CATHODIC PROTECTION OF ABOVEGROUND PETROLEUM STORAGE TANKS

ERGIL GROUP Submitted by; Emrah ZELK 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 wellknown 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- 4OHFigure 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 pHdependent 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 25C. (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+ + e2,714 AKTF Mg = Mg+2 + 2e2,363 Al = Al+3 + 3e1,662 Mn = Mn+2 + 2e1,180 Zn = Zn+2 + 2e0,763 Fe = Fe+2 + 2e0,440 Cd = Cd+2 + 2e0,403 H2 = 2H+ + 2e0 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