Minimise corrosion while maximising

distillate
Reducing atmospheric fractionator overhead temperatures to maximise middle
distillate production requires a full understanding of resulting corrosion mechanisms
Brandon Payne
GE Water & Process Technologies

ustained growth in the demand

for jet fuel, diesel and other
middle distillate products is
expected to have a continuing
impact on unit operations, product
pricing, product selection and refining margins into the foreseeable
future. As more and more new
facilities come online to supply the
demand for tighter product sulphur
specifications, refiners will continue
to maximise distillate production in
their atmospheric distillation units
to take advantage of favourable
product pricing. However, maximising the production of these fuel
streams requires a continual assessment of the entire processing system
beyond the mechanical capability of
pumps, piping and valves to ensure
reliable operation of the unit in a
market environment that favours
distillate production. As refineries
continue to lower tower top temperatures in an effort to increase
product draws in the distillate
sections of the column, the conditions for introducing salt fouling
and corrosion mechanisms into
areas that previously were not
affected come to the forefront.
Refiners must address the hazards
of unmonitored distillate maximisation on corrosion in the crude
distillation column top section and
overhead system. In this article,
overhead corrosion control strategies
and guidelines are discussed to help
refiners maintain reliable unit operation while maximising distillate
production.

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Reprinted from PTQ, 3rd Quarter issue, 2012, pp 75-81

Overhead salt point and lower tower

top temperatures
Crude unit overhead corrosion deals
with corrosion affecting the upper
sections of the crude unit atmospheric
fractionation
column,
including the top tower trays, overhead condenser system and top
pumparound circuits. Corrosion in
the crude unit overhead system is
primarily due to acid attack at the

Corrosion in the
crude unit overhead
system is primarily
due to acid attack
at the initial water
condensation point
initial water condensation point
(ICP), resulting in low pH conditions
and the associated aggressive corrosion of the systems metal surfaces.
Secondary corrosion mechanisms in
the tower top and overhead are typically due to amine-chloride salt
deposition driving under-deposit
corrosion.
Neutralisers are used to control the
pH of condensing overhead waters
within an optimal range to maximise
the reduction of corrosion rates while
minimising the tendency for salt
deposition caused by the neutralisation reaction with the acidic species.
The type of neutraliser used in an

overhead system is selected based on

three primary factors: neutralisation
capacity (the strength of the neutraliser), the water partition coefficient
(the rate at which it will enter the
first water droplets formed in the
overhead system) and the neutralisers salt point.
The salt point is defined as the
temperature at which the first
neutralisation salts begin to precipitate from the vapour phase. These
salts can be very corrosive themselves and can also give rise to
under-deposit corrosion at certain
points in the system. In order to
control the deposition and corrosivity of these salts, a water wash is
often used to provide a means of
diluting and washing the corrosive
salts from the overhead system. In
these cases, the salts are scrubbed
from the overhead vapour, washed
from the overhead piping and
condenser system, and flow into the
overhead receiver. However, as the
overhead process temperature is
lowered in an effort to force additional material into the distillate
draw section of the column, the location of the salt point temperature
moves further upstream into the
overhead line, pumparound circuits
and tower top internals where there
is no water wash.
Without the means of removing
deposited salts in these areas, corrosion can be severe and equipment
failure rapid. Therefore, it is critical
to continuously re-evaluate the
neutraliser being used to determine

PTQ Q3 2012

Neutraliser

Water wash

Amine

Accumulator

Amine
recycle
Tower top reflux

Desalter

Amine
recycle
Stripping
steam

Fractionation
column

Tank
farm
Wash
water

Figure 1 Typical amine recycle loops

if it is still appropriate for changes in

overhead and operating conditions.
The ideal neutraliser for the system
will form its amine chloride salt at a
temperature that is 15F (8C) lower
than the water dew point in the
system. To protect against the deposition of precipitated amine-chloride
salts inside of the distillation column,
the neutraliser salt point temperature
must also be 25F (14C) lower than
the tower top temperature.

Role of excess chlorides and

tramp amines

Chloride control in the overhead

system is one of the most important
aspects of a good corrosion control
programme. This is because altering
chloride levels has the largest overall
impact on the corrosion potential by
dramatically affecting both pH and
the salt point deposition temperatures. The lower chloride levels
entering the distillation column are,
the greater the degree of corrosion
control that is possible from a treatment programme. Therefore, with
the desalter having the greatest
impact on the condition of the charge
to the distillation tower, all efforts
should be made to ensure optimal

PTQ Q3 2012

desalter
performance,
reducing
desalted crude chlorides to the
lowest possible levels. However,
maintaining low chlorides alone is
not sufficient to guarantee good
overhead corrosion control. The
amines present in the system are
equally important to the overhead
systems fouling and corrosion
potential.
Neutralising amines that are intentionally added to control overhead
pH conditions are not the only amine
species that play a role in overhead
salt formation. The presence of tramp
amines may play a larger role in
undesired salt formation in the overhead and tower top than the injected
neutraliser amines. Tramp amines
are broadly defined as any amines,
other than the appropriate neutraliser being used, found cycling in the
system. Tramp amines that are entering and recycling in the system will
strongly affect overhead pH and
typically have very high salt points.
Sources of these tramp amines
include incoming crude and slop
oils, steam neutralisers, alkanol
amine units, sour water strippers,
H2S scavangers and cold wet reflux.
Such amines can make it virtually

impossible to either keep salt points

below the water dew point or to
drop pH to desirable levels. The
most desirable condition is to have
overall tramp amines in the system
low enough to enable the usage of a
quality neutraliser with a low salt
point. If tramp amine levels are high
enough, the net system salt point can
negate the impact of a quality
neutraliser. This situation can cause
salt point temperatures to exceed the
tower top temperature and cause
various deposition problems that can
become quite severe and affect tower
operation and charge rates. Efforts
should always be taken to understand total amine loading.
Both elevated chloride levels and
amine levels will negatively impact
overhead corrosion due to salt point
effects. While chloride control is a
relatively direct and straightforward
effort, lowering levels of tramp
amines can be much more difficult.
This is often because operational
practices prevailing in the refinery
will give rise to high levels of tramp
amines cycling up in the crude unit
overhead. These practices are often
caused by units outside the crude
unit boundary. Four primary sources
of tramp amine entry are the sour
water stripper, steam production,
alkanolamine scrubbing units, and
amines entering the refinery with the
incoming crude oil. An overall
understanding of tramp amine backgrounds, surges and sources is
necessary to enable targets and intervention for control of these species.
Levels as low as 5 ppm of certain
tramp amines can have a dramatic
impact on salt points and associated
corrosion. Figure 1 illustrates typical
tramp amine cycles.
The tendency for all these amines
to cycle up in the system is largely
driven by overhead receiver pH and
desalter effluent brine pH. As the pH
rises above 5.5, the tendency for
these species to cycle up is substantially increased. This is because the
partitioning rate at which amines
migrate from the hydrocarbon to the
water phase are strongly influenced

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by pH. Once cycled up, the rate at

which amines will blow down is
dependent on the pH of both the
desalter effluent brine and the overhead receiver waters, as well as the
relative rate of amine input. A lower
pH will cause a faster blow-down at
a constant input of amines to the
recycling system. The dynamic
aspects of amines having reduced
partitioning rates, reduced recycling
rates and increased blow-down rates
as pH is lowered has important
consequences.
GE Water & Process Technologies
(GE) has developed a comprehensive
methodology to address the drivers
of system salt points, salt deposition
rates and subsequent corrosion rates
in systems with significant salt fouling problems through a systematic
review of amine inputs. By properly
controlling these inputs and system
pH, the most rapid reduction in
deposition and corrosion potential
can be achieved. Although lowering
pH offers positive benefits, as
described above, iron should be
monitored in the overhead waters.
The effective minimum pH will be
dictated by the onset of increased
iron production due to ICP corrosion
at the water dew point. The pH
should never be lowered beyond this
level in order to keep ICP corrosion
under control.

Overhead water wash systems

Water washing is used as a means of

forcing the water dew point temperature to higher levels and to
physically dilute and wash salts. This
is accomplished by raising the
amount of free liquid water in the
system. This free water will then
dilute corrosive species at the ICP
and also wash away any neutralisation salts formed at temperatures
below the wash water injection
temperature, or mixed exit temperature. However, it should be noted
that an inadequate water wash can
be worse than no water wash. Water
wash should be injected in two
stages using high-efficiency nozzles
in a co-current configuration to

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Figure 2 LoSalt ionic equilibrium model input

provide a small droplet size with a

large surface area and dispersal
pattern. This will impact both the
wall wetting capability of the spray,
as well as the vapour scrubbing
efficiency.
The first injection stage should be
a single point injected into the overhead vapour line near the top of the
column, while the second stage
needs to be multiple points injected
in parallel just prior to the exchanger
inlets. In a well-controlled unit, the

Selection of the
proper treatment
chemistry is critical
to the programmes
success and the units
equipment reliability
first-stage wash injection should
provide just enough water to form
20% of total liquid water and primarily saturate the overhead vapour.
The second injection stage should
then inject the remainder of the total
water needed to achieve the wash
water target. Enough water should
be added to achieve a minimum of
5% free water. While 5% is a minimum value, 10-15% water wash can
be even more effective. However,

care must be taken to make sure that

the overhead receiver can handle the
additional amount of water flux and
still provide acceptable water separation. Water carry-over in the
overhead reflux can be a very significant problem, as high levels of
water-soluble amine salts will be
carried back to the tower. This can
lead to a large cycling effect that will
dramatically increase salt points, as
well as place salts directly on tower
internals. Additionally, the water can
cause wetting of already existing
salts and increase their corrosion
potential considerably. Care should
also be taken to ensure that overhead
vapour velocity stays within a range
of 30-80 ft/s.

Caustic usage

A target of <15 ppm chlorides, with

<5 ppm upside variation, is an ideal
target. While effective programmes
can be maintained with higher levels
of chlorides, it generally becomes
more difficult and expensive if either
chlorides or variation increase. A
large variation in chloride levels can
be very detrimental, as either low
pH acid attack or high pH salt deposition can occur. Therefore, efforts
should be prioritised to maintain
effective chloride control within
control ranges. The injection of caustic (NaOH) into the desalted crude
oil can be used as a polisher to
further reduce chlorides after the

PTQ Q3 2012

18.1

180

14.8
11.5

130
8.3

80
30

5.0
1.7

10

30

50

70

90

110

Neutraliser rate

Salt points

230

21.4
19.7
17.7
15.7
13.7
11.7
9.7
7.7
5.7
3.7
1.7

Amine
Ammonia
Water dew point
Top temperature
Operating point
GPD

Chlorides in boot, ppm

6

pH at 25C

5
4
3
2
1
0

10

20

30

40

50

60

70

80

90 100

Water condensed, %

Operating point at intersection of pH profile and red line

Figure 3 LoSalt ionic equilibrium model output

best performance is obtained from

the desalters. However, caustic usage
must be carefully evaluated and
monitored to determine accurately
the downstream impacts and the
critical threshold concentrations. It
should not be used as a replacement
for optimising desalter operation.

Proper selection of filming corrosion

inhibitors and neutralisers

In order to properly control corrosion in a crude unit overhead system,

a three-pronged strategy comprised
of an organic neutralising amine, a
filming inhibitor and a water wash
should be implemented. Every corrosion control programme will utilise
these three elements to varying
degrees, based upon the unit design,
crude diet and operating envelope.
Therefore, the selection of the proper
treatment chemistry is critical to the
programmes success and the units
equipment reliability.
Under normal conditions, the ideal
neutraliser utilised will form its

PTQ Q3 2012

amine-chloride salt at a temperature

that is at least 15F (8C) lower than
the water dew point in the system.
Calculating the ICP and salt point
are critical to controlling corrosion.
The use of modelling software, such
as GE Water & Process Technologies
proprietary LoSalt Ionic Equilibrium
model (see Figures 2 and 3), allows
for the rapid and efficient prediction
of the overhead system salt point.
These modelling tools can be used to
quickly determine the best neutralising
amine
and/or
operating
parameters by predicting salt points
for various amines and the ICP for
various operating conditions.
The LoSalt Ionic Equilibrium
model has been effectively used to
assist refiners in optimising tower
top temperatures by establishing the
operating limits they must not exceed
in order to prevent salt formation
and deposition in the system. In one
case, the operational changes made,
based on the information provided
by the ionic modelling analysis,

allowed the refinery to decrease

average overhead corrosion rates by
80% to a corrosion rate of <5 mpy
(verified by consecutive UT thickness
readings).
Filming inhibitor chemistries are
the mainstay of the overhead corrosion inhibitor programme. Filmers
work by coating the metal surface
with a hydrophobic barrier, which
prevents corrosive species from reaching and reacting with the metal
surface. While a neutraliser has a
maximum theoretical limit to the
overall reduction of corrosion rates,
filmer chemistries are not constrained
by such a limit. The level of corrosion
protection from a filming corrosion
inhibitor can approach 100%, given
adequate dosage and the proper
conditions. However, the practical
aspects of the filmer application
generally do not allow such a degree
of protection. It is, however, relatively
easy to realise 90-95% protection for
coated surfaces at reasonable dosages.
Traditional filmers require a pH

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above 4 to maintain optimal film

stability. The newest filmers in the GE
Water & Process Technologies pHilmPlus line can offer film stability down
to a pH of 2. This is especially important during desalter upsets and
high-chloride events, which can drive
overhead system pH to very low
levels. In addition to providing a
significant further reduction in corrosion rates, over and above that
available with a neutraliser, certain
filmers can act as salt dispersants. As
such, they help reduce the risks associated with salt fouling due to
amine-based neutralisers or tramp
amines present in the system. Filmers
have been used with success in the
dispersion of deposited salts in areas
where no water wash is present, such
as pumparound circuits and tower
trays.
Unlike neutralisers, filming inhibitors will not vaporise in the overhead
system and will remain
liquid.
Therefore, filmers must be atomised
into the overhead at the point of
injection. Nozzles and dilution
streams must be used to achieve
proper distribution. Since the filmer
injection exists as an entrained droplet distribution in the overhead
vapour stream, it follows a twophase flow profile. Liquid droplets
will impact with and coat the wall
through direct interaction. Both the
choice of application point and the
droplet size distribution of the
injected liquid play a large role in

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the overall effectiveness of a filmer.

Larger droplets in the flow field have
a tendency to impinge onto the
outside wall of any bends or turns in
the line. A loss of filmer coverage
can be caused by 90-degree elbows
or U-bends due to the momentum of
the travelling droplets forcing them
to move to the outside wall of the
curves via centripetal forces. Also,
vapour-liquid route preferencing and
maldistribution can cause poor filmer
coverage downstream of splits, T-s
and in manifolds. Droplet sizes
larger than 50 microns will have a
greater tendency to be lost prematurely to the wall for systems with
complex bends. For this reason, highquality hydraulic nozzles that are
properly designed for the system
flows and pressures should be
utilised to achieve a minimum droplet size distribution. Also, at least
two stages of filmer distribution are
recommended for most systems,
similar to a water wash system.
The first stage should be near the
beginning of the overhead vapour
line, preferable into the 90-degree
elbow pointing down the vertical
pipe near the side of the tower. The
second stage should be distributed
over parallel legs, just upstream of
the individual exchangers. The injection direction should be co-current
with the flow, and each injection
point should use its own carrier
stream that is metered and controlled. Filmer injection points should

be at least 10 pipe diameters away

from other injection points. The first
filmer
injection
is
preferred
downstream of the neutraliser injection point, and both should
be significantly upstream of the
water dew point and salt point
locations.

Conclusion

As refiners reduce atmospheric tower

top temperatures to maximise diesel
and middle distillate production, a
thorough understanding of the ICP,
salt point and control of amine recycle loops is critical to maintaining
plant reliability in changing plant
operational conditions. By practising
good operational diligence, treatment
programme stewardship and utilising predictive diagnostic tools, such
as GEs proprietary LoSalt Ionic
Equilibrium model to predict amine
salt points, refiners can establish safe
operating regimes for diesel and
middle distillate maximisation and
ensure the long-term safety and profitability of refinery assets.
LoSALT and pHilmPLUS are trademarks of
General Electric Company and may be registered
in one or more countries.
Brandon Payne is a Product Applications
Specialist with GE Water & Process Technologies
Refinery Corrosion Center of Excellence. He
is responsible for global support of refinery
corrosion treatment programmes, and has over
14 years of refinery engineering and process
treatment experience.

PTQ Q3 2012