Beyond the Usual Suspects: Unveiling

Hidden Factors in Amine Corrosion

Mustafa Hashim

PhD. MIcorr. NACE Senior Corrosion Technologist. Senior Corrosion Consultant at Add-value
consultancy
7 artículos
10 de febrero de 2024

This article delves into the atomic and chemical mechanisms driving these phenomena, focusing
on key aspects often overlooked in conventional approaches. By equipping ourselves with a
microscopic lens, we can better understand the interplay of temperature, flow velocity,
contaminants, and the inherent properties of different amines like monoethanolamine (MEA),
diglycolamine (DGA), and N-methyldiethanolamine (MDEA).

The Impact of Temperature and Flow Velocity

In the intricate world of amine corrosion and cracking, temperature and flow velocity act as
complex and intertwined forces. Understanding their influence at both the chemical and atomic
levels is crucial for navigating this labyrinth and mitigating risks.

Elevated temperatures amplify reaction rates, including those causing amine degradation and
corrosion. This translates to faster breakdown of the protective oxide layer, leaving the
underlying steel vulnerable. Moreover, when temperatures rise beyond specific thresholds,
volatile components like H₂S in amine solutions can flash, releasing corrosive acidic gases like
CO₂ into the vapor phase. This adds another layer of attack on the already weakened steel. The
shifting thermodynamics at high temperatures can favour the formation of less protective or
more soluble corrosion products, further hindering the effectiveness of the protective barrier.

At atomic level, increased thermal energy due to higher temperatures translates to faster
movement of atoms and molecules. This includes both the diffusion of corrosive species deeper
into the steel and the movement of metal atoms themselves, potentially weakening the material's
structure. Elevated temperatures increase atomic mobility, including the diffusion of hydrogen
atoms within the steel. This faster diffusion allows hydrogen to penetrate deeper and reach areas
where it can interact with metal defects and initiate cracks.

Higher flow rates enhance mass transfer, bringing fresh corrosive species to the steel surface
faster. This can be beneficial for heat transfer but exacerbate corrosion if the protective layer is
compromised. Furthermore, at high velocities, the flowing amine solution can physically erode
the protective oxide layer, exposing fresh metal and triggering a synergistic phenomenon known
as erosion-corrosion, with significantly faster deterioration.

Overstripped Amine: A Paradoxical Threat:

While it might seem counterintuitive, overstripped amine (containing less H2S and CO2) can be
more corrosive than fully loaded amine. This seemingly paradoxical behaviour arises due to
several factors:

Loss of Protective Shields: Amine solutions, when loaded with acidic gases like CO₂, develop
protective carbonate films on the steel surface. These films act as physical barriers, hindering
direct contact between the corrosive species and the underlying metal. Overstripping depletes
these CO₂ molecules, leaving the steel vulnerable to attack.

Role of Free Radicals in Overstripped Amine: The detrimental role of free radicals, highly
reactive molecules generated during amine degradation. Examples of free radicals:

v Hydroxyl Radicals (OH·): Formed through various reactions involving oxygen and water,
these aggressive radicals readily attack organic molecules and iron atoms, weakening the steel's
protective oxide layer.

v Alkyl Radicals (R·): Generated during amine degradation, particularly when H₂S is absent,
these radicals directly react with iron in the steel, accelerating corrosion.

v Superoxide Radicals (O₂•-): Formed when oxygen interacts with the amine solution, these
radicals participate in chain reactions that ultimately contribute to further free radical production
and accelerated corrosion.

These radicals roam freely within the solution. Their aggressive nature manifests in several
ways:

v Direct attack: They directly attack the steel's protective oxide layer, exposing fresh metal to
further corrosion.

v Chain reactions: Their electron-stealing behaviour triggers cascading reactions, generating

even more free radicals, exponentially amplifying the damage.

v Synergistic destruction: They work in concert with other corrosive species, like chlorides,
present in some water sources, accelerating the overall corrosion rate.
Furthermore, increased free amine concentration in overstripped solutions readily adsorbs onto
the steel surface. While initially seeming like a protective film, this interaction often disrupts the
natural oxide layer, further exposing the metal to attack. Therefore, understanding the
multifaceted interaction between overstripping, free radical generation, and their detrimental
effects on the steel surface is crucial for safe and efficient operation of gas treatment plants.
Optimizing amine loading and minimizing overstripping, combined with targeted corrosion
inhibitors, becomes essential for protecting equipment and ensuring process integrity.

The Atomic Roots of Amine Corrosion Hierarchy

To understand the science behind the varying corrosivity of MEA, DGA, and MDEA. This
section will examine the chemical and atomic interactions between these amines and steel,
focusing on the factors that dictate their different corrosion behaviours, or in another word
(corrosion hierarchy). To identify how the specific atomic structures of DGA and MDEA
contribute to their improved corrosion resistance compared to MEA.

MEA: A Susceptible Amine for Steel Corrosion

Monoethanolamine (MEA), a primary amine, exhibits unique chemical and atomic

characteristics that influence its interaction with H₂S and contribute to its increased susceptibility
to corrosion in steel compared to other commonly used amines. This can be understood via:

Chemical Level:

MEA's inherent susceptibility to corrosion lies in the interplay between its high nucleophilicity
(the ability to donate electrons and thus attract positively charged atoms) and low steric
hindrance (Steric hindrance refers to the presence of nearby atoms that create spatial crowding
around the amine group). On the one hand, its lone pair of electrons on the nitrogen atom readily
engages in nucleophilic substitution reactions, making it highly attractive to the positively
charged sulfur atom in H₂S. This attraction leads to the formation of an MEA-H₂S salt through a
covalent bond. However, the lack of significant steric hindrance around the lone pair allows for
close interaction and a strong bond with H₂S.

Yet, the seemingly advantageous strong bond harbours a hidden drawback. The formed MEA-
H₂S salt suffers from inherent instability due to resonance structures (complex structure within
the amine molecules). These resonances delocalise the negative charge across different atoms,
ultimately weakening the crucial C-S bond. This weakness creates a vulnerability, as the bond
easily breaks, releasing a free H⁺ ion into the solution.

Atomic Level:

While the chemical level analysis detailed the overall reaction and product formation, delving
deeper into the atomic realm reveals the intricate dance of electrons and nuclei governing MEA's
susceptibility to corrosion.
Initially, the nitrogen atom's lone pair in MEA, with its negative charge cloud, is strongly
attracted to the positively charged sulfur atom in H₂S. This significant overlap between their
electron clouds leads to the formation of a robust covalent bond. However, the inherent
resonance structures within the MEA-H₂S salt molecule come into play at the atomic level.
These structures represent various electron distribution possibilities, ultimately weakening bonds
– particularly the crucial C-S bond connecting MEA and H₂S. Imagine this weakening as a
gradual loosening of the initially strong bond.

The consequence of this weakened bond is its vulnerability to breaking under minimal thermal
energy. This bond breakage, akin to a sudden release, leaves behind a free H⁺ ion and disrupts
the molecule's stability. The released H⁺ ion readily reacts with water molecules, forming highly
acidic hydronium ions (H₃O⁺). These hydronium ions act as microscopic saboteurs, attacking the
protective iron oxide layer on the steel surface by breaking the iron-oxygen bonds. This
weakening, analogous to eroding a castle wall, leaves individual iron atoms exposed and
susceptible to further attack by water and dissolved oxygen, initiating the corrosion process at its
atomic core.

DGA: A Two Sides in Corrosion Resistance

Unlike MEA, diglycolamine (DGA) paints a more delicate picture regarding corrosion. Its
chemical and atomic characteristics present both advantages and disadvantages in its interaction
with H₂S. On the positive side, DGA possesses significantly lower nucleophilicity than MEA.
This translates to a weaker initial attraction to the positively charged sulfur atom in H ₂S, leading
to a less readily formed salt. While this might seem counterintuitive, the weaker initial bond
proves advantageous. With less electron overlap, resonance structures have a lesser impact on
weakening the C-S bond, leading to greater overall stability. Additionally, DGA boasts higher
steric hindrance due to its bulkier structure. This physical crowding around the reaction site
further hinders the formation of a strong bond with H₂S, again contributing to the stability of the
complex.

However, the reduced reactivity brings its own set of drawbacks. The weaker initial attraction
between DGA and H₂S means lower absorption capacity compared to MEA. This necessitates
larger volumes of DGA for equivalent H₂S removal, potentially impacting operational costs.
Additionally, the lower reactivity can translate to slower reaction kinetics, meaning slower
capture of H₂S, which might be undesirable in specific applications. Therefore, DGA offers a
trade-off: lower corrosivity due to weaker bonding but potentially higher operational costs and
slower reaction kinetics.

MDEA: Balancing Reactivity and Stability

N-Methyldiethanolamine (MDEA) occupies a middle ground between MEA and DGA in terms
of corrosivity. Compared to MEA, MDEA exhibits lower nucleophilicity due to the electron-
donating methyl group attached to the nitrogen atom. This translates to a weaker initial attraction
to H₂S and reduced salt formation, similar to DGA. Consequently, resonance structures have less
impact on bond weakening, contributing to improved stability compared to MEA.
However, MDEA's steric hindrance lies between MEA and DGA, meaning it allows for a
somewhat stronger initial bond with H₂S compared to DGA. This provides a better balance
between reactivity and stability. MDEA demonstrates an improved H₂S absorption capacity over
DGA while maintaining lower corrosivity than MEA. This makes it a popular choice for
applications where a balance between these factors is crucial. Therefore, each amine possesses
unique chemical and atomic features impacting its interaction with H ₂S and steel corrosion,
understanding these nuances empowers informed selection for specific gas treatment
requirements.

Summary:

Shedding light on the atomic and chemical mechanisms governing amine corrosion and cracking,
and understanding the influence of temperature, flow velocity, contaminants, and the unique
properties of different amines empowers us to navigate this intricate landscape, ensuring the safe
and efficient performance of steel equipment in this crucial industrial process.