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CORROSION CHALLENGES IN PETROLEUM REFINERY AND PETROCHEMICAL

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Technical Report · May 2013

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 A TERM PAPER ON

CORROSION CHALLENGES IN
PETROLEUM REFINEEY AND
PETROCHEMICAL INDUSTRY

BY

OKORO FAITH EFEREMO (08CN08413)

OJURI OLUWAFUNTO IBININUOLAOLUWA (08CN08410)
ONOCHIE JIDECHUKWUADEDAYO (08CN08421)
OKOBOH STEPHEN (08CN08411)
ADELAJA OLUAWTOBI VICTOR(08CN08366)
PETROLEUM ENGINEERING DEPARTMENT

COVENANT UNIVERSITY

BEING A PAPER SUBMITTED AS A REQUIREMENT

FOR PET 525: PETROLEUM REFINEERY

MAY 2013

1 CORROSION CHALLENGES IN PETROLEUM REFINEERY AND PETROCHEMICAL INDUSTRY

 TABLE OF CONTENT

ABSTRACT.......................................................................................................................... 3

1. INTRODUCTION......................................................................................................... 4-5
2. AREAS OF MAJOR CORROSION IMPACT……………………………………… 6
2.1. Water Related Corrosion………………………………………………………… 6
2.2. Processing Related Corrosion…….……………………………………………… 6-7
2.3. Naphthenic Related Corrosion……………………………………………........... 7
3. MATERIALS OF CONSTRUCTION……………………………………………… 8
3.1. Introduction…………………………………………………………………….. 8
3.2. Column…………….………………………………………………………….... 8-9
3.3. Exchangers and Piping………………………………………….......................... 9-11
3.4. Fired Heaters………………………………………..…………………………. 11
4. MATERIALS AND CORROSION CHALLENGES………………………………. 12
4.1. Introduction……………………………………………………………………. 12
4.2. Inorganic Salt…………………………………………………………………. 12-13
4.3. Sulphur Compound…………………………………………………………… 13-14
4.4. Organic Acid…..…………………………………………………………….… 14
4.5. Organic Chloride………………………………………………………………… 14
5. CASE STUDY……………………………….………………………………………… 15
5.1. Corrosion Related Failure in the Refinery…………………………………….. 15
6. THE WAY FORWARD………………………………….……………………..…. 16-18
7. REFERENCES……………………………………………………………………….. 19-20

2 CORROSION CHALLENGES IN PETROLEUM REFINEERY AND PETROCHEMICAL INDUSTRY

 ABSTRACT

Many corrosion problems have occurred with related ecological damage, during the 90 years of
the existence of the oil refining industry. Many corrosion problems have been solved. Some of
them have not. Why? Sometimes corrosion damages occur at certain facilities, but not at others.
A lot of companies manufacture different materials and equipment for corrosion control and
monitoring. In spite of this, corrosion problems remain the main danger to the oil refining and
petrochemical industry.
The aim of this work is to survey the corrosion situation at the oil refining industry and
petrochemical industry in order to estimate cost of corrosion; to define the reasons for corrosion
problems and to find effective measures to solve them, and, as a result, to improve reliability,
availability and profitability at the refinery facilities including ecology.
Every industry, even every plant, has its own distribution of corrosion phenomena that occur
with different frequency. About 75% of all corrosion failures happened because of insufficient
information and knowledge, as well as inadequate interaction among different groups responsible
for the acceptance and approval of anti-corrosion decisions. The human factor was the main
reason of corrosion failures. Anti - corrosion management must be designed in such a manner
that will increase human potential in performance of correct decisions. The corrosion risk is
related to environmental pollution by hazardous chemicals, fuels, and gases, resulting in possible
fires and explosions, damage to people, animals, plants, air, soil and water. The causes of
corrosion damage of aboveground storage tanks, pipes, heat exchangers, and other equipment, as
well as preventive measures are analyzed. Most corrosion costs can be saved and quality
improved by means of control measures, and analysis of failures, dissemination of knowledge,
and use of monitoring techniques.

3 CORROSION CHALLENGES IN PETROLEUM REFINEERY AND PETROCHEMICAL INDUSTRY

 1.0. INTRODUCTION

Petroleum refining begins with the desalting (dehydration) of feedstock followed by distillation,
or fractionation, of crude oils into separate hydrocarbon groups. The resultant products are
directly related to the characteristics of the crude oil processed. Most distillation products are
further converted into more usable products by changing the size and structure of the
hydrocarbon molecules through cracking, reforming, and other conversion processes as
discussed in this sector. These converted products are then subjected to various treatment and
separation processes, such as extraction, hydro-treating, and sweetening to remove undesirable
constituents and improve product quality. Integrated refineries incorporate fractionation,
conversion, treatment, and blending operations, and may also include petrochemical processing.
An outline of the refining process is shown in the figure below

Figure 1.0: Outline of the Refining Process

4 CORROSION CHALLENGES IN PETROLEUM REFINEERY AND PETROCHEMICAL INDUSTRY

Crude oil often contains water, inorganic salts, suspended solids, and water-soluble trace metals.
As a first step in the refining process, to reduce corrosion, plugging, and fouling of equipment
and to prevent poisoning the catalysts in processing units, these contaminants must be removed
by desalting (dehydration). The two most typical methods of crude oil desalting – chemical and
electrostatic separation – use hot water as the extraction agent. In chemical desalting, water and
chemical surfactants (demulsifiers) are added to the crude and heated so that salts and other
impurities dissolve into the water or attach to the water, and are then held in a tank where they
settle out. Electrical desalting is the application of high-voltage electrostatic charges to
concentrate-suspended water globules in the bottom of the settling tank. Surfactants are added
only when the crude has a large amount of suspended solids. Both methods of desalting are
continuous. A third and less common process involves filtering heated crude using diatomaceous
earth. After desalting, crude oil is continuously drawn from the top of the settling tanks and sent
to the crude distillation (fractionating) tower. Fractionation (distillation) is the separation of
crude oil in atmospheric and vacuum distillation towers into groups of hydrocarbon compounds
of differing boiling-point ranges called fractions or cuts. Conversion processes change the size
and/or structure of hydrocarbon molecules. These processes include decomposition (dividing) by
thermal and catalytic cracking, unification (combining) through alkylation and polymerization,
and alteration (rearranging) with isomerization and catalytic reforming. Treatment processes are
intended to prepare hydrocarbon streams for additional processing and to prepare finished
products. Treatment may include the removal or separation of aromatics and naphthenes, as well
as impurities and undesirable contaminants. Treatment may involve chemical or physical
separation such as dissolving, absorption, or precipitation using a variety and combination of
processes, including desalting, drying, hydrodesulfurizing, solvent refining, sweetening, solvent
extraction, and solvent dewaxing. Formulating and blending is the process of mixing and
combining hydrocarbon fractions, additives, and other components to produce finished products
with specific performance properties. Other refinery operations include light-end recovery, sour-
water stripping, solid waste and wastewater treatment, process-water treatment and cooling,
storage and handling, product movement, hydrogen production, acid and tail-gas treatment, and
sulfur recovery.

5 CORROSION CHALLENGES IN PETROLEUM REFINEERY AND PETROCHEMICAL INDUSTRY

 2.0. AREAS OF MAJOR CORROSION IMPACT

2.1. WATER RELATED CORROSION

Crude oil desalting and distillation generates considerable wastewater. Typical wastewater flow
from a desalter is approximately 8 L (2.1 gal) of water per barrel of oil processed. This water
contains accelerative corrosive components such as H2S, CO2, chlorides, and high levels of
dissolved solids. The wastewater also contains a fraction of crude oil, which may be recovered
during the water treatment process.

In addition to generated wastewater, cooling water (either fresh water or saltwater) is used
extensively in refining operations. The corrosivity of the cooling water varies greatly depending
on the process, so it is difficult to describe typical cooling water problems; however, corrosivity
is highly dependent upon the level and type of dissolved solids and gases in the cooling water,
including chlorides, oxygen, dissolved gases, and microbes. Cooling water temperature can also
affect corrosivity.

Figure 2.1: Effect of Microorganism on the bottom of a Crude Storage Tank

2.2. PROCESSING RELATED CORROSION

The top section of a crude unit can be subjected to a multitude of corrosive species. Hydrochloric
acid, formed from the hydrolysis of calcium and magnesium chlorides, is the principal strong
acid responsible for corrosion in the crude unit top section. Carbon dioxide is released from
crudes typically produced in CO2-flooded fields and crudes that contain a high content of

6 CORROSION CHALLENGES IN PETROLEUM REFINEERY AND PETROCHEMICAL INDUSTRY

naphthenic acid. Low molecular fatty acids such as formic, acetic, propionic, and butanoic acids
are released from crudes with a high content of naphthenic acid. Hydrogen sulfide, released from
sour crudes, significantly increases corrosion of the crude unit top section. Sulfuric and sulfurous
acids, formed by either oxidation of H2S or direct condensation of SO2 and SO3, also increase
corrosion.
2.3. NAPHTHENIC CORROSION
High-temperature crude corrosivity of distillation units is a major concern of the refining
industry. The presence of naphthenic acid and sulfur compounds considerably increases
corrosion in the high temperature parts of the distillation units and, therefore, equipment failures
have become a critical safety and reliability issue. Naphthenic acid is the generic name used for
all of the organic acids present in crude oils. Most of these acids are believed to have the
chemical formula R(CH2)nCOOH, where R is a cyclopentane ring and n is typically greater than
12. In addition to R(CH2)nCOOH, a multitude of other acidic organic compounds are also
present; however, not all of them have been analyzed to date. Isolated deep pits in partially
passivated areas and/or impingement attack in essentially passivation-free areas are typical of
naphthenic acid corrosion (NAC). Damage is in the form of unexpected high corrosion rates on
alloys that would normally be expected to resist sulfidic corrosion. In many cases, even very
highly alloyed materials (i.e., 12 Cr, AISI types 316 and 317) have been found to exhibit
sensitivity to corrosion under these conditions. NAC is differentiated from sulfidic corrosion by
the nature of the corrosion (pitting and impingement) and by its severe attack at high velocities in
crude distillation units. Crude feedstock heaters, furnaces, transfer lines, feed and reflux sections
of columns, atmospheric and vacuum columns, heat exchangers, and condensers are among the
types of equipment subject to this type of corrosion.

Figure 2.2: Effect of corrosion on Heat Exchanger Tubes

7 CORROSION CHALLENGES IN PETROLEUM REFINEERY AND PETROCHEMICAL INDUSTRY

 3.0. MATERIALS OF CONSTRUCTION

3.1. INTRODUCTION

The majority of the equipment in a Crude Unit is made of carbon steel regardless of whether the
crude slate is “sweet” or “sour.” The term sour refers to the release of H2S, but is often applied to
a crude oil based on its sulfur content, with less than 0.5 wt% sulfur called “sweet” or greater
than 1.0% called sour. This use of carbon steel is possible because at temperatures below about
450°F (230°C), except for the pre-flash and atmospheric column overhead systems, the streams
are essentially non-corrosive to carbon temperatures exceed 450°F (230°C), problems with high
temperature sulfur attack and naphthenic acid corrosion may begin. In the over-head system, the
formation of acidic deposits of condensates occurs below at about 250°F (120°C), and often
necessitates the use of highly alloyed materials. The purpose of this section is to point out where
problems occur in major equipment and systems, and to discuss the materials commonly used to
alleviate those problems.

3.2. COLUMNS

Figure 3.1: Columns

In a Crude Unit designed to process “sweet” crude, the Pre-flash Column will typically have
UNS 04400 cladding in the top zone which operates near or below the dew point. The remainder
of the shell will be bare carbon steel. This Ni-Cu alloy will be corroded by sulfur compounds
above about 350°F (177°C). Since the inlet temperature is about 500°F (260°C), crude units
typically have a 12% chrome lining in the bottom to protect against sulfur corrosion.

8 CORROSION CHALLENGES IN PETROLEUM REFINEERY AND PETROCHEMICAL INDUSTRY

The Atmospheric Column is commonly lined more extensively than the Pre-flash Column
because the feed, at about 690°F (365OC), is not only hotter, but also contains larger amounts of
HCl and H2S. The top of the column is often lined with UNS 04400 to protect against
condensing HCl. Even though the top temperature may be above the water dew point, the
addition of “cold” reflux can cause localized condensation and conditions extremely corrosive to
carbon steel. Typically, the lower 2/3 to 3/4 of the column will be lined with 12% chrome
cladding to protect against high temperature sulfur corrosion. In the area of the feed inlet, or
flash zone, Type 316 stainless steel may be required in those plants processing crudes high in
naphthenic acid con-tent. It is important to make sure that the nozzles in each area are lined with
the same material as the shell. After exposure to service, the shell immediately above and below
the cladding should be closely monitored for wall loss. It is not uncommon to find that the
original clad areas need to be ex-tended. In the absence of naphtenic acids, the Vacuum Column
is typically lined with 12% chrome, with the exception of the top few feet and head. The flash
zone is often one of the worst naphthenic acid problem areas. For highly naphthenic crudes,
Type 316 or 317 stainless steel cladding may be required in all areas of the column operating
above 450°F (230°C).

3.3. EXCHANGERS AND PIPINGS

Figure 3.2: Exchangers and Piping

Heat exchanger metallurgy varies with stream composition and temperature. The majority of the
exchangers are 100% carbon steel. In fresh water cooled exchangers, admiralty brass tubes have
been used to prevent water-side fouling and corrosion. Due to the cost of the brass bundles and
improvements in cooling water treatment, many brass bundles are being replaced with carbon
steel. Where sea water or brackish water is used, admiralty titanium, and some of the super
ferritic and duplex stainless steels have been used successfully where carbon steel failed to per-

9 CORROSION CHALLENGES IN PETROLEUM REFINEERY AND PETROCHEMICAL INDUSTRY

form. The use of austenitic stainless steels has been limited in water service due to their
susceptibility to chloride stress cracking and under-deposit pitting. In hot hydrocarbon service,
the use of 5% chrome materials in heat exchangers is common. As the sulfur content in the crude
increases, the use of high chrome tubes and 12% chrome shell and channel linings becomes
necessary. Austenitic stainless steels are also used to great advantage in this service. Generally,
the most severe corrosion problems are in the areas of initial condensation in the atmospheric
column and pre-flash column overhead systems. This may include the top of the column, the
overhead vapor line, the naphtha exchangers, coolers and interconnecting piping. These are the
areas where HCl vapor, formed by the hydrolysis of the magnesium and calcium chloride salts in
the pre-heat, dissolves in the condensing water to form hydrochloric acid. HCl, along with
hydrogen sulfide which is also present, creates a very corrosive environment. Usually the UNS
04400 lining and tray the tops of the columns are effective in resisting the acid attack unless
chloride salt deposits form. The overhead vapor line, which is typically carbon steel, can be
severely attacked if un-neutralized condensate is present. A good pH control program in
conjunction with corrosion inhibitors can be very effective in protecting the bare steel line. The
chlorides in the overhead receiver water should be kept below 25 WPPM, which can usually be
accomplished with effective desalting of the crude oil and judicious use of caustic addition to the
desalted crude. This will go a long way toward solving the acidic condensate corrosion problems.

However, if the chlorides exceed about 30 PPM (mg/L), the solution to the problem may be quite
difficult. It is sometimes necessary to install UNS.04400, or UNS 04400 clad, vapor line. The
heat exchangers closest to the point of initial condensation or chloride salt deposition may
require alloy tubes, ranging from admiralty brass to titanium. Where chloride salt fouling and
corrosion occurs, titanium exchanger tubes have worked well. The unlined carbon steel
exchanger shells may be strongly attacked, particularly around the inlet nozzles. This may
require UNS 04400 clad-ding or weld overlay in this area. If the pH of the system is well
controlled, as measured at the over-head receiver, and inhibitors are properly used, the remainder
of the piping and exchangers downstream can be carbon steel with few serious problems. The
overhead vacuum condensers may have admiralty brass tubes and Type 316 stainless steel lined
shells and Type 316 SS outlet lines. The stainless steel may be needed because of CO2 and H2S
in the condensing vapors. However carbon steel is often used successfully. Sometimes 90-10 or
70-30 copper-nickel tubes are used in the Vacuum condensers as part of standard vendor steam

10 CORROSION CHALLENGES IN PETROLEUM REFINEERY AND PETROCHEMICAL INDUSTRY

ejector packages. In some case, 90-10 can experience accelerated corrosion since copper-nickel
alloys are not highly resistant to H2S. Materials such as Admiralty or Aluminum brasses may be
considered.
3.4. FIRED HEATERS

The fired heaters have corrosion and material problems due to the elevated temperatures
experienced both on the process side and in the fire-box. The Atmospheric Heater receives
flashed crude at about 500°F (260°C) and sends it to the Atmospheric Column at about 690°F
(365°C). For sweet crude, the radiant tubes and lower rows of convection tubes are typically 5%
chrome with carbon steel in the upper rows of the convection section. In the Vacuum Heater,
with a 680°F (360°C) inlet and 720°F (380°C) outlet the radiant tubes and convection tubes
would be 5% chrome for sweet and 7 - 9% chrome for sour crudes. Some plants running very
sour crudes have Type 316 austenitic stainless steel radiant tubes. This material would also be
used where naphthenic acid attack is severe. High fire-box temperatures of >= 1500°F (815°C)
also create materials problems. Tube supports and hangers suffer excessive oxidation and pre-
mature failure if they are not sufficiently alloyed. Historically, HH casting alloy (25% chrome -
12% nickel) was the industry standard. This material did well in the cooler convection section,
but failed in the radiant section. The substitution of HK alloy (25% chrome - 20% nickel) added
extra life in the hot areas. Higher nickel materials give excellent service where low sulfur fuel is
burned. How-ever, where sulfur is high, these alloys suffer from sulfidation. This is also true for
the high nickel welding electrodes commonly used to fabricate or repair the Cr-Ni castings. Units
which burn fuel oil high in sodium and vanadium may have refractory lined HK alloy or solid 50
Cr-50 Ni support to resist fuel ash corrosion The transfer lines from the heaters to the columns
are usually alloyed much the same as the heater tubes. The vacuum heater outlet piping and
transfer line may be severely attacked by naphthenic acid, requiring the use of Type 316 stainless
steel.

11 CORROSION CHALLENGES IN PETROLEUM REFINEERY AND PETROCHEMICAL INDUSTRY

 4.0. MATERIALS AND CORROSION CHALLENGES

4.1. INTRODUCTION
Crude oil is a mixture of different compounds, generally combinations of carbon and hydrogen
and some impurities that are extremely corrosive. The more common of these potential damaging
impurities are
 Inorganic Salt
 Sulfur Compound
 Organic Acids
 Organic Chlorides

4.2. INORGANIC SALT

Inorganic salts are present in brine produced with the crude oil or picked up as a contaminant
from tanker ballast. The bulk of the salts present in the water are sodium chloride (NaCl),
magnesium chloride (MgCl2) and calcium chloride (CaCl2), commonly reflecting the
composition of sea water (~85%, 10%, 5%, respectively). However, these ratios can vary widely.
The total salt content by weight can vary from less than three pounds per thousand barrels of
crude oil (PTB) to 300 PTB or more.

When the crude oil is preheated, most of the MgCl2 and a small amount of Cacl2 begin to
hydrolyze at about 250oF(120OC) and form hydrogen chloride(HCl) vapor. At 700°F (370°C),
approximately 95% of the MgCl2 and 15% of the CaCl2 have hydrolyzed. The chemical reaction

A similar reaction occurs for the CaCl2. The NaCl, being more temperature stable, does not
hydrolyze to any appreciable extent. The HCl vapor thus formed is not corrosive at temperatures
above the water dew point. For this reason, there is no corrosive acid attack in the preheat system
where no liquid water is present. However, in the pre-flash and atmospheric columns, the HCl is
carried up the columns with the hydrocarbon where, being highly water soluble, it dissolves in

12 CORROSION CHALLENGES IN PETROLEUM REFINEERY AND PETROCHEMICAL INDUSTRY

the condensing water to form hydrochloric acid. This highly corrosive acid poses a serious
problem. The resulting corrosion reaction with steel is

The presence of H2S (which will be covered later) keeps the reaction going as follows:

The formation of additional HCl thus perpetuates the cycle. Above the water dew point, HCl can
also react with NH3 to form solid ammonium chloride (NH4Cl). The temperature at which
NH4Cl forms is depend-ent upon the partial pressures of HCl and NH3. NH4Cl is hygroscopic
so may absorb moisture even though water is not condensing. Wet NH4Cl is highly corrosive to
many materials. Ammonia is often added to neutralize HCl.

4.3 SULPHUR COMPOUND

Other than carbon and hydrogen, sulfur is the most abundant element in petroleum. It may be
present as elemental sulfur, hydrogen sulfide, mercaptans, sulfides, and polysulfides. Sulfur at a
level of 0.2 percent and greater is known to be corrosive to carbon and low-alloy steels at
temperatures from 230 °C (450 °F) to 455 °C (850 °F). At high temperatures, especially in
furnaces and transfer lines, the presence of naphthenic acids may increase the severity of sulfidic
corrosion. The presence of these organic acids may disrupt the sulfide film, thereby promoting
sulfidic corrosion on alloys that would normally be expected to resist this form of attack (i.e., 12
Cr and higher alloys). In some cases, such as in side-cut piping, the sulfide film produced by H2S
is believed to offer some degree of protection from naphthenic acid corrosion. In general, the
corrosion rate of all alloys in the distillation units increases with an increase in temperature.
Naphthenic acid corrosion occurs primarily in high-velocity areas of crude distillation units in
the 220 °C to 400 °C (430 °F to 750 °F) temperature range. No corrosion damage is usually
found at temperatures greater than 400 °C (750 °F), probably due to the decomposition of
naphthenic acids or protection from the coke formed at the metal surface. Velocity and, more
importantly, wall shear stress are the main parameters affecting NAC. Fluid flow velocity lacks
predictive capabilities. Data related to fluid flow parameters, such as wall shear stress and the
Reynold’s Number, are more accurate because the density and viscosity of liquid and vapor in

13 CORROSION CHALLENGES IN PETROLEUM REFINEERY AND PETROCHEMICAL INDUSTRY

the pipe, the degree of vaporization in the pipe, and the pipe diameter are also taken into account.
Corrosion rates are directly proportional to shear stress. Typically the higher the acid content, the
greater the sensitivity to velocity. When combined with high temperature and high velocity, even
very low levels of naphthenic acid may result in very high corrosion rates.

4.4. ORGANIC ACID

Many crude oils contain organic acids, but seldom do they constitute a serious corrosion
problem. However, a few crudes contain sufficient quantities of organic acid, generally
naphthenic acids, to cause severe problems in those parts of the crude unit operating over 450°F
(230°C). Thus, naphthenic acid attack often occurs in the same places as high temperature sulfur
attack such as heater tube outlets, transfer lines, column flash zones, and pumps. In sour crude
units a crude TAN (Total Acid Number) of 1.0 (mg KOH/g) is sufficient to be concerned about
potential naphthenic acid corrosion. In sweet units, a TAN of 0.5 may be high enough to cause
corrosion. Both high temperature sulfur and naphthenic acid mechanisms are strongly affected
by velocity. Whereas sulfur corrosion is characterized by a smooth surface with a sulfide scale
deposit, naphthenic acid corrosion results in sharp edged, smooth grooves, gouges or holes with
no corrosion scale or deposit. Those materials commonly used to prevent high temperature sulfur
corrosion, primarily 5% to 12% chrome steels, can be severely attacked by naphthenic acid. The
most commonly used material is type 316 stainless steel, it does well because of its molybdenum
content. Type 304, which contains no molybdenum, has some resistance to lower levels of
naphthenic acids, but in most cases it is no better than carbon steel.

4.5. ORGANIC CHLORIDES

Organic chlorides constitute a contaminant in crude oil, often resulting from the carryover of
chlorinated solvent which are used in the oil fields. They can also be picked up by the crude
during transportation in contaminated tanks or lines. Organic chlorides are not removed in the
de-salters. Some of them can decompose in the heaters, forming HCl, causing erratic pH control
and accelerated corrosion in the crude unit as well as in downstream units.

14 CORROSION CHALLENGES IN PETROLEUM REFINEERY AND PETROCHEMICAL INDUSTRY

 5.0. CASE STUDY

5.1. CORROSION RELATED FAILURE IN THE REFINEERY

This example clearly illustrates the hazards associated with amine absorber pressure vessels used
in refineries. On July 23, 1984, a refinery at Romeoville, Illinois, owned and operated by the
Union Oil Company of California, experienced a disastrous explosion and fire.(10,15) An amine
absorber pressure vessel ruptured and released large quantities of flammable gases and vapors.
Seventeen lives were lost, 17 individuals were hospitalized, and more than $100 million in
damages resulted. The National Bureau of Standards (NBS) conducted a detailed investigation,
which included chemical analyses, fracture mechanics analyses, stress corrosion cracking (SCC)
susceptibility tests, and hydrogen cracking susceptibility tests. Preliminary NBS test results
indicated that the subject plate material (ASTM A516, Grade 70 carbon steel) of the amine
absorber was susceptible to hydrogen-induced cracking. Furthermore, repair welds that were
done in the field and that had not been stress relieved, were especially sensitive to amine-induced
corrosion and cracking. Figure 6 is an example of SCC both parallel and perpendicular to the
weld, but not in the weld. Thepropagation of the crack clearly distinguishes SCC and reflects the
different stresses along the weld area.

Figure 5.1: Stress corrosion cracking near a weld

15 CORROSION CHALLENGES IN PETROLEUM REFINEERY AND PETROCHEMICAL INDUSTRY

 6.0 THE WAY FORWARD

Characterization and evaluation of corrosion damage in refineries is of critical importance due to

the need for safety, reliability, throughput and operational integrity for plant facilities.
Appropriate corrosion assessment, prediction, ionic modeling/analyses and monitoring have the
potential to eliminate expensive failures, minimize damage to the environment, and eliminate
abnormal situations that can restrict asset availability.

The most significant issues when evaluating corrosion damage to refinery equipment and
installations are the dominant mechanisms of deterioration and failure related to corrosion
damage. Corrosion damage, in turn, requires a clear understanding of the role of equipment
metallurgy and dominant corrosion mechanisms such as naphthenic acid corrosion, sour water
corrosion, ammonium chloride effects, corrosion due to cyanides, amine corrosion, etc., as well
as relevant cracking concerns such as carbonate cracking, hydrogen induced cracking (HIC),
stress oriented hydrogen induced cracking (SOHIC), and sulfide stress cracking (SSC).

The ability to characterize the potential for corrosion and cracking damage and to use such
knowledge to monitor and control corrosion will allow the refiner to “Enhance the Reliability”
by proactively managing corrosion versus conventional methods whereby plant personnel act
reactively to corrosion issues. An integrated corrosion management solution that incorporates
thermodynamic, process and corrosion modeling tools (collectively referred to as Modeling) can
be used effectively to manage refining corrosion problems. Such a solution is designed to allow
the plant to identify critical spots in the operations from a corrosion standpoint and have the
ability to run refinery processes within appropriate system boundaries to ensure safe unit
operations. Once corrosion is effectively being managed the resulting data and information can
be easily integrated to Asset and Boundary Management applications to link process and
corrosion management to operations allowing to:

 Understand when operating conditions cause an adverse impact on corrosion

 Enable Operators’ awareness about critical limits (for process and corrosion)
 Set appropriate alarms according to identified limits for corrosion and other relevant,
critical parameters

16 CORROSION CHALLENGES IN PETROLEUM REFINEERY AND PETROCHEMICAL INDUSTRY

  Alert plant management about the impact of deviations on equipment reliability, as well
as plausible remediation paths to address the deviations
 Align with the site’s management of change process to approve any changes to
operations when deviation from limits occurs

Monitor critical boundaries (Integrity Operating Windows), enabling operator comments on

causes and corrective actions for deviationValidate material performance, chemical/neutralizer
injection, water wash, inspection frequencies and locations, monitoring locations, etc
Achieve the benefits of enhanced asset integrity, i.e., reduced cost of maintenance, inspection,
turn-around, failure-risk, improved reliability, safety and efficiency.

A corrosion monitoring program provides comprehensive monitoring of all critical

components of industrial objects, assets, facilities and plants for signs of corrosion. For reliable
operation it is important to identify the location, rate, and underlying causes of corrosion. A
corrosion monitoring program identifies any non-conforming alloy components, as these are
generally susceptible to accelerated corrosion and can give relatively frequent cause for
catastrophic failure. Corrosion Monitoring can provide significant advantages when integrated
into both preventative maintenance and the processes inherent to safety management programs.
Based on the results of the Corrosion Monitoring program, informed decisions can be made, not
only regarding the remaining life of the object affected by corrosion but also regarding life
extension strategies, prospective material selection, and cost-effective methods for remedy of
corrosion issues and problems. This corrosion and asset integrity methodology represents a life-
cycle based approach to corrosion control, and integrates multiple, comprehensive components
of corrosion control in a complementary closed-loop control framework.

Activities

An effective corrosion monitoring program includes a wide range of activities:

 Identification of all critical components

 Identification of component alloy composition
 Measurement of the location and extent of corrosion
 Prediction of remaining life

17 CORROSION CHALLENGES IN PETROLEUM REFINEERY AND PETROCHEMICAL INDUSTRY

  Identification of failure mechanisms
 Determination of fitness for service condition
 Inspection scheduling
 Development of recommendations for remedy and correction of problems
 Development of corrosion prevention strategies

Why Monitor Corrosion

Corrosion is a major problem in many industries, particularly in the petrochemical industry.

Corrosion is one of the most serious ageing mechanisms impacting the equipment and assets of
refineries and plants. Uncontrolled corrosion can cause leaks and component failures, bringing
about a reduction in both the performance and reliability of important equipment. In extreme
cases, corrosion can lead to unexpected failures that can be costly in terms of repair costs,
environmental damage and potential harm to humans.

Methods

Corrosion Monitoring uses a wide range of measurement techniques. Non-Destructive Testing

(NDT) methods are the most effective and broadly applied testing methods. Suitable NDT
methods for the monitoring of corrosion include:

 Ultrasonic Testing
 Radiographic Testing
 Guided Wave Testing
 Electromagnetic Testing

The selection of the appropriate method as well as the detection and monitoring of corrosion
requires knowledgeable and experienced personnel.

18 CORROSION CHALLENGES IN PETROLEUM REFINEERY AND PETROCHEMICAL INDUSTRY

 7.0. REFERENCES

1. NACE Group Committee T-8 Minutes.

2. White, R. A. and Ehmke, E. F., “Materials Selection for Refineries, Pipelines, and
Associated Facilities.”
3. 3. Krystow, P.E., “Atmospheric Crude Distillation,” NACE Task Group T-8-5 Refining
Industry Corrosion Handbook.
4. 4. Biehl, J. A. and Schnake, E. A., “ProcessingCrude Oil at Low pH,” presented at 24th
Mid-year Meeting of API Division of Refining, May 1959.
5. 5. Couper, A. S., “Corrosion Control in Crude Oil Distillation Overhead Condensers,”
presented at 29th Midyear Meeting of API Division of Refining, May 1964.
6. Energy and Environmental Profile of the U.S. Petroleum Refining Industry, report by
Energetics Inc. for the U.S. Department of Energy, 1998.
7. Petroleum Industry of the Future, www.oit.doe.gov/petroleum, October 2000.
8. Petroleum Supply Annual 1999, Vol. 1, Energy Information Administration.
9. Petroleum Refining Corrosion, www.hghouston.com/refining.html#top, October 2000.
10. R.A. White, Materials Selection for Petroleum Refineries and Gathering Facilities,
NACE, 1998.
11. Refinery Materials of Construction, www.corrmet.ndirect.co.uk/steel.htm.
12. C. Shawber and P. Manning, Haynes International, Personal Communication, August
and September 2000.
13. The Impact of Environmental Compliance Costs on U.S. Refining Profitability, Energy
Information Administration, October 1997.
14. D. Ditz, J. Ranganathan, and R. Banks, Green Ledgers: Case Studies in Corporate
Environmental Accounting, World Resources Institute, May 1995.
15. Reduced Corrosion in Amine Gas Absorption Columns,
www.hydrocarbonprocessing.com/archive/archive_99-10/99-10_reduce-mogul.htm,
October 2000.
16. Petroleum Project Fact Sheet – Fouling Minimization, U.S. Department of Energy,
Office of Industrial Technologies, January 1999.

19 CORROSION CHALLENGES IN PETROLEUM REFINEERY AND PETROCHEMICAL INDUSTRY

 17. J. Skippins, D. Johnson, and R. Davies, Corrosion Mitigation Program Improves
Economics for Processing Naphthenic Crudes”, Oil & Gas Journal 98, 2000.
18. Corrosion Inhibitors Market Analysis, Publications Resource Group Inc., 1999.
19. Process Incidents, August 2000, www.saunalahti.fi/ility/PI0008.htm, October 2000.
20. V. Novokshchenov, Proceedings of Fifth Middle East Corrosion Conference, Oct 28-30,
1991, Manama, Bahrain, pp. 209-223

20 CORROSION CHALLENGES IN PETROLEUM REFINEERY AND PETROCHEMICAL INDUSTRY

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