Chapter 1

Corrosion and
Other Failures

Class Exercise
Discuss and summarize
expectations/reservations

1:2

Learning Goals
Examine process units found in refineries
Describe specific refinery processes
Identify and examine corrosion and
metallurgical problems found in process
units
Examine process monitoring and practices
used to control corrosion

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NACE Defines Corrosion as...

The deterioration of a material, usually a
metal, because of a reaction with its
environment.

1:4

Figure 16.1 Simplified Refinery Flow Diagram

Refinery Corrosion Categories

Low-temperature corrosion
Below 500F (260C)
Water present

High-temperature corrosion
Above 500F (260C)
No water present

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Low-Temperature Refinery
Corrosion
Aqueous corrosion
Wet corrosion
Electrochemical corrosion

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Corrosion of a Metal
Oxidation reaction
Produces electrons
Occurs at anode, which corrodes

Reduction reaction
Consumes electrons from oxidation
Occurs at cathode, which does not
corrode

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Corrosion Reactions
Fe Fe+2 + 2e

oxidation of iron

2H+ + 2e H2 (gas)

hydrogen evolution in acid solutions

O2+ 2H2O + 4e 4OH

oxygen reduction in neutral or basic

solutions

2HS + 2e H2 (gas) + 2S2

bisulfide reduction in sour solutions

1:9

Corrosion Reactions
2Fe + 2H2O + O2 2Fe+2 + 4OH 2Fe(OH)2
2Fe(OH)2 + H2O + O2 2Fe(OH)3

(ferrous hydroxide)

(solid ferric hydroxide) = red rust

1:10

Corrosion Rates
Determine the suitability of a material for a
specific service environment
Measured as weight loss per unit area
Expressed in mils or mm of penetration
per year (mpy or mm/yr)
Acceptable for long-term service if below 5
mpy (0.125 mm/yr)
1:11

Polarization
Activation polarization
Corrosion controlled by reaction sequence at
metal surface
Controls corrosion in concentrated acids

Concentration polarization
Corrosion controlled by diffusion
Controls corrosion in very dilute acids
Analogy is wind chill factor
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Passivity
Increases corrosion resistance in some
metals and alloys
Results from the formation of protective
surface films
Damaged in highly reducing or oxidizing
environments or by active ions
Maintained by dissolved oxygen in water

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Galvanic Corrosion
Form of wet corrosion
Two metals are joined electrically
Requires
Electrolyte
Anode
Cathode
Metallic pathway

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Galvanic Series
Corroded EndAnodicMore Active
Magnesium
Zinc
Aluminum
Steel
3xx, 4xx stainless steel (active state)
Copper Alloys
3xx, 4xx stainless steel (passive state)
Titanium
Graphite
Protected EndCathodicLess Active/More Noble

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Galvanic Corrosion

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Dissimilar Metals in Contact

Leading to Galvanic Corrosion
Weld or heat-affected zone may be anodic
to parent metal
New steel connected to old steel corrodes
more rapidly
Steel pipe connected to copper pipe or
tubing
Steel propeller shaft operating in a bronze
bearing
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Galvanic Attack Factors

More severe near junction of two dissimilar
metals
Severity related to electrical conductivity of
solution
Anode should be large compared to cathode
Insulate dissimilar metals
Paint or coat entire assembly or cathode
Corrosion inhibitors and sacrificial anodes
reduce galvanic effects
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Increasing the Corrosion Rate

Temperature increases
Can double corrosion rates for activation
polarized corrosion
Can increase water amounts in liquid
hydrocarbon and vapor streams

Concentration increases
Generally increase corrosion
Considered in terms of water present
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Causes of Low-Temperature
Refinery Corrosion
Contaminants
Present in crude oil
Produced from refinery processes

Water
Air (oxygen)

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TABLE 1.1
Crude Oil
S

Corrosives
Found in
Refining
Processes

N
Nap Acid
Cl

Refinery
NH3
CNH2S
HCl
HF
H2SO4
Polythionic Acid
O2
CO2
1:21

High-Temperature Refinery
Corrosion
Other names
Dry corrosion
Direct chemical combination

Associated with high temperatures

Occurs above the dew point
Typically caused by gases and liquids

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Metal Oxide Formation

Oxidation reaction
Metal exposed to air
Oxidized to an ion at metal/scale interface

Reduction reaction
Oxygen is reduced at scale surface

Corrosion reaction combines oxidation

and reduction to form metal oxide

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High-Temperature Oxidation
Limits
(Table 1.4)
Alloy

Temperature

Carbon steel

1050F (565C)

5 Cr-1/2 Mo

1200F (648C)

9 Cr-1 Mo

1300F (704C)

410 SS

1300F (704C)

304/316/321/347 SS

1600F (871C)

309 SS (HT)

2000F (1093C)

310 SS (HK)

2100F (1149C)

Alloy 625

2000F (1093C)

Alloy 825

2000F (1093C)
1:24

Factors Influencing Diffusion

of Metal and Oxygen Ions
Temperature
Temperature fluctuations
Integrity of the oxide layer
Presence of other gases in the
atmosphere

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Factors Influencing Scale

Formation
Dissolution of oxygen atoms in some
metals
Low melting points and high volatility
of some oxides
Existence of grain boundaries in the
metal and the scale

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High-Temperature
Corrosion Rate Laws
Linear Rate Law
Nonprotective oxide layer permits oxygen
access to metal
Oxide layer thickness increases with time

Parabolic Rate Law

Oxide layer forms protective barrier
Protection relates to oxide layer thickness
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High-Temperature
Corrosion Conditions
High pressures
High flow velocities
Sulfur compounds
Naphthenic acids

1:28

Refinery Damage and Damage

Mechanisms
Metal loss due to general and/or localized
corrosion
Stress corrosion cracking (SCC)
High-temperature hydrogen attack (HTHA)
Metallurgical effects
Mechanical failures
Other forms of corrosion
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Summary
Low-temperature corrosion
High-temperature corrosion
Major classifications of damage
and damage mechanisms

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Additional Damage
Mechanisms

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Pitting
Highly localized corrosion in form of
small holes or pits
Occurs in stagnant flow conditions in
presence of chloride ions
A problem with martensitic, ferritic, and
austenitic stainless steels
Alloying with molybdenum reduces
pitting in stainless steels
1:32

Crevice Corrosion
Localized corrosion
Promoted by stagnant solutions in crevices a few
mils wide
Most severe in high chloride environments
Also called under-deposit corrosion
Mitigation includes
Designing for proper drainage
Welding instead of bolting or flanging

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Crevice Corrosion

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Atmospheric Corrosion
Mostly a problem in coastal refineries
Accelerated by the presence of
Sulfur compounds (hydrogen sulfide)
Chlorides
Fly ash
Chemical dusts

1:35

Intergranular Attack
Localized attack at and adjacent to grain boundaries
Little corrosion on grains, resulting in grain
separation
Caused by
Corrosive action of a chemical
Enrichment or depletion of alloying element
300 series Austenitic SS most vulnerable
Additional details during PTA discussion

1:36

Soil Corrosion
Caused by differential concentration cells
in the soil
Oxygen
Water
Chemicals

Problem with underground piping and

tank bottoms
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Stress Corrosion Cracking (SCC)

Spontaneous cracking of materials
Combination of corrosion and tensile
stresses
Two types of stresses
Residual
Applied

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Stress Corrosion Cracking

Susceptible Materials
Environment
Tensile Stress
Residual
Applied

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Stress Corrosion Cracking

(Table 1.5)
Cl3xx SS
NaOH (and other caustics) CS, 3xx SS
NH4 Cu-base (especially brass)
Amines
CS, Cu-base
H2S CS (High Strength), 4xx SS
HCO3 = (carbonates)
NO3 = (nitrates)
PTA

CS

CS

(polythionic acids)

Sensitized 3xx and 800

1:40

Chloride Stress Corrosion Cracking

(ClSCC)
Chloride ions (only traces are required)
Temperature above 130F to 175F (54C to 79C)
Either a low pH or the presence of dissolved
oxygen
Tensile stress
Water

1:41

Chloride SCC
Crack
started at
highstress
area at
ring joint
corner

1:42

Alkaline Stress Corrosion

Cracking (ASCC)
Tensile stress
Alkaline cracking from exposure to
caustic, amine, or carbonate solutions
Temperatures above 150F (66C), 75F
(23.9C), or 100F (37.8C), respectively
Concentrations of 50 ppm to 100 ppm
caustic cause cracking
1:43

Caustic
Soda
Service
Graph
From: NACE
Corrosion Data
Survey

1:44

Cracking from caustic carryover

into boiler superheater tube

1:45

Caustic Cracking in Dead Leg Bypass

Piping at Crude Furnace Inlet

A cross-section view of the flange

and pipe. The arrow marks the ID
crack.

A micrograph of the ID cracking.

Note that the cracking is
intergranular and there is a gray
scale in the crack. This is typical of
caustic stress-corrosion cracking in
carbon steel. Nital etch,
magnification 500x.
1:46

Boiler Feed Water

Can result in low-temperature corrosion
problems
Causes of corrosion
Dissolved oxygen
Low pH

Treatment includes mechanical

deaeration and chemical treatments
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Boiler Feed Water Corrosion

1:48

Steam Condensate Corrosion

Caused by dissolved oxygen and carbon dioxide
Shows up as pitting (oxygen) or uniform metal
loss (carbon dioxide)
Controlled by
Deaeration to remove dissolved gases
Chemical treatments to reduce alkalinity of makeup
water

1:49

Carbon Dioxide (CO2) is

found in...
Steam condensate systems
Hydrogen plants
Vapor recovery section of catalytic cracking
units

1:50

Carbon Dioxide Corrosion

1:51

Cooling Water Corrosion

Can be very costly to refiners
Caused by
Airborne contaminants
Concentrated dissolved minerals
High temperatures

Controlled with corrosion inhibitors and proper

material selection

1:52

Cooling Water Corrosion in Carbon

Steel Heat Exchanger Tubes

1:53

Mechanical Failures
Operational changes in process temperature
or pressure/upsets
Overfiring of furnaces to increase throughput
Control instrument failures
Exposure to fire
Overloading of structural members
Over-tightening of bolts

1:54

Incorrect or Defective Materials

Material mix-ups by suppliers
Vendor substitutions
Substitution of castings for wrought or
forged shapes
Discontinuities in wrought materials
Material substitutions during shutdowns

1:55

Mechanical Fatigue
Failure caused by cracking after continued
application of cyclic stress
Promoted by stresses higher than
endurance limit (in CS)
Risk increased by deep scratches, sharp
corners, and weld intersections
Minimized by eliminating stress raisers

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Fatigue
Failure

1:57

Corrosion Fatigue
Corrosion (pitting) promotes mechanical
fatigue
Two-stage process
Stage 1: Formation of corrosion pits
Stage 2: Development of cracks

Mitigated by
Stress relieving
Corrosion inhibitors/protective coatings

No endurance limit

1:58

Cavitation Damage
Caused by rapid formation and collapse of vapor
bubbles in liquid at a metal surface, resulting from
pressure variations
Accelerated by corrosion and turbulence or
vibration
Reduced by
Use of resistant alloys
Proper design to avoid turbulence/cavitation

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Mechanical Damage
Misuse of tools or other equipment
Wind damage
Careless handling of equipment when
moved or erected
Wear or mechanical abrasion

1:60

Abrasive Service Alloys

Tungsten carbide/sintered carbide compacts
High-chromium cast irons/hardfacing alloys
Martensitic irons/hardfacing alloys
Austenitic cast irons/hardfacing alloys
Pearlite steels
Ferritic steels
Austenitic steels, i.e., 13% manganese

1:61

Overloading
Hydrostatic testing of vessels, which applies
excess weight
Excessive bending stresses from attachment of
pipe support brackets to vessel shells
Addition of piping to existing pipe supports, or
piping left overhanging on supports
Weakened metal members from corrosion, fire,
or change in shape or position
Thermal expansion and contraction
1:62

Overpressuring
Application of pressure in excess of
maximum allowable working pressure
Causes
Buckling
Bulging
Ruptures
Splits

1:63

Brittle Fracture
Loss of ductility, resulting in poor impact
strength
Occurs at low temperatures
Impact loading
Constant stress
Catastrophic failure accompanied by loud noise
Characteristic chevron or herringbone pattern

1:64

Figure 1-Aerial View

1:65

Fracture
Origin
300 Feet

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Origin
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450 Feet

1:68

Crack initiated at backing bar weld

on vessel ID

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Chapter 1
Corrosion and
Other Failures