Proceedings of the 6th International Mechanical Engineering Conference &

14th Annual Paper Meet (6IMEC&14APM) 28-29 September 2012, Dhaka, Bangladesh

IMEC&APM-ABS-000

CORROSION AND ITS CONTROL IN CRUDE OIL REFINING

PROCESS
Palash Kumar Bhowmik1, MD. Emam Hossain2 and Jubair Ahmed Shamim2
1
Assistant Manager, Department of Instrumentation and Communication, Eastern Refinery Limited,
Chittagong, Bangladesh, E-mail: pkbcuet@yahoo.com
2
Assistant Manager, Department of Inspection, Eastern Refinery Limited, Chittagong, Bangladesh

ABSTRACT
Corrosion has always been a major problem in the crude oil refining industry. It becomes more numerous
and complex within the recent decades due to the rising expenditure of materials and labor. The purpose of
this paper is to discuss about the corrosive element encountered in crude oil refining process, how these
results in deterioration of equipment and the preventive action to minimize the corrosion affects. The
corrosion problem attributed to constituents present in crude oil and the chemicals used in crude oil refining
process are focused as the main sources of corrosion in this paper. Authors wish that this study will helps
the professionals to get a clear understanding about the cause, effect and preventive action of corrosion
problem in chemical process plants and oil refining industries.

Keywords: Crude oil refining process, Corrosion components, Corrosion problem and preventive action.

1. INTRODUCTION
Corrosion in crude oil refining units is a common 2.2 Corrosion Location and Types
problem worldwide and the most important corrosion is In the bellow table the corrosive compounds in
overhead corrosion. Due to the variation of process fluid different location and equipment of crude oil refining
chemical composition and the process parameter like; process are given-
temperature, pressure, pH and moisture etc, the
percentage of corrosive components is diverse in the Table 1: Corrosive compounds according to the location/
refining process system [1]. As a result various corrosion equipment in crude oil refining process [1] [6] .
problems will arise and that forces to adopt different Location/
Corrosive compounds
types of preventive actions to minimize the corrosion equipment
affects. Respective chemical dosing, inhibitor dosing, HCl, H2S, dissolve O2 and
Tank
water dosing, suitable desalting, using proper materials water
and maintaining appropriate operating process parameter Preheat
HCl, H2S
to minimize the corrosion affects economically is also exchanger
recommended in this paper. The general practice of Furnace H2S and S-compounds
preventing corrosion problem in crude oil refining H2S, S-compounds and
Flash zone
process of Eastern Refinery Limited, Bangladesh is taken organic acids
as a reference to give a clear understanding about the Middle zone H2S
practical practice and the standard. Top zone HCl and water
Tower overhead
2. CORROSION IN CRUDE OIL REFINING HCl, H2S and water
system
PROCESS Bottom
The corrosion problem in refining operations can be H2S and S-compounds
exchanger
divided into three groups- corrosion from components
present in the crude oil, corrosion from chemicals used in From the above table it easy to predict that the
refinery processes and environmental corrosion [1]. corrosive compounds in crude oil refining process is
2.1 Sources of Corrosion mainly HCl, H2S, organic and inorganic Cl and S
The corrosion problem attributed to constituents compounds. Due to different types of corrosive
presents in the crude oil are mainly for hydrogen chloride, compounds different type of corrosion occurs in crude oil
organic and inorganic chlorides, hydrogen sulfide, refining process plant. To control this corrosion relevant
mercaptans and organic sulfur compounds, carbon chemical dosing is used in suitable location of the
dioxide, dissolved oxygen and water, organic acids and process system that are represented in figure 1.
nitrogen compounds [1].

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Fig 1. Chemical dosing in crude oil refining process
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 300~400F.
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 135C and becomes
lower in overhead lines that finally cause corrosion as it
get contact with water at 100 C.
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 C).
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 sulfide
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 H2S which ultimately exposing fresh metal surface.
FeS + 2HCl FeCl2 + H2S (4)
Corrosion caused by H2S is hydrogen blistering and
hydrogen embrittlement.
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2.4.2 High Temperature Sulfur Corrosion [1][4]
Temperature plays important parts in corrosion by H2S.
In refineries that process sour crude oils, severe
corrosion may occur in crude oil distillation units in
those locations where the metal temperatures exceed
450F. At this temperature and above, decomposition of
S compounds to H2S, and rates as high as 0.5 in. per year
have occurred in carbon steel furnace tubes. This
corrosion occurs in the equipment where metal
temperature within 450F~900F. Above 900F,
corrosion reduced due to coke formation that acts a
protective coating on metal surface.
2.4.3 High Temperature Sulfur Corrosion in
Presence of Hydrogen (H2)
The presence of hydrogen, for example hydro-treating
and hydro-cracking operations, increases the severity of
high temperature sulfide corrosion. H2 converts almost
all detectable sulfur to H2S and corrosion becomes a
function of either partial pressure or H2S concentration.
2.5 Corrosion due CO2
CO2 is combined with water and cause corrosion.
These CO2 is formed from decomposition of bicarbonate
or steam used to aid distillation. Corrosion by CO2 is
very severe which cause metal dissolution, inter-granular
affects and provide the environment for stress corrosion
cracks. Appreciable corrosion occur in carbonic acid
solution at a pH of 6.0.
2.6 Corrosion due to Dissolve Oxygen & Water
While moisture and oxygen in storage tanks may be
introduced with the oil, much of it is drawn into the tanks
by breathing during temperature changes and pumpings.
The amount of moisture and oxygen, and consequently
the corrosion rate, is therefore proportional to the number
of temperature changes and the number of pumpings.
The moisture condenses on the roof and the shell, and
corrosion occurs in the vapor space.
2.7 Corrosion due to organic acids
Organic acids are not very corrosive at low
temperatures. At their boiling temperatures, however,
these acids are very corrosive, the most severe form of
which generally occurs upon condensation. Under these
conditions, corrosion rates as high as 0.35 in. per year has
been reported on carbon steel.
2.8 Corrosion due to Nitrogen (N) compounds
Organic nitrogen compounds in crude oil alone do not
contribute to a corrosion problem unless converted to
ammonia or hydrogen cyanide. This occurs primarily in
catalytic cracking, hydro-treating and hydro-cracking
operations where, the ammonia and hydrogen cyanide, in
combination with H2S and other constituents, become the
highly corrosive to carbon steel.
2.9 Corrosion due to Chemical used in Refining
Process
Corrosion caused by frequently used chemicals in
crude oil refining process are sulfuric acid, caustic,
ammonia and chlorine. Sulfuric acid at lower
concentrations (bellow 85%) used in water treatment
plant cause prominent corrosion affect to carbon steel in
the form of pits or general metal loss with pits. Caustic
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and ammonia are mainly used in refinery operations for
the neutralization of acid components but improper or
over dosing of them causes metal loss or stress corrosion
cracking to carbon steel and copper-base alloys.
2.10 Environmental Corrosion
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 surface.
This 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.
The principle in this separation is very simple; under a
charged electric field the polar molecules orients. A
potential of 20~70kV is applied between electrodes
though which crude is passed. Water presents in the form
of emulsion also coalesces and agglomerates in to a
stream entrapping all the salts in this process. Brine
collects at the bottom of the desalter, which crude floats
above and forms a separate stream [1].
Fig 2. Electric desalting system schematic diagram
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 120~260C, pressure 5~6 kg/cm2
and pH 505~7.0. Chemical assistance (termed as
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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 C (5)
MgCl2 + H2O Mg(OH)2 + 2 HCl >205 C (6)
NaCl + H2O NaOH + HCl >480 C (7)
Furnace outlet crude temperature typically ranges
frome 360~380 C in which NaCl is mostly stable but
most MgCl2 and 20~50% of CaCl2 are hydrolyzed.
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 vapor
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 [5]. 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 [1] [3] [6]
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.
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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 (8)
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 Inhibitor
Most 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.
In ERL practice, this dose is about 5~15 ppm of TG (total
gasoline) that is 0.60~1.7 kg of TG/ 1000 bbl of crude oil
[2]. Inhibitors are non-corrosive to equipment at
treatment dosage dilutions, but near 100% concentration
they may be corrosive to injection equipment.
3.3.5 Water Dosing [1] [6]
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 [1] [2] [6]
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-
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(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 ~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.
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6. CONCLUSION
Measuring the corrosion rate and type and then taking 7. NOMENCLATURE
feedback actions are not effective enough. Without
accurate, frequent and timely testing, corrosive incidents Symbol Meaning
may be completely missed or discovered only after HCl Hydrochloric acid
significant damage has occurred. So that preventive H2S Hydrogen sulfide
action should be taken in a systematic way. To ensure S Sulfur
higher efficiency, effectiveness and reliability of Fe Iron
corrosion management program in an economical way, Cl Chloride
this paper would be a great scope. It will also provide NaCl Sodium chloride
better flexibility in customization of corrosion control MgCl2 Magnesium chloride
with minimum effort. The paper has furnished itself to CaCl2 Calcium chloride
study the integral parts of the entire process, their FeCl2 Ferrous chloride
implementation and the problems that can occur have NaOH Sodium hydroxide
also been investigated with due importance. Ca(OH)2 Calcium hydroxide
Mg(OH)2 Magnesium hydroxide
7. REFERENCES FeS Ferrous sulfide
NH3 Ammonia
1. Guide for Inspection of Refinery Equipment; Cr Chromium
Chapter-II, Condition Causing Deterioration of Ni Nickel
Failures, Page8-15. SS Stainless steel
2. Operation Guidelines and Process Operation Data N Nitrogen
of Eastern Refinery Limited, Chittagong, H2 Hydrogen gas
Bangladesh. Cl2 Chlorine
3. Corrosion in Crude Distillation Unit Overhead Mo Monel
Operations: A Comprehensive Review; NACE NH4Cl Ammonium chloride
Paper No.11360. CO2 Carbon dioxide
4. Experience with Naphthenic Acid Corrosion in
Low TAN Crudes; NACE Paper No.08551.
5. Refinery Caustic Injection Systems: Design,
Operation and Case Studies; NACE Paper
No.08551.
6. Crude Unit Corrosion and Corrosion Control;
Technical Paper- GE.

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