Corrosion Control in Crude Units

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 Published on Published onDecember 4, 2017

Henk Helle

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This article contains sections from my

book.  (see http://www.corrosioncontrol.nu/manual-corrosion-control-
crude-units.html ).         I intend to publish other sections from time to
time. Comments are welcome.
Aqueous corrosion in the top of the tower

Direct NH4Cl formation by de-sublimation may occur in the top of the column.
If this happens, the desublimation automatically limits the [NH3]*[HCl]
concentration product in the overhead to its equilibrium value. If the value of
the product in the column top is above the equilibrium desublimation level,
excess reactant will desublime and is carried down or remains on the trays.

Note that this mechanism may give a very misleading impression of the actual
chloride level of the system and hence of the effectiveness of desalting and
neutralization: for instance, when desalter pH and hence NH3-levels are high,
overhead chloride level may become quite low due to desublimation in the
tower. A quick check of the saturation level of NH4Cl is made through the
following equation:

Tsubl + 273 (°C) = ( 176200 / (8.3412 * ln(p²*M(HCl)*M(NH3))-285)

Where M are the respective mol fractions in the vapor, and p is the system
pressure in bara.

When T is below Tsubl, at least part of the HCl remains in the column as
NH4Cl. Crystals or brine can be carried down with the liquid hydrocarbon until
the salt dissociates again at a higher temperature or is removed with the kero or
heavy naphtha product stream. A circulation of NH3 and HCl may establish an
accumulation process as shown in the figure below. Where the deposits become
slightly wet, aqueous corrosion can follow; it can also cause damage by
enhancing naphthenic acid HT corrosion processes, and finally, by causing
corrosion in the downstream systems: stabilizer reboilers of the heavy naphtha
and kero, the hydrotreaters and HDS exchangers.
A wet salt formation process tends to be a localized phenomenon. An aqueous
phase in the top of the tower may be caused by condensation of water, a wet or
cold reflux, or by separation of water from the naphtha in the TCR-cooler. The
formation of ammonia salts, amine-salts or persistent brines is the next step.

A corrosive phase in the column top, often localized, may have four possible
causes:

1. a wet reflux or a reflux containing amine

2. too much reflux or too low TCR temperature, or both, causing water
condensation.
3. water drop-out from the naphtha due to low TCR heat-exchanger coolant
temperatures
4. sulfuric acid condensation

The corrosion processes that may develop in each of these cases tend to be
different in nature and location. A conceptual description of each:
1)   Both a top-pumparound reflux and an overhead condensate reflux are likely
to be water-wet some of the time in most of the units and all of the time in an
occasional unit. The difference with the other sources is that it can involve a
significant volume of water which will tend to collect and flow down. Upon
evaporation of the water, any dissolved salts are deposited, probably between
the second and fourth tray. From a reflux stream that contains amine, corrosive
amine-salt deposition is possible.

2)   Condensation of water at a cold spot, for instance, against a cold wall or

where cool reflux or pumparound return enters the tower, absorbs acids and
ammonia as it moves across the tray and down where it either evaporates and
leaves a salt deposit, or is drawn into the TCR. Especially when the condensing
water volume is large, a water circulation may establish in the column top. This
water will become a concentrated brine wherever evaporation takes place.

3)   Increased water content in the top may cause water separation from the
naphtha on the TCR tube bundle can lead to the formation of corrosive brines on
those tubes, especially in combination with NH4Cl desublimation in the column
top. The water may attract salts and acids from the naphtha which corrode the
tubes and form a porous scale in which corrosion continues even more rapidly.

4)   Sulfuric acid condensation may already occur at a temperature above the

water dewpoint when SO3 levels are high. Sulfuric acid typically condense from
the vapor. The dilute acid will corrode C-steel and Alloy 400. This condition is
quite rare, but recurrent corrosion problems on the top trays have been attributed
to sulfuric acid [18] or oxidants. 

The obvious mitigation measure is raising the column top temperature to a level
25°C above the theoretical dewpoint, but this is an economically rather sensitive
process step. Other, less constraining measures include:
 Reduce the NH3 and amine in the desalted crude. Apply slightly acidic
conditions i.e. pH ~ 6.5 in the desalter. This may affect the corrosion in
the overhead so inject extra ammonia in the overhead line!
 Prevent neutralizing amine from entering the reflux, or do not use the cold
reflux at all.
 Use materials in the column top and the 4 upper trays that resist corrosive
brines: Hastelloy C276, Incoloy 825.