CATHODIC PROTECTION OF

ABOVEGROUND PETROLEUM
STORAGE TANKS

ERGIL GROUP
Submitted by; Emrah ÖZÇELİK
Cathodic Protection Engineer
 OUTLINE
• Corrosion
• Cathodic Protection
• Aboveground Storage Tanks CP Systems
 CORROSION

• Corrosion is,
– The surface wastage that occurs when metals are
exposed to reactive environments.
– The result of interaction between a metal and
environments which results in its gradual destruction.
– An aspect of the decay of materials by chemical or
biological agents.
– An extractive metallurgy in reverse. For instance, iron
is made from hematite by heating with carbon. Iron
corrodes and reverts to rust, thus completing its life
cycle. The hematite and rust have the same
composition.
 CORROSIVE ENVIRONMENT
• Corrosion cannot be defined without a reference to
environment. All environments are corrosive to some degree.
Following is the list of typical corrosive environment.
– Air and humidity
– Fresh, distilled, salt and marine water.
– Urban, marine and industrial atmospheres
– Steam and gases, like chlorine.
– Ammonia and Hydrogen sulfide
– Sulfur dioxide and oxides of nitrogen
– Fuel gases
– Acids
– Alkalines
– Soils
 CONSEQUENCES OF
CORROSION
• Some important consequences of corrosion can be
summurized.
– Plant shutdowns. Shutdown of nuclear
plants, process plants, power plants and refineries may
cause severe problems to industry and consumers.
– Loss of products, leaking containers, storage tanks,
water and oil transportation lines and
fuel tanks cause significant loss of product and
may generate severe accidents and hazards.It is well-
known that at least 25% of water is lost by leakage.
- Loss of efficiency. Insulation of heat exchanger tubings
and pipelines by corrosion products reduces heat
transfer and piping capacity.
 CONSEQUENCES OF
CORROSION

• Contamination. Corrosion products may contaminate

chemicals, pharmaceuticals, dyes, packaged goods, etc.
with dire consequences to the consumers.
• Nuclear hazards. The Chernobyl disaster is a continuing
example of transport of radioactive corrosion products in
water, fatal to human, animal and biological life.
 COST OF CORROSION

• Corrosion Costs are staggering and a figure of about 350

billion US dollars appears to be a reasonable estimate for
another two to three years. At least 35% of the above
amount could have been saved by taking appropriate
corrosion control measures.
• In UK, the corrosion cost is estimated to be 4-5% of the
GNP.
• In Japan, the cost of corrosion is estimated to be 5258
trillion Yen per year.
• For most industrialized nations, the average corrosion
cost is 3.5-4.5% of the GNP.
 BASIC CONCEPT IN
CORROSION
• For corrosion to take place, the of a corrosion cell is
essential. A corrosion cell is essentially comprised of the
following four components;
– Anode
– Cathode
– Electrolyte
– Metallic path

Figure 1 –Corrosion cell

 BASIC CONCEPT IN
CORROSION
1 - ANODE :
– One of the two dissimilar metal electrodes in an
electrolytic cell, represented as the negative terminal
of the cell.
– Electrons are released at the anode, which is the more
reactive metal.
– Electrons are insoluble in aqueous solutions and they
only move, through the wire connection into the
cathode.
Fe → Fe+2 + 2e-
 BASIC CONCEPT IN
CORROSION
2 - CATHODE :
– One of the two electrodes in an electrolytic cell
represented as a positive terminal of a cell.
– Reduction takes place at the cathode and electrons are
consumed.
O2 + 2H2O + 4e- → 4OH-
Figure 2 - A galvanic cell (Daniel Cell)
 BASIC CONCEPT IN
CORROSION
3 – ELECTROLYTE
– It is the electrically conductive solution (e.g. salt
solution) that must be present for corrosion to occur.
4 – METALLIC PATH
– The two electrodes are connected externally by a
metallic conductor. Metals provide a path for the flow
of conventional current which is actually passage of
electrons in the opposite direction.
 BASIC CONCEPT IN
CORROSION
• ANODIC REACTIONS CHARACTERISTICS
(1) Oxidation of metal to an ion with a charge.
(2) Release of electrons.
(3) Shift to a higher valence state.

• CATHODIC REACTIONS CHARACTERISTICS

(1) Cathodic reactions are reduction reactions which
occur at the cathode.
(2) Electrons released by the anodic reactions are
consumed at the cathode surface.
 BASIC CONCEPT IN
CORROSION
• The most common cathodic reactions in terms of electrons
transfer are given below:
(a) 2H+ + 2e —> H2 (in acid solution)
(b) 02 + 4H+4e -> 2H20 (in acid solution)
(c) 2H20 + 02 + 4e —> 40H- (in neutral and
alkaline solutions)
(d) Fe3+ + e -» Fe2+ (metal ion reduction in ferric salt
solutions)
(e) Metal deposition: M2+ + 2e -> M
Ni++ + 2e -> Ni
Cu2+ + 2e -> Cu
(f) Bacterial reduction of sulfate:
SO2- + 8H+ + 8e -> S- + 4H20
 CHARACTERISTICS OF A
POURBAIX DIAGRAM
(1)pH is plotted on the horizontal axis and redox potential E
vs SHE on the horizontal axis.
(2)The horizontal lines represent electron transfer reactions.
They are pH -independent, but potential-dependent. These
lines separate the regions of stability, e.g. Fe and Fe2+ in a
potential-pH diagram for Fe-F^O system. Variation of
concentration of Fe2+ (10~6 -1) leads to several parallel
lines.
(3)The vertical lines are potential-independent but pH-
dependent and not accompanied by any electron transfer,
e.g. lines corresponding to the following reactions:
Fe2++2H2O = Fe(OH)2+2H+
Fe3 + 3H2O = Fe(OH)3 + 3H+
 CHARACTERISTICS OF A
POURBAIX DIAGRAM
(4) The sloping, straight lines give the redox potentials of a
solution in equilibrium with hydrogen and oxygen,
respectively. These equilibria indicate electron transfer as
well as pH, e.g.
Fe203+6H-+2e = 2Fe2 ++3H20
The above reaction indicates both electron transfer and pH
change.
(5) The concentration of all metal ions is assumed to be 10- 6
mol per liter of solution. At lower concentration, corrosion
should not occur.
(6) The diagram is computed for the equilibrium conditions at
25°C.
(7) The upper end of the redox potential axis is the noble end
and the lower end, the active end, meaning that the
oxidizing power increase with increasing potential.
CHARACTERISTICS OF A
POURBAIX DIAGRAM
 CHARACTERISTICS OF A
POURBAIX DIAGRAM
Standard Elektrode Potantial Series
Elektrode Potantiel Volt (Oxidation)
• Na = Na+ + e- 2,714 AKTİF
• Mg = Mg+2 + 2e- 2,363
• Al = Al+3 + 3e- 1,662
• Mn = Mn+2 + 2e- 1,180
• Zn = Zn+2 + 2e- 0,763
• Fe = Fe+2 + 2e- 0,440
• Cd = Cd+2 + 2e- 0,403
• H2 = 2H+ + 2e- 0
• Cu = Cu+2 + 2e- -0,337
• 4OH- = O2+2H2O+4e- -0,401
• Ag = Ag+ + e- -0,799
• Au = Au+3 + 3e- -1,500 SOY
 TYPES OF CORROSION
1 – UNIFORM CORROSION
• It is the uniform thinning of a metal without any localized attack.
• Corrosion does not penetrate very deep inside. The most familiar
example is the rusting of steel in air.
• Environment
(1) Dry atmosphere.
(2) Damp atmosphere.
(3) Wet atmosphere.
(4) Acids (HC1, HCIO4, H3PO4).
(5) Atmospheric contaminants.
(6) Process water containing hydrogen sulfide.
(7) Brines.
(8) Industrial atmosphere.
(9) Hydrocarbon containing wet hydrogen
sulfide.
 TYPES OF CORROSION
• Examples of Uniform Corrosion
(1) Tarnishing of silver ware.
(2) Tarnishing of electrical contacts.
(3) Rusting of steels in open air.
(4) Corrosion of offshore drilling platforms.
(5) Corrosion of galvanized steel stairways.
(6) Failure of distillation columns.
(7) Corrosion of electronic components.
(8) Corrosion of underground pipes (composite asphalt coated).
(9) Corrosion of automobile bodies.
(10) Corrosion of heat exchanger tubes.
(11) Corrosion of structural steels.
 TYPES OF CORROSION

2 - GALVANIC CORROSION
• Galvanic corrosion occurs when two metals with different
electrochemical potentials or with different tendencies to
corrode are in metal-to-metal contact in a corrosive
electrolyte.
• When two metals with different potentials are joined, such
as copper (+0.334 V) and iron (—0.440 V), a galvanic cell is
formed. A cell in which the chemical change is the source
of energy, is called a galvanic cell The corrosion which is
caused due to the formation of the galvanic cell is,
therefore, called galvanic corrosion.
 TYPES OF CORROSION

• The driving force for corrosion is a potential difference

between different materials. This force was described by
Luigi Galvani, late in the eighteenth century.
• Between the two different materials connected through an
electrolyte, the less noble will become the anode and tend
to corrode.
 TYPES OF CORROSION

3 - CREVICE CORROSION
• This is a localized form of corrosion, caused by the
deposition of dirt, dust, mud and deposits on a metallic
surface or by the existence of voids, gaps and cavities
between adjoining surfaces
• An important condition is the formation of a differential
aeration cell for crevice corrosion to occur. This
phenomenon limits the use, particularly of steels, in
marine environment, chemical and petrochemical
industries.
 TYPES OF CORROSION

• Factors affecting crevice corrosion

(a) Crevice type.
(b) Alloy composition.
(c) Passive film characteristics.
(d) Geometry of crevice.
(e) Bulk composition of media.
(f) Bulk environment.
(g) Mass transfer in and out of crevice.
(h) Oxygen.
 TYPES OF CORROSION
Figure 3 - Factors affecting crevice corrosion.
 TYPES OF CORROSION

4 - PITTING CORROSION
• It is a form of localized corrosion of a metal surface where
small areas corrode preferentially leading to the formation
of cavities or pits, and the bulk of the surface remains
unattacked.
• Metals which form passive films, such as aluminum and
steels, are more susceptible to this form of corrosion.
• It is the most insidious form of corrosion. It causes failure
by penetration with only a small percent weight-loss of the
entire structure.
 TYPES OF CORROSION

• It is a major type of failure in chemical processing

industry. The destructive nature of pitting is illustrated by
the fact that usually the entire system must be replaced.
• Generally, the most conducive environment for
pitting is the marine environment. Ions, such as Cl-, Br- and
I- , in appreciable concentrations tend to cause pitting of
steel. Thiosulfate ions also induce pitting of steels.
• Aluminum also pits in an environment that cause the
pitting of steel. If traces of Cu2+ are present in water, or
Fe+3 ions are in water, copper or iron would be deposited
on aluminum metal surface and pitting would be initiated.
 TYPES OF CORROSION

• Oxidizing metal ions with chloride, such as cupric, ferric

and mercuric, cause severe pitting.
• Presence of dust or dirt particles in water may also lead to
pitting corrosion in copper pipes transporting seawater.
 TYPES OF CORROSION
5 - STRESS CORROSION CRACKING AND HYDROGEN DAMAGE
– Stress corrosion is the failure of a metal resulting from the
conjoint action of stress and chemical attack.
– It is a phenomenon associated with a combination of static
tensile stress, environment and in some systems, a
metallurgical condition which leads to component failure
due to the initiation and propagation of a high aspect ratio
crack.
– It is characterized by fine cracks which lead to failure of
components are potentially the structure concerned.
Stress corrosion cracking is abbreviated as SCC.
– The following conditions are necessary for SCC to occur:
(1) A susceptible metal.
(2) A specific environment.
(3) A tensile or residual
stress.
 TYPES OF CORROSION
Various types of SCC are distinguished as below:

(a) Chloride stress corrosion cracking. It occurs in austenitic

steels under tensile stress in the presence of oxygen, chloride
ion and high temperature.
(b) Caustic stress corrosion cracking. Cracking of steels in
caustic environments where the hydrogen concentration is
high, for instance, cracking of Inconel tubes in alkaline
solutions.
(c) Sulfide stress corrosion cracking. Cracking of steels in
hydrogen sulfide environment as encountered in oil drilling
industry.
(d) Seasonal cracking. The term is now obsolete. It had a
historical significance only. It refers only to SCC of brass in
ammoniacal environment, but still occasionally occurs in
refrigeration plant using ammonia refrigerant..
 TYPES OF CORROSION

• Table 1 - sources of stress for SCC :

 TYPES OF CORROSION
EXAMPLES OF TYPICAL ENGINEERING MATERIALS WHICH
UNDERGO SCC
(1) High strength steel in water.
(2) High strength aluminum alloys in chloride
solutions.
(3) Copper alloys in ammonical solutions.
(4) Mild steels in hydroxide and nitrate solutions.
(5) Austenitic steels in hot chloride solution and
hydroxide solution.
(6) Titanium alloys in chloride solutions and hot
solid chloride.
(7) High nickel alloys in high purity steam.
 TYPES OF CORROSION

HYDROGEN DAMAGE (HIGH TEMPERATURE HYDROGEN

ATTACK)
Steels are also damaged by hydrogen blistering at high
temperatures. Thus, there are three categories of hydrogen
damage;
(a) High temperature hydrogen attack (hydrogen
damage)
(b) Hydrogen blistering
(c) Hydrogen embrittlement.
TYPES OF CORROSION

Hydrogen Induced Cracking (HIC)

 TYPES OF CORROSION
• For the HIC to occur, the following conditions must occur:
(a) The presence of water phase.
(b) The presence of atomic hydrogen.
(c) An agent that retards the formation of molecular
hydrogen at the surface.
(d) Presence of grain boundaries or
inclusions.
(e) Maintenance of an active surface.
(f) Discontinuity in metal, such as slag, inclusion
and/or void.
 TYPES OF CORROSION

6 - CAUSTIC CORROSION
• Austenitic nickel-chromium stainless steels and
mild steel are subject to stress corrosion cracking in
caustic soda (caustic cracking) at elevated temperatures.
• The phenomenon, 'caustic cracking' is mostly encountered
in boilers.
• Caustic is added as an additive to boiler water in order to
preserve the thin film of magnetic iron oxide by raising the
pH.
 TYPES OF CORROSION
7 - SULFIDE STRESS CORROSION CRACKING
• Mechanisms sulfide stress corrosion cracking
CATHODIC PROTECTION
 CATHODIC PROTECTION
• If we supply additional electrons to a metallic structure,
more electrons would be available for a cathodic reaction
which would cause the rate of cathodic reaction to
increase and that of anodic reaction to decrease, which
would eventually minimize or eliminate corrosion. This is
basically the objective of cathodic protection.
• The anode would become more negative and the cathode
more positive. Cathodic protection is, therefore, achieved
by supplying an external negative current to the corroding
metal to make the surface acquire the same potential to
eliminate the anodic areas. The anodic areas are
eliminated by transfer of electrons.
CATHODIC PROTECTION
 CATHODIC PROTECTION

• After a sufficient current flow, the potential of

anodic areas would become negative enough for
corrosion to stop.
(a) There must be an anode, a cathode, an
electrolyte and a metallic path for the transfer of
electrons.
(b) A source of DC current to supply electrons.
(c) Sufficient direct current should be appliedto
eliminate the potential difference between the
anode and the cathode.
CATHODIC PROTECTION
 CP TYPES
• Two types of cathodic protection systems exist:
(1) Galvanic Anode or Sacrificial Anode CP System
• Cathodic protection can be applied by connecting
sacrificial anodes to a structure.
• Basically, the principle is to create a galvanic cell,
with the anode representing the less noble material
that is consumed in the galvanic interaction.
• The following advantages are associated with
sacrificial anode CP systems:
– No external power sources required.
– Ease of installation (and relatively low installation costs).
– Unlikely cathodic interference in other structures.
SACRIFICIAL ANODE CP
SYSTEMS
 SACRIFICIAL ANODE CP
SYSTEMS
– Low-maintenance systems (assuming low current demand).
– System is essentially self-regulating.
– Relatively low risk of overprotection.
– Relatively uniform potential distributions.

Unfortunately, these relatively simple systems also have some

limitations such as;

– Limited current and power output.

– High-resistivity environments or large structures may require
excessive number of electrodes. Maximum resistivity of 6000 to
10,000 ohm-cm is generally regarded as the limit, depending on
coating quality.
– Anodes may have to be replaced frequently under high current
demand.
– Anodes can increase structural weight if directly attached to a
structure.
 SACRIFICIAL ANODE CP
SYSTEMS
• ANODE TYPES ;
For land-based CP applications of structural steel, anodes
based on zinc or magnesium are the most important.

1 – Zinc Anode
• Zinc anodes employed underground are high-purity Zn alloys, as
specified in ASTM B418-95a.
• Only the Type II anodes in this standard are applicable to buried
soil applications.
• For zinc anodes, the mass-based theoretical capacity is
relatively low at 780 Ah/kg, but efficiencies are high at around
90 percent.
SACRIFICIAL ANODE CP
SYSTEMS
 SACRIFICIAL ANODE CP
SYSTEMS
2 – Magnesium Anode
• Magnesium anodes generally have a low efficiency at 50 percent
or even lower.
• The theoretical capacity is around 2200 Ah/kg.
• The magnesium alloys are also high-purity grades and have the
advantage of a higher driving voltage.

3 – Aluminum-Indium Anode
• These are mostly employed for seawater applications.
• The base metal contains 98-99% of aluminum.
• The rate of consumption varies between 7 and 9 lb/A-year. The
efficiency varies between 87 and 95%.
 IMPRESSED CURRENT CP SYSTEMS

(2) Impressed Current CP System

• In impressed current systems cathodic protection is
applied by means of an external power current source.
• In contrast to the sacrificial anode systems, the anode
consumption rate is usually much lower. Unless a
consumable “scrap” anode is used, a negligible anode
consumption rate is actually a key requirement for long
system life.
• Impressed current systems typically are favored under
high-current requirements and/or high-resistance
electrolytes.
IMPRESSED CURRENT CP SYSTEMS
 IMPRESSED CURRENT CP SYSTEMS

• Advantages ;
– High current and power output range.
– Ability to adjust (“tune”) the protection levels
– Large areas of protection.
– Low number of anodes, even in high-resistivity environments.
– May even protect poorly coated structures.
• Disadvantages ;
– Relatively high risk of causing interference effects.
– Lower reliability and higher maintenance requirements.
– External power has to be supplied.
– Higher risk of overprotection damage.
– Running cost of external power consumption.
– More complex and less robust than sacrificial anode systems in
certain applications.
ABOVEGROUND STORAGE
TANKS CP SYSTEMS
 ABOVEGROUND STORAGE
TANKS CP SYSTEMS
• Storage Tanks are applied two different and independent
cathodic protection systems.These are;

1 - External cathodic protection system of the tank.

2 - Internal cathodic protection system of the tank.
 ABOVEGROUND STORAGE
TANKS CP SYSTEMS
1 - External cathodic protection system of the tank
• External part of the tank is embedded to the soil over
the tank base.
• Soil is very resistive and corrosive media.
• The tank base is protected with impressed current
cathodic protection system.
• The reason of applying the impressed current system
is requirement lots of galvanic anode. So, galvanic CP
system is more expensive than Impressed current CP
system.
 ABOVEGROUND STORAGE
TANKS CP SYSTEMS
2 - Internal cathodic protection system of the tank
• There are seawater inside of the petrolium storage tank
because of making more viscous petrolium.
• The seawater is bottom of the petrolium. Because the
density of seawater is bigger than petrolium.
• Seawater height is between 1 and 1.5 metres.
• Seawater is dangerous corrosive media. So, that area has
to be protected against the corrosion.
• The Internal CP system of the tank is galvanic anode
cathodic protection.
• Al-In anode is used in these CP systems.
• The anodes is settled to the tank base.
ABOVEGROUND STORAGE
TANKS CP SYSTEMS
ABOVEGROUND STORAGE
TANKS CP SYSTEMS
THANKS FOR YOUR
ATTENTION