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Corrosion in Petroleum Industry

By
Chem./ M.MOSTAFA

1
BASICS OF CORROSION

Corrosion of Metals

All interactions between a metal ( or alloy )


with its environment.

2
BASICS OF CORROSION

Corrosion of Metals

Wet Dry

Occurs in wet Occurs in dry


environments environments @ high
or elevated temp.

3
BASICS OF CORROSION

Dry Corrosion
Direct chemical reaction between metal and environment
Occurs at high temperatures > 200 oC ; e.g.

Oxidation : reaction of iron with O2

Carburization : reaction of iron with CO2

Sulphidation : reaction of iron with S or H2S


4
BASICS OF CORROSION

Wet / Aqueous Corrosion of Metals


Occurs in water – containing environments
Occurs at ambient temperatures

Environment

Water ( fresh or sea water )


Soil ( wetted )
Atmospheric air ( humid )

5
BASICS OF CORROSION

Electrochemical Nature of Corrosion

Corrosion of metals (e.g. iron) in water is basically an


electrochemical reaction in nature,

i.e.

A chemical reaction accompanied by the passage of an


electric current ( due to movement of electrons ).

6
BASICS OF CORROSION

Why Metals Corrode?


Metals tend to corrode in order to retain their natural
form (ore).
Metals are usually extracted and purified from their
ores via high-energy input processes.
For example :

Thermal energy (high furnace for Fe)

Electric energy (electrolytic paths for Al)

7
BASICS OF CORROSION

Electrolytic reduction of Al oxide to Al

Blast furnace of reducing iron


ore to iron

The extracted free metal has a high energy content. i.e. active state

8
BASICS OF CORROSION

Active free metals tend to react easily to produce


compounds, such as salts and oxides.

Metals in the compounded forms have less energy


content, i.e. stable state.

Corrosion is governed by the Law of


Conservation of Energy :

Energy Gained = Energy Lost

9
BASICS OF CORROSION
Corrosion
Thermodynamic Cycle
Iron oxides
Oxides, Ore thermodynamically stable
+
Mining &
Extraction

Corrosion

Mining & Extraction Steel


+
Corrosion

Equipment fabrication,
thermodynamically unstable
Iron oxides
10
BASICS OF CORROSION
Thermodynamics of
Thermodynamics ofCorrosion
Corrosion

In a chemical reaction :
Reactants Products
∆G = Gprod – Greact
Reactant

In all corrosion reactions


Gprod < Greact. Therefore,
Product
∆G is –ve
Hence, the corrosion reaction is :
spontaneous
irreversible
11
BASICS OF CORROSION

Occurrence of Corrosion
Corrosion is initiated at the metal surface defects since they are
the highest energy sites, i.e. the most active sites.

B
A
C

(a) (b) (c)


Schematic model of a free metal surface
Atom Degree of Freedom
C , Terrace (Plane) 1
B , Step (Ledge) 2
A , Kink 3
Activity Order : A > B >C
Dislocation
12
THEORY OF CORROSION
Corrosion Process
Due to the electrochemical nature of corrosion, there shall
be electron transfer

Electron transfer requires presence of anode sites and


cathode sites on the metal surface

Due to potential difference ( ∆V ) between anodes and


cathodes electrons migrate from anodes to cathodes

Electrons liberated at anodes should be consumed at


cathodes

13
THEORY OF CORROSION

Corrosion Process
@ Anode Sites :
Surface defects
More -ve potentials
Metal atoms have high energy, i.e. unstable & active
Thus, metal atoms ionize by losing their electrons, i.e.
oxidation reaction : M0 Mn+ + ne-
As a result, metal loss occurs, i.e. metal dissolution

OILRIG
Oxidation Is Loss of electrons
Reduction Is Gain of electrons

14
THEORY OF CORROSION

Corrosion Process
@ Cathode Sites :
Intact ( un-defected ) surface areas
More +ve potentials
Metal atoms have low energy, i.e. stable & un-active
Receive electrons to be consumed, i.e. reduction reaction
As a result, no metal loss occurs, i.e. no corrosion

OILRIG
Oxidation Is Loss of electrons
Reduction Is Gain of electrons

15
THEORY OF CORROSION

Corrosion Process

The corrosion process involves two reactions:

A. Anodic Reaction (metal dissolution / oxidation )

B. Cathodic Reaction ( reduction )

16
THEORY OF CORROSION

Corrosion Process
A. Anodic Reaction (metal dissolution)
Fe Fe 2+ + 2e-

B. Cathodic Reaction
1. Oxygen reduction reaction

O2 + 2H2O + 4e- 4 OH-

Predominates in aerated
Near-Neutral solutions pH > 5

17
THEORY OF CORROSION

B. Cathodic Reaction
2. Hydrogen evolution reaction
2H+ + 2e- 2H (adsorbed) H2 (gas)
Predominates in acid solutions pH < 5

18
THEORY OF CORROSION

2H++2e 2H H2
In conclusion:

A piece of metal immersed


in an electrolyte acts as its
own:

Anode
Cathode
Electrical connection

19
THEORY OF CORROSION

The Corrosion Cell 2H++2e 2H H2

In a corrosion cell:

Electrons leave the anode


and migrate to cathode
within the metal;
i.e. electronic movement

The circuit is close by


migration of +ve & -ve
ions between anode and
cathode in the electrolyte;
i.e. ionic movement

20
THEORY OF CORROSION

For Corrosion to occur :

There must be a positive or anodic area,


referred to as the “anode”

There must be a negative or cathodic area,


referred to as the “cathode”

There must be a path for ionic current flow,


or “electrolyte”

There must be a path for electronic current


flow which is normally a “metallic path”

21
THEORY OF CORROSION

Factors of Corrosion

1- Water
2- Oxygen
3- Acidity

22
THEORY OF CORROSION

Testimony

An environment is considered corrosive if it contains


Water with dissolved Oxygen and / or Acidity ( H+ ions )

Fe

23
THEORY OF CORROSION

Corrosion Rate
The rate at which metal loss occurs due to corrosion is
expressed in terms of:

mpy milli- inch per year


Or
mmpy milli- meter per year

24
THEORY OF CORROSION

NACE International Ranking for Steel Corrosion


Corrosion Rate Level of corrosion
(mpy)
<1 Low

1-5 Moderate

5-10 Severe

>10 Intense

NACE= National Association for Corrosion Engineers

25
FORMS OF CORROSION

Types of Corrosion:

1. Uniform (General) Corrosion

1. Localized Corrosion

Pitting and Crevice Corrosion

Stress Corrosion Cracking

Hydrogen Damage ( Embrittlement / Blistering )

Galvanic Corrosion

26
FORMS OF CORROSION

According to the National Physical Laboratory – UK :

30% of equipment failures are due to uniform corrosion

70% of equipment failures are due to localized corrosion

27
FORMS OF CORROSION
General Corrosion
In general corrosion there is no distinction between the anode and
the cathode sites

i.e. the whole metal surface is acting as anode and cathode, so:

Anodic current ( Ia) = Cathodic current ( Ic) , and

Area of anode ( Aa) = Area of cathode ( Ac)

Hence,
Anodic current density ( ia) = Cathodic current density ( ic)

Therefore, the metal loss is equally and uniformly distributed all


over the surface, i.e. corrosion proceeds horizontally along the
metal surface
28
FORMS OF CORROSION
Localized Corrosion
In localized corrosion there is clear distinction between the anode and
the cathode sites

The anode sites are being very small compared with the large cathode:
Anodic current ( Ia) = Cathodic current ( Ic) , and

Area of anode ( Aa) << Area of cathode ( Ac)


Hence,
Anodic current density ( ia) >> Cathodic current density ( ic)

Therefore, the metal loss is concentrated in local areas, i.e. corrosion


proceeds downwards perpendicular to the metal surface

29
FORMS OF CORROSION

Pitting corrosion

Occurs with metals having oxide ( Passive )


film
I.e. the metal is in the zone of Passivity, e.g.
stainless steels, due to film local film
breakdown
Chloride ions (Cl-) have damaging effect on
oxide film of stainless steels

30
FORMS OF CORROSION

Pitting corrosion

31
FORMS OF CORROSION

Pitting corrosion

In Absence of Chloride Ions

Intact Oxide Film Scratched Oxide Film Film Self-repair


32
FORMS OF CORROSION

Pitting corrosion

What is the role of chloride ions in localized corrosion;


pitting ?
Help in breaking down the passive oxide film, specially
at weak point
Allow a very low pH to be achieved inside the pit, due
to the formation of HCl
Metal chlorides are very soluble

33
-
Cl Cl -
Cl
-
-
Cl -
Cl
-
Cl -
-
Cl -
Cl
Cl
-
Cl -
Cl
-
Cl -
Cl
-
Cl O2
O2 Cl-Cl - -
Cl
-
Cl
Cl - -
Cl
-
Cl -
Cl -
Cl
Cl Cl
-
- -
Cl
-
OH
-
OH

MCl + H2O = MOHH++ HCl


H + -
OH e
-
-
e
H+ H+ -OH
+
M
+
M
O2 + 2H2O
H + 4e -> 4(OH ) +
H+ - H+
H+ -
e
-
-
e H+
-
OH +
M
+
M -
OH
-
e
H+
-
e Pitting
-
OH
+
M
+
M Corrosion
34
FORMS OF CORROSION

Pitting corrosion

Pitting may lead to pipe perforation

35
FORMS OF CORROSION

Crevice corrosion

36
FORMS OF CORROSION

Crevice corrosion under gasket

37
FORMS OF CORROSION

Pitting corrosion on
free surface

Crevice corrosion
under washers

38
FORMS OF CORROSION

Stress Corrosion Cracking (SCC)

Caused by the simultaneous effects of tensile stress and a


specific corrosive environment.

Stresses may be due to:


applied loads ( static / dynamic )

residual stresses from the


manufacturing process, or

combination of both

39
FORMS OF CORROSION

Stress Corrosion Cracking (SCC)


Dynamic Test :
Slow Strain Rate Test

Stress
In Air

In Environment

Strain
40
FORMS OF CORROSION
Stress Corrosion Cracking (SCC)

Agar gel containing : Phenolphthalein


& HexaCyanoIron Fe(CN)6-

@
@Cathodes
Cathodes::
PhPh
PhPh++OH
OH-
-

Iron nails
Pink
PinkColor
Color
@
@Anodes
Anodes::
H.C.I.
H.C.I.++Fe
2+
Fe2+

Sites of Stress =
Sites of stress
Anodic Sites
Prussian
PrussianBlue
Blue 41
FORMS OF CORROSION

Stress Corrosion Cracking (SCC)


Atoms of metal at stressed areas have high energy ,
i.e. very active

High localized corrosion rates at such areas

Localized metal loss leading to cracking

Cracked Pipe Cracked weld

42
Stress Corrosion Cracking

Stress corrosion cracking of brass

43
FORMS OF CORROSION
Stress Corrosion Cracking
The crack is initiated at a pit or a crevice located within a stressed area

The crack growth may be:

Cutting through the grains ,


i.e. Transgranular Cracking
e.g. Sulfide stress cracking
Cl- or S2-

S2- Cl-
Along the grain boundaries
( in between the grains )
i.e. Intergranular Cracking
e.g. Chloride stress cracking

44
FORMS OF CORROSION
Transgranular SC

Intergranular SC

45
FORMS OF CORROSION
Hydrogen Damage
Hydrogen Blistering
Surface bulges, resulting from subsurface
voids produced in a metal by hydrogen
Grain Boundaries
absorption in (usually) low-strength alloys.

46
FORMS OF CORROSION

Hydrogen Blistering Mechanism:

H+ H+

H H2 H H H H H

e
-

-
e H2

H2
47
FORMS OF CORROSION
Hydrogen Blistering

Cross-section of a carbon steel plate


Hydrogen blistering of
showing a large hydrogen blister
a carbon steel plate

48
FORMS OF CORROSION

Hydrogen Embrittlement

49
FORMS OF CORROSION

Galvanic Corrosion

Occurs when two dissimilar metals are in


direct electric contact

Dissimilar metals have different reactivities


since they have different positions in the
Electrochemical Series

50
FORMS OF CORROSION

Nobel (+)

GALVANIC SERIES
OF METALS

Active (-)
51
FORMS OF CORROSION
Galvanic Corrosion

Due to the potential difference


between dissimilar metals :

The less noble metal is more Active


and acts as Anode ; i.e. it dissolves

The more noble metal acts as


Cathode ; i.e. it remains intact.

52
FORMS OF CORROSION

Uncoupled Dissimilar Metals

Anodic rxn : Zn = Zn2+ + 2e- Fe = Fe2+ + 2e-


Cathodic rxn: 2H+ + 2e- = H2 2H+ + 2e- = H2
Zn strip Fe strip

Both metals corrode but @


different rates
More active metal ( Zn )
H2 gas
being FASTER
bubbles

Dil. HCl soln

53
FORMS OF CORROSION

Coupled Dissimilar Metals

e e
V

Anodic rxn: Zn = Zn2+ + 2e- Cathodic rxn: 2H+ + 2e- = H2

More active Less active


metal is eaten metal remains
away rapidly, intact with H2
gas evolution
i.e. corrodes

Dil. HCl soln

54
FORMS OF CORROSION
Galvanic Corrosion
Carbon steel Inconel ring

Cu

Al

55
FORMS OF CORROSION

Surface area effect in galvanic corrosion

Small cathode Large anode combination is Acceptable

Stainless
Steel Valve
Carbon Steel
SS CS

56
FORMS OF CORROSION

Surface area effect in galvanic corrosion

Small anode Large cathode combination is NOT Acceptable

X Carbon Steel
Valve
Stainless Steel
CS SS

57
FORMS OF CORROSION
Surface area effect in galvanic corrosion

Which is better ???


X
Brass bolt in a steel structure Steel bolt in a brass structure
Small brass cathode will
cause small increase in Small steel anode will
corrosion of steel suffer large increase in
structure. Bolt will be corrosion due to
protected from corrosion coupling with brass
by coupling to steel structure.
58
FORMS OF CORROSION

Galvanic Corrosion

SS

Carbon Steel Bolt

59
CORROSION CONTROL

Corrosion Control

1. Anodic : by blocking the anodic reaction

2. Cathodic : by blocking the cathodic reaction

3. Mixed : by blocking both anodic & cathodic reactions

60
Corrosion Control Techniques

Corrosion Control Techniques

1. Materials Selection

1. Improved design

1. Chemical Treatment

1. Protective Coatings

1. Cathodic Protection

61
Corrosion Control Techniques
1. Materials Selection
A. Information needs
Process flow diagrams (PFD) showing design/ operating/
upset conditions of:
• Temperature (min. & max.)
• Pressure
Stream chemical analyses showing the corrosive
constituents and their concentrations:
• H2O
• Dissolved gases (O2, CO2, H2S)
• Cl-
• TDS (total dissolved salts)
• pH
• TAN (total acid number ) for crude oil
• Total Sulfur Content
62
Corrosion Control Techniques
1. Materials Selection

Effect of dissolved gases

63
Corrosion Control Techniques
1. Materials Selection

Effect of dissolved gases


GUIDANCE FOR PREDICTING CO2 CORROSION

PPCO2 (psi) Expected corrosion

<3 Non-corrosive
3-30 May indicate corrosion
>30 Indicates corrosion

64
Corrosion Control Techniques
1. Materials Selection
PREDICTING CO2 CORROSION

65
Corrosion Control Techniques
1. Materials Selection

Effect of dissolved salts

Dissolved salts ions speed up


the corrosion process due to
ionic movement

a) Pure water b) NaCl solution

66
Corrosion Control Techniques
1. Materials Selection

Effect of dissolved salts

Sea water is an excellent


electrolyte, i.e. very corrosive

At high salts concentrations,


corrosion rate drops due to :
Lesser
dissolved O2

Lesser ionic movement


because of crowdedness
67
Corrosion Control Techniques
1. Materials Selection

Stream Velocity
Corrosion rate and corrosion type are function of flow
velocity

CORROSION RATE
Corrosion Rate

GENERAL CORROSION EROSION CORROSION CAVITATION CORROSION


LAMINAR FLOW TURBULENT FLOW CAVITATION
Ucrit FLOW VELOCITY

68
Corrosion Control Techniques
1. Materials Selection

Stream Velocity

69
Corrosion Control Techniques
1. Materials Selection

Stream Velocity

70
Corrosion Control Techniques
1. Materials Selection

C. Materials Selection Factors:


Corrosion Resistance

Cost Effectiveness
Mechanical
Properties

Availability
71
Corrosion Control Techniques
1. Materials Selection

Engineering Materials

Metallic Non-Metallic

PVC
Ferrous Non-Ferrous
Polyethylene
Copper Alloys Polypropylene
Cast Irons
Nickel Alloys Teflon
Carbon Steels
Aluminum GRE / GRP
Stainless Steels
Ceramics

72
Corrosion Control Techniques
1. Materials Selection

Fiber glass vessels

73
Corrosion Control Techniques
1. Materials Selection

Fiber glass pipes

Above-ground interconnecting
Under-ground GRP GRP piping
pipeline GRP piping

74
Corrosion Control Techniques
1. Materials Selection

Fiber glass piping connections

Flanged Connection Bell-Spigot Connection


with Key Lock

75
Corrosion Control Techniques
1. Materials Selection

Advantages of Using Non-Metallics :

No need for any corrosion control method, e.g. chemical


treatment, cathodic protection, painting
Ease of handling and transport
Ease of installation

76
Corrosion Control Techniques
1. Materials Selection

Limitations of Non-metallics :

The use of most non-metallics is restricted to relatively


narrow range of temperature and pressure
Under-ground structures can be easily damaged in case of
soil movement
Care must be taken not to damage above-ground structures

77
Corrosion Control Techniques
1. Materials Selection

Important Notice on Non-Metallics Application

Always check and make sure of :


Compatibility of material with the medium chemical
analysis, such as pH, organic solvents
Suitability of material for the service conditions of
temperature and pressure
Possibility of soil movement in case of buried piping

78
Corrosion Control Techniques
1. Materials Selection

Cost of Material

Criteria: to reach a compromise between the capital


expenditure (CAPEX) and operation expenditure (OPEX)

Usually select a cost effective material, e.g. CS, in association


with one or more Supportive Corrosion Control Techniques

79
Corrosion Control Techniques
1. Materials Selection
CLADDING

Can be used for


economical reasons

80
Corrosion Control Techniques
2. Improved Design

Examples of
Impingement Corrosion

81
Corrosion Control Techniques
2. Improved Design

Examples of avoiding
impingement corrosion
by design

82
Corrosion Control Techniques
2. Improved Design

Examples of avoiding
crevice corrosion by Good
design

Bad

83
Corrosion Control Techniques
2. Improved Design

Examples of avoiding
crevice corrosion by Improper Weldments
design

Proper Weldment

84
Corrosion Control Techniques
2. Improved Design

Improved Design, e.g.:

Incorporation of corrosion allowance

t (required) = t min + CA

Life time = corrosion allowance (mm) / corrosion rate (mm/year )

85
Corrosion Control Techniques
2. Improved Design

• Incorporation of corrosion allowance


CYLINDRICAL SHELLS SPHERE SHELS PIPES
PR PR PR
T= + C.A T= + C.A T= + C.A
SE-0.6 2SE-0.2P SE-0.6P

P: design pressure in N/mm2 CA: corrosion allowance, mm


R: inside radius, mm t : min. corroded thickness, mm
S: stress value of material, N/mm2
E: joint efficiency

86
Corrosion Control Techniques
2. Improved Design

Avoiding contact
between dissimilar
metals

Nobel

Active

87
Corrosion Control Techniques
3. Chemical Treatment

Chemical treatment involves injecting chemicals that


Retard the corrosion of a metal.

Types of Treatment :

Neutralization ( pH control )
Removal of dissolved gases ( scavengers )
Corrosion inhibitors
Biocides

88
Corrosion Control Techniques
3. Chemical Treatment

A. pH Control

89
Corrosion Control Techniques
3. Chemical Treatment
A. pH Control
Steel corrosion rate related to
hydrogen ion concentration in electrolyte

To avoid acid corrosion, the pH of the


medium shall be raised up to about 7
by injection of
• Caustic Soda NaOH
• Ammonia NH3

Periodical check on pH by means of pH probes

90
Corrosion Control Techniques

Crude Oil Fractional Distillation

91
Corrosion Control Techniques

Crude Oil Fractional Distillation

92
Corrosion Control Techniques

Crude Oil Fractional Distillation

Prior allowing the crude


into the distillation
tower, most of water &
dissolved salts are
removed by
Desalter and Hydro-
treater

93
Corrosion Control Techniques

Crude Oil Fractional Distillation

Process
Flow

94
Corrosion Control Techniques

Inside the lower section of the crude


distillation tower, hydrolysis of remaining
dissolved salts occurs at high temperatures:

MgCl2 + 2H2O Mg (OH)2 + 2HCl


CaCl2 + 2H2O Ca (OH)2 + 2HCl
NaCl + H2O no reaction

95
Corrosion Control Techniques

Water condenses in the colder overhead section of the


tower along with HCl acid.
Condensed water has pH of 1.5
Hence, acid corrosion occurs

96
Corrosion Control Techniques
3. Chemical Treatment

B. Removal of Dissolved Gases

Dissolved oxygen can be removed by injection of oxygen


scavengers

Amine unit can be used for removal of CO 2 & H2S

Mechanical deaerator can also be used to remove all


dissolved gases: O2, CO2, H2S

Periodical checks on dissolved O2 concentration by means


of O2 probes

97
Corrosion Control Techniques
3. Chemical Treatment

Mechanical Removal of Dissolved Gases


by Deaerator

98
Corrosion Control Techniques
3. Chemical Treatment

C. Corrosion Inhibitors

NACE definition :
“ Chemicals which reduce the corrosion rate when added
to a normally corrosive medium in small concentrations.”

Inhibitors selection is based on:

metal
environmental chemical composition
service condition (e.g. temperature, flow rate)

99
Corrosion Control Techniques
3. Chemical Treatment

Application of Corrosion Inhibitors

- Oil refineries
- Petrochemical plants
- Oil and gas production
- Desalination plants
- Cooling water installations

- storage facilities
- Hydro tests
A Cooling Tower Unit

100
Corrosion Control Techniques
3. Chemical Treatment

Classification of Inhibitors:

Inhibitors for Acid media

pH < 5

Inhibitors for Near-Neutral media

pH 5 – 10

Above pH 10, the alkalinity (OH- ions) of the medium is


self-inhibiting

101
Corrosion Control Techniques
3. Chemical Treatment
A. Inhibitors for Acid media

Usually organic compounds with long hydrocarbon chains


with polar (charged) head

102
Corrosion Control Techniques
3. Chemical Treatment

Film forming theory

Mechanism:

1) Formation of physical
barrier, thus blocking the
reaction sites (anode and
cathode sites).

2) Interference with adsorbed


H- atoms, thus prevents
H- embitterment / blistering.

103
Corrosion Control Techniques
3. Chemical Treatment
B. Inhibitors for Near Neutral Media

Usually are inorganic compounds

Anodic

Cathodic, or

Mixed ( Mixtures of both anodic and cathodic inhibitors )

104
Corrosion Control Techniques
3. Chemical Treatment
Inhibitors for Near Neutral Media

In case of absence of the inhibitor: usually are categorized as:

Safe or Dangerous

• Safe General Corrosion


• Dangerous Localized Corrosion

105
Corrosion Control Techniques
3. Chemical Treatment
Anodic Inhibitors

- Block the anodic sites by formation of iron oxides


- All are O-containing
- All are dangerous
e.g. Chromates CrO4-2
Molybdates MoO4-2
Silicates SiO4-2
nitrites NO2-
COO-
benzoate
phosphates PO4-3
106
Corrosion Control Techniques
3. Chemical Treatment
Cathodic Inhibitors

- Block the cathodic sites by formation of scales


- All are safe inhibitors
e.g. Zinc ions Zn 2+
Calcium ions Ca 2+

Zn 2+ + 2 OH- Zn (OH)2
Scale on cathode
at cathode

Ca 2+ + 2 OH- Ca (OH) 2
Scale on cathode
at cathode

107
Corrosion Control Techniques
3. Chemical Treatment

Mixed Inhibitors

Mixtures of both anodic and cathodic inhibitors

Block both anodes and cathode

Compatible mixture

108
Corrosion Control Techniques
3. Chemical Treatment

Efficiency of inhibitors :

Expressed as :

Protective Power ( Z)

where,
Z = [(RO-R) / RO] X 100

Ro: Corrosion rate in absence of inhibitor.

R : Corrosion rare in presence of inhibitor.

109
Corrosion Control Techniques
3. Chemical Treatment

Curve showing drop in corrosion


rate as a function of inhibitor
concentration

Corrosion rate
Minimum Inhibitive
Concentration

Corrosion inhibitor
concentration

110
Corrosion Control Techniques
3. Chemical Treatment

D. Biocides:

Definition
A substance that is capable of killing a certain
micro-organism or spectrum of Micro-organisms

Biocidal activity
The concentration needed to kill the micro-
organisms

MKC VALUE = minimum killing concentration

111
Corrosion Control Techniques
3. Chemical Treatment

Biocides role in corrosion control:

Kill micro-organisms that feed on the corrosion inhibitors

Kill micro-organisms that produce corrosive metabolites

Sulfate-reducing bacteria ( SRB )

112
Corrosion Control Techniques
3. Chemical Treatment

113
Corrosion Control Techniques
3. Chemical Treatment

Control of Microbial Corrosion


Use of biocides in closed systems

- capable of killing wide range of microbes

- biodegradable, environmentally friendly

- non-harmful for humans and other living organisms

- compatible with the metal, i.e. non-corrosive

- two different biocides to be used alternatively

114
Corrosion Control Techniques
3. Chemical Treatment

Scale Inhibitors ( Anti-scaling


Agents ) ( Scale Removers )

Chemicals added to the stream to prevent or


remove scales ( deposits )
Corrosion can proceed underneath the deposit ,
Under- Deposit Corrosion
Microbial ( SRB ) Corrosion is initiated under the
deposits
Scaling tendency is determined by process
engineers

115
Corrosion Control Techniques
3. Chemical Treatment

Scale Inhibitors ( Anti-scaling Agents )


( Scale Removers )

Under- Deposit Corrosion

116
Corrosion Control Techniques
3. Chemical Treatment

Typically fouled ( heavy scale )


heat exchanger tube resulting
in poor heat transfer

117
Corrosion Control Techniques
3. Chemical Treatment

EXCHANGER
PERFORMANCE

118
Corrosion Control Techniques
3. Chemical Treatment
Chemical Injection

Chemical Injection Skid :

Chemical Tanks &


Non-metallic Tanks
Chemical Injection
( Dosing ) Pumps

Stainless Steel Tanks

119
Corrosion Control Techniques
3. Chemical Treatment
Chemical Injection

Chemical Injection Point

High Alloy
Quell

120
Corrosion Control Techniques
3. Chemical Treatment
Chemical Injection

Chemical Injection Using


Internal Jet

121
Corrosion Control Techniques
3. Chemical Treatment

Treatment
reserve Waste of Chemicals X
Ideal

No Protection

Time

BAD CONTROL

122
Corrosion Control Techniques
3. Chemical Treatment

Ideal

Time

GOOD CONTROL

123
Corrosion Control Techniques
4. Protective Coatings

Definition of a

A material that adheres to and covers the metal surface

The coating can be applied :


onto external surfaces; external coating
and / or
onto internal surfaces; internal coating ( Lining )

124
Corrosion Control Techniques
4. Protective Coatings

Paints

Definition :

“ a liquid material, which can be applied on a surface,


and which – after drying – forms a thin, cohesive,
non-porous film with good adhesion to the surface “.

125
Corrosion Control Techniques
4. Protective Coatings

Surface Preparation : prior to coating application

Criteria :

• Surface Cleanliness

Surface Roughness

126
Corrosion Control Techniques
4. Protective Coatings

Surface Cleaning

The surface has to be free of dust

The surface has to be


free of salts

Presence of salts causes


paint blistering by osmosis,
i.e. osmotic blistering

127
Corrosion Control Techniques
4. Protective Coatings

Surface Preparation

Surface Cleanliness

Removal of scales, rust, dirt, grease, etc…

Done by :

Water jetting
Abrasive blasting ( provides surface roughness )

Sand blasting
Grit blasting

128
Corrosion Control Techniques
4. Protective Coatings

Surface Cleaning

Water Jetting

129
Corrosion Control Techniques
4. Protective Coatings

Abrasive Blasting

Sand blasting

not recommended as it causes


air pollution by increasing the
amount of suspended solids

Sand Blasting
Provides reasonable surface
roughness
130
Corrosion Control Techniques
4. Protective Coatings

Abrasive Blasting
Grit / Shot blasting

By using metal shots with sharp


edges

Grit Shot
Recommended as it does not cause
air pollution

Provides excellent surface


roughness ( profile )

Recyclable
131
Corrosion Control Techniques
4. Protective Coatings

Abrasive blasting
nozzles

Abrasive blasting
for pipe internal
Abrasive blasting
pot
132
Corrosion Control Techniques
4. Protective Coatings

Surface Profile

The blasted metal surface is Rough


The roughness is due to presence of Profile or Anchorage
The surface ( anchor ) profile consists of Peaks & Valleys

Peaks (Craters) Valleys

133
Corrosion Control Techniques
4. Protective Coatings

Surface Profile
3 parameters are important to obtain acceptable surface profile:
1- Peak to valley depth

2- Shape of craters Rmax

3- Density of peaks: number of craters per linear inch or cm

Sharp & Dense


3 different
surfaces Sharp but less
of same Dense (grit)
Rmax
Dimpled (shot)
134
Corrosion Control Techniques
4. Protective Coatings

Surface Cleanliness International Standards

Surface USA Spec. British Std. Swedish SIS Japanese Std.


Finish NACE
SSPC BS 4232 05 5900 SPSS
White Metal SSPC-SP 5 NACE 1 st quality 1 SA 3
Near White JA Sh2 or
Metal SSPC-SP 10 NACE 2 nd quality 2 SA2 1/2
JA Sd2
Commercial JA Sh1 or
Blast SSPC-SP 6 NACE 3 rd quality 3 SA 2
JA Sd1
Brush Off
Blast SSPC-SP 7 NACE 4 - SA 1 -

135
Corrosion Control Techniques
4. Protective Coatings

Surface Preparation Affects Coating Durability

136
Corrosion Control Techniques
4. Protective Coatings

Types of Coatings

Paints Wrapping Heat-Shrinkable


Sleeves
Applied Applied
Applied
externally & externally only
externally only
internally

137
Corrosion Control Techniques
4. Protective Coatings

Chemical Composition of Paints

Primary Components :
Resin ( binder / vehicle / base )
Hardener ( curing agent )
Solvent ( thinner )

Secondary Components :
Color Pigments
Cementing Particles
Corrosion Inhibitors

138
Corrosion Control Techniques
4. Protective Coatings
Classification of Paints
Chemically drying paints:

initially by solvent evaporation

then a chemical reaction between the resin and the


hardener (curing agent): Resin + Hardener Polymer

They are irreversible paints,


i.e. solvent non-sensitive

supplied in TWO cans

e.g. Epoxies, Polyurethanes


139
Corrosion Control Techniques
4. Protective Coatings

Chemically drying paints:

The curing agent can be the Binder + O2(air) Polymer


atmospheric oxygen. In this
case, the paint is called
oxidative drying paint Oxidation is the polymerization
process of alkyds, modified
alkyds and epoxy-ester binders
Oxidative paints are
supplied in Single cans

Chemically drying paints take into consideration Pot


Life and in some cases Induction Time.

140
Corrosion Control Techniques
4. Protective Coatings

Classification of Paints

According to the paint drying mechanism :

Physically drying paints :

drying by evaporation of solvent / thinner

they are known as reversible paints, i.e. solvent sensitive

supplied in single cans

e.g. Zinc-rich paints


141
Corrosion Control Techniques
4. Protective Coatings

Wrapping & Sleeves


Used mainly for field joints

142
Corrosion Control Techniques
4. Protective Coatings

Wrapping & Sleeves


Used mainly for field joints

143
Corrosion Control Techniques
4. Protective Coatings

Wrapping & Sleeves


Wrapping can be used for under- ground in-plant
piping, e.g. open & closed drain piping network

144
Corrosion Control Techniques
5. Protective Coatings

Painting Application

Paint Application Methods


Paint Application Conditions
Paint Application Defects
Paint Inspection

145
Corrosion Control Techniques
5. Protective Coatings

Paint Application Methods

Brush
Roller
Spraying :
Air Spray
Airless Spray
Electrostatic Spray

146
Corrosion Control Techniques
5. Protective Coatings

Paint Application Methods

Brush:
Very effective
Very slow
Used for small objects and touch-ups
Roller:
Ineffective
Porous film
Slow
Used for gates and fences

147
Corrosion Control Techniques
5. Protective Coatings

Paint Application Methods

Fan
Spraying = Atomization

Atomization : converting a liquid into


tiny minute droplets

148
Corrosion Control Techniques
5. Protective Coatings

Paint Application Methods

Spraying

Fast
Very effective
Uniform film
Requires skillful operators
Most commonly used method
20% approx. loss is expected

149
Corrosion Control Techniques
5. Protective Coatings

Paint Application Methods

Air Spray :
Atomization of paint is assisted by air

Requires air compressor + air filters

Air quality is a must

Not suitable for paints containing


oxidizable metal particles ,
e.g. zinc-rich paints

150
Corrosion Control Techniques
5. Protective Coatings

Paint Application Methods

Airless Spray :
Suitable for metal-containing paints
Requires high pressure pumps
Atomization is due to ∆P

151
Corrosion Control Techniques
5. Protective Coatings

Paint Application Methods

Electrostatic Spray :
Needs DC power supply between
spray gun & work piece
Paint loss down to ~ 2%
Excellent uniform appearance
Most expensive

152
Corrosion Control Techniques
5. Protective Coatings

Paint Application Methods

Electrostatic Spray :

153
Corrosion Control Techniques
5. Protective Coatings
Painting System ( Cycle )
The 3-layer paint system :
Primer :1st layer
provides corrosion protection
provides adhesion to metal surface

Inter-coat : 2nd layer


provides mechanical strength to the system

Top (Finish) : 3rd outmost layer


provides UV resistance Steel
provides abrasion resistance
provides the specified color code

154
Corrosion Control Techniques
5. Protective Coatings
Typical 3-Layer Painting System :

Primer : Zinc-rich compounds


Inter-coat : High build / solids epoxy
Top (Finish) : Polyurethanes

Recommended paint system For external steel surfaces


at ambient temp. up to 940C

For higher temperatures, special painting systems


to be specified

For internal surfaces, No need for neither top coat Nor color
code. Use extra thicker inter-coat instead
155
Corrosion Control Techniques
5. Protective Coatings

Typical Pipeline Coating

3-Layer System
Polyethylene

Or

Polypropylene

2-3 mm thick

156
Corrosion Control Techniques
5. Protective Coatings
Typical Steps of 3-Layer Pipeline Coating

3
2
1

1 Fusion Bonded Epoxy ( FBE )

2 Copolymer Adhesive

3 Polyethylene ( PE ) or Polypropylene ( PP )

157
Corrosion Control Techniques
5. Protective Coatings
Typical Steps of 3-Layer Pipeline Coating

1 2 3

1- Surface Preparation
2- Surface Inspection
3- Induction Heating
4- Coating Application

4
158
Corrosion Control Techniques
5. Protective Coatings

2
1

1 Anti-corrosion Painting System

2 Concrete Weight Coating

159
Corrosion Control Techniques
5. Protective Coatings

Keys of Coating Success :

Surface Preparation
Materials
Coating Application
Inspection

160
Corrosion Control Techniques
5. Protective Coatings

Conditions of Successful Painting Application :

1. Adequate lighting 500-1000 lumen / m2

2. Proper ventilation for confined or closed areas


to ensure paint drying

161
Corrosion Control Techniques
5. Protective Coatings

3. Temperature of steel structure (skin temp.)


should be above the dew point by 3º C (5o F) min. and
does not exceed 45º C. Since at high temperatures the drying
and curing of paint is rather rapid.

Rapid drying causes:


Paint defects
Dry spray: i.e. loss of solvent
during application

162
Corrosion Control Techniques
5. Protective Coatings
Dew Point Calculation Chart

163
Corrosion Control Techniques
5. Protective Coatings

Dew Point Instrument

164
Corrosion Control Techniques
5. Protective Coatings

4. Climatic conditions:

No rain

No dust

Relative humidity does not


exceed 85%, since solvent
evaporation slows down
in saturated atmospheres

165
Corrosion Control Techniques
5. Protective Coatings

4. Climatic conditions:

No winds to avoid over-spraying

Atmospheric temperature
should be above 10º C. At lower
temperatures :
Solvent evaporation may stop
altogether
Increased possibility of ice and frost

166
Corrosion Control Techniques
5. Protective Coatings
5. Accessibility of work piece
(Scaffolding )

167
Corrosion Control Techniques
5. Protective Coatings

6. Paint inspection
• integrity of cans
• Shelf-life
• Pot life
• Induction time
• Color code (top coat)

7. Paint system / cycle


• Primer
• Inter-coat Steel
• Top or finish coat

168
Corrosion Control Techniques
5. Protective Coatings

8. Paint technical data sheet


• Generic type
• Curing time
• DFT (dry film thickness) limits

9. Paint application data sheet


• Mixing ratio
• Safety regulations during application

10. Paint safety data sheet

11. Operator skills ( Workmanship )

169
Corrosion Control Techniques
5. Protective Coatings

Operator Skills

Cross Spraying is required


when very high and uniform
film thickness is required

170
Corrosion Control Techniques
5. Protective Coatings

Operator Skills

The spray gun must be perpendicular to


the steel surface and ~ 50 cm away from it

Operators must stick to


Safety Regulations

171
Corrosion Control Techniques
5. Protective Coatings
Steel Company

172
Corrosion Control Techniques
5. Protective Coatings
In order to perform effectively, a corrosion resistant painting must be
characterized by some essential properties.
– Water resistance
– Chemical resistance
– Proper adhesion
– Coherent
– Abrasion resistance
– Ability to expand and contract
Environmentally Friendly
– Weather resistance
– Non-porous Alligatoring / Crocodiling
– Pleasing appearance

Rigid non-flexible paint


173
Corrosion Control Techniques
5. Protective Coatings

Inspection : a certified paint inspector shall check for :

Surface cleanliness
Surface roughness
Conditions of paint application & equipment
Coating defects & holidays
Coating adhesion
Coating dry film thickness

174
Corrosion Control Techniques
5. Protective Coatings

Steel skin temperature devices

Left for 5 min. in contact with steel surface Instantaneous read-out

175
Corrosion Control Techniques
5. Protective Coatings

Surface Cleanliness

Visual inspection for surface


solid particles, e.g. dust

Magnifying Lenses Torch Masking Tape

176
Corrosion Control Techniques
5. Protective Coatings
Surface Cleanliness
SA 2.5 : Near-white, for external
surfaces
SA 3 : White, for internal
surfaces
Comparator

177
Corrosion Control Techniques
5. Protective Coatings
Surface Roughness tools
1

Press – O – Film ( Replica )


For curved surfaces, e.g.
piping 2

178
Corrosion Control Techniques
5. Protective Coatings

Surface Roughness tools


For flat surfaces

Analog Gauge Digital Gauge

179
Corrosion Control Techniques
5. Protective Coatings

Paint Inspection by Holiday Detector

Holiday detection is
carried out for external
coatings of buried piping
and pipelines.

Spring Coil

180
Corrosion Control Techniques
5. Protective Coatings

Holiday Detector

181
Corrosion Control Techniques
5. Protective Coatings

Holiday Detector
Holiday detection is
carried out for internal
coatings of piping and
pipelines.

182
Corrosion Control Techniques
5. Protective Coatings

Painting inspection by Wet Sponge Holiday Detector for flat surfaces

183
Corrosion Control Techniques
5. Protective Coatings

Painting inspection by Brush Holiday Detector for flat surfaces

184
Corrosion Control Techniques
5. Protective Coatings

Holiday Detector Voltage

The applicable voltage depends on the coating thickness

The required voltage can be calculated by NACE equation :

Testing voltage = V = 7900 (t)1/2


Where t = average coating thickness in mm

Testing voltage = V = 1250 (t)1/2


Where t = average coating thickness in mils

185
Corrosion Control Techniques
5. Protective Coatings
Cross Hatch Adhesion Test

Test Tools

Masking tape

Muti-plade cutter

186
Corrosion Control Techniques
5. Protective Coatings

Cross Hatch Adhesion Test


Test Procedure

2- Apply tape
1- Using the cutter
onto lattice
make lattice. Cuts
must be deep enough
to reach metal surface
187
Corrosion Control Techniques
5. Protective Coatings

Cross Hatch Adhesion Test


Test Procedure

3- Remove tape and


evaluate coating flaking
due to loss of adhesion

ASTM D - 4541

188
Corrosion Control Techniques
5. Protective Coatings

Cross Hatch Adhesion Test

X- Hatch Test Evaluation : According To German / American


Specification

Description DIN ASTM


No edges are detached 0 5
area affected at intersections of cuts 5%< 1 4
area detached at edges 5-15% 2 3
area detached, coating flaked at edges 15-35% 3 2
area detached 35-65% 4 1
area detached 65%> 5 0

189
Corrosion Control Techniques
5. Protective Coatings

Simple Cross Hatch ( Peal-off ) Test

190
Corrosion Control Techniques
5. Protective Coatings

Dry film thickness ( DFT )

Ultrasonic Thickness (UT) Gauges

Calibration Shims

UT gauges require calibration


before usage
191
Corrosion Control Techniques
5. Protective Coatings

Dry film thickness ( DFT )

Magnetic ( Banana )
Gauge
192
Corrosion Control Techniques
5. Protective Coatings

Wet film thickness

Wheel Triangle Comb

193
Corrosion Control Techniques
5. Protective Coatings

Painting Supplier Factors

194
Corrosion Control Techniques
5. Protective Coatings

Painting Cost

195
Corrosion Control Techniques
5. Protective Coatings

Important Remarks

Paints containing Lead (Pb), Chromium (Cr), and other heavy


metals are environmentally prohibited.

Surface roughness is measured in microns. Recommended


range 50-75 micron. Must refer to paint data sheet.

Internal coatings of potable water tanks should be approved


from international health organizations, e.g. WHO, FAD.

196
Corrosion Control Techniques
5. Protective Coatings

Important Remarks

Stainless steel surfaces exposed to marine environment need


to be painted against atmospheric corrosion. Paints should
be Zn-free epoxies.

Grit blasting of stainless steel surfaces to be done using


chloride-free non-ferrous shots, e.g. Al2O3.

Best protection is achieved by coatings + cathodic protection.


Coating being the 1st line of defense, whereas CP the 2nd line.

197
Corrosion Control Techniques
5. Protective Coatings

Paint Color Coding System

Since 1927, color charts have been


the standard for precise coloring worldwide

= Reichsausschuss fur Lieferbedingungen


= Committee of the German Reich for Terms
and Conditions of Sale

198
Corrosion Control Techniques
5. Protective Coatings

RAL started with only 40 colors

Recently, RAL includes about


2000 colors & shades

199
Corrosion Control Techniques
5. Protective Coatings

According to the RAL


system, each color or
shade is given a
specific RAL number

200
Corrosion Control Techniques
5. Protective Coatings

There are 3 Primary Colors

Blue
Red Yellow
Mixing any 2 1ry colors

Secondary Colors

201
Corrosion Control Techniques
5. Protective Coatings

Mixing the 3 1ry colors


Or Tertiary Color
Mixing 1ry color + 2ry color

Black & White are added to vary the shade;


i.e. darker or lighter

202
Corrosion Control Techniques
5. Protective Coatings
Purpose of Color coding
In oil & gas plants, different equipment are usually painted
with different colors; i.e. each type of equipment has its
own Color Code
Color Code helps in :
Quick identification
Warning against deadly objects; e.g. radioactivity
Better visibility , specially off-shore
Avoiding risk of fire, specially in gas plants

203
Corrosion Control Techniques
5. Protective Coatings
Examples of Color coding :

Fire Fighting Safety Red


LPG spheres/condensate Light Gray
& crude tanks
Steel structure Light Gray
Nitrogen lines Blue
Water lines Green
Crane moving parts Black + Yellow
Platform deck Yellow - Orange
Fired heater/Stakes Black
204
Corrosion Control Techniques
5. Protective Coatings
Examples of Color coding :

205
Corrosion Monitoring Techniques

Corrosion Monitoring

Definition :

“ the systematic measurement or evaluation of the


corrosion rate and type of corrosion occurring on
an equipment “ .

206
Corrosion Monitoring Techniques

Advantages of Corrosion Monitoring

avoids unplanned shutdowns


avoids loss of production resulting from unforeseen
corrosion failure
effective scheduling of maintenance works
reduction of inspection activities

207
Corrosion Monitoring Techniques

The efficiency of corrosion inhibitors is checked by


means of monitoring system.

Coupons

Electrical Probes

208
Corrosion Monitoring Techniques

Corrosion Coupons

Strip Coupons

Cylindrical Coupons
209
Corrosion Monitoring Techniques

Scaling Coupons

210
Corrosion Monitoring Techniques

Description of Type of Attack on a Coupon

Corrosion Product :

If the coupon surface was covered by corrosion product,


scale or deposit, they will be removed and collected for
chemical analysis

211
Corrosion Monitoring Techniques

Description of Type of Attack on a Coupon

Corrosion Product :
1- In Aerated Near-Neutral Solutions: Oxygen Corrosion
2 Fe 2 Fe2+ + 4 e-
O2 + 2 H 2 O + 4 e - 4 OH-
2 Fe + O2 + 2 H2O 2 Fe(OH)2
Iron Hydroxide
Brown Rust

212
Corrosion Monitoring Techniques

Description of Type of Attack on a Coupon

Corrosion Product :
2- In Acidic Media , e.g. HCl / H2SO4
Fe Fe2+ + 2 e-
2 H+ + 2 e - 2H H2

Fe + 2H+ Fe 2+
+ H2 Hydrogen Gas
Soluble ions
Monitoring
No solid product

213
Corrosion Monitoring Techniques

Description of Type of Attack on a Coupon

[Fe2+]

Time
Graphical Presentation of Iron Ions Concentration
with Time Showing the Effect of Chemical Treatment

214
Corrosion Monitoring Techniques

Monitoring of Acid Inhibitors by Iron Count

Graph of Corrosion rate

Start of Treatment Program

215
Corrosion Monitoring Techniques

Description of Type of Attack on a Coupon

Corrosion Product :
3- In Solutions of CO2 ( Sweet Corrosion )
CO2 + H2O H2CO3 carbonic acid
H2CO3 H+ + HCO3-
Fe Fe2+ + 2 e-
2 H+ + 2 e - 2H H2

2Fe2+ + 2HCO3- 2 FeCO 3– White


Iron Carbonate + 2H +
Scale
Precipitation is Temperature Dependant

216
Corrosion Monitoring Techniques

Description of Type of Attack on a Coupon

Corrosion Product :
4- In Solutions of H2S ( Sour Corrosion / Service )
H2S + H2O H + + HS-
Fe Fe2+ + 2 e-
2 H+ + 2 e- 2H H2

Fe2+ + HS- FeS + H +


Iron Sulfide
Black ppt.

217
Corrosion Monitoring Techniques

Typical corrosion monitoring point

218
Corrosion Monitoring Techniques

Coupon Handling

Retrieving the coupon Removal of Removal of The coupon is


corrosion corrosion accurately
product by soft product by weighed
wire mesh soaking in
inhibited acid

219
Corrosion Monitoring Techniques

Electrical Resistance (ER)


Probe- Corrosometer

For a wire or cylindrical shape :

R=pL/a

R = resistance
p = resistivity of the material
L = length
A = cross sectional area

220
Corrosion Monitoring Techniques

Electrical Resistance (ER)


Probe- Corrosometer

Wire-Loop

Flush

Cylindrical

221
Corrosion Monitoring Techniques

Electrical resistance probe


measurements for mild steel
coupons

A. In corrosive media
B. In non-corrosive media

A
B

222
Corrosion Monitoring Techniques

Corrosion Monitoring Point

Usually includes:
Corrosion Coupon ; mainly for visual evaluation of
corrosion type

Electrochemical Probe ;
for more accurate
instantaneous corrosion
rate determination, e.g.
ER probe

223
Corrosion Monitoring Techniques

On-Line Wall Thickness ( UT ) Measurements


Useful on-stream follow-up monitoring
tool

Transducer

Wall Thickness
Transmission Reflection 224
Calibration Block
Corrosion Monitoring Techniques

On-Line Wall Thickness ( UT ) Measurements

Base-line readings are taken at selected


locations before and placing the
equipment in service
Types of UT :
A-scan ( Spot ) ,
B-scan ( Linear ) ,
C-scan ( 3D )

225
Corrosion Monitoring Techniques

On-Line Wall Thickness ( UT ) Measurements

C-scan ( 3D )

226
Corrosion Monitoring Techniques

On-Line Wall Thickness ( UT ) Measurements

227
Corrosion Monitoring Techniques

On-Line Wall Thickness ( UT ) Measurements

Without Inhibition With Inhibition

228
Corrosion Monitoring Techniques

Monitoring of SRB Biocide Performance by Cultivation

Blackening the
medium indicates
presence of SRB

229
Corrosion Control Techniques
4.Cathodic Protection

Idea of Cathodic Protection

Cathodic protection system controls corrosion by making


the whole metal surface a cathode

230
Corrosion Control Techniques
4.Cathodic Protection
Cathodic Protection Principle
Sea Water
a) Without Cathodic Protection
Fe2+
Steel pipe wall corrodes freely O2 + 2H2O 4OH-

Both anodic & cathodic e- e- Pipe Wall


reactions occur
Pipe Inside

b) With Cathodic Protection


Sea Water
Anodic reaction stops
Cathodic reaction continues O2 + 2H2O 4OH-

External Supply of e- e- e- e- e- e- e- e- e- Pipe Wall


Electrons
Pipe Inside

231
Corrosion Control Techniques
4.Cathodic Protection

Application of CP Systems

On-Shore

232
Corrosion Control Techniques
4.Cathodic Protection
Application of CP Systems Off-Shore

Vessels

Subsea Pipelines

Jackets
Piles

233
Corrosion Control Techniques
4.Cathodic Protection

Types of CP Systems

According to the source of external supply of electrons,


there are two types of CP systems:

1- Sacrificial anode system

2 - Impressed current system

234
Corrosion Control Techniques
4.Cathodic Protection

1- Sacrificial anode system Magnesium ACTIVE


Zinc
Simplified Galvanic Aluminum
Series Iron
Lead
Tin
e- Nickel (Active)
Brass
Copper
Nickel (Passive)
410 Stainless
Titanium
304 Stainless
Zn Silver
Gold
Platinum NOBLE

Fe
235
Corrosion Control Techniques
4.Cathodic Protection

Galvanic Couples in Saline Water

Fe/Al Fe Fe/Cu Fe/Ag Cu/Ag

Without electrolyte With electrolyte

236
Corrosion Control Techniques
4.Cathodic Protection

Arrangement of a Sacrificial CP System

Anode e- Fe

237
Corrosion Control Techniques
4.Cathodic Protection

Common Sacrificial Anodes

238
Corrosion Control Techniques
4.Cathodic Protection

Common Sacrificial Anodes


Anode Recommended Electrolyte
Magnesium (Mg) Soils & hot water

Zinc (Zn) Soils & fresh / sea water

Aluminum (Al) Sea waters

At temp. > 600 C : Al & Zn oxidize leading to Reverse Polarity

Indium is added to Al anodes to prevent its oxidation


239
Corrosion Control Techniques
4.Cathodic Protection

Generalization :
Aqueous media with low resistivity, Al anode are
preferred, e.g. seawater
Mg anodes are used in higher resistivity aqueous
media, e.g. wetted soils.
Water electric resistivity can be calculated using
this formula :
0.7
Rw = X 1,000,000 ohm.cm
TDS (ppm)

240
Corrosion Control Techniques
4.Cathodic Protection

Prepackaged Sacrificial Anode

For soil applications: prepackaged Mg & Zn anodes

Backfill:
75% Gypsum +
20% Bentonite clay +
5% Sodium sulfate
Role of Backfill: to absorb
and maintain the soil water,
so keeping the anode in
wet environment
241
Corrosion Control Techniques
4.Cathodic Protection
Main types and shapes of Al & Zn anodes:

1. Slender ( stand-off ) 1

2. Flush mounted

3. Half-shell bracelet 2

4. Spherical

5. Ribbon

4 3

242
Corrosion Control Techniques
4.Cathodic Protection

5 Ribbon Anodes ( Zinc / Magnesium )

243
Corrosion Control Techniques
4.Cathodic Protection

Applications of sacrificial cathodic protection system:

Buried / sub sea pipelines


Buried piping
Platforms and rigs
Maine piles
Tank internals

244
Corrosion Control Techniques
4.Cathodic Protection

Sacrificial anodes for


onshore piping

245
Corrosion Control Techniques
4.Cathodic Protection
Typical CP of a buried
pipeline with prepackaged
sacrificial anodes

246
Corrosion Control Techniques
4.Cathodic Protection

Sacrificial anodes for


platform jackets

247
Corrosion Control Techniques
4.Cathodic Protection

Sacrificial anodes for


offshore pipeline

248
Corrosion Control Techniques
4.Cathodic Protection

Subsea pipeline laying Bracelet anode FLUSH with


cement coating
249
Corrosion Control Techniques
4.Cathodic Protection

Sacrificial Anode Cathodic


Protection for External Side
of Tank Bottom

250
Corrosion Control Techniques
4.Cathodic Protection

Sacrificial anodes for vessel internals

Mist Eliminator

Sacrificial Anode

251
Corrosion Control Techniques
4.Cathodic Protection

Sacrificial anodes for tank internals

252
Corrosion Control Techniques
4.Cathodic Protection
Anodes Distribution on
Tank Shell

N
N
HH Level

SEC A-A EL +7500

SEC B-B EL +5500

SEC A-A SEC A-A EL +3500

SEC B-B EL +1500

LL Level
SEC A-A EL +500

SEC B-B
253
Corrosion Control Techniques
4.Cathodic Protection

Sacrificial Anodes
Layout on Tank
Bottom

254
Corrosion Control Techniques
4.Cathodic Protection

Sacrificial Anodes for Ship Hulls

255
Corrosion Control Techniques
4.Cathodic Protection

2- Impressed current system

DC source

Ground bed

e
I

256
Corrosion Control Techniques
4.Cathodic Protection

Basics of Impressed current system

Steel nails fixed to The steel nails Results:


dry battery terminals immersed in saline 1- The nail at +ve
water terminal Corrodes
2- The nail at –ve
terminal remains
Uncorroded
257
Corrosion Control Techniques
4.Cathodic Protection

Impressed current system

Nothing happens since


the nails are in different
electrolytes

258
Corrosion Control Techniques
4.Cathodic Protection
Transformer Rectifiers (T/R)
• AC input
Voltage, Single/ three phase, Frequency

• DC maximum output Amp, Volt

• Air Cooled: with sun-shade


Oil Cooled: with thermometer

• Location: according to area classification


• Explosion proof (hazardous area)
• Non-explosion proof (non-hazardous area)

• Maximum ambient temperature

259
Corrosion Control Techniques
4.Cathodic Protection

Transformer Rectifiers

T/R with sun-shade


260
Corrosion Control Techniques
4.Cathodic Protection
Transformer Rectifiers

Explosion-proof Wall-mounted/indoors Pole-mounted

261
Corrosion Control Techniques
4.Cathodic Protection
Transformer Rectifier

Alternating Current Direct Current

262
Corrosion Control Techniques
4.Cathodic Protection

Common Impressed current anodes:

Consumable Anodes Non Consumable Anodes

Si – Fe Mixed Metal Oxide (MMO)

Si – Cr – Fe Platinized

Graphite

263
Corrosion Control Techniques
4.Cathodic Protection

Common Impressed current anodes:


Si – Fe

Si – Cr – Fe

264
Corrosion Control Techniques
5.Cathodic Protection

Fe Si Anodes

• Are the most common impressed current anodes

• Are used in soil, water or sea water

• Come in two grades; FeSi and FeSiCr for sea water


applications

• Cable connection to anode shall be handled with great


care.

265
Corrosion Control Techniques
4.Cathodic Protection

Common Impressed current anodes:

Mixed Metal Oxide (MMO) Anodes

MMO is an electrically conductive


coating that is applied onto a
Titanium substrate in order to
make it act as an Anode

266
Corrosion Control Techniques
4.Cathodic Protection

Common Impressed current anodes:

Mixed Metal Oxide (MMO) Anodes

MMO Coating

267
Corrosion Control Techniques
4.Cathodic Protection

Common Impressed current anodes:

Graphite Anodes

268
Corrosion Control Techniques
4.Cathodic Protection

Common Impressed current anodes:

Platinized Anodes

269
Corrosion Control Techniques
4.Cathodic Protection

Types of ground beds:

• Deep-well GB
• Horizontal shallow GB
• Distributed Anodes

270
Corrosion Control Techniques
4.Cathodic Protection

Deep well > 50m depth

Sand topping

Carbonaceous backfill Non-metallic


for anodes section vent tube

271
Corrosion Control Techniques
4.Cathodic Protection

Shallow Bed

Depth 3-5m

272
Corrosion Control Techniques
4.Cathodic Protection

273
Corrosion Control Techniques
4.Cathodic Protection
Distributed Impressed Current Anodes Arrangement
Distributed Impressed Current Anodes Arrangement

274
Corrosion Control Techniques
4.Cathodic Protection

Anode Connection :
Anodes cables are connected to anode / positive junction box
Each anode can be connected via a variable resistance to
control the current output
A header cable connects the PJB to e +ve terminal of T/R

275
Corrosion Control Techniques
4.Cathodic Protection

Anode Connection :

Connection via Direct connection


variable resistance to +ve bus bar
276
Corrosion Control Techniques
4.Cathodic Protection

• Impressed current anodes are


some times cannistered with the
Carbonaceous backfill.

277
Corrosion Control Techniques
4.Cathodic Protection
Carbonaceous backfill
Property 218-L 4518
• Resistivity,
0.02 0.01
ohm-inch
• Resistivity,
0.05 0.03
ohm-cm
• Carbon (L.O.I.
99.0 99.9%
method)
• Moisture 0.10% 0.02%
• Ash 0.35% 0.10%
• VCM 0.30% 0/22%
• Sulfur 3.75% 4.3%
• Bulk Density
46-50 62-66
(lbs/ft3)

• General Sizing
+ 4 Mesh +4M < 10% 4M 10%
+ 8 Mesh +8M > 90% +20M > 80%
- 8 Mesh -8M < 10% -20M 10%

278
Corrosion Control Techniques
4.Cathodic Protection

Typical Impressed Current System Arrangement

Ground Bed
279
Corrosion Control Techniques
4.Cathodic Protection

Positive current flux through soil to buried


pipeline and resulting distribution of current
density on pipe wall

280
Corrosion Control Techniques
4.Cathodic Protection

Pipeline attenuation and


multiple ground beds

V vs CSE
GB1 GB2 GB3

281
Corrosion Control Techniques
4.Cathodic Protection

Typical Under-Tank Cathodic Protection


System for New Tanks

282
Corrosion Control Techniques
4.Cathodic Protection
Under tank
cathodic protection
MMO anode grid

283
Corrosion Control Techniques
4.Cathodic Protection

SCH. 40" 3

Solution Installation of Under-Tank Watering System


PVC END CAP

Concrete Ring

Compacted
Soil

Laser Slotted PVC Tubes

Slotted PVC Pipes


284
Corrosion Control Techniques
4.Cathodic Protection

SCH. 40" 3
PVC END CAP

Installation of Under-Tank Watering System


PVC Watering Pipe

Tank

To T/R
ICCP Anode Grit

Compacted Soil

285
Corrosion Control Techniques
4.Cathodic Protection

Peripheral Anode Cathodic Protection


System for Existing Tanks
Existing Tank
Protecting outermost bottom

MMO strip
Horizontal GB
anode

286
Corrosion Control Techniques
4.Cathodic Protection

Impressed Current Cathodic


Protection for Tank Internals

Hanging
ICCP
anode

287
Corrosion Control Techniques
4.Cathodic Protection

Impressed Current Cathodic


Protection for Tank Internals

PVC Support ICCP anode

Anode Cable extended to


outside along vent tube

288
Corrosion Control Techniques
4.Cathodic Protection

ICCP for jackets

1- Hanging Anodes

289
Corrosion Control Techniques
4.Cathodic Protection

ICCP for jackets

2- Sub-sea Sleds

290
Corrosion Control Techniques
4.Cathodic Protection

Cathodic Protection Criteria


2.0
1.6
1.2 3+
Fe
Pourbaix diagram showing the 0.8

Potential
theoretical conditions for
0.4
corrosion, passivation, and Fe2+ Passivity
immunity of iron in water and 0.0
dilute aqueous solutions -0.4 Corrosion
-0.8
-1.2 Immunity
-1.6
0 7 14
pH

291
Corrosion Control Techniques
4.Cathodic Protection
Fe-to-Soil Potential in Potential vs Cu/CuSO4 Description
Low Resistivity Soils mV
showing the degree of -500
corrosion Intense Corrosion

-600 Free Corrosion

-700 Some Protection

-800 Zone
Zoneof
ofCathodic
CathodicProtection
Protection

The value – 850 mV is -900 Some Over-Protection


the CP criterion for -1000 Increased Over-Protection
protecting steel in
aggressive soils -1100 Sever
SeverOver-Protection
Over-Protection
Problems
Problems
-1200

292
Corrosion Control Techniques
4.Cathodic Protection

Excessive negative potentials


can cause :

Cathodic Disbonding : i.e.


loss of adhesion between
the coating and the metal
surface
Hydrogen Damage : due
hydrogen evolution at –ve
potentials

293
Corrosion Control Techniques
4.Cathodic Protection

Potential criteria for cathodic protection of some metals


and alloys at 25º C (1)
Metal/ Alloy Potential criterion (mV)
vs Cu/ Cu SO4
Iron, steel, stainless steel:
Aerobic conditions -850
Anaerobic conditions -950

Lead -600
Copper -500
Aluminum -950 (2)

294
Corrosion Control Techniques
4.Cathodic Protection

According to ISO 15589-1 Part 1, 2003 concerning the


CP protection criteria of On-Land Pipelines :

“The CP system shall be capable of :


polarizing all parts of the buried pipeline to
potentials more negative than – 850 mV referred to
CSE,
&
to maintain such potentials throughout the design
life of the pipeline”.

295
Corrosion Control Techniques
4.Cathodic Protection

According to ISO 15589-1 Part 1, 2003 concerning the


CP protection criteria of On-Land Pipelines :

“For pipelines operating in soils with very resistivity,


a protection potential more positive than – 850 mV
referred to CSE may be considered, e.g. as follows”:

- 750 mV for 10,000 < p < 100,000 ohm.cm


- 650 mV for p > 100,000 ohm.cm p = Soil Resistivity

i.e., the value of – 850 mV is only for soils with p < 10,000 ohm.cm

296
Corrosion Control Techniques
4.Cathodic Protection

Cathodic protection monitoring

Potential Measurement

Structure/Electrolyte Potential is measure by means of a


reference electrode :

Copper / Copper Sulfate Soil

Silver / Silver Chloride Sea Water

297
Corrosion Control Techniques
4.Cathodic Protection

Copper / Copper Sulfate


reference electrode

Portable Type

298
Corrosion Control Techniques
4.Cathodic Protection

Copper / Copper Sulfate


reference electrode

In order to measure the structure – to – soil potential,


the CSE must become part of the soil

This is fulfilled by inter-mixing of the CSE content with


the soil content due to diffusion down a concentration
gradient

299
Corrosion Control Techniques
4.Cathodic Protection

Typical Arrangement for Pipe


– to – Soil Measurement
CuSO4 Saturated Copper Rod
Solution
HIGH SO42- IONS AVO meter
CONTENT

SO42-
Porous Disc

SO42- H2O (Soil) HIGH WATER CONTENT Pipe


Sulfate ions migrate Water molecules
from CSE to soil migrate into CSE

300
Corrosion Control Techniques
4.Cathodic Protection

Permanent Copper / Copper Sulfate


reference electrode

Prepackage CSE

301
Corrosion Control Techniques
4.Cathodic Protection

Electrode Placement

For structures : closest

For pipelines : on-the-line

302
Corrosion Control Techniques
4.Cathodic Protection

Structure-to-Soil potential measurement using Voltmeter.

303
Corrosion Control Techniques
4.Cathodic Protection

Permanently Installed Reference Electrode & Test Post

304
Corrosion Control Techniques
4.Cathodic Protection

Permanent Monitoring for


Under Tank Cathodic
Protection

Tank Diameter (m) No. of Electrodes


Required
5-10 1
10-23 2
23-36 3
45 and above 4

305
Corrosion Control Techniques
4.Cathodic Protection
Reference Electrodes Locations for
Under - Tank CP Systems

1/8D 1/6D 1/4D


3/8D
2/8D
2/6D

D=45m and above D=23-36m D=10.5-22.5m D=5-10m


Key : Reference Electrode

306
Corrosion Control Techniques
4.Cathodic Protection
Test Posts for CP Monitoring

Flush – to – ground

307
Corrosion Control Techniques
4.Cathodic Protection

Correct method for measuring structure


potentials when surface is covered with
concrete or asphalt.
AVO
CSE in Wet Soil

Concrete / Asphalt

Buried Pipe

308
Corrosion Control Techniques
4.Cathodic Protection
Potential Measurement of jackets / platform legs

Diver with portable


reference electrode

309
Corrosion Control Techniques
4.Cathodic Protection
Potential Measurement of jackets / platform legs

Transponder CP
monitoring

310
Corrosion Control Techniques
4.Cathodic Protection

Potential plot after data


analysis

311
Corrosion Control Techniques
4.Cathodic Protection
Potential Measurement of subsea pipelines
Trailing-wire potential survey

312
Corrosion Control Techniques
4.Cathodic Protection

CP System Design :
Basic information for design considerations
1. Type of electrolyte (environment)
• Soil
• Fresh/ saline water.
2. Availability of power supply
3. Temperature
4. Type of coating
5. For pipelines:
• Pipeline route
• Crossings (foreign pipeline, roads, rivers, etc.)
• Presence of high transmission power lines
• Presence of foreign metallic structures.

313
Corrosion Control Techniques
4.Cathodic Protection

There are numerous codes and references that shall be


referred to when dealing with cathodic protection among
these are:
NACE RP 0169
NACE RP 0176
NACE RP 177
NACE RP 575
ISO 15589-1, PART I – 2003, “On-land Pipelines”
ISO 15589-2, PART II – 2004, “Offshore Pipelines”
DnV RP B 401
API 651
J. Morgan, “Cathodic Protection”
A.W. Peabody, “Control of Pipeline Corrosion”
314
Corrosion Control Techniques
4.Cathodic Protection

Soil resistivity
Soil represents the electrolyte

Soils with low resistivity have high conductivity; i.e.


corrosive

NACE ranking

Soil resistivity (ohm. m) Corrosivity


up to 10 Severely corrosive
10-50 Corrosive
50-100 Moderately corrosive
100-200 Slightly corrosive
200 and above Non-corrosive 315
Corrosion Control Techniques
4.Cathodic Protection

Four-Terminals (Wenner)
Measurement of Soil Resistivity.

316
Corrosion Control Techniques
4.Cathodic Protection
4-Terminals Arrangement

Ohm’s Low : R = V/I

R : Resistance (ohm)
V : Applied Voltage
a a a
I : Recorded Amperage
Depth = a

317
Corrosion Control Techniques
4.Cathodic Protection
Current demand for CP:
Current density : it is the current required to cathodically protect
1 meter2 of bare steel in a given electrolyte.

Temperature : current demand shall be increased by 25% per


every 10º C incremental rise above 30º C. This requirement is
described by the following equation:

i = i0 + [i0 x 0.25 (t-t0)] / 10


Where,
i = current density at operating temperature, Amp/m2
i0 = base current density at standard temperature, Amp/m2
t = operating temperature ºC
t0 = standard temperature (30ºC)

318
Corrosion Control Techniques
4.Cathodic Protection

Current density determined in mA/m2 is dependant on the


media aggressivity.
Therefore if soil resistivity is low then current density shall be
high
Current density increases with increasing temperature
Media Current Density
mA/m2
Aggressive Soil 10
Normal soil 5
Sea water 90
Fresh water 30

319
Corrosion Control Techniques
4.Cathodic Protection

Power Supply :

The T/R is fed with AC current from the nearest power


supply.

If there is no power supply available, Solar Units to be


used instead of T/R.

320
Corrosion Control Techniques
4.Cathodic Protection

240 Watt Solar Array


0-24 Volt

321
Corrosion Control Techniques
4.Cathodic Protection

Sun
Regulator
Junction Box

Converter

(+) (-) Structure


Solar Modules
Batteries

Typical Arrangement for ICCP Using Solar Energy

GB Pipe to be protected

322
Corrosion Control Techniques
4.Cathodic Protection

Typical Coating Resistances for various coating qualities

Coating quality Range of specific


leakage resistance
(RC), ohm.m2
Poor 1,000-2,500

Fair 5,000-10,000

good 25,000-50,000

Excellent 100,000-500,000

323
Corrosion Control Techniques
4.Cathodic Protection

Typical Coating Breakdown Values

Coating type % breakdown


Initial Mean Final
Thick coating ≤1 5 10
Epoxy coal tar ≤2 5-10 10-20
Fusion bonded 1-2 5-10 5-20

CP current
epoxy
Polypropylene (25 0.5 2 5
yrs)
Polyethylene (25 yrs) 0.5 1 3

324
Corrosion Control Techniques
4.Cathodic Protection

Recommended potential limits for different coatings


to avoid coating disbondment

Coating type Volt (vs Cu/ CuSO4)

Asphalt Enamel -2
Epoxy coal tar -1.5
Fusion bonded epoxy -1.5
Tape wrap -1.5
Polyethylene -1.0
325
Corrosion Control Techniques
4.Cathodic Protection

Pipeline Route

Cross-country P/L’s pass through different types of soils,


i.e. different electrolytes

Presence of high voltage power transmission lines

326
Corrosion Control Techniques
4.Cathodic Protection

Pipeline Route

327
Corrosion Control Techniques
4.Cathodic Protection

Pipeline AC interference from


electromagnetic field

328
Corrosion Control Techniques
4.Cathodic Protection

For protection against stray


current from high tension lines,
zinc ribbon and polarization
cells are used

329
Corrosion Control Techniques
4.Cathodic Protection
Stray current interference
In case of pipe-crossing of cathodically
protected pipelines BONDING is
required by means of :

Solid boning, or

Resistance bonding

330
Corrosion Control Techniques
4.Cathodic Protection
Electrical Isolation
Structures to be protected shall be
electrically isolated from portions that
doesn’t require protection.
Electrical isolation is made by :
Isolating flange kit ( IFK )

331
Corrosion Control Techniques
4.Cathodic Protection

Isolating flange kits


In hazardous areas , IFK’s are
protected by means of Spark Gaps Spark Gap

332
Corrosion Control Techniques
4.Cathodic Protection

Electrical Isolation

Monolithic Blocks

333
Corrosion Control Techniques
4.Cathodic Protection

The monolithic blocks are


protected against electrostatic
Monolithic Blocks
charges and lightening by
polarization cell + Polarization Cell
334
Corrosion Control Techniques
4.Cathodic Protection
Sacrificial VS Impressed Current CP
Sacrificial Impressed current
No need for external power source Requires an external power source
Easy to design and install Requires skillful design and
installation
uncontrollable Can be controlled
Used only for limited surface areas Can be used for uncoated surfaces
and well coated structures and used for any surfaces
Has no detrimental effects Can cause serious problems if not
handled carefully
Is limited to low resistivity can be used at any resistivity

Low maintenance High maintenance

335
Corrosion Control Techniques
4.Cathodic Protection

Sacrificial VS Impressed Current CP

336
Middle_east@night.oil

Thank You Good Luck

Forest Fires
City Lights
Oil/Gas Fields Flares

337