In 2016, Turkish Petroleum Refineries Co.

(Tupras) faced corrosion issues in the

crude columns of its batman refinery. After commencing operation, a leak and fire
ocurred due to corrosion in the line of the white spirit drawing section. this
forced the crude unit to be shut down before it was replaced with a new white
spirit line, which also leaked in the same location. Because of this, possible
remedies for corrosion in the crude units were investigated and actions for its
elimination were identified.
Important precautions were taken to solve the corrosion problem, including:
increasing the temperature of the column, decreasing the dew point temperature at
the top of the column, steam optimisation, reducing the amount of water returning
to the column, preventing the injection of chemicals inside the column, caustic
optimisation, and healing the chemical dosage systems. The performance of the
refinerys's chemical injection system was also improved considerably. this article
aims to highlight corrosion elimination mechanism for use in crude columns.
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Crude units.
The Batman Refinery - one of four refineries operated by Tupras - was founded in
1954 to help meet petroleum demands in turkey's west regions. In 1972, the
refinery's processing capacity had reached 1.1 million tpy. The refinery was
designed to process domestic crude oil extracted by TPAO (Turkish Petroleum Anonym
Partnership) in Batman, Turkey. Hence, the API of the crude oil is between 18-20.
the batman refinery contains two crude units that are very similar to each other,
with atmospheric towers that produce naphtha, "white spirit", kerosene, light and
heavy diesel, and atmospheric residue (bitumen). Basic process flow diagramns
(PFDs) are shown in Figures 1 and 2.
The following chemicals are used in the crude towers:
A caustic, which can be used to decrease the hydrogen chloride (HCl) concentrations
from salts at the outlet of the desalter and injected to the desalter outlet line.
A corrosion inhibitor that aims to create a protective filming layer at the top of
the atmospheric column system.
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A neutralising amine that stabilises pH values and decreases the acidic effect at
top of the column line.
A demulsifier that ensures better separation of water and crude oil at the
desalter.
Wash water, with is given to the desalter to dissolve salts in the water, is used
to remove the salts at the top of the column.

Corrosion in crude towers

During scheduled maintenance in 2016, all equipment (including the distillation
column), was opened for inspection. severe corrosion and contamination were seen
inside the column. As figure 3 demonstrates, the top seven trays of naphtha and
white spirit cut were eroded due to corrosion.
After turnaround of the maintenance programme, two units commenced operation in
februaryy 2016, but a leak and fire ocurred in the white spirit drawing line. The
line was then changed before a second leak ocurred after 40 days in the same
location, causing the unit t obe shut down.
In the wake of shutting down the unit, several studies were conducted to find the
root cause and the most effective solution to the corrosion. Figure 4 highlights
possible corrosion types that can occur in crude towers, as clarified in the API
571 document. According to damage mechanisms, the most common corrosion types in
crude columns are outlined below.

HCl corrosion.
Processed crude oil in the Batman Refinery contains varying amounts of chloride,
calcium and magnesium salts (MgCl2), (CaCl2). The Hcl is envolved from the
hydrolysis of MgCl2 and CaCl2 during heating in the crude distillation unit (CDU)
preheat train and associated furnaces. The amount of salt in the crude oil is as
high 300 ppm. The efficiency of the desaltier is 95%+, and the salt value in the
desalter outlet can be decreased to approximately 10 - 15 ppm.
In overhead systems in the CDU tower, HCl does not usually cause corrosion
problems at temperatures of above the aqueous dew point. However, at temperatures
that are equal to or below the aqueous dew point, HCl readily dissolves in water
to form corrosive hydrocloric acid. Based on this, the column top temperature in
the Batman refinery was -10�C above the dew point due to the specification of
naphta drawn from the top of the column before the upsets. this can lead to the
formation of HCl corrosion in crude columns.
Another cause of HCl corrosion is mismeasurement of Cl- analysis, which is the most
important indicator of HCl formation in overhead systems.In normal operation
caustic can be given according to Cl- values. However, caustic was given as minimum
dosage because of low Cl- values in boot water. When investigating Cl- analysis ar
the refinery, it was observed that the standard Cl- laboratory method would not be
suitable for the specific reflux water used in the Batman Refinery. For this
reason, Cl- values were always lower than guarentee limit and not enough caustic
injection was given to prevent HCl fomation.

Ammonium chloride corrosion

Ammonium chloride (NH4Cl) salts area a type of under-deposit corrosion type, formed
by a reaction of HCl and NH3 at temperatures above the aqueous dew point. NH4Cl is
hygroscopic that can absorb moisture, even though water has not condensed. In fact,
a sufficient quantity of condensed water tends to dissolve abd remove NH4Cl salts
deposits. Wet NH4Cl is highly corrosive to many materials. When opened during
maintenance, NH4Cl formation was observed at naphta and in the white spirits trays
inside the crude column. This corrosion mechanism can generally be seen in the
overhead systems (overhead lines, exchangers, etc.) and it can be eliminated by
demolishing HCl formation using wash water in the overhead systems and neutralising
amine that has less potential for salt formatuon than ammonia. In the past, the
neutraliser injected in the columns was ammonia rather than neutralising amine. It
was fed through a pump to the column before the upsets. These double effects can
induce NH4Cl corrosion and damage to the trays and inside of the column.
Aside from the above corrosion types, on account of low API, high total acid number
(0.41 mg KOH/g) and sulfur content(5 wt%) of processed crude oil in the Batman
refinery (19 API), the occurrence of H2S, FeS and other corrosion due to the
acidity properties of crude oil were possible in crude towers.the actions taken to
prevent this problem will be explained in the following section of article.

Precaution and actions

To prevent similar problems to those outlined above, operational and chemical
precautions and actions were implemented.

Operational improvements
Dew point and column top temperature
One of the primary causes of corrosion is high dew point temperature, which systems
from high partial pressure of water in the overhead systems. The difference between
the column top temperature and dew point temperature should be a minimum of 15�C in
all refinery applications. For this reason, the column top temperature should be
increased. Within the scope, the T95 specification of naphtha was increased to 20�C
by contacting the planning department for the purpose of optimising the downstream
unit. Thanks to his action, the difference between dew point temperature and column
top temperature was 20-25�C, minimising the possibility of corrosion.

Dew point and stripping steam optimisation

When increasing the stripping steam in the column, the amount of vapour in the
overhead systems increases, leading to an increase in dew point temperature and the
occurrence of HCl corrosion. The stripping steam in Tupras refinery was above the
desired value to get bitumen specifications before improvement actions. Therefore,
to minimise the steam effect, the stripping steam was decreased to the point of
optimum steam value, providing stable column operation and on-specification bitumen
product. the ratio of stripping steam to feed amount is decreased from 12.7% to
11.6%. The effect of stripping steam optimisation provide an approximate 3-4�C
reduction in dew point temperature.

Overhead hydrocarbon load

in the refinery's rude towers, there is only a cold reflux system. This means that
all overhead hydrocarbons are condensed in the reflux drum and cold reflux is given
to the column. As it is moved to the overhead load, the dew point temperature can
be decreased. therefore, the top reflux value was increased as a ratio of
approximately 10% by decreasing the pump around amount in a controlled manner.
Consequently, dew point temperature was decreased by approximately 1-2�C.
Operational parameters before the upsets and after taking action are summarised in
table 1.

Water optimisation return to column and water quality.

the amount of water inside the columnn is a paremeter. in this case, the water
inside the naphtha was high and fed into the column via the top reflux. In order to
solve this issue, the naphtha level was increased carefully and the water level was
increased inversely in the top reflux drum.
thus, water in the naphtha was reduced to 50-70%. with the existence of water
minimised, the possibility of corrosion decreased.
In addition, the water quality of the overhead exchangers is very important for
removing salts deposits. If there is any O2 inside the water, this speeds up the
corrosion mechanism. For this reason, the boiler feed water in this case was
started before the overhead exchanger to wash away possible salt deposits after the
upsets.
Drawn white spirit amount and temperature
Two different leaks and fires were seen in the same location - at a line where
white spirits is drawn. After the first leak, the line was replaced, but the new
line leaked after 40 days.Before the leaks, fouling and plugged tubes at the
exchangers indicated that corrosion had formed.
To decrease fouling and corrosion, the white spirit drawing quantify was increased
to provide a high enough fluid velocity passing from lines and exchangers. Moreover
the drawing temperature was increased.

Chemical Improvements
while studying the reasons for corrosion in the crude towers, the chemical dosage
system and dosage amounts spplied in the refinery were investigated and compared
with other refineries.

Changing the location and type of chemicals.

Before upsets, ammonia was fed into the column at the side reflux line. Feeding the
ammonia directly into the column caused the formation of NH4Cl salt and, thus,
corrosion. In all chemical applications systems in crude unit, chemicals should be
given out of the line to avoid accumulating salts deposits. It was calculated that
the temperature of NH4Cl formation was 130�C before upset.
As such, all salts occurred inside the column, specially in the white spirit
section. Therefore, Tupras changed the location of the ammonia injection as a first
action,
Moreover, neutralising amine is more stable and has less potential to form salt and
its derivates. The differences between ammonia and neutralising amine are outlined
in table 2.
the refinery had an ongoing project for installing an amine skid system in its
crude towers. However, this project was expedited after upsets were experienced un
August 2016. From that point, neutralising amine has been given to the top of the
column. After changing chemicals to neutralising amine and talking all of the above
operational actions, NH4Cl formation caused the salt point to decrease form 130�C
to 102�C.
Clarified method of Cl- analysis and caustic optimisation
A low amount of caustic given to the desalter outled line was one of the root
causes of corrosion in the refinery's crude tower in 2016. the reason for given low
caustic dosage was mismeasurement of Cl- analysis. The boot water was within the
limit (<10 ppm) before upsets.
However, after conducting a laboratory analysis survey, it was identified that Cl-
analysis (S-STD-4500-Cl) was not an appropiate method for process reflux water. As
a result, tupras changed its Cl- analysis method and found that the Cl- values were
so high before the upsets due to low caustic dosages. To determine accurate Cl-
value, the amount of caustic was increased to optimum value and Cl- values were
within the limit value (<10ppm).

As shown in figure 5, the NH4Cl sublimation temperature increases with chloride

content in crude overhead water. During these upsets and high Cl- content in
overhead water, the NH4Cl formation temperature was around 120-140 �C, which
explains salt formation inside the column. SUbsequent to correcting the Cl-
analysis method, The NH4Cl formation temperature decreased to below 100�C, which
mean that NH4Cl salts could be carried outside of the column.
Futhermore, studies covering how the acidic effects is measured in white spirit
line after fires and upsets were examined and an experiment was conducted to
examine how the pH value of fresh water is reduced after mixing with water in white
spirit product.
This experiment was performed at the time of the upsets. Initially, the pH value of
the refinery's fresh water was 6.5. After mixing, the fresh water was separated
from the white spirit product by the Karl-Fischer Method and the pH value of the
mixed water decreased to 4. This reduction in pH value highlighted the acidic
effect of the white spirit section.
After correcting its method of Cl- analysis and increasing its caustic amount, the
pH value of fresh water can increase to approximately 6-7, with water inside white
spirit. It can be concluded that acidic effects, and thus corrosion, can be
decreased by means of caustic optimisation.

Chemical trials
The Batman refinery did not previusly have a chemical dosages programme managed by
one chemical company. All of the chemical belonged to different firms, which meant
that the performance of the chemicals was not monitored properly, and it was
impossible to know which chemicals were most suitable for the refinery.
A chemical firm was selected to manage the crude unit's entire chemical
performance. As a result of test-runs, demulsifier and neutralising amine began to
be injected and all related corrosion parameters, such as pH, Fe and Cl values,
were stabilised accordingly. The desalter and overhead system values were also
satisfied.

Conclusion
FOllowing the fires and upsets experienced in 2016, the refinery solved one of its
key problem: crude column corrosion. This was achieved by correcting Cl- analysis,
increasing top column temperature, stripping steam optimisation, increasing the
temperature and amount of white spirit drawn, reducing the amount of water in the
reflux drum, enhancing the quality of wash water, replacing the neutralier chemical
from ammonia to neutralising amine, decreasing the NH4Cl salt point from 130�C to
102�C, and changing the location of chemical according to best practices.

Taking these actions has considerably reduced the corrosion problem in crude
column, as shown in figure 6. Every month, an inspection team now measured overhead
and white spirit line thickness. Figure 6 shows little corrosion inside the column,
indicating good development in terms of corrosion and fouling in the columns. While
the corrosion seems under control, further decreases in corrosion should be seen.