Professional Documents
Culture Documents
Alec Groysman
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 nor at others. There are many corrosion experts, institutes and laboratories,
corrosion magazines, books, standards, and conferences. 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 industry and to ecology.
The aim of this work is to survey the corrosion situation at the oil refining industry during the
past four years, 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. Examples of distribution of corrosion damages that occurred during
the last four years as well as the solutions of their prevention are given. 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. Examples of wrong use of corrosion control
measures, such as corrosion inhibitors` type and their concentrations, alloys, coats, and
technological regimes are given. Insufficient, or sometimes lack of use of corrosion
monitoring methods result in a non-controlling corrosion situation.
Indirect cost of corrosion is connected with the ecological impact on the environment, loss of
expensive chemicals, a contamination of technological streams by corrosion products, loss of
efficiency, overdesign and shutdowns. 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. A model of interconnections of all groups at the oil refining industry
with the aim to diminish corrosion risk was suggested. Anti-corrosion management quality
includes design, manufacture, improvement, and control at all stages.
1
Introduction
The Oil Refining industry exists for about 90 years. All types of corrosion phenomena known
to corrosion experts, plus some specific problems (such as naphthenic acid corrosion, sulfide
corrosion, and hydrogen induced corrosion), were found at the Units of the Oil Refineries.
Many corrosion problems have been solved [1 - 3]. Some of them have not. Why? Sometimes
corrosion damages occur at certain facilities, but not at others. There are many corrosion
experts, corrosion magazines, books, standards, and conferences, such as ours, etc. A lot of
companies manufacture different materials and equipment for corrosion control and corrosion
monitoring. Many institutes and laboratories waste much money and time for corrosion
researches. In spite of this, corrosion problems remain the main danger to the oil refining
industry and to ecology.
The aim of this work is to survey the corrosion situation in the refining industry in Israel,
during the past four years, in order to estimate the cost of corrosion; to define the reasons for
corrosion problems and to find effective measures to solve them, to define correct ways for
anti-corrosion management, and, as a result, to improve reliability, availability and
profitability at the oil refinery facilities.
How do we define a corrosion case? It is any failure that occurred because one of the
following corrosion phenomena: general corrosion, pitting, crevice, galvanic, intergranular,
stress corrosion cracking (SCC), microbiologically induced corrosion (MIC), dezincification,
erosion-corrosion, cavitation, fatigue corrosion, caustic embrittlement, hydrogen sulfide and
hydrogen induced corrosion, corrosion under thermal insulation, dew point corrosion, stray
current corrosion, under deposit corrosion, over-heating corrosion, chemical cleaning
corrosion, and welding corrosion. Failure of one of the corrosion control measures such as
incorrect use of protective coatings or corrosion inhibitors, or unsuitability of materials to
standards, or plugging because of deposits` (corrosion products) formation is also considered
corrosion case. Estimation of the direct corrosion cost gave the value of about 10 million
dollars per year at one refinery.
We analyzed the reasons in every corrosion case (Table 2). About 75% (average value in
2001 2004) of all corrosion failures happened because of insufficient information and
knowledge. Thus, the human factor was the main reason for corrosion failures. The human
factor was divided into the lack of awareness and knowledge, insufficient control and
supervision, unwillingness to improve the situation, wrong operation and design. The
importance of human factor in occurring of corrosion failures resulted in development correct
anti-corrosion management which must be designed in such a manner that it will increase the
human potential in performance of correct decisions. In general human factor diminished
from 85% to 65% during the last four years. We can compare this value with human factor of
80 to 90% in chemical, naval and aviation industries [4]. This diminishing is explained by the
2
development of correct anti-corrosion management, and, first of all, introduction of analysis
of corrosion failures for technical personnel, and spreading of corrosion monitoring methods
at the units.
Table 2.
Causes of corrosion failures in 2001 2004
3
experience of personnel. The last two issues are included in the anti-corrosion
management, and we shall talk about it later.
Table 3.
Corrosion phenomena with the equipment at the Oil Refineries in 2001 2004
4
Analysis of corrosion cases with different equipment at the units of Oil Refineries in 2004
showed that about 60% of total failures occurred with heat exchangers, condensers, pipelines
and tanks (Table 4) [12]. But stacks, coils, pumps, compressors, furnaces, towers, reactors and
valves were also subjected corrosion.
Table 4.
Corrosion failures of equipment at the Oil Refineries` Units in 2004
Analysis of corrosion failures at different units at the Oil Refineries showed that most
corrosion cases occurred at CCR (Continuous Catalytic Cracking) unit, Distillation Crude
units, Hydrodesulfurizers, FCC (Fluid Catalytic Cracking) units, with aboveground storage
tanks and pipelines (Table 5). It is important to emphasize that no corrosion failures occurred
at places where corrosion control (inhibitor and neutralizer injection) and monitoring
(periodical with corrosion coupons and on-line continuous) methods were used. This fact
confirms existence of efficient control methods and introducing corrosion monitoring in new
places where corrosion failures are expected and can occur.
Table 5.
Number of corrosion failures at different units in 2001 2004
Unit Year
2001 2002 2003 2004
Distillation Crude Unit 6 9 8 10
Continuous Catalytic Reforming 5 4 4 12
Fluid Catalytic Cracking 1 2 11 8
Pipelines 19 11 9 7
Aboveground Storage Tanks 7 6 2 9
Hydrodesulfurizers 8 6 5 11
Power Station 0 0 0 3
Merox 0 0 0 1
Visbraker 2 0 0 2
Asphalt 0 1 1 0
*
Petrochemical Plant 4 3 6 7
Total 52 42 46 70
*
Petrochemical Plant: manufacture of organic solvents.
5
Examples of corrosion cases
Here are several examples of correct and wrong use of corrosion control measures, such as
use of alloys, coating systems, and technological regime at the refinery units.
1. General corrosion of the bed of the catalyst and pipe in the stripper column at the
Continuous Catalytic Reforming Unit (Figure 1).
Figure 1. The carbon steel bed for the catalyst and pipe in the stripper column at the
Continuous Catalytic Reforming Unit.
The medium was the 1% aqueous soda solution containing 1000 ppm of chlorides and 6 ppm
of iron. Severe corrosion of carbon steel internals occurred after 8 years of operation.
Laboratory examination of corrosiveness of this medium showed corrosion rate of 1 mm/year
for carbon steel. It was found in laboratory tests that some kinds of Duplex steels, high
molybdenum stainless steel and Monel were resistant to the corrosive medium in the stripper.
The human factor was responsible in this case, because carbon steel was wrongly chosen as
the material of construction at the project stage.
2. General corrosion and incorrect use of material corrosion of heat exchanger tubes made
of carbon steel after 8 years of operation (Figure 2).
Crude oil flew inside of the tubes, outside vacuum bottom. The temperature varied from 280
to 320oC. Sulfur content in crude oil varied from 4.3 to 5.6%. It is well known that carbon
6
steel is not resistant to high sulfur (above 1% weight) crude oil and vacuum bottom at
temperatures above 290oC [7]. Insufficient control (that is, the human factor) at the stage of
the manufacture of carbon steel heat exchanger tubes was the reason for this corrosion failure.
The correct decision is to use a low alloy steel containing 5% Cr.
3. Failure of protective coating systems (Figure 3 and 4). The pipeline was made of carbon
steel. Outside the pipeline was the industrial atmosphere of the Oil Refinery. Water from the
desalter at 90oC flew inside this pipeline (Figure 3). The coating system resistant to industrial
atmosphere at ambient temperature of about 25oC was chosen. This coating failed after
several months of use. Temperature is the critical parameter for use of coating systems.
Another example is the coating system for the air cooler ventilator (Figure 4). The
temperature sometimes rose to 100oC in this area. This coating failed after 2 years of use.
Human factor was responsible for the failures in these two failures.
Figure 3. Failed coating on the pipeline in the atmosphere of the Oil Refinery.
7
4. Erosion corrosion failure relates to the over-loading of materials incorrect process
conditions and variables: concentrations of reagents, temperature, pressure, presence of
aggressive contaminants and flow rate. The pump made of stainless steel 316 was intended
for pumping the light cycle oil at the processing line at the Fluid Catalytic Cracking Unit.
Catalyst containing particles of silica and alumina entered the pump suddenly (Figure 5). The
pump worked about four years without failure. Erosion corrosion is usually an unexpected
failure and could occur during several months or less. The remedial operation is a prevention
of catalyst penetration into the pump.
5. Microbiologically Induced Corrosion (MIC) inside of the bottom of a crude oil storage
tank after 18 years of use (Figure 6) [12].
The typical pattern on the inner surface of carbon steel bottom could be determined as a result
of microbial attack. Usually very dense sludge of the height of 1 to 2 meters is formed at the
bottom, and it is impossible to take a sample from the bottom - bottom for the microbial
analysis. The results of the microbial analysis of crude oil do not always show the real picture
of the microbial contamination at the bottom surface. The only solution is to coat the bottom
surface inside the tank and periodical cleaning from the sludge [6]. Sometimes MIC can result
in corrosion damage of equipment in contact with water deteriorated by microorganisms even
in several weeks [13].
8
Corrosion monitoring methods at the Oil Refineries Units
Many problems of correct use of corrosion control measures (for example, injection of
chemicals such as inhibitors, neutralizers, biocides and others) may be solved by means of
corrosion monitoring methods [15 17]. Here are two examples, how we use corrosion
monitoring at the process units and in the cooling water systems. Figure 7 shows the
atmospheric distillation column with air cooler and condensers (overhead). All pipelines,
tubes in the air cooler, naphtha and kero heat exchangers are made of carbon steel. Tubes in
condensers were originally made of carbon steel and Admiralty brass CDA 443, but were
replaced for titanium (Ti Gr. 2 and Ti Gr.12) 12 years ago because of severe acidic and under
deposit corrosion. Hydrocarbons containing water vapors, hydrogen chloride and hydrogen
sulfide, leave the distillation column at 130oC. This mixture becomes very corrosive when
cooled below the dew point temperature of 100oC. In order to prevent high acidic corrosion in
air cooler and condensers, neutralizers and corrosion inhibitor are injected in the overhead of
the distillation column. Weight loss coupons and electrical resistance (ER) probes were
installed in many places and OM On-line Monitoring by means of ER-probes. They were
also installed in the naphtha pump-around and kero pump-around lines. The electrical
resistance probes show the corrosion situation continuously. We change the weight loss
coupons every several months, in order to compare with the results of the ER-probes and to
examine the danger of chloride attack (pitting corrosion). This is very important, and the more
points in the unit that are included for corrosion monitoring, the fuller is the corrosion
coverage we receive. Figure 8 shows typical on-line data dial reading of the ER-probes with
time in one of the condensers in the overhead of the distillation column.
9
Figure 8. Dial Reading ER-probe vs Time.
One can receive such a picture on the screen of his computer. The sudden rise of corrosion
rate of carbon steel is analyzed for every period. The acceptable corrosion rate of 5 mpy (0.11
mm/year) for carbon steel is defined for units at the oil refineries [15]. Therefore any increase
above 5 mpy is analyzed and the causes are determined. There were two short periods when
the corrosion rate increased above 5 mpy (see Figure 8). Insufficient injection of neutralizer
was the reason of a sudden increase of corrosion rate of carbon steel. Thus, we can monitor
the anti-corrosion program and as a result the corrosion situation in the overhead of the
distillation column.
The average corrosion rate for any period can be compared with the results received by means
of the weight loss coupons (Figure 9). Usually we receive good correlation between these two
methods.
Figure 9. Average corrosion rate with ER-probe (0.037 mm/year) and weight loss coupons
(0.025 mm/year).
Corrosion and deposit monitoring in the cooling water system
Three main problems exist in every cooling water system in the Oil Refining Industry:
corrosion, inorganic deposits containing carbonate scale, corrosion products of iron,
phosphates, silicates and some others, and biofouling (microbial contamination). Two on-line
corrosion and deposit monitoring systems are used in the cooling water system at our
Refinery [2]. Such systems allow monitoring the general corrosion of carbon steel (or any
other alloy) at ambient temperature (non-heated steel surface) and at the drop temperature in
10
the heat exchanger (heated steel surface), pitting tendency also for heated and non-heated
surface, and heat transfer resistance the quantitative value of inorganic and organic deposits
(fouling). General corrosion rate is defined by means of the LPR (Linear Polarizarion
Resistance) method, and the pitting tendency is based on the Electrochemical Noise
Measurements (ENM). The typical change of Heat Transfer Resistance versus Time is
presented at Figure 10. One can calculate the cleaning factor in percent according to these
data. The drawback of these data is that general fouling is measured: total sum of inorganic
and organic deposits.
Heat Transfer Resistance vs Time
DATS data
0.4
0.38
Heat Transfer Resistance,
0.36
x1000, o Cm 2/KW
0.34
0.32
0.3
0.28
0.26
0.24
0.22
0.2
27/09/99 17/10/99 06/11/99 26/11/99 16/12/99 05/01/00 25/01/00 14/02/00
Figure 10. Heat Transfer Resistance vs Time (DATS Deposit Accumulation System data).
Figure 11 presents the dial reading data of general corrosion by LPR corrosometers and
pitting tendency by ENM. Thus, on-line corrosion infromation is received continuously.
On-line Corrosion Rate of Mild Steel vs Time
0.3
0.25
Corr. Rate, m py
0.2
0.15
0.1
0.05
0
27/09/99 17/10/99 06/11/99 26/11/99 16/12/99 05/01/00 25/01/00 14/02/00
Figure 11. On-line corrosion rate of mild steel (general corrosion and pitting tendency) in the
cooling water system vs Time.
11
We developed and continue to develop the procedures, specifications and standards for
corrosion prevention, control and supervision. Some of them were introduced into practice.
For example, a standard of coating systems for the protection of structures and equipment at
the Oil Refineries. Every two years we revise these systems after analysis of experience and
new data of study of resistance of coating systems under different conditions at the Oil
Refineries. Another example: cathodic protection of underground structures. This document
was introduced into practice for all industrial enterprises in the Haifa area 13 years ago.
Protection of equipment during storage and material control during purchasing are a very
important part of anti-corrosion management. Some kinds of equipment (heat exchangers,
tubes, bundles, elbows, valves, etc.) are not used immediately after purchasing. Therefore,
anticorrosion measures must be carried out for the temporary protection. We have to find
criteria for penalty and prize for anti-corrosive management, computerize the library of
corrosion cases, and disseminate information and knowledge about corrosion, corrosion
control and corrosion monitoring methods.
Supervision at the Economical Benefit of
design stage for estimation of usage of
suitability of material corrosion losses corrosion
choice, protective supervision
measures and methodss
corrosion controll
Direct Indirect
Avoidable Unavoidable
Developing of Protection
procedures, of Material
specifications, equipment control
standards for during during
corrosion storage. purchasing.
prevention,
control and Insurance in corrosion
supervision: damage.
12
The cost of corrosion includes two components: corrosion loss and investments in corrosion
control (use of preventive anti-corrosion measures plus corrosion monitoring methods)
(Tables 6 and 7) [18]. Any study of corrosion cost should include the investigation of places
where corrosion costs occur, the size of these costs and their predictability [19]. We suggest
the following approach which allows determining the costs of corrosion loss and proper
responsibility for these data (Table 6).
Table 6.
Corrosion loss (cost per year - example)
Total, $.
Note: A, B, C, etc. are the specific cost values.
13
stated period of time, or at a given point in time [20]. Availability is the quality of being
present or ready for immediate use [21].
Profitability is a valuable return, or net income for a given period of time [21].
Certainly, quality is mostly well connected with reliability, both may be interpreted in the
values of probabilities. Corrosion influences reliability which is a part of quality. Both
quality and reliability are influenced by the human factor. We saw that human error was the
primary cause of process corrosion failures: from 65% (our estimation in this work) in the
refining industry to 80 - 90% in chemical, naval and aviation fields [4]. While improving anti-
corrosion management, we can get better quality. The inverse statement is also correct: while
improving the quality, we can get better anti-corrosion management. Anti-corrosion
management is supervision at the design stage for suitability of material selection, protective
anti-corrosion measures (corrosion control) and corrosion monitoring. We can show how
investments in corrosion control affect the quality of goods, materials, work, services,
profitability, forecasted opportunities, customer satisfaction, safety, and effectiveness (Table
7).
Table 7.
14
Corrosion Control Use / Means Investments, Responsible
Method or Other $ Group/Unit
Investments
Sacrificial anodes for S1 Maintenance
heat exchangers with Division
cooling water
Consultancy T1 Electrical Division
Polymeric U1 Maintenance
materials Division, and
Ceramic materials W1 Development
Composites X1
Corrosion Resistant Heat exchangers Y1 Maintenance
Alloys Pumps A2 Division, Technical
Pipes and tubes B2 Services Division,
Reactors C2 and Development
Other equipment D2
Corrosion Coupons (Weight Loss E2 R&D Corrosion
Monitoring Method) Laboratory,
Electrical Resistance F2 Maintenance
Probes Division,
Linear Polarization G2 Production Division
Resistance
corrosometers
On-line monitoring in H2
cooling water systems
(Deposit Accumulation
Testing System)
Research & R&D development I2 R&D Division, Plant
Development Consultancy and outer J2 Inspection
(R&D) laboratories` service Department
Total, $.
Note: A1, B1, C1, etc. are the specific cost values.
15
standard of coating systems for use at oil refineries under various conditions [6, 28]. This
standard helps to improve the quality of corrosion control measures.
16
Conclusions
1. The Chinese Taoist philosopher Lao Tzu who lived more than 2600 years ago, said:
Stop thinking, and end your problems. We saw that human factor was responsible in 65% to
85% of corrosion failures. By the human factor we mean: the absence of awareness and
knowledge, of control and supervision, wrong operation and design, and lack of a wish to
improve the corrosion situation.
2. Human error potential can be managed. The human factor is of paramount
importance in both corrosion events and improving the quality. The scheme of
diminishing the corrosion cost and consequently of increasing quality was suggested.
It is impossible to reduce corrosion cost to zero, because methods of corrosion control
and corrosion monitoring are necessary for preserving quality, but they may be
optimised and cost effective.
3. The investments should be at all stages of anti-corrosion management and quality
improvement, including design, fabrication, operation, monitoring, maintenance,
education, training, research, and policy. Every industry and enterprise should have a
program of anti-corrosion management which will allow improving quality.
4. The corrosion cost of each job, of every failure, and of the implementation of specifications
and standards should be recorded. Any corrosion cost study must include the analysis where
corrosion costs take place, the sizes of these costs, and their predictability.
5. The previous French president George Pompidou said: The problems are not solved. We
live with the problems. We live with old problems of general and pitting corrosion, erosion
cavitation, coatings failure and SCC. We know them well and can avoid if we would
emphasize the role of a human factor and corrosion monitoring methods.
6. Insufficient, or sometimes lack of use of corrosion monitoring methods result in a non-
controlling corrosion situation. Periodical and on-line corrosion monitoring in the overhead of
crude distillation columns and cooling water systems proved its high efficiency. Corrosion
failures diminished drastically in these places. Corrosion monitoring methods are universal as
they can be used in all industries. The main our task is to install corrosion monitoring systems
in all critical places, in order to avoid sudden failures and to reach high reliability, availability
and profitability.
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17
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