter solution
chemistry. Corrosion Impact: Degradation products can increase the solution’s corrosivity by lowering pH or forming chelating agents that dissolve protective oxide layers on steel. They may also increase solution viscosity or foaming, which affects flow
dynamics and promotes localized corrosion in areas like heat exchangers or pumps.
4. Other Contaminants: Types of Contaminants: Oxygen: Oxygen ingress can lead to oxidative degradation of amines and the formation of corrosive organic acids. It also promotes general corrosion by acting as a cathodic reactant. Solid
Particulates: Suspended solids, such as iron sulfide or corrosion products, can cause erosion-corrosion or deposit under which pitting can occur. Organic Acids: Trace amounts of formic, acetic, or other organic acids in the feed gas can react with amines
12 Compounds like mercaptans or thiophenes can form corrosive byproducts.
to form HSAS. Sulfur Compounds: API RECOMMENDED
Impact: These P RACTICE 571
contaminants exacerbate corrosion by altering the chemistry of the amine solution, promoting acidic conditions, or physically
damaging protective scales.

3.2 Amine Corrosion

3.2.1 Description of Damage

a) Amine corrosion is typically localized corrosion that occurs principally on carbon steel in amine treating
processes. Corrosion is not caused by the amine itself but results from dissolved acid gases (CO2 and H2S),
heat stable amine salts (HSAS), amine degradation products (e.g. bicine, oxalate, and formate salts), and
other contaminants.

b) SCC of carbon steel in amine services is discussed in 3.3.

3.2.2 Affected Materials

Primarily carbon steel. 300 series SS and other grades of stainless steel are more resistant.

3.2.3 Critical Factors

a) Corrosion depends on design and operating practices, the type of amine, contaminants, temperature, and
velocity.

b) Amine corrosion is very closely tied to the operation of the unit. With a few exceptions, carbon steel is suitable
for most components in a properly designed and operated unit. Most problems can be traced to faulty design,
poor operating practices, or solution contamination.

c) Corrosion is also dependent on the type of amine used. In general, alkanolamine systems can be rated in
order of aggressiveness from most to least as follows: monoethanolamine (MEA), diglycolamine (DGA),
diisopropylamine (DIPA), diethanolamine (DEA), and methyl diethanolamine (MDEA). Heat Stable Salts (HSS):
HSS increase the conductivity of the
solution and lower its pH, creating a
more corrosive environment. At
d) Lean amine solutions are generally not corrosive because they have low conductivity and high pH. However, concentrations above 2%, HSS can
disrupt the protective iron sulfide film
an excessive accumulation of heat stable salts, e.g. bicine, oxalate, formate, and acetate salts above about amine systems (e.g., downstream of
on carbon steel surfaces, In hot lean

2 %, depending on the amine, can significantly increase corrosion rates in hot lean amine. the reboiler), high temperatures
exacerbate the corrosivity of HSS,
Lean amine at high temperature will cause HSS accumulation accelerating metal dissolution.
Oxygen is not naturally present in amine units, as they operate
e) Oxygen in-leakage causes high corrosion rates and contributes to heat stable salt formation. under anaerobic conditions, but it can enter through leaks. Oxygen
also oxidizes amines and their degradation products, forming
organic acids (e.g., formic, acetic, or oxalic acid) that contribute to
HSS formation.
f) Lean amine solutions contain a small amount of H2S, which helps maintain a stable iron sulfide film.
Overstripped lean amine solutions can be corrosive if there is inadequate H2S present to maintain the
protective iron sulfide film. In overstripped solutions, the lack of H₂S allows other corrosive species (e.g., CO₂, HSS, or organic acids) to attack the metal surface, accelerating corrosion.

g) Corrosion rates increase with increasing temperature, particularly in rich amine service. Temperatures above
about 220 °F (105 °C) can result in acid gas flashing, if the pressure drop is high enough, with severe
localized corrosion.Rich amine at high Temperature (>105°C) with high CO₂ and H₂S, forms acidic species that lower pH and increase corrosion,where acid gas flashing (sudden
vaporization of dissolved CO₂ or H₂S in areas of pressure drop, creates two-phase flow) causes severe localized corrosion due to cavitation or erosion-corrosion.

h) Process stream velocity will influence the amine corrosion rate and nature of attack. Corrosion is generally
uniform; however, high velocities and turbulence will cause localized thickness losses. For carbon steel,
velocities are generally limited to 3 fps to 6 fps (1 m/s to 2 m/s) for rich amine and about 20 fps (6 m/s) for
lean amine.

3.2.4 Affected Units or Equipment

a) Amine units, which remove H2S, CO2, and mercaptans from process streams in many units including crude,
coker, FCC, hydrogen-reforming, hydroprocessing, and tail gas units.

b) The regenerator reboiler, including the feed and return lines, and the regenerator are areas where the
temperature and turbulence are the highest in the amine system and therefore are locations of potentially
significant corrosion.

If excessive regeneration occurs in the reboiler (i.e. > 5 % of the total amine regeneration occurs in the
reboiler), it can lead to acid gas corrosion in the reboiler, its vapor return line, and the bottom of the
regenerator.
 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 13

Ammonia, H2S, and hydrogen cyanide (HCN) accelerate corrosion in the regenerator overhead
condenser and outlet piping as well as reflux piping, valves, and pumps.

c) The rich amine side of the lean/rich exchangers, the hot lean amine piping, the hot rich amine piping, the
stripper overhead condenser piping, the amine solution pumps, and the reclaimers are also areas where
corrosion problems commonly occur.

d) In amine absorber systems, the locations most susceptible to amine corrosion are where amine or acid gas
impinge on the shell, as well as downstream of pressure letdown valves and other areas of high velocity in
the rich amine piping.

3.2.5 Appearance or Morphology of Damage

a) Carbon steel and low-alloy steels mostly suffer uniform thinning in localized (isolated) locations or localized
under-deposit attack. (Figure 3-2-1 to Figure 3-2-6)

b) When the process stream velocity is low, thinning will be more uniform and widespread. At locations with
high velocity or turbulence, it will be more localized with greater metal loss.

c) Welds can be preferentially attacked. (Figure 3-2-1 and Figure 3-2-3)

3.2.6 Prevention/Mitigation

a) Proper operation to the amine system is the most effective way to control corrosion, with particular attention
paid to acid gas loading levels. In addition, to avoid corrosive amine degradation products, the process
temperature should not exceed recommended limits. Proper control of the reboiler rate and temperature is
necessary in order to maintain proper regenerator temperatures.

b) Proper attention should be given to avoiding the buildup of heat stable salts to unacceptable levels.

c) The system design should incorporate measures to control local pressure drop to minimize flashing. In areas
where it is unavoidable, upgrading to 300 series SS or other corrosion-resistant alloys may be needed. Type
410 SS trays and internals are commonly used in absorber and stripping towers.

d) Avoid air ingress into the system as this will lead to formation of corrosive heat stable salts.

e) Storage tanks and surge vessels should be blanketed with oxygen-free inert gas to prevent introduction of
oxygen and in-leakage of air.

f) Solids and hydrocarbons should be removed from the amine solution by filtration and through process control.

g) Corrosion inhibitors may be required to control amine corrosion within acceptable levels.

3.2.7 Inspection and Monitoring

a) Visual inspection (VT) of internal surfaces at flow impingement areas, turbulent flow areas, liquid/vapor
interfaces, and of welds/heat-affected zones (HAZs) is effective in identifying localized corrosion. Sometimes
a pit gauge is used in conjunction with visual examination to provide specific data on extent of metal loss.

b) Thin regions:

external ultrasonic testing (UT) is typically used to map the thickness of components to identify local thin
regions;

profile radiographic testing (RT) can be effective for identifying localized attack, particularly at
welds/HAZs and turbulent locations;
14 API RECOMMENDED PRACTICE 571

UT can sometimes be used in conjunction with VT, laser scanning, structured white light imaging, and/or
pit gauges to determine the extent of metal loss.

c) Permanently mounted thickness monitoring sensors can be used.

d) Corrosion monitoring can be performed by installing corrosion coupons and/or inserting corrosion probes.

e) The level of amine degradation products (e.g. bicine, oxalate, and formate salts), should be monitored. An
increase in iron content of the amine solution will coincide with an increase in the level of these degradation
products.

f) Fouling of exchangers and filters can be a sign of corrosion problems on the unit.

3.2.8 Related Mechanisms

Amine SCC (3.3).

3.2.9 References

1. J. Gutzeit, “Refinery Corrosion Overview,” Process Industries Corrosion—The Theory and Practice, NACE
International, Houston, TX, 1986, pp. 171–189.

2. L.R. White and D.E. Street, “Corrosion Control in Amine Treating Units,” Proceedings of the Special
Symposium on Corrosion in the Oil Refining Industry, NACE International, Houston, TX, 1996.

3. R.B. Nielsen et al., “Corrosion in Refinery Amine Systems,” Paper No. 571, Corrosion/95, NACE
International, Houston, TX.

4. API Recommended Practice 945, Avoiding Environmental Cracking in Amine Units, American Petroleum
Institute, Washington, DC.

5. M.A. Saleem and A.A. Hulaibi, “Corrosion Challenges in Gas Treating Units,” Paper No. 08416,
Corrosion/2008, NACE International, Houston, TX.

6. P. Quiroga et al., “Improving Amine Unit Reliability with On-line Corrosion Monitoring & Modeling,” Paper No.
08421, Corrosion/2008, NACE International, Houston, TX.

7. D. Fan et al., “Role of Impurities and H2S in Refinery Lean DEA System Corrosion,” Paper No. 00495,
Corrosion/2004, NACE International, Houston, TX.
AMINE CORROSION
Description Appearance
Amine is used in refinery to General or localised corrosion
remove H2S and CO2 from and LOWT
process streams. LCS is
corroded by C02 and H2S
gases, dissolved in the amine
and amine salts
k1

Inspection: VT and UT thickness measurements.

Corrosion coupons/probes.
Monitoring of exchangers and filters for
corrosion debris.
Critical factors: Most problems of amine corrosion of LCS are
caused by operating upsets or contamination.
Corrosion rates increase with temperature
(approx. > 104°C (220nF)).
Two-phase flow and high fluid velocities
(> 6 m/s for lean amine) will greatly increase
the speed of attack.
FFP/Severity: 300 series SS are highly resistant so do not cause
FFP problems in amine service.
LOWT results in leaks rather than catastrophic
cracking failure.
API 579 (Sec. 4.5) can be used for LOWT
assessments, once the corrosion rate has been
arrested.
References: API 571 (5.1.1.1).
 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 15

Figure 3-2-1—Localized amine corrosion at the weld found in piping from the reboiler to the
regenerator tower in an MEA unit. Many other similar cases were found, some going as deep as half
thickness. They were originally found with shear wave UT inspection and mistaken as cracks.

Figure 3-2-2—Hot lean amine corrosion of carbon steel attributed

to increased CO2 content in the MEA solution.
16 API RECOMMENDED PRACTICE 571

Figure 3-2-3—Preferential weld corrosion in lean amine. (Reference 5)

Figure 3-2-4—Preferential corrosion in an amine regenerator reboiler return elbow. (Reference 6)

 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 17

Figure 3-2-5—Corrosion near the liquid level in a reboiler exchanger shell from an amine
regeneration unit. (Numbers drawn on figure are UT thicknesses in inches.)
Nominal wall: 0.550 in. (Reference 7)

Figure 3-2-6—Corroded amine regenerator column shell near a downcomer. (Numbers drawn on
figure are UT thicknesses in inches.) Nominal wall: 0.5 in. (Reference 7)