CORROSION IN AMINE UNITS

Amine Corrosion
Description
■ 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.
Rich Amine / Lean Amine / Sour Gas / Sweet Gas

■ Rich Amine = Amine saturated with acid gases

(H2S and/or CO2)
■ Lean Amine = Rich Amine after regeneration and
the removal of acid gases.
■ Sour Gas = Gas containing acids typically H2S and
CO2
■ Sweet Gas = Gas after removing acid components
Fresh Amine is not corrosive
■ Corrosion (metal loss) of carbon steel components
in amine units is not caused by the amines
themselves.
■ Fresh amine is typically not very corrosive due to its
low conductivity and moderate pH (8-11).
■ Corrosion usually results from dissolved acid gases,
including hydrogen sulfide and carbon dioxide.
■ Corrosion can also be caused by a variety of amine
degradation products including heat stable salts,
such as bicine.
Rich Amine / Lean Amine Corrosion

■ In rich amine, typically the corrosion rate is higher

than that of lean amine because of:
high conductivity and/or low pH, and
the rate increases with increasing temperature.
■ In lean amine, the corrosion rate is generally lower
than that in rich amine, but an excess of heat
stable salts above 2 weight percent may
significantly increase corrosion rates on carbon
steel
Amine Corrosion / Amine Type

■ Alkanolamine systems can be rated in order of aggressiveness from

most to least as follows:
 Monoethanolamine (MEA): Primary Amine,
 Diglycolamine (DGA): Primary Amine,
 Diisopropylamine (DIPA): Secondary Amine,
 Diethanolamine (DEA): Secondary Amine,
 Methyl diethanolamine (MDEA): Tertiary Amine.
Amine Corrosion / HSAS (Limit 2%)

 Heat Stable Salts refer to amine salts of ionic species such as acetate,
formate, oxalate, acetate, thiosulphate, thiocyanate and chloride, that are
thermally stable and are not dissociated to any great extent in the
regenerator.
Amine Corrosion / HSAS (Limit 2%)
 Amines show basic nature and they also react with acid to form a salt.
 Amine thus can react with other acids (not only H2SO4)
 Lean amine is reginerated by applying heat to the rich amine solution and
removing the amine salts
 In some cases amine react with other acids to form other amine salts from
which lean amine cannot be regenerated by heat. These are the Heat Stable
Amine Salts
 Oxygen is known to degrade amines and to form numerous compounds as
glycine, ammonia, amides, bicine, as well as several weak acids as formic,
acetic, oxalic, glycolic acids. Then, these carboxylic acids yield to formate,
acetate, oxalate and glycolate usually named Heat Stable Salts (or HSS)
 Heat-stable salts are corrosive because they:
 lower the amine solution pH,
 increase solution conductivity,
 act as chelating agents, dissolving the protective film covering the base
metal.
Amine Corrosion / Bicine
 Bicine is an amino acid that results from amine degradation due to the
presence of oxygen and/ or sulphur dioxide.
 The amine solvents experiencing this degradation are MDEA, DEA, TEA and
mixed amine solvents containing any of these amines as components.

 H2S attack on carbon steel  formation of FeS  the protective layer of FeS
formed on the carbon steel prevents further corrosion  when bicine is
present, the protective layer is continuously destroyed or not formed at all 
The unprotected carbon steel is once again attacked by the H2S, resulting in
an accelerated corrosion rate
Amine Corrosion / Bicine
 Bicine by itself in an amine solution is
not corrosive to carbon steel. As shown
in these figures: There is no increase in
the instantaneous corrosion rate of a
30 wt % MDEA solution when H2S is not
present

 FeS + Bicine → Bicine-Fe++ + S=

 S= + H2O → HS- + OH-
 2 HS- + Fe → FeS + H2 + S=

 As long as bicine and H2S are present,

Fe will be continuously chelated from
any available source.
Amine Corrosion / Flashing

 Flash evaporation, or flashing, is the process of volatile

components suddenly vaporizing from their liquid
state.
 The most common problem encountered in the
lean/rich cross exchanger is corrosion due to flashing
acid gases at the outlet of the exchanger or in the rich
amine feed line to the regenerator.
 In many applications, especially for MEA and DGA
Agent, a stainless steel (304 or 316) lean/rich
exchanger tube bundle should be considered.
 Adequate pressure should be maintained on the rich
solution side of the lean/rich exchanger to reduce acid
gas flashing and two-phase flow through the
exchanger.
Amine Corrosion / Reboiler Excessive Regeneration

Figures shows examples of

reboilers that have been corroded
due to excessive acid gas break
out in the reboiler. In both cases,
a large proportion of the stripping
was occurring in the reboiler
rather than the regenerator.
Amine Corrosion / Amonia and Cyanide

 Corrosion in the overheads of the regenerator takes a different form from

that occurring elsewhere in the amine unit. H2S, NH3 and HCN are
important factors that are involved, which can cause corrosion since they
remove sulfide scales..
 Cyanide: Promote Hydrogen charging into material increasing sour service
severity and cracking risk. It Increases corrosion rate by converting iron
sulfide scale deposit into soluble iron salt complex, also react with H2S to
form thiocyanate which react with amine to form HSS.
 Amonia: react with H2S to form very corrosive and erosive compound of
ammonium bisulfide which accumulates in the stripper overhead reflux
circuit
Lean Amine Corrosion / Overstripping

 Overstripping= excessive elimination of H2S

 H2S Corrosion  Ion Sulfade scale  passivation and protection of the
steel surface  Corrosion rate decrease
 Overstripping  Film scale not formed  Corrosion will percist  For lean
amine service it is advisable to have a minimum amount of H2S on the
steam
Amine Corrosion / Erosion

 Carbon steel + Rich Amine = velocities are generally limited to 1 m/s to 2 m/s
 Carbon steel + Rich Amine = velocities are generally limited to 6 m/s
 Note: Flashing of the dissolved gas in the amine:
 Can lead to enormous increase in the velocity of the resulting two phase
flow
 Greatly increases scouring potential and reducing component life
 Presence of ammonia enhance the corrosion/erosion problem
 Presence of sulfide leaching entities enhance enhance the corrosion/erosion
problem such as Bicine, HSAS, Cyanides …
Amine Corrosion / Erosion
Amine Corrosion / Contaminant effects
Amine Corrosion / Contaminant effects
Amine Corrosion / Construction Material
Amine Corrosion / API 581 Corrosion rate
Amine Corrosion Flash Card
Carbon steel

Flashing Localized

Excessive
regeneration Acid Gases
in reboiler
Amine
Corrosion

Heat Stable
Amonia and Amine Salts
Cyanide
2%

Bicine Oxygen