CORROSION

CORROSION
• Introduction.

• Corrosion Process.

• Forms of Corrosion.

• Factors influencing Corrosion.

• Detection & Measurement of Corrosion.

• Measurement Rate.

• Control Techniques.
 INTRODUCTION
• Corrosion is the deterioration of a material caused by its environment .

• It is a spontaneous chemical reaction which results in reversion from purified

metal to an ionic metallic compound.

• Rate of corrosion is expressed in mils penetration per year (mpy).

• Corrosion rate is dependent on the surface area of the original

material exposed & the duration of exposure time.
 CORROSION PROCESS

We observe corrosion process in our environment in the following areas;

• Motor vehicles – the bright body turns rusty with time.

• Water pipes in older houses .

• Roof of houses made of iron sheets.

• Kitchen utensils.

• Underground & Underwater pipes.

 CORROSION PROCESS cont’d
Electrochemical reaction in corrosion process require the flow of current
through a closed circuit. the circuit consist of;

• The anode (positive pole) – Losses electron by the reacting iron.

• The cathode (negative pole) – Electron is gained at this site.

• An electrolyte – A conductive solution which provides the path for current

between the two poles.

• Conductor – The electro flow through the conductor (as metal)

 FORMS OF CORROSION.
Corrosion could be classified as follows;

• Uniform attack and/or weight loss corrosion.

• Oxygen corrosion (called Rusting).

• Galvanic Corrosion.

• Crevice corrosion or Stress Corrosion (Sulphide Stress Cracking, SSC)

• Pitting.
 UNIFORM ATTACK OR WEIGHT LOSS CORROSION

• Most common type of corrosion normally characterized by a chemical

reaction.

• It proceeds uniformly over the entire exposed surface.

• The rate varies greatly depending on the susceptibility of the material.

• The metal becomes thinner and eventually fails.

 OXYGEN CORROSION (RUSTING)

• Oxygen corrosion (called Rusting) is a common type.

• Oxygen is more corrosive in salt water than fresh water.

• The dissolved oxygen is the major cause of drill pipe corrosion.

• Corrosion increases drastically when carbon dioxide or hydrogen sulphide is

dissolved in oxgen-contaminated water.

• Oxygen causes severe corrosion at very low concentration(<1ppm)

 GALVANIC CORROSION

• Corrosion of less-resistant metal is increased while the attack of resistant

material decreases.

• Less resistant metal is the anodic and the other one cathodic.

• The cathodic metal does not usually corrode in this type of couple.
 CREVICE CORROSION/STRESS CORROSION

• Include combined effect of stress & corrosion on the behavior of metal

which leads to accelerated attack & cracking.

• The stress could be either cyclic or static.

• Cyclic stress is observe in rotating drill string.

• Effect of cyclic stress on metal is influenced by degree of corrosiveness of

fluid (mud) in which the drill string is immersed.
 CREVICE CORROSION/STRESS CORROSION cont’d

• The form cracking in oil & gas production are sulphide stress cracking
(SSC) and Chloride stress cracking.

• Other unique forms under environmental conditions are;

Caustic,

Carbon-monoxide,

Hydrogen – induced cracking and

Liquid metal embrittlement.

 PITTING

• A form of localized attack that results in the development of holes in the

metal.

• Pitting corrosion is difficult to detect because pits are likely to be covered

with corrosion products.

• Pits are so small & close together that they are mistaken for surface
roughness.

• Pitting corrosion is reported the most destructive form of corrosion.

• Most pitting failure are caused by chloride ions.

 FACTORS INFLUENCING CORROSION

The factors can be categorized into two groups;

• Factors associated mainly with the metal.

• Factors associated mainly with the environment.

 FACTORS ASSOCIATED MAINLY WITH THE METAL

• Effective electrode potential of the metal.

• Over voltage of hydrogen on the metal.

• Tendency of metal to form an insoluble protective film.

• Chemical and physical homogeneity of the metal surface

 FACTORS ASSOCIATED MAINLY WITH ENVIRONMENT

• Oxygen concentration.

• Presence of H2S (sour-gas).

• Presence of CO2 in gas condensates, under high pressure resulting in low

PH or acidity of solution.

• Relatively low resistivity of formation water.

• Nature, concentration & distribution of electrolytes such as carbonic acid

due to CO2. Presence of acids & acid generating salts.
 FACTORS ASSOCIATED WITH ENVIRONMENT cont’d

• Tendency of environment to deposit a protective film on the metal surface.

• Rate of flow of solution (high pressure well effluent) against metal.

• Temperature.

• Static or cyclic stresses.

• Contact with dissimilar solutions.

• Contact with dissimilar metals.

• Stray currents.
 DETECTION & MEASUREMENT OF CORROSION
Various techniques used to detect & measurement corrosion include;

• Visual inspection.

• Chemical test.

- Analysis of composition of produced fluids to determine CO2, H2S &

organic acid content.

- Analysis of formed scales, etc

- Iron count.

• Bacteriological tests of aerobic or anaerobic bacteria.

 DETECTION & MEASUREMENT OF CORROSION

• Electrochemical test to check surface lines, well casings or other buried

structures.

• Test for pipelines.

- Resistivity of soils.

• Tests for current flow in well casings to determine casing-potential profile.

• X-ray.

• Electrical resistance probes.

- Corrosimeter.

- Linear polarization meter.

 DETECTION & MEASUREMENT OF CORROSION cont’d

- Galvanic probe.

Others include;

• Corrosion coupons.

• Hydrogen probe.

• Corrosion records.

• Caliper surveys.
 CORROSION CONTROL TECHNIQUES

The following corrosion control techniques may be used.

• Inhibition.

• Chemical scavenging.

• Use of biocides.
 METHOD OF MINIMIZING CORROSION IN PETROLEUM INDUSTRY

The methods includes,

• Painting.

• Cathodic Protection.
- Impressed current system.
- Sacrificial anode system.
- A combination

• Use of inhibitor.
- Inorganic
- Organic
- They are applied into the wells by means of batch flush, tubing
displacement.
 METHOD OF MINIMIZING CORROSION IN PETROLEUM INDUSTRY cont’d

• Material selection.

• Control through original engineering design.

• Use of internal & external coatings.

- Organic coatings (epoxies etc)

- Inorganic coatings (cement etc)

• Removal of corrosive gases.

- By use of chemical scavengers.

 MATERIAL SELECTION
• Improper selection of metals is primary the cause of galvanic corrosion.

• High priced alloys are more economical in certain corrosive environments

than iron & steel.

• Hydrogen embrittlement is a big problem in H2S environment, metal lose

is the problem in CO2 & O2 environment.

• Generally concrete & ceramics are corrosion resistant in all types of

produced field .

• Cement pipes which are mixtures of portland cement & abestors are
widely used as transit pipes, oil & water gathering lines.

• All materials selected must conform to API and NACE standards.

 SELECTION OF COATINGS

• Coatings such as paints, plastics, cement , rubber and ceramics have been
used to prevent contact between metal & corrosive environments.

• Cathodic protection type coatings are also in use.

• Coating also improve appearance of steel structures.

• Type of paint, preparation of surface and method of application, determine

the durability and protective value of paints.

• Cost of labour contributes heavily to cost of painting.

 CATEGORIES OF COATINGS

Coatings can be categorized by their composition into:

• Organic.

• Inorganic, and

• Metallic.
 ORGANIC COATING

• Organic coatings are most commonly used in the petroleum industry.

• They are subdivided into :

Thin film (about 5 mils) paints for atmospheric exposure inside drill pipes
and tubings.

Heavy coating such as bituminous paints applied to buried or submerged

structures.
 INORGANIC COATING
• Cement is an example of inorganic coating used to line pipes in salt
water service.

• In acidizing operations the use of such pipes is not recommended.

• Cement pipes are cheaper than plastic pipes.

• Coatings for pipes and vessels pipes.

internal Vessel internal
Cement(lined) Coal tar Expoxy
Expoxy Coal tar
Coal tar Expoxy Expoxy
Phenolics PVC (liner)
Polyurethane Polyesters.
polyesters
 METALLIC COATING

• Zinc and aluminium coatings are common in oil production operations more
in atmospheric protection than in buried or submerged structures.

• Others are chromium coatings used in some pumps which apart from
coating help in improving hardness & resistance to wear.

• Cadmium-plated bolts are used mainly in offshore operations.

• Zinc silicate paint provides the best and most economic protection as
undercoat but also for atmospheric protection.

• The process of hot-dip, spraying and electroplating are used in the

coatings.
 INTERNAL & EXTERNAL COATINGS

Internal coating

• For new or used – pipes in good conditions, multiple coats of different

points are applied after careful cleaning by sandblasting.

• Each coat must be baked at controlled temperature.

• Cement –lined pipes are frequently used in salt water service & as water
inject on lines.
 INTERNAL & EXTERNAL COATINGS

EXTERNAL COATING

• Buried & submerged pipes are often protected by cathodic protection.

• A shield of asbestos felt & reinforcement of felt or fibreglass improves the

strength and durability of coating.

• For tank bottoms, concrete and asphalt mastic have been used for pads.

• Sand pads are used where the soil is dry and well drained.

• Success of coating depends on adequate surface preparation, coating

thickness and uniformity of coating.
 DESIGNING PRODUCTION FACILITIES

Among other things, the following should be noted when designing production
facilities.

• Concentration cell corrosion often result in crevices & poorly drained flow
lines and equipment. Trace amounts of oxygen cause concentration cells.

• Dissimilar metals cause galvanic corrosion.

• Improper selection of metal for H2O, CO2 & O2 service will cause
problems.

• Non-insulation of well from flow-lines or insufficient insulation with

insulating flanges or plastic nipples disastrous.

• Cavitation from pumps disastrous.

 DESIGNING PRODUCTION FACILITIES cont’d

• Undersizing of air (oxygen) exclusion equipment should be avoided.

• Improper coating detrimental.

• Cathodic protection systems must be well designed.

• Ensure adequate protection of casing.

• Provide subsurface chemical injection valves for possible injection of

chemical.

• In the case cathodic production, care must be taken to provide

adequate earthing (grounding) of structures against lighting &
accidental failure of electrical insulation.
 QUESTION ON CORROSION

• A steel water–tank was to be protected by “Cathodic Protection” with the

dc current applied so that the tank would have negative polarity. The tank
was 4m tall, closed at the top and 3m in diameter. The wall thickness was
0.9652cm and the practical life of the tank was considered at an end when
any part reached 0.46cm in thickness. The current flow was adjusted so
that 0.5382amp/m2 was impressed. Accidentally, wrong connections
were made and the tank was made anodic.
The error was not notice for 2years and the blame was attributed to
corrosion. Assuming the reaction is
Fe → Fe+ + 2e- at 100%
Efficiency and that 26.3amp/hr are capable of dissolving 27.93gms of iron.

(a) How much iron has dissolved in the 2years?

(b) What was the wall thickness after 2 year?

(c) What fraction of the tanks life was used up?

δFe = 7.8gm/s, Atomic weight of steel = 5585gm, F = 96500
coulumbs.
Solution
3m

4m

Tank

Soil level
 Fe → Fe+ + 2e-
• Given,
Wall thickness = 0.9652cm
Current, I = 0.5382 amp/m2
Valency = 2
Efficiency = 100%
radius = 3 /2 = 1.5m
Useful wall thickness = 0.9652 – 0.46 = 0.5052cm

The total surface Area is shown below

Top Area (Circular top
Note, Density is defined as Mass .
Vol
∴M = vδ

Where δ is given

Height Curved Surface Area

V = A x thickness of corroded part.
A = total surface Area.

Base Area (Circular Base

• Thus, total surface area when both top and base are closed with tank
probability filled.

Total surface area = Top Area + Base Area + Curved surface Area.

Where
Top Area = πr2
Base Area = πr2
Curved Surface Area = Base circumference

∴ Total surface Area = πr2 + πr2 + 2πrh

= 2πr2 + 2πrh

= 2πr (r + h)

Total surface Area = 3.142(1.5)2 + 2(3.142) (1.5) (4)

= 7.0695 + 37.704
= 44.7735m2
Thus, m
volume corrected = 44.7735m2 x 0.5052cm x
100cm
= 0.226m3
 100 3 cm 4
M = .δFe = 0.226m x 7.8gm/cm x
m3

M = 1762800gm
M = Zit
Where
Z =
i = 0.5382 amp/m2
t = 2 years
• Hence time = 2years, convert it to second.
365 day 24 hr 3600 sec
t = 2yrs x x x
1 yr 1 day 1 hr

55.85gm 0.5382amp 44.7735m2 2yrs 365day 24hrs 3600s

M= x x x x x x
(2) (96500)columbs m2 1 1 1 yr 1 day 1 hr

55.85 x 0.5382 x 44.7735 x 2 x 365 x 24 x 3600 gm amp.sec

M =
2 x 96500

8.4884 x 10 10
M =
2 x 96500 M = 439812 .14gm
• M@100% efficiency = (1.0) (439812.14) = 439812.14gm

(b) What was wall thickness after 2 yrs

Note, M = Vδ
Where
Vol = Total surface Area x thickness of corroded part.

And where,

thickness = d
M
d =
δA
Substituting the values
439812.14gm
d =
7.8gm/cm3 x 44.7735m2 x 1003 cm3
m3m

439812.14 100cm
d = m 0.00126m x
349233300 m
d = 0.00126 m , d = 0.126cm
(c) What fraction of tank life was used up?
0.126 cm
= 0.126
0.9652 - 0.4cm 0.5052 = 24.9%
 QUESTION ON CORROSION
• A sacrificial magnesium anode was used to protect a pipeline transporting
crude oil to Bonny Terminal. It weight 1501bs. It is designed in such a
way that only half of the anode is used effectively in the protection of the
pipeline. After 2years,
1. Calculate the effective weight of the anode used up.
2. Also calculate the fraction of the effective life of the anode, the current
generated is 2 amperes.
3. Write the corrosion reaction equation and assume 100% efficiency.
Atomic wt of Mg is 24.32gm, 1 faraday = 96500 conloumbs = 26.8amp/m.

Solution
At the anode:
Mg → Mg2+ + 2e –
At cathode:
Fe – 2e → Fe-
Valency of Mg = 2
Current = 2 amp.
t = 2yrs
M = Zit
 where Z = At. weight = 24.23
= 0.000126gm/Amp
Val.F (2) 96500
Mass used after 2 years

24.23gms 2amp 365day 24hr 3600 sec

M= Zit = x x 2yr x x x
(2)(96500) 1 1yr 1day 1hr

24.23x2x2x 365x24x360 0
M=
(2 )(96500 )
3056469120
M=
193000

M= 15836.63gm
Hence the former weight was given in 1bs, therefore, convert the Mass used after 2 years in 1bs.

1ib
15836.63gm x = 34.91 ibs
453.6 gm
• Effective wt = 34.91 ibs
From the design, the effective Mass

1
(150 ) Ibs = 75 Ibs
2
Fraction of Effective life

= 34.91 = 0.466
75

∴ % = 0. 466 x 100

= 46.6%
 Evaluation of corrosiveness
• This depends on the partial pressure of C02, Pv.

• Pv = (%mole fraction C02) (total wellhead pressure).

• The higher the C02 content and wellhead pressure the higher
the partial pressure and the more corrosive the well.