Crude distillation overhead system”: Corrosion and Control.
M.A. Fajobi 1*, R.T. Loto 1 and O.O. Oluwole
Corrosion and crude distillation concept
Material and Control Mechanism
In crude distillation overhead system prevention and control of corrosion is highly necessary in
order to minimize huge cost of corrosion incurred from time to time.
Ameh et al. [37] stated that the control of corrosion in petrochemical equipment is done by
selecting high corrosive resistant materials and it is the core method of control. Another method
is the protective coatings and this helps to cover the layers of the steel materials used for crude
distillation overhead system [38]. Sometimes, the steel layers are painted or coated in order to
form a metallic lining or covering on the steel [21]. Bio-corrosion effect in petrochemical
equipment are also prevented by protective coatings [39]. Cathodic Protection as described by
Papavinasam [21] showed that reduction of corrosion in petrochemical equipment occurs by
minimizing the potentials difference across its cathode and anode. In addition, Hasan et al. [40]
showed that corrosion inhibitor is a chemical used in reducing the rate of corrosion occurrence on
materials used for crude distillation overhead system. Corrosion inhibition forms film protection
on surface of metallic structures of crude distillation overhead system [41]. This confirms that
corrosion inhibition on crude distillation overhead system is the most trusted,
proven and time-tested application in petrochemical industries.
Conclusion
The effect of corrosion in crude distillation overhead system has been reviewed pointing out that
contaminants from crude oil, such as chlorides, carbon dioxide, acids and sulfides etc, are the
main cause. As a result of these, they are exposed to contaminants which causes damage to them
by reducing their life span over time.
Among which are material selection, protective coating, cathodic protection and use of inhibitor.
Material selection showed great control measure over long period of time, while the use of
inhibitor turned out to be the most reliable and time tested in crude distillation overhead system.
CORROSION AND ITS CONTROL IN CRUDE OIL REFINING
PROCESS
Palash Kumar Bhowmik1, MD. Emam Hossain2 and Jubair Ahmed Shamim2
1. INTRODUCTION
Corrosion in crude oil refining units is a common problem worldwide and the most important corrosion is
overhead corrosion. Due to the variation of process fluid chemical composition and the process parameter like;
temperature, pressure, pH and moisture etc, the percentage of corrosive components is diverse in the refining
process system [1]. As a result various corrosion problems will arise and that forces to adopt different types of
preventive actions to minimize the corrosion affects.
Respective chemical dosing, inhibitor dosing, water dosing, suitable desalting, using proper materials
and maintaining appropriate operating process parameter to minimize the corrosion affects economically is also
recommended in this paper. The general practice of preventing corrosion problem in crude oil refining process
of Eastern Refinery Limited, Bangladesh is taken as a reference to give a clear understanding about the practical
practice and the standard.
2. CORROSION IN CRUDE OIL REFINING PROCESS
The corrosion problem in refining operations can be divided into three groups- corrosion from components
present in the crude oil, corrosion from chemicals used in refinery processes and environmental corrosion
2.1 Sources of Corrosion:
The corrosion problem attributed to constituents presents in the crude oil are mainly for hydrogen chloride,
organic and inorganic chlorides, hydrogen sulfide, mercaptans and organic sulfur compounds, carbon dioxide,
dissolved oxygen and water, organic acids and nitrogen compounds [1].
2.2 Corrosion Location and Types
In the bellow table the corrosive compounds in different location and equipment of crude oil refining
process are given
From the above table it easy to predict that the corrosive compounds in crude oil refining process is
mainly HCl, H2S, organic and inorganic Cl and S compounds. Due to different types of corrosive
compounds different type of corrosion occurs in crude oil refining process plant. To control this corrosion
relevant chemical dosing is used in suitable location of the process system that are represented in figure 1.
2.3 Corrosion Due to HCl, Inorganic and Organic Chloride [1] [2]
Because brine is produced along with the crude oil, and the separation of crude from brine is not perfect, all
crudes contain salt of NaCl, and MgCl2 that dissolved in water and then form HCl by hydrolysis at 300~400ºF.
Dry HCl is not corrosive but when it mixes with water it becomes highly corrosive. After forming HCl it passes
through pre heat exchanger, furnace and entered to the
distillation column. At the top of distillation column where temperature is low, near about 135ºC and becomes
lower in overhead lines that finally cause corrosion as it get contact with water at 100 ºC.
HCl make reaction with iron (Fe), causes corrosion.
Fe + HCl FeCl2 + H2 (1)
With the presence of H2S this above reaction repeats several times and cause more corrosion.
FeCl2+ H2S FeS + 2HCl (2)
To lessen this corrosion NH3, NaOH and organic corrosion inhibitors are properly dosed in overhead
system and pH of water should maintain higher than 5. Top temperature of the crude distillation column should
higher than the water dew point (100 ºC).
2.4 Corrosion due to H2S and S-compounds
These corrosive components are presents in crude oil or formed by the decomposition of S (sulfur) components
in the process. Here, corrosion is depends on the presence of S components and process temperature.
2.4.1 Sulfur Corrosion at Low and Intermediate Temperature [1]
H2S cause corrosion even at atmospheric temperature. These corrosive components are presents in crude oil or
formed by the decomposition of S (sulfur) components H2S make reaction with iron (Fe) and creates iron
sulphide scale in the overhead systems of distillation equipment where water is presents.
Fe + H2S FeS + H2 (3)
If HCl presents it dissolves the scale and generating more H 2S which ultimately exposing fresh metal surface.
FeS + 2HCl FeCl2 + H2S (4)
Corrosion caused by H2S is hydrogen blistering and hydrogen embrittlement.
2.10 CUI
Carbon steel is the most common material of construction for refinery equipment is corroded because
of the presence of water and oxygen mainly in the [Link] corrosion can be lessening by eliminating the
water from the surface of the metal by means of a protective barrier or coating. Other types of atmospheric
corrosion are: corrosion under insulation or fireproofing, corrosion
of pipeline, corrosion of structures and cooling water corrosion.
3. PREVENTIVE ACTION TO MINIMIZE CORROSION
The following preventive actions are taken to minimize the corrosion affect in crude oil refining
process plant-
3.1 Desalting:
Crude oils are complex mixtures that contain high
degree of impurities such as water, salts, solids and
metals. Thus impurities have adverse effects like
corrosion, fouling and unit upsets. The main purpose of
using desalter is to remove the salts typically calcium,
magnesium and sodium to minimize corrosion. Among
the different type of desalting, electric desalting is better
in performance than other type like: settling techniques
and centrifugal separation. It also require less time and
cost. Desalting and dehydration is achieved
simultaneously with a spectacular removal of more than
90% of salt from raw crude oil in just less than half an
hour.
Performance of electric desalting system depends on
the following key parameters: crude oil properties,
desalting temperature, pressure, pH, residence time,
water wash quality and rate, wash water mixing and
finally effective separation. For effective desalting
required temperature 120~260ºC, pressure 5~6 kg/cm2
and pH 505~7.0. Chemical assistance (termed as emulsion breaker, wetting agents, and/or demulsifiers) is
extremely important for the desalting operation. The
Power consumption is also very small, frequently of the
order 0.01 KWhr per barrel. Experience shows that
chloride content of the desalted crude that exceeds 20
ppm have the potential of leading significant corrosion
and fouling issue in overhead lines.
3.2 Chemical Dosing Chemical dosing in crude oil refining process for
preventing corrosion are widely vary with crude type,
equipment and operating parameters. The common
chemical dosing for this purpose is given bellow-
3.2.1 Emulsion Breakers or Demulsifiers This is the chemical that assists the desalting operation.
It will not only enhance the speed of separation, but will
assist residence time, improve solids removal, minimize
water carryover/ oil under carry and reduce the emulsion
layer. For effective performance it must be well dispersed
before it arrives in the desalting vessel, normally injected
into suction of the crude charge pump.
Recommended dose limit is few ppm to about 100
ppm. In ERL practice dose is about 6 ppm of crude oil
that is 6kg of separol/ 1000MT of crude oil. Overdosing
must be avoided because it incurs the risk of reversing
the emulsion [2].
3.2.2 Caustic Soda Injection
Crude contains water and inorganic salts NaCl, MgCl2
and CaCl2. Hydrolysis of CaCl2 and MgCl2 occurs when
crude oil is heated in the pre heat exchangers and fired
heater (furnace). The hydrolysis of gaseous HCl as
depicted in the following chemical reaction [1] [5]-
CaCl2 + H2O Ca(OH)2 + 2 HCl >120 ºC (5)
MgCl2 + H2O Mg(OH)2 + 2 HCl >205 ºC (6)
NaCl + H2O NaOH + HCl >480 ºC (7)
Furnace outlet crude temperature typically ranges frome 360~380 ºC in which NaCl is mostly stable butmost
MgCl2 and 20~50% of CaCl2 are hydrolysed Caustic is added to the crude charge, downstream of the desalter, to
react with MgCl2 and CaCl2 , forming the more stable NaCl. Caustic also reacts with any HCl vapour product
and produce more stable NaCl and accumulates
in the distillation column bottoms, rather than the overhead system. The exact amount of caustic injection is
based on the Cl content of the water in the crude-column overhead reflux drum. A reasonable Cl target is 10~20
ppm. For most situation the maximum caustic injection rate is 2.27 kg/1000 bbl crude [5]. In ERL practice
caustic dose is about 5~10 ppm of crude oil that is 0.66~0.32 kg NaOH / 1000 bbl of crude oil [2]. Overdosing
must be avoided because it incurs general
corrosion of carbon steel, stress corrosion cracking of non-post weld heat treated carbon steel, stainless steel and
nickel alloys.
3.2.3 Neutralizer (NH3) Injection
Ammonia is used in the refining industry for the neutralization of acidic components in such locations as the
overhead streams. HCl condensation in the overhead systems causes severe strong acid attack if neutralization is
not provided. Water dew point pH values as low as 1.5 have observed where neutralization feed was interrupted.
NH3 injection adjust the condensed water pH to near
neutral (5.5~6.5), therefore reducing the corrosion. Water
dosing is recommended to avoid NH4Cl fouling effect.
NH3 + HCl = NH4Cl
Disadvantages of improper NH3 injection, where this
material is permitted to contact copper-base alloys in pH
ranges of 8.0 and above, severe corrosion in the form of
general metal loss and stress corrosion cracking will
occur. Moreover NH3 attack of copper- alloy equipment
may result sever fouling.
3.3.4 Corrosion InhibitorMost corrosion control program includes the injection
of proprietary film forming organic inhibitors;
commonly referred to as “filmers”. This inhibitor
establish a continuously replenished thin film which
forms a protective barrier between acids in the system &
the metal surface underneath the film. For maximum
results, proper pH control of the system is essential.
Generally, it is dosed to overhead of the crude distillation
column just before the aero-condenser to prevent
corrosion of aero-condenser tubes. A typical injection rate is of the order of 3~5 vppm for
operation [6]. During startup or unit upset, injection
results may be temporarily increased to levels such as 12
vppm to help establish on reestablish the protective film.
3.3.5 Water Dosing Water is added with the crude in desalter for ensuring
proper salt separation. De-mineralized water is also
dosed in the overhead systems to scrubs salt (NH4Cl) and
to raise the pH at the dew point. Further care should be
taken to assure separator vessels to promote good
separation of water and hydrocarbon to prevent reflux of
water containing salt back to the crude column.
Excessive water dose may results in erosion issues and
grooving the lines. Too little water dose can just add to
the acid making process. Water contain high dissolve
oxygen can dramatically accelerate corrosion. The ideal
water injection rate is 5~10% of the overhead stream. The most effective and reliable water wash systems
should have the characteristics: sufficient water with an
excess of 25~50% at all times, injection in a location that
will provide distribution of water to all the bundles and a
high pressure drop atomizing spray nozzle to provide
good liquid-vapor contact.
3.4 Proper Material Selection Most petroleum and petrochemical refinery
construction materials fall into the following general
categories : carbon steels, carbon-molybdenum and
chromium-molybdenum alloy steels, martensitic and
ferritic chromium stainless steels, austenitic
chromium-nickel stainless steels, copper alloys (brass,
bronze, cupro-nickel), nickel alloys (nickel, monel,
inconel, incoloy), aluminum alloys, titanium and
hastelloys etc. A brief of commonly used material and
protective cladding for lessening corrosion affects due to respective corrosion compounds are given below-
(l) HCl, organic and inorganic chloride- Monel is
generally resistant to corrosion by weak HCl and is
commonly used in the top section of crude towers,
condensers and distillate drum liners, and in pipe still
overhead systems. So protective monel cladding is used
at the top portion of crude distillation column. Typical
corrosion rates for monel is very up to 0.002 inch/ year.
(2) H2S, organic sulfur compounds- The straight
Cr-steel, 12% Cr and those with ½~1% Mo, such as
5,7,9% Cr have good resistance to this corrosion. In
addition, the austenitic stainless steels such as
18Cr-8nickle steel have excellent corrosion resistance.
(3) CO2- Monel, Al, SS and Carpo-Nickel are good
against the corrosion due to CO2. The attack of wet CO2
on steel is lessened by the addition of Cr (12%), although
tpe 304 SS is widely used and found most satisfactory.
(4) Organic acid- Cu alloys have more resistance then
steel and 5~9Cr Steel for corrosion due to organic acid,
but Cr-Ni SS (type 316) is very resistance to napthalic
acid corrosion [1] [4].
(5) Nitrogen compounds- Stainless steel or plastic
lying may be required for protection against corrosion
due to N compounds.
4. CORROSION MEASURMENT AND MONITOR In the crude oil refining process plant, most and sever
corrosion occurs during plant start up and unstable
emergency shutdown period. Ninety percent of crude
unit overhead corrosion occurs during just 10% of
operating time. This period of unstable operation may
occur during crude tank switches, slop oil processing,
processing of opportunity crudes, or other interruptions
to normal operation. The following methods are used to
ensure efficiency and effectiveness of crude unit
corrosion control programs-
(l) Water analysis- for pH, metal, chloride & hardness
(2) Hydrocarbon analysis- inhibitor, residual & metals
(3)Corrosion rate measurement by- electrical
resistance probe, weight loss coupon and linear
polarization resistance probe
(4) On stream non-destructive examination by UT
(ultrasonic thickness gauging) or RT (radiography test).
5. RECOMMENDED PREVENTIVE ACTION To minimize the corrosion affects in crude oil refining
process plant the following preventive action can be
taken which are proved fruitful and effective-
(l) Determine the crude nature especially chloride salts, sulfurs content and acid number for the purpose of
developing a proper corrosion management strategy.
(2) Maintain suitable operating process parameter like temperature, pressure, pH and water content that control
corrosion without interrupting the main process system.
(3) Apply all chemical dosing without interruption. During start up or unit upsets, corrosion inhibitor
injection may be temporarily increased to higher levels then normal.
(4) Ensure effective crude desalting and proper material selection.
(6) Effective corrosion measurement tools should installed in proper location and corrosion trends should be
analyzed to take necessary preventive action.
6. CONCLUSION
Measuring the corrosion rate and type and then taking feedback actions are not effective enough. Without
accurate, frequent and timely testing, corrosive incidents may be completely missed or discovered only after
significant damage has occurred. So that preventive action should be taken in a systematic way. To ensure
higher efficiency, effectiveness and reliability of corrosion management program in an economical way, this
paper would be a great scope. It will also provide better flexibility in customization of corrosion control with
minimum effort. The paper has furnished itself to study the integral parts of the entire process, their
implementation and the problems that can occur have
also been investigated with due importance.
7. NOMENCLATURE
Symbol Meaning
HCl Hydrochloric acid
H2S Hydrogen sulfide
S Sulfur
Fe Iron
Cl Chloride
NaCl Sodium chloride
MgCl2 Magnesium chloride
CaCl2 Calcium chloride
FeCl2 Ferrous chloride
NaOH Sodium hydroxide
Ca(OH)2 Calcium hydroxide
Mg(OH)2 Magnesium hydroxide
FeS Ferrous sulfide
NH3 Ammonia
Cr Chromium
Ni Nickel
SS Stainless steel
N Nitrogen
H2 Hydrogen gas
Cl2 Chlorine
Mo Monel
NH4Cl Ammonium chloride
CO2 Carbon dioxide
Corrosion prevention of crude and vacuum distillation column
overheads in a petroleum refinery: A field monitoring study
