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Amine Corrosion

Description
General amine corrosion,
as distinct from amine SC,
manifests itself in several
forms. The mechanism of
such corrosion, which is not
always fully understood,
appears to be driven by
conditions which are
specific for different parts of
an amine unit and vary
(deteriorate) with time. This
section relates specifically
to the general weight-loss
corrosion of carbon steel.

Apart from metal loss,


which may affect the
integrity of a unit, the
resulting corrosion products
and deposits can have a
Amine corrosion of carbon steel heat-exchanger tubes in a Sulfinol-D detrimental effect on the
reboiler. process by causing
foaming, (partial) blockages
and reduced heat transfer.

Pure amines are non-corrosive, presumably due to their alkalinity. However, in the presence of acid gases,
the potential for corrosion is determined by the stability of protective scales formed by reaction of the acid
gas (or respective anion) with the base metal, and the corrosivity of the solvent once the scale has been
removed. Degradation of the solvent in time increases the corrosivity. For carbon steel in CO2-containing
solvents, the iron dissolution reaction is only partly inhibited by the formation of a relatively friable iron-
carbonate film.

In contrast, the iron-sulphide scale, formed in the presence of H2S, is very protective, and even small
quantities of H2S, reduce the rate of CO2corrosion of carbon steel by enhancing the protective nature of the
iron carbonate/sulphide scale present on the steel surface. Due to the other factors influencing scale
stability, there has understandably been some variability reported in the exact amount of H2S required to
achieve this enhanced protection. Units handling feed with a H2S fraction higher than 5% (volume) of the
total acid gas (H2S + CO2) have been reported to experience less corrosion. Experience has led to the
demarcation between a "H2S-case" and a "CO2-case" for amine corrosivity at a H2S/CO2mole ratio of the
acid gas of 0.01.

Other conditions which can affect the stability of protective films/scales, and hence the corrosion rate,
include high velocities, bubble/droplet impingement, the presence of aggressive anions, complexing
agents, and particulates. Increasing the temperature or decreasing the pressure of rich solvent can cause
flashing of acid gases and hydrocarbons. Apart from the mechanical action of the boiling solution on any
protective films, such changes may also result in an increase in local acidity.

In some H2S cases in Sulfinol plants, severe corrosion and/or blistering has been experienced in the
bottom of the absorber and at the liquid/vapour interface in flash vessels. Criteria have been developed to
predict this attack, e.g.:

There is an empirical correlation between the incidence of corrosion/blistering and H2S /CO2mole
ratios of the process gas greater than 8. A possible explanation is the discharge of CO2 from the
solvent in favour of H2S absorption in the bottom of the absorber.

The amount of flashing of acid gases and hydrocarbons which causes scale disruption, is rather difficult to
estimate, particularly considering the parallel influence of other factors. For new CO2-removal amine plants
a design limit on flashing of 3% (volume vapour in the fat solvent at the process temperature and pressure)
has been set for the use of carbon-steel, heat-exchanger tubes up to a temperature of 95C. In practice,
carbon steel lean/rich heat exchanger tubes have been used successfully in Sulfinol-D at temperatures
below 80C with flashing greater than 3%, but similar tubes have leaked within one year at 85C with 15%
flashing. Considering the fact that variation can occur between design and actual flashing conditions (in the
failure referred to above, the exchangers were designed for less than 3% flashing) and that flashing is
difficult to calculate, it may be best to limit the service temperature of carbon steel under potential flashing
conditions, rather than putting an arbitrary limit on the amount of flashing. In this respect guidance can be
gained from laboratory tests with CO2-rich Sulfinol-D which showed that flashing significantly increases
carbon steel corrosion rate at temperatures above 90C.

While oxazolidone is not corrosive, other amine degradation products are strongly implicated in the
increased corrosivity of amine solvents. For example, field experience and laboratory tests have shown
that the ingress of oxygen, which is known to cause solvent degradation, increases corrosion problems.
The tolerable oxygen ingress via the feed, for instance, depends on the type of operation. In general,
efforts should be made to keep the oxygen ingress into amine plants as low as possible.

The mechanism by which degradation products increase corrosion has not been clearly identified,
however, it probably involves chelation of iron. Several degradation products, such as diamines and
polyamines, are iron chelating agents which could interfere with the formation of protective iron scales. The
presence of organo-iron complexes also explains the location of sulphide and carbonate fouling often
found in amine units. Iron-sulphide complexes are unstable at low temperature and high pressure, causing
FeS precipitation in the absorber, whereas iron-carbonate complexes are unstable at high temperature and
low pressure causing FeCO3precipitation in the regenerator. In both cases the chelate is released
(regenerated) at the point of precipitation and is again available to complex iron.

The presence of chelates increase the solubility of iron in the solvent. Thus the level of dissolved iron in a
solvent is a good indication of the complexing power of the solvent. Iron concentrations less than about 10
ppm (weight) indicate a solvent with low complexing power (low concentration of chelating agents). Iron
concentrations higher than 80-100 ppm would indicate solvents with high complexing power, and possibly,
high corrosivity.

Aggressive anions such as chloride and sulphate can destabilise protective films. Chloride concentrations
> 8000 ppm are known to cause high general corrosion rates of carbon steel in amine solutions.

Finally, particulates, including precipitated iron sulphide and carbonate, may physically damage any
protective films, particularly in high velocity areas.

After removal of the protective films/scales, the rate of corrosion will depend on the corrosiveness of the
solvent. In this respect high temperatures and high acid-gas loading, particularly CO2loading, will promote
corrosion. The presence of heat-stable salts, whether originating from solvent degradation or carboxylic
acids in the feed, are also likely to increase the corrosivity of solvents to bare-metal surfaces.

Consistent with the above discussion, weight-loss corrosion in rich solvent has been found where flashing
or impingement has occurred. Typical locations are lean/rich heat exchanger tubes, downstream of let-
down or control valves, near downcomers, baffle plates in flash vessels, and vessel walls adjacent to inlet
nozzles. The absorber bottoms of a number of amine units have also suffered severe weight-loss
corrosion, often associated with blistering.

Most of the factors which affect corrosion in rich solvent also apply to lean solvent. However, the potential
for corrosion is generally much lower due to the very much lower acid-gas loadings. (In this respect the
potential for corrosion in lean Sulfinol is lower than for the other amine solvents because Sulfinol is
stripped to very much lower acid-gas concentrations. Corrosion has occurred, however, in areas of high
turbulence (pumps, inlet of lean amine cooler tubes, outlet of reboiler/inlet of regenerator). This corrosion is
often aggravated by inadequate CO2stripping and/or very low residual H2S, which makes it difficult to form
a protective sulphide scale. In one set of tests carbon steel in degraded lean Sulfinol, with an H2S loading
of 0.004 moles/mole solvent, had a corrosion rate of 0.53 mm/year, compared to a corrosion rate of 0.037
mm/year in the same solvent with a H2S loading of 0.05 moles/mole solvent.

High temperatures can also cause corrosion of reboiler and reclaimer tubes. Excessive solvent
temperatures can result from inappropriate heating medium temperature or steam blanketing on the
solvent side.

Two particular forms of damage which probably result from a combination of the above factors, together
with abrasive wear, are baffle cutting, which is occasionally found in kettle-type reboilers, and corrosion of
the legs of snap-in valves.

Parameters affecting severity

Parameter Influence Remarks

Material Only carbon steels and low-alloy Stainless steel is much more resistant
steels

Type of amine Differing limits for gas loading

Gas loading < 0.4 mole/mole: low corrosion ( H2S + CO2) 0.40 for MEA and DEA,
rate 0.1 for MDEA
> 0.4 mole/mole: increases
corrosion rate

H2S concentration Lowers pH, increases corrosion

CO2concentration Lowers pH, increases corrosion

Heat stable salts > 2% (weight): increases


corrosion rate

Degree of flashing < 3% volume: low corrosion rate


(vaporisation) > 3% volume: increases corrosion
rate

Velocity < 2 m/s: low corrosion rate


> 2 m/s increases corrosion rate
pH 10-12: low corrosion rate due to iron oxide passive film
< 10: increase corrosion rate

Temperature < 90C: low corrosion rate

Prevention / mitigation
Amine corrosion should be combated in an integrated (multidisciplinary) approach by attention to:

solvent circulation rates, solvent loading and control of desorption and de-entrainment
solvent composition
heat input and skin temperatures in the reboiler
feed quality
avoidance of fouling and foaming
control of solvent losses and bleeding practices
regenerator overhead corrosion and process control
monitoring filter cleaning and solvent degradation
solvent reclaiming
good housekeeping in multi-absorber systems
inspection and corrosion monitoring
inhibition and material upgrading
demisting, heat tracing

The formation of heat-stable amine salts (HSAS) should be hindered by preventing the ingress of HCN and
SO2/O2. Once formed, they should be managed by either purging or reclaiming.

Inspection Techniques
wall loss, general

References
R.B. Nielsen, K.R. Lewis, J.G. McCullough, and D.A. Hansen, "Corrosion in Refinery Amine
Systems", CORROSION/95, paper no. 571, NACE.
M.J. Litschewski, "More Experiences with Corrosion and Fouling in a Refinery Amine System",
CORROSION/96, paper no. 391, NACE.
N.N. Bich, F. Vacha, and R. Schubert, "Corrosion in MDEA Sour Gas Treating Plants: Correlation
between Laboratory Testing and Field Experience", CORROSION/96, paper no. 392, NACE.
D. Ballard, "How to Operate an Amine Plant", Hydrocarbon Processing, Vol. 45, p. 137-144
(1966).
M.S. Dupart, T.R. Bacon, and D.J. Edwards, "Understanding Corrosion in Alkanoamine gas
treating plants, Part 1", Hydrocarbon Processing, April, p. 75-80 (1993).
M.S. Dupart, T.R. Bacon, and D.J. Edwards, "Understanding Corrosion in Alkanoamine gas
treating plants, Part 2", Hydrocarbon Processing, May, p. 89-94 (1993).
L.R. White and D.E. Street, "Corrosion Control in Amine Treating Units" in "Corrosion in the Oil
Refining Industry", NACE (1998), Conference Proceedings.

API RP945 "Avoiding environmental cracking in amine units".