(UOP) Corrosion and Fouling PDF

Introduction to Low
Temperature Corrosion
Corrosion and Fouling

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Intro to low temp corr
distributed for any purpose whatsoever except by written permission of UOP LLC and except as authorized under agreements with UOP LLC.
Oct, 01 1
Philosophy
• Provide the student with a basis for

understanding aqueous corrosion
• Start from a point of everyday familiarity

– Corrosion is electrical so we will start from a
car battery and a copper/zinc galvanic cell

Oct, 01 2
Topics
• Corrosion Definitions • Concentration Cells

• Aqueous • Kinetics
Electrochemistry • Active/Passive
Fundamentals Materials
• Electrochemical Cells

Oct, 01 3
Topics
• Definitions
• Electrochemistry review (thermodynamics)
• Electrochemical kinetics

Oct, 01 4
Definitions

Oct, 01 5
Definition of Corrosion
• Many possible definitions

– Changes in definition change scope of study
• All interactions between a material and the
environment
• Undesired interactions between a material
and the environment
• We will use both definitions
Oct, 01 6
Low Temperature Corrosion
• Low temp corrosion

– <500F (260C)
– “Aqueous”
• Over 500F considered high temp
– Liquid water unlikely
– Cutoff temp varies with industry
• “Dry” oil environments hard to classify
Oct, 01 7
Basic Corrosion Mechanism
• All corrosion is electrochemistry

– Low temp is generally aqueous
– Fe(s) +2 H+(aq) + 2Cl-(aq) =>
Fe2+(aq) + H2(g) + 2Cl-(aq)
• Keep track of ions and states

Oct, 01 8
Strong and Weak Acids
• Strong acids
– 100% dissociation
– HClO4, H2SO4, HCl, HNO3, HI, HBr
• Weak Acids
– Less than 100% dissociation
– CO2(g) + H2O(g) <--> H2CO3(aq) <-->H+(aq) +
HCO3-(aq) <--> 2H+(aq) + CO32-(aq)
Oct, 01 9
Strong and Weak Bases
• Strong Bases
– 100% dissociation e.g. NaOH
• Weak Bases
– Less than 100% dissociation e.g. NH3
– NH3(aq) + H2O(l) <--> NH4+(aq) + OH-(aq)
• Ca(OH)2 and Mg(OH)2 are weak bases

Oct, 01 10
Aqueous Corrosion
Electrochemistry Review

Oct, 01 11
Electrochemistry
• Essentially all low temperature corrosion is

aqueous
• Aqueous corrosion is electrochemistry
• What follows are some key points to
remember
– More details are in section 2

Oct, 01 12
Copper Zinc Electrochemical Cell
- V
e Cu
e-
Cathode KCl Anode
+ -
Cu Zn
2+ 2+
Cu Zn

Oct, 01 13
• For infinite resistance voltmeter
– Arrows represent ATTEMPTS to flow
– Potential is a measure of “how much” electrons
“want” to flow
• Cu2+ + Zn --> Zn2+ + Cu 1.1V
• Half reactions
– 2e- + Cu2+ --> Cu V half reaction?
– Zn --> Zn2+ + 2e- V half reaction?
Oct, 01 14
Standard EMF Series
Standard EMF Standard Reduction Potential
Pt-Pt2+ Pt2+ + 2e- --> Pt 1.2 V
Ag-Ag+ Ag+ + e- --> Ag 0.799 V
Cu-Cu+ Cu+ + 2e- --> Cu 0.337 V
H-H+ H+ + e- --> H 0.799 V
Pb-Pb2+ Pb2+ + 2e- --> Pb -0.126 V
Ni-Ni2+ Ni2+ + 2e- --> Ni -0.250 V
Fe-Fe2+ Fe2+ + 2e- --> Fe -0.440 V
Cr-Cr3+ Cr3+ + 3e- --> Cr -0.744 V
Zn-Zn2+ Zn2+ + 2e- --> Zn -0.763 V
Al-Al3+ Al3+ + 3e- --> Al -0.744 V
Mg-Mg2+ Mg2+ + 2e- --> Mg -2.363 V
Oct, 01 15
• Standard Reductions
– Cu2+ + 2e- --> Cu 0.337 V
– Zn2+ + 2e- --> Zn -0.763 V
• Half Reactions (reverse oxidation half rxn)
– Cu2+ + 2e- --> Cu 0.337 V
– Zn --> Zn2+ + 2e- -(-0.763) = 0.763 V
• Sum = Cu2+ + Zn --> Zn2+ + Cu 1.1V
Oct, 01 16
Concentration Cell
V
e- Cu
e-
Cathode KCl Anode
+ -
Cu Cu
2+ 2+
Concentrated Cu Cu Dilute

Oct, 01 17
Concentration Cell
• Why?
– Lechatlier’s Principle
– Equilibrium will shift to make concentrations
even
• Nernst Equation
0.059 [products]
E = Eo − log
n [reac tan ts]
– Equation is not important - concept is

Oct, 01 18
Electrochemical Kinetics
Flow of Electrons - Not Just the

Tendency to Flow

Oct, 01 19
Kinetics
• The rate of corrosion is proportional to the

flow of electrons
• Cell potential is related to cell current
• Must understand this concept to understand
the behavior of active/passive metals
• Consider almost dead car battery

Oct, 01 20
Car Battery
12 Nothing On
Radio On
9
Lights On
potential (V)
3 Starter On
0
0
Current (A)
Oct, 01 21
Car Battery
• The higher the current the lower the voltage
• Actually the higher the current the lower the

∆V between anode and cathode
• Consider the copper zinc cell again

Oct, 01 22
Copper Zinc Cell, Current
- V A R
e Cu
e-
Cathode KCl Anode
+ -
Cu Zn
2+ 2+
Cu Zn

Oct, 01 23
Copper Zinc Cell, Current
• Ammeter has no resistance

• Arrows represent flow of electrons and ions -
not just the potential for flow
• If potential was also measured would voltage

be the same as the no current condition?

Oct, 01 24
Copper Zinc Cell Current
0.4
Potential (V)
0.2
Log i
0
-0.2
-0.4 Potential and

current
-0.6 of corroding cell
-0.8

Oct, 01 25
Copper Zinc Cell Current
• Slope of lines
– Anodic and cathodic not necessarily same
– Varies with environment
• Measurement of potential on an absolute
scale requires reference electrode
• With apparatus as drawn can only measure
difference in potential
Oct, 01 26
Active / Passive Materials
Where making conditions worse

actually reduces corrosion

Oct, 01 27
Active Passive
• Some alloy/environments form film which

affects corrosion behavior
– Iron, Chromium, Nickel, Titanium
• Produces counterintuitive corrosion results

Oct, 01 28
Iron and Nitric Acid
• Will DILUTE nitric acid corrode iron?
Dilute
HNO 3
Fe

Oct, 01 29
Iron Nitric Acid
• With vigor!
Dilute
HNO 3
Fe

Oct, 01 30
Iron Nitric Acid
• Will iron corrode in concentrated nitric

acid?
Conc
HNO 3
Fe

Oct, 01 31
Iron Nitric Acid
• No
Conc
HNO 3
Fe

Oct, 01 32
Iron Nitric Acid
• Will iron that has been in concentrated

nitric acid corrode when put into dilute
acid?
Conc Dilute
HNO 3 HNO 3
Fe

Oct, 01 33
Iron Nitric Acid
• No
Conc Dilute
HNO 3 HNO 3
Fe

Oct, 01 34
Iron Nitric Acid
• If the dilute acid is shaken, will the iron

corrode?
Conc Dilute
HNO 3 HNO 3
Fe

Oct, 01 35
Iron Nitric Acid
• Yes
Conc Dilute
HNO 3 HNO 3
Fe

Oct, 01 36
Why
• NO3 is an oxidizer
• Iron will passivate

Oct, 01 37
Recall Copper Zinc Cell
• Potential/current relationship for copper

represented by lower line
• Potential/current relationship for zinc

represented by upper line
• Lines cross at corrosion potential/current

Oct, 01 38
Recall Copper Zinc Cell
0.4
Potential (V)
0.2
Log i
0
-0.2
-0.4 Potential and

current
-0.6 of corroding cell
-0.8

Oct, 01 39
Iron Potential/Current
• For active passive metal like iron, potential

current diagram very different

Oct, 01 40
Iron Potential/Current Diagram
Iron
Potential (V)
Log i
0

Oct, 01 41
Iron Corrosion Potential/Current
• Corrosion potential/current is still the

location where anodic and cathodic
reactions cross

Oct, 01 42
Iron Potential/Current Diagram
Iron
Con
c NO -
3
Dilu
te N -
Potential (V)
O3
Log i
0
Wa
ter
H+

Oct, 01 43
What We Should Learn
• Iron corrodes slowly in water

• Iron corrodes faster in acid
• Iron corrodes very slowly in concentrated
nitric acid because concentrated nitric acid
passivates the iron
• Corrosion rate of iron in dilute nitric acid
depends on the existence of a passive film
Oct, 01 44
• With an active/passive metal, making the

situation “worse” sometimes makes it better
• Current = corrosion rate
• Don’t operate where pre-existing passive

film is required for system to be passive
Oct, 01 45
• Active/passive state not answer to all “odd”

corrosion behavior
• Moderate concentration sulfuric acid
corrodes steel more rapidly than
concentrated
– Probably due to availability of H+ ions
– Pure H2SO4 without water does not ionize

Oct, 01 46
Sulfuric Acid vs. Steel
7
6
Rel. Corr. Rate
5
4
3
2
1
0
0 10 20 30 40 50 60 70 80 90 100 110
Wt% H2SO4

Oct, 01 47
General Low Temperature
Corrosion Mechanisms

General Low Temp
Oct, 01 1
Philosophy
• Provide an overview of how low

temperature corrosion is categorized
• Relate electrochemistry of corrosion to the
appearance and location of corrosion
• Specific, refinery corrosion problems are

covered elsewhere
General Low Temp
Oct, 01 2
Topics
• Galvanic corrosion
• General corrosion
• Under deposit corrosion
• Crevice corrosion
• Pitting
• Environmental cracking
• Erosion corrosion
General Low Temp
Oct, 01 3
Galvanic Corrosion
An electrochemical cell without wires

General Low Temp
Oct, 01 4
Galvanic Corrosion
• Similar to electrochemical cells

• Corrosion current driven by potential
difference between metal types
• Cathode reaction may be H+ or O2
• Pay attention to anode/cathode areas

General Low Temp
Oct, 01 5
Galvanic Corrosion
Solution
Zn 2+
Zn
-
e
-
4OH
O2
Cu 2H O
2

General Low Temp
Oct, 01 6
Good and Bad Galvanic Corrosion
• Galvanized steel?
• Zinc blocks on steel ship hull?
• Aluminum window screen with steel staples?

General Low Temp
Oct, 01 7
Area Effects
• Big anode, little cathode not bad

– Anodic current density small
• Big cathode little anode causes trouble
– Anodic current density large

General Low Temp
Oct, 01 8
Area Effects

General Low Temp
Oct, 01 9
Area Effects
Corrosive
Environment
Coating
Carbon Steel Stainless Steel

General Low Temp
Oct, 01 10
Galvanic Series
• Not exactly the same as EMF series

• Galvanic series
– Corrosion of alloys in seawater
• EMF series
– Potential of elements under standard conditions
• Although some differences, series generally
parallel each other
General Low Temp
Oct, 01 11
Galvanic Series
• Cathodic – Aluminum
– Platinum – Zinc
– Gold – Magnesium
– Silver • Anodic
– Hastelloy C
– Austinitic Stainless • Active stainless steels
– Copper (brass bronze) and nickel alloy are
– Hastelloy B slightly more cathodic
– Steel than steel
General Low Temp
Oct, 01 12
Refinery Examples
• Heat exchangers with different bundle/shell

metallurgies
• Titanium exchangers

General Low Temp
Oct, 01 13
What to do about it
• Consider the consequences of any

bimetallic connection
• Fully isolate bimetallic bolted connections

General Low Temp
Oct, 01 14
Insulate Flanged Connections
Insulating
Washer
Flange
Bolt
Gasket
Flange
Insulating Nut
Sleeve

General Low Temp
Oct, 01 15
General Corrosion
One type of one metal corrosion

General Low Temp
Oct, 01 16
General Corrosion
• Normally one metal corrosion
– Anode reaction often H+ or O2
• Can be uniform or non uniform
– Non uniform often called pitting
• Closely spaced shallow pits
• Be aware of the difference between pitting
and pitting as reported by inspectors
General Low Temp
Oct, 01 17
General Corrosion
Metal Solution
Anode
m
2+
m
-
e
H2O
O2
Cathode +
H3O
Anode and cathode locations are almost random and

move with time
General Low Temp
Oct, 01 18
General Corrosion
Iron
Potential (V)
Log i
0
General
Corrosion

General Low Temp
Oct, 01 19
General Corrosion
Ox
yg
en
pH
1.0 0
Potential (V)
0.5
Ox
yg
en
pH
14
0 Log i
Fe
-0.5
General Low Temp
Oct, 01 20
General Corrosion
• General corrosion is the only corrosion

type for which thickness measurements
and (typically) field electrochemical
measurements are reliable!!!!!

General Low Temp
Oct, 01 21
Refinery Examples
• Many locations
– Liquid water
– Acids or oxygen
– Chlorides
– Sites of condensation
• Crude tower overhead

General Low Temp
Oct, 01 22
What to do about it
• Understand the environment
• Understand the chemistry
• Remember the trace contaminants
• Monitor the environment and the corrosion
rate
• Metallurgy upgrade AFTER understanding
problem
General Low Temp
Oct, 01 23
Under Deposit Corrosion

General Low Temp
Oct, 01 24
General Concepts
• Films and deposits change the environment

to which the metal is exposed
– Can be advantageous or detrimental to
corrosion
• Anode and cathode may be separated
– Location of deposits not necessarily the same as
location of metal loss

General Low Temp
Oct, 01 25
General Concepts
• Under deposit corrosion is at least partly a
concentration cell
• Recall the copper concentration cell
• Same concept works for anode and cathode

reactions
General Low Temp
Oct, 01 26
Concentration Cell
V
e- Cu
e-
Cathode KCl Anode
+ -
Cu Cu
2+ 2+
Concentrated Cu Cu Dilute

General Low Temp
Oct, 01 27
Water Drop
Water Drop
en
Hig
xyg
De xyg
hO
cr
hO
ea n
xyg
O
sin
Hig
en
g
e
O
- 2
2+ OH
Fe
Fe2O3
e-

General Low Temp
Oct, 01 28
Location of Anodes and Cathodes
• Consider a garden shovel partly covered

with wet dirt
– Where will the rust stains be
– Where will metal be lost from

General Low Temp
Oct, 01 29
Location of Anode and Cathode
Wet Dirt

General Low Temp
Oct, 01 30
Location of Anode and Cathode
rust
Metal Loss

General Low Temp
Oct, 01 31
Effect of Films
• Films can reduce corrosion by altering

corrosive environment
• Corroding iron forms an iron hydroxide

(Fe(OH)2) film
– Film has pH of 9
• Recall iron, oxygen, pH diagram
General Low Temp
Oct, 01 32
Iron, Oxygen, pH
Ox
yg
en
pH
1.0 0
Potential (V)
0.5
Ox
yg
en
pH
14
0 Log i
Fe
-0.5
General Low Temp
Oct, 01 33
Iron, Oxygen, pH
• Corrosion rate higher at low pH

• Corrosion rate should change linearly with pH
• Because of film iron sees higher pH than bulk
environment

General Low Temp
Oct, 01 34
Iron, pH Corrosion Rate
12
Relative Corrosion Rate
10
8
6
4
2
0
0 2 4 6 8 10 12
pH

General Low Temp
Oct, 01 35
Effect of Scales
• Scales, thick films and foulant material
exclude oxygen and create a concentration
cell
• If chlorides are present, H+ “drawn” under
deposits
– pH drops to below 4, corrosion rate increases
• How this happens is described in “pitting”
section
General Low Temp
Oct, 01 36
Refinery Examples
• Any location in which in which scaling

and/or fouling occur especially if oxygen
and chlorides are present

General Low Temp
Oct, 01 37
What to do about it
• Treat the source of the problem (i.e. corrosion
or fouling)
• Anti foulant may be helpful
– Consider downstream implications
– Start early in run - antifoulant prevents but does
not reverse many types of fouling
• Metallurgy upgrades may solve corrosion
problem but not performance loss
General Low Temp
Oct, 01 38
Crevice Corrosion
Geometry dependent one metal

corrosion

General Low Temp
Oct, 01 39
Crevice Corrosion
• Crevice Corrosion and pitting can be related

– Crevice can be a preformed pit
• Crevice Corrosion also related to
under-deposit corrosion
• We will consider the most simple aspect of

crevice corrosion
General Low Temp
Oct, 01 40
Crevice Corrosion
High Oxygen
Low Oxygen
Cathode
Anode
Corroded Area Flange
Gasket
General Low Temp
Oct, 01 41
Crevice Corrosion
Rolling
Grooves
Tube
Sheet
Tube
Crevices Crevices

General Low Temp
Oct, 01 42
Crevice Corrosion
• Crevice corrosion is an oxygen cell

• Crevice must be small enough to form
stagnant zones
• Corrosion uses up oxygen in crevice
– Anode
• Oxygen plentiful outside crevice
– Cathode
General Low Temp
Oct, 01 43
Refinery Examples
• Anywhere where there is a crevice and

general corrosion may be expected
– Flanged connections especially with fiber gaskets
– Threaded connections
– Tube/tubesheet connections
– Plate type heat exchangers

General Low Temp
Oct, 01 44
What to do about it
• Use materials less sensitive to pitting

• Eliminate crevices - especially those with
porous gaskets

General Low Temp
Oct, 01 45
Pitting
Random, local, one metal corrosion

General Low Temp
Oct, 01 46
Pitting
• What inspectors call pitting and actual

pitting are sometimes different
• Pitting is normally discrete pits that are
deeper than they are wide
• Pitting is most common on the tops of
horizontal surfaces and rare on the bottoms
of horizontal surfaces
General Low Temp
Oct, 01 47
Pitting
• Normally found in active/passive metals in

passive state
• Requires incubation time for pit to initiate
• Some crevice corrosion is pitting in a
preformed pit (crevice)

General Low Temp
Oct, 01 48
Strong and Weak Bases
• Some metal hydroxides are strong bases and
others are weak
• Strong bases dissociate completely in water
• M(OH)2 <=> M2+ + 2OH-
– Sodium - all the way to the right
– Calcium, Magnesium - substantially to the right
– Iron - far to the left
General Low Temp
Oct, 01 49
Hydrolysis
• Adding M2+ + 2OH- <=> M(OH)2

and H2O <=> H+ + OH-
Gives M2+ + 2H2O <=> M(OH)2 + 2H+
• Cations which form weak base hydroxides
react with water to form the molecular base
and an acid solution

General Low Temp
Oct, 01 50
Pitting Mechanism
-
O2 OH -
H2 O Cl
Passive Passive
+
H Fe(OH)
2
e- Fe
2+
H 2O
Active

General Low Temp
Oct, 01 51
Pitting Comments
• Without hydrolysis, no pits - metal

hydroxide does not form - water does not
acidify, chloride does not concentrate
• Pits random - must get active spot on
surface to remain stable until pit forms
• Pitting relies on ion rich solution in pit -
grows best with gravity.
General Low Temp
Oct, 01 52
Refinery Examples
• 300 Stainless + chlorides

– Under chloride leaching insulation
– Seawater cooling systems
• Remember that not all of what is reported to

be pitting actually is

General Low Temp
Oct, 01 53
What to do about it
• Understand environment
• Avoid material/environment combinations
prone to pitting
• If unavoidable or exist in present design watch:
– velocity
– temperature
– cleanliness
General Low Temp
Oct, 01 54
Environmental Cracking

General Low Temp
Oct, 01 55
• Specific interaction between metal and
environment
– Marginal passivation and/or differences in
electrochemical potential within metal (e.g.
grains to grain boundary
• Hydrogen embrittlement
– Adsorption of H0 (created by general corrosion)
by the metal
General Low Temp
Oct, 01 56
A Few Problem Combinations
• 300 series stainless - chlorides

• Carbon steel - hydroxides
• Brass - ammonia
• Aluminum - chlorides

General Low Temp
Oct, 01 57
Refinery Examples
Environment/Metal Combination
• Boil dry of caustic
• crude units
• Vent gas wash towers
• Stainless steel in sea or brackish water
• Admiralty brass in ammonia environments
• Condensers in crude overheads
• Shut down of reformers
– Water, chlorides, thermal stress at nozzles
General Low Temp
Oct, 01 58
Hydrogen Embrittlement
• Can accompany any wet corrosion

involving H+
• Normally associated with carbon steel
• Often involves H2S

General Low Temp
Oct, 01 59
Hydrogen
• Wet corrosion, H+ initially --> H0
• H0 combines to H2
• If too much generated or recombination
poison present, H0 penetrates steel
– poisons include CN-, As, S2-
• Depending on conditions embrittles or
forms blisters
General Low Temp
Oct, 01 60
What to do about it
• Avoid combinations sensitive to cracking

• Pay close attention to conditions in which
cracking occurs
– Concentrations
– Temperature
– Contaminants

General Low Temp
Oct, 01 61
Refinery Examples
• HF alkylation
• Sour water scrubbers
• FCC (cyanides)
– High pressure separator/low pressure separator
– Stripper tower overhead

General Low Temp
Oct, 01 62
What to do about it
• Minimize corrosion to minimize hydrogen

production
• Pay attention to hydrogen recombination
poisons
• Monitor hydrogen
• Use clean, killed steels or upgraded
metallurgy
General Low Temp
Oct, 01 63
Erosion Corrosion
The combined effects of erosion and

corrosion

General Low Temp
Oct, 01 64
Erosion Corrosion
• Combination of general corrosion and the
physical process of erosion.
• May be just flowing fluid or may be 2 phase
flow (gas/liquid, liquid/solid)
• Active/passive metals which depend on
surface films most vulnerable
• Turbulence and Impingement are critical
General Low Temp
Oct, 01 65
Refinery Examples
• REACs
• Heater tubes
• Any location with two phase flow is suspect

General Low Temp
Oct, 01 66
What to do about it
• Pay attention to velocities!!!!!!

• Understand corrosion environment and
minimize corrosion
• Filters may help especially in raw water
cooling systems

General Low Temp
Oct, 01 67
Introduction to High
Temperature Corrosion

Intro to High Temp.
Oct, 01 1
Topics
• Definition of high temperature corrosion
• Basic mechanism of high temperature
corrosion
• Kinetics
• Evaluation of high temperature corrosion
damage
• Chemical composition of scale
Intro to High Temp.
Oct, 01 2
Definitions

Intro to High Temp.
Oct, 01 3
High Temperature Corrosion
• Low temp corrosion
– <500F (260C)
– “Aqueous”
• Over 500F considered high temp
– Liquid water unlikely
– Cutoff temp varies with industry
• “Dry” oil environments hard to classify
Intro to High Temp.
Oct, 01 4

Intro to High Temp.
Oct, 01 5
• All corrosion is electrochemistry
– High temperature corrosion is typically a
direct reaction between species (unlike low
temperature corrosion which is a reaction
between ions
– 2Fe(s) + O2(g) <==> 2FeO(s)
• Keeping track of states not so important

Intro to High Temp.
Oct, 01 6
• Result of high temperature corrosion is
normally a scale
• Scale growth normally due to diffusion of
cations and/or anions through the scale

Intro to High Temp.
Oct, 01 7
Scale Growth
Cation Diffusion
Scale Scale Scale
2e- O2-
Metal
Metal
Metal
O
O-O M2+ M2+
O O
Anion Diffusion
Scale Scale Scale
2e-
Metal
Metal
Metal
O2- O2-
O-O M2+ M2+
O O

Intro to High Temp.
Oct, 01 8
Kinetics

Intro to High Temp.
Oct, 01 9
Scale Growth Rate
• Because diffusion path gets longer as scales
grow, growth is normally parabolic
– Scale thickness proportional to square root of
time
• Other rate laws possible
• Linear if scale flakes off

Intro to High Temp.
Oct, 01 10
Scale Growth Rate
12
10
Thickness
8
6
4
2
0
0 50 100
Time

Intro to High Temp.
Oct, 01 11
Evaluation of High Temperature
Corrosion Damage

Intro to High Temp.
Oct, 01 12
Damage Evaluation
• Weight gain
• Weight loss
• Scale thickness
• Total depth of attack

Intro to High Temp.
Oct, 01 13
Weight Gain
• Good for adherent scales
• In lab can be continuously measured
– good for corrosion mechanism determination

Intro to High Temp.
Oct, 01 14
Weight Loss
• Good for non-adherent scales
• Scale removal still an involved process

Intro to High Temp.
Oct, 01 15
Scale Thickness
• An indicator of corrosion rate
– Doesn’t really tell rate of metal loss or extent
of damage

Intro to High Temp.
Oct, 01 16
Total Depth of Attack
• Measures total metal To
compromised by
corrosion
• Total depth of attack =
Tm
(To -Tm) / 2
Internal Metal Loss

Penetration

Intro to High Temp.
Oct, 01 17
Chemical Composition of Scale

Intro to High Temp.
Oct, 01 18
Chemical Composition of Scale
• Scale Composition varies
– Position in scale
– Composition of alloy
– Composition of environment
– Temperature
• Analysis of scale very good diagnostic tool

Intro to High Temp.
Oct, 01 19
Chemical Analysis of Scales
• Energy Dispersive Spectroscopy /
Wavelength Microprobe
– Scanning electron microscope techniques which
give elemental compositions at a “spot” on the
surface of the scale

Intro to High Temp.
Oct, 01 20
Chemical Analysis of Scales
• X ray Diffraction
– Analyzes bulk scale, gives crystal structure
– Crystal structure important
• Some crystal structures give tight adherent

scales others flaky porous ones

Intro to High Temp.
Oct, 01 21
Low Temperature Corrosion,
Specific Mechanisms of Interest
in Refineries

Specific Low Temp.
Oct, 01 1
Contents
• Sensitization (general) • Chloride Stress
• Rapid sensitization Corrosion Cracking
• Weld Decay • Alkaline Cracking
• Knife Line Attack • Hydrogen damage
• Slow sensitization • Black Water
• Polythionic Acid • Ammonium Bisulfide
Stress Corrosion • Dew Point Corrosion
Cracking
Specific Low Temp.
Oct, 01 2
Sensitization

Specific Low Temp.
Oct, 01 3
Sensitization
• Thermal process by which chromium and
carbon react to form chrome carbides
• Time and temperature are important
• Not a corrosion mechanism

Specific Low Temp.
Oct, 01 4
Materials Affected
• Austenitic stainless steels
– primarily 304, 316, 317
– 321, 347 after long term exposure and specific
welding and heat treat conditions
– 904 - potentially after long exposure

Specific Low Temp.
Oct, 01 5
Cause
• Stainless steel must have over about 14% Cr
to be stainless
• 300 series stainless has about 18% Cr
– Cr must be in solution (not bound in CrxCy)
– Not a lot of “extra” chrome available
• Chemical reactions involving Cr and C are
critical
Specific Low Temp.
Oct, 01 6
Cause
• Reduction in the available free Chromium to
below that required to maintain passivation
in the grain boundary area
– i.e. grain boundaries become “non stainless”
– corrosive agent will corrode grain boundaries as
if they were carbon steel

Specific Low Temp.
Oct, 01 7
Chromium/Carbon Reactions
• Below 950oF (510oC)
– Carbon diffusivity slow
– Carbon/chromium reaction kinetics slow
• Nothing happens over the short term
• Below 700oF (370oC)
– Diffusivity and kinetics very slow
• Nothing happens over the long term

Specific Low Temp.
Oct, 01 8
• Between 950oF and 1450oF (510 and 785oC)
– Carbon diffusivity high
– Carbon/chromium reaction kinetics high
– Chromium carbides thermodynamically stable
compared to dissolved chromium and carbon
– Chromium carbides precipitate

Specific Low Temp.
Oct, 01 9
• Above 1450oF (785oC)
– Carbon diffusivity high
– Carbon/chromium reaction kinetics high
– Chromium carbides thermodynamically
UNstable compared to dissolved chromium and
carbon
– No precipitate formed

Specific Low Temp.
Oct, 01 10
Sensitization Process
• Dissolved carbon ==> to grain boundaries
• At correct temperatures chromium reacts
with carbon to form chrome carbides
• Dissolved chromium depleted to less than
14% near grain boundaries
• Grain boundaries preferentially corroded
• Continuous chromium carbides, problem
Specific Low Temp.
Oct, 01 11
Time Scale
• Sensitization occurs on both short and
longer time scales
– Short - associated with welding
– Long - associated with process conditions

Specific Low Temp.
Oct, 01 12
Rapid Sensitization

Specific Low Temp.
Oct, 01 13
Materials Affected
• Primarily 304, 316, 317

Specific Low Temp.
Oct, 01 14
Cause
• Given sufficient carbon (.08%) sensitization
can occur in seconds
• Narrow band in weld HAZ meets criteria
– Closer to weld, cools too fast
– Farther from weld, temps too low

Specific Low Temp.
Oct, 01 15
Weld Thermal History
• Consider a weld operation in which
thermocouples are placed at varying
distances from the weld
• Recall the critical temperature range is

about 950 to 1450oF (510 and 785oC)

Specific Low Temp.
Oct, 01 16
Weld Time Temp Position
2500
2000
Decay
1500
(a)
1000 (b)
Weld (a)
(c) (b)
500 (d) (c)
0 (d)
0 10 20 30
Time (sec)

Specific Low Temp.
Oct, 01 17
Time Temp Position (a)
2500
10 seconds in
2000
sensitizing range
1500
Decay
1000
(a) Weld (a)
500
(b)
0 (c)
0 5 10 15 20 25 30
(d)
Time (sec)

Specific Low Temp.
Oct, 01 18
Time Temp Position (b)
2500
12+ Seconds in
2000 sensitizing range
1500 Decay
1000
(b) Weld (a)
500 (b)
0 (c)
(d)
0 5 10 15 20 25 30
Time (sec)

Specific Low Temp.
Oct, 01 19
Time Temp Position (c)
2500
11 seconds in
2000
sensitizing range
1500 Decay
1000
Weld (a)
500 (c) (b)
0 (c)
(d)
0 5 10 15 20 25 30
Time (sec)

Specific Low Temp.
Oct, 01 20
Time Temp Position (d)
2500
0 seconds in
2000
sensitizing range
1500 Decay
1000 Weld (a)

(b)
500
(c)
0 (d)
0 5 10 15 20 25 30
Time (sec)

Specific Low Temp.
Oct, 01 21
Summary
• Primarily a function of time in the
sensitizing temperature zone (950-1450oF)
(510 and 785oC)
• Other issues play a role

Specific Low Temp.
Oct, 01 22
Weld Decay

Specific Low Temp.
Oct, 01 23
Problem
• Intergranular corrosion in a narrow band of
the weld heat affected zone
• Corrosion occurs when material is exposed

to an environment which is corrosive to
carbon steel

Specific Low Temp.
Oct, 01 24
Alternatives
• Heat treat after welding - not practical
• Use low carbon steels
– Below 0.05 C sensitization by welding unlikely
• Use stabilized steels
– Type 321 - titanium stabilized
– Type 347 - columbium stabilized
• Ti and Cb “lock up” C by forming carbides
• Cr remains in solution
Specific Low Temp.
Oct, 01 25
Refinery Examples
• Anywhere welded 304 or 316 including L
grades are used
– L grades occasionally have a problem because
welders tend to “clean” surfaces with oily rags
before welding

Specific Low Temp.
Oct, 01 26
Knife Line Corrosion

Specific Low Temp.
Oct, 01 27
Problem
• Very narrow band of intergranular corrosion
immediately adjacent to weld
– Closer to the weld and narrower than weld decay
• Corrosion occurs when material is exposed

to an environment which is corrosive to
carbon steel
Specific Low Temp.
Oct, 01 28
Materials Affected
• 321 (titanium stabilized)
• 347 (columbium (niobium) stabilized)

Specific Low Temp.
Oct, 01 29
Cause
• Welding and post weld heat treat remove
stabilizing titanium or columbium carbides
and allow the formation of chromium
carbides

Specific Low Temp.
Oct, 01 30
Carbide Reactions
Columbium Chromium
Temp (F) Carbides Carbides Temp (C)
Tm Tm
Dissolve
2250 1230
Form Dissolve
1450 785
Form
No Reaction
950 510
Slow kinetics and diffusion No Reaction
Slow kinetics and diffusion
32 0

Specific Low Temp.
Oct, 01 31
Summary
• Band near weld heated so columbium
carbides dissolve
• Cools rapidly so no carbides form
• Heat treat temps typically in chromium
carbide formation zone
• Material sensitized
– subject to intergranular corrosion
Specific Low Temp.
Oct, 01 32
Refinery Examples
• Not common but possible in refineries
• Heat treating welded 321 or 347 not a
common practice
– Could occur by accident

Specific Low Temp.
Oct, 01 33
Long Duration Sensitization

Specific Low Temp.
Oct, 01 34
Materials Affected
• 304, 316 (including low carbon versions)
• 321, 347
• Unstabilized nickel alloys 600, 800
• Stabilized nickel alloys 800H, 835
• One source reported no sensitization in

nickel alloys 825, 625
Specific Low Temp.
Oct, 01 35
Cause
• Conversion of Cb or Ti carbides to Cr
carbides
• Diffusion of carbon from the environment
into the steel followed by the formation of
Cr carbides
– Primarily at grain boundaries
• Surface Cr depletion
Specific Low Temp.
Oct, 01 36
Long Term Sensitization
304, 304L
650 1200
C F
304
600
1100
Temp
550 304L
1000
500
900
450
1 10 100 1000 10000
Time (hr)

Specific Low Temp.
Oct, 01 37
Long Term Sensitization
321, 347
650 1200
C F
321
600
1100
Temp
550 347
1000
500
900
450
1 10 100 1000 10000
Time (hr)

Specific Low Temp.
Oct, 01 38
Summary
• Long term sensitization of all 300 series
stainless steels will occur
• Time and temperatures required vary with
material
• 700oF is considered the minimum temperature

for sensitization
Specific Low Temp.
Oct, 01 39
Problem
• Sensitized material has corrosion resistance
of carbon steel
– Primarily along grain boundaries
– Environments not normally corrosive to
stainless steels will corrode it

Specific Low Temp.
Oct, 01 40
Solutions
• Assume steel is sensitized
• Avoid corrodants corrosive to carbon steel
• Neutralize acids
• Exclude oxygen

Specific Low Temp.
Oct, 01 41
Polythionic Acid Stress
Corrosion Cracking

Specific Low Temp.
Oct, 01 42
Problem
• Cracking of austenitic stainless steels
exposed to sulfur at high operating
temperatures occurs during down time
• Attributed to direct reaction of polythionic
acid and sensitized austenitic stainless steel
• Polythionic acid is a class of acids H2SxOy
– Worst H2S4O6

Specific Low Temp.
Oct, 01 43
Polythionic Acid SCC

Specific Low Temp.
Oct, 01 44
Conditions
• Sensitized austenitic stainless steel
• Sulfide scale
• Liquid water
• Oxygen
• Stress

Specific Low Temp.
Oct, 01 45
Conditions
• Sensitization
– Welding
– Long term exposure 800-1500oF (425-815oC)
– 304, 316 sensitize relatively quickly
– 321, 347 take longer - 347 longer than 321

Specific Low Temp.
Oct, 01 46
Conditions
• Sulfide Scale
– High temperature operation
– Sulfur present in feed
– Sulfur injected to prevent coking or carburization
– Sulfur present in fuel gas

Specific Low Temp.
Oct, 01 47
Conditions
• Liquid water
– Condensed water vapor from air is sufficient

Specific Low Temp.
Oct, 01 48
Conditions
• Oxygen
– Oxygen from air is sufficient
– Unclear if dissolved oxygen from water is
sufficient

Specific Low Temp.
Oct, 01 49
Conditions
• Stress
– Must be tensile stress
– High stress not required
• Residual stresses are sufficient
• Must assume always present

Specific Low Temp.
Oct, 01 50
Solutions
• NACE RP-01-70
• Must assume sulfur and stress present
• Should assume sensitized
• Eliminate water and/or oxygen
– Keep equipment hot, use nitrogen purge
• 2% sodium carbonate wash
– Neutralizes acids as form
Specific Low Temp.
Oct, 01 51
Solutions
• Soda ash wash precautions
– Good coverage
– 2 hour wash - soak through scale
– Drain solution well (chlorides and carbonates
can build up)
– 150 ppm chlorides max
– Repeat if carbonate residue disturbed

Specific Low Temp.
Oct, 01 52
Refinery Examples
• Hydrodesulfurizers
• Hydrocrackers
• Hydrogen Reformers
• FCC
• Fired Heaters (outside of tubes)

Specific Low Temp.
Oct, 01 53
Chloride Stress Corrosion
Cracking and Pitting

Specific Low Temp.
Oct, 01 54
Problem
• 300 Series stainless steel (and some nickel
alloys) crack or pit in the presence of
chlorides

Specific Low Temp.
Oct, 01 55
Pitting Conditions
• Primarily 304
– Mo in 316 retards pitting
• PPM level chlorides
• Pitting due to
– Marginal passivation
– Acid formation in the pit

Specific Low Temp.
Oct, 01 56
Chloride SCC Crack

Specific Low Temp.
Oct, 01 57
Chloride SCC Crack

Specific Low Temp.
Oct, 01 58
Cracking Conditions
• ppm level Cl-
• ppm level O2 for neutral pH
• No oxygen required acid pH
• Above 140oF (60oC)
– Lower with other contaminants (H2S)
• Tensile stress
• Sulfur can speed cracking or sub for O2
Specific Low Temp.
Oct, 01 59
Cracking Conditions
• Field survey 304, 316, and 321 performed
the same
• Either intergranular or transgranular
– Normally transgranular
• Branched

Specific Low Temp.
Oct, 01 60
Stress, Time, Material
80
70 304 305 310
304L 309 314
60
316
Stress (ksi)
50 347
40
30
20
10
0
0.1 1 10 100 1000
Fracture Time (hr)

Specific Low Temp.
Oct, 01 61
Time, Temp, Material
400
350
Temperature (F)
300 347
250 316
200
150
100
50
0
0 20 40 60 80 100 120
Time to crack (hr)

Specific Low Temp.
Oct, 01 62
Oxygen, Chlorides
1000
100
Oxygen (ppm)
10
0.1
0.1 1 10 100 1000
Chlorides (ppm)

Specific Low Temp.
Oct, 01 63
Examples
• Seawater piping or exchanges
• Under insulation
– SS compatible insulation a must
• Anywhere SS and chlorides are present

Specific Low Temp.
Oct, 01 64
Alkaline Cracking

Specific Low Temp.
Oct, 01 65
Problem
• Cracking is observed under certain
conditions when carbon steel is exposed
to caustic, carbonates, and amines

Specific Low Temp.
Oct, 01 66
Materials Affected
• Carbon steel
• Stainless steel

Specific Low Temp.
Oct, 01 67
Conditons, Caustic
• Over 150oF - varies with concentration
• Needs some oxygen but not a lot
• Normally intergranular
• Normally not branched

Specific Low Temp.
Oct, 01 68
Conditions, Caustic
280
260
Nickel Alloys
240
220
Temperature (F)
200 Stress Relieved

180 Carbon Steel
160
140
120 Carbon Steel
100
80
60
40
0 10 20 30 40 50 60
Wt % NaOH

Specific Low Temp.
Oct, 01 69
Caustic Cracks

Specific Low Temp.
Oct, 01 70
Caustic Cracks

Specific Low Temp.
Oct, 01 71
Conditions, Carbonate
• Over 100oF
• Cracks may be either intergranular or
transgranular
• Slow growing cracks intergranular

Specific Low Temp.
Oct, 01 72
Conditions, Amine
• Cause not completely clear
• May be due to carbonate
• Occurs in non-post weld heat treated material

Specific Low Temp.
Oct, 01 73
Solutions
• Caustic
– Control temperature
– Proper metallurgy
• Carbonate, Amine
– Stress relieve
• All related
– Marginal passivation
Specific Low Temp.
Oct, 01 74
Examples
• Caustic Cracking
– Boilers
– Use care in Merox, crude units
• Carbonate
– Downstream of downtime protected units
• Amine/Carbonate
– Sour gases / Amine units
Specific Low Temp.
Oct, 01 75
Hydrogen Damage

Specific Low Temp.
Oct, 01 76
Low Temp Hydrogen Damage
• Several terms applied
– Hydrogen blistering
– Hydrogen induced cracking (HIC)
– Stress oriented hydrogen induced cracking
(SOHIC)
– Sulfide stress cracking (SSC) or hydrogen
stress cracking
• All variations of same phenomenon
Specific Low Temp.
Oct, 01 77
General Mechanism
• Penetration of atomic hydrogen (H0) into steel
• At low temperatures (<400oF or 204oC)
molecular hydrogen does not react with steel
and does not penetrate
• Atomic hydrogen comes from any wet
corrosion reactions which makes H2
– Often associated with H2S

Specific Low Temp.
Oct, 01 78
General Mechanism Cont.
• Atomic Hydrogen generated by corrosion
normally combines to form molecular
hydrogen and escapes into solution
• Some doesn’t
• Recombination poisons promote penetration
– CN-, As, S2-

Specific Low Temp.
Oct, 01 79
Hydrogen Blistering
• Low tensile strength steel (high ductility)
• Voids and inclusions
– Particularly MnS stringers
• Atomic hydrogen finds void and
recombines to molecular hydrogen

Specific Low Temp.
Oct, 01 80
Hydrogen Blistering
H0 H+
Void
or H2
Inclusion
H0 H+
H2
H0 H+
S2-
H0 H+
Steel Solution

Specific Low Temp.
Oct, 01 81
Hydrogen Induced Cracking
• Starts at elongated MnS inclusions
• Cracks start at tips of blisters and grow
parallel to steel surface
• Link by growing perpendicular
• Want low Mn and S steel with shape
controlled inclusions

Specific Low Temp.
Oct, 01 82
Hydrogen Induced Cracking
H2
H2
H2

Specific Low Temp.
Oct, 01 83
Stress Oriented Hydrogen
Induced Cracking (SOHIC)
• Starts from wet corrosion producing H0
which diffuses in
• H0 collect at lattice defects but don’t
necessarily form voids
• Cracks form in plane of inclusions and link
in plane perpendicular to stress
• Often at hard spots near welds
Specific Low Temp.
Oct, 01 84
Stress Oriented Hydrogen
Induced Cracking
Stress Stress

Specific Low Temp.
Oct, 01 85
Sulfide Stress Cracking
• High strength steel or hard welds
• Stress or residual stress
• Temperature and hydrogen flux affect
cracking
• Unlike other types of hydrogen damage
significant wet corrosion is not required
• Heat treat steel, welds < HRc 22 (HV 248)
Specific Low Temp.
Oct, 01 86
Sulfide Stress Cracking,
Hydrogen Stress Cracking
Stress Stress
High Strength Steel

Specific Low Temp.
Oct, 01 87
Examples
• HF units
• Sour water strippers
• FCC
– HP and LP separators
– Stripper tower overhead

Specific Low Temp.
Oct, 01 88
What to do about it
• Minimize wet corrosion (generates H0)
• Minimize recombination poisons (H2S etc.)
• Use low Mn, S steels with inclusion shape
control
• Avoid high strength steels
• Heat treat welds to below HRc 22

Specific Low Temp.
Oct, 01 89
Black Water
The Effect of pH on Sulfide Scales

Specific Low Temp.
Oct, 01 90
Black Water
• pH, chlorides and cyanides have dramatic
effect on corrosivity of wet H2S
environments
• Many complex equilibria
– Extent to which sulfide scale protects metal
from further corrosion depends on equilibria

Specific Low Temp.
Oct, 01 91
Hydrogen Sulfide
• H2S <==> H+ + HS-
• HS- <==> H+ + S=
• Position of equilibrium depends on pH

Specific Low Temp.
Oct, 01 92
Iron Sulfide
• Iron sulfide very low solubility
• Low pH, H2S almost all in molecular form
– Fe corrodes due to H+ present
– Fe finds what little S= is present and
precipitates in solution
• Scale formation is minimal and porous
• Corrosion rate is high
Specific Low Temp.
Oct, 01 93
Iron Sulfide
• At higher pH > 7 S= in solution exceeds Fe2+
– Fe, S reaction occurs at metal surface
• Scale formed is tight and protective

Specific Low Temp.
Oct, 01 94
Iron Sulfide
• At intermediate pH (6-8) HS- ion
concentration is high
• Forms soluble complex ion FeSH+
• Increases iron in solution, should increase
corrosion rate
– Must compete with scale formation reactions

Specific Low Temp.
Oct, 01 95
Complications
• Competing reactions from chlorides,
cyanides and oxygen make H2S reactions
more difficult to predict
• FeS + H+ + Cl-<==> FeSH+ + Cl-
– Driven by the Cl- which disrupts scale
• FeS + 6NH4CN + 6H2O <==>
Fe(CN)64- + 6NH4OH +6H+ + S=
– Increases Fe solubility and therefore corrosion
Specific Low Temp.
Oct, 01 96
Black Water
250
Corrosion Rate (mpy)
200
50000 ppm NH4Cl
150
5000 ppm NH 4Cl
100
0 ppm NH4Cl
50
0
0 2 4 6 8 10
pH

Specific Low Temp.
Oct, 01 97
Black Water
• Named because tail water turns black when
crossing or operating in high corrosion
range
• UOP idealized representation

– Remember this in operating your unit
– Don’t cross black water region
Specific Low Temp.
Oct, 01 98
Black Water
14
Corrosion Rate (mpy)
12
10
8
6
4
2
0
2 4 6 8 10
6.8 7.3
pH

Specific Low Temp.
Oct, 01 99
Ammonium Bisulfide

Specific Low Temp.
Oct, 01 100
Ammonium Bisulfide Formation
• High temperature, catalyst, nitrogen, sulfur,
hydrogen
– 2N + 3H2 <==> 2NH3
– S + H2 <==> H2S
• As gases cool
– NH3 + H2S <==> NH4HS

Specific Low Temp.
Oct, 01 101
Ammonium Bisulfide Issues
• Ammonium bisulfide condenses from gas to
white fluffy solid
– Aggressive foulant
– Highly water soluble
• Water wash to combat fouling creates
corrosive solution/slurry

Specific Low Temp.
Oct, 01 102
Refinery Examples
• Reactor effluent air coolers (REACs) for
hydrotreaters and hydrocrackers
• Sour water stripper overhead
• FCC fractionation section

Specific Low Temp.
Oct, 01 103
Solutions
• Water wash
– Prevent fouling
– Reduce corrosivity

Specific Low Temp.
Oct, 01 104
Operating Guidelines
• Kp (mol% H2S x mol% NH3 in dry gas)
– No corrosion to carbon steel if Kp < 0.02

Specific Low Temp.
Oct, 01 105
• Header configuration / single vs. multiple
water injection points
– Balanced system with multiple injection points
reduced corrosion
– Unbalanced system
• Significant corrosion at Kp > about 0.1
– Balanced system
• Significant corrosion at Kp > 0.2 to 1.0
Specific Low Temp.
Oct, 01 106
Balanced REAC

Specific Low Temp.
Oct, 01 107
• Water vaporization
– Retain 20% (min) liquid water at injection point
• Prevents fouling
• Prevents dew point corrosion of HCl if present

Specific Low Temp.
Oct, 01 108
• Ammonium bisulfide concentration in water
• Significant corrosion when concentration > 2wt%
– Balanced system
• Significant corrosion when concentration > 8wt%

Specific Low Temp.
Oct, 01 109
• Velocities
• Corrosion at velocities > about 3 m/s
– Balanced system
• Corrosion at velocities > 6 m/s

Specific Low Temp.
Oct, 01 110
• Alloy materials
– Alloys 800, S31803, 321, and 400 have
performed well
– Alloy 825 should perform well
– Consider polythionic acid for austenitic alloys
(e.g. alloy 800)
– Consider pitting failure for alloys subject to
chloride pitting (e.g. alloy 800 and 321)
Specific Low Temp.
Oct, 01 111
• Advantages of alloy materials
– Increased Kp
– Increased velocities (9 m/s)
– Potential reduction in water wash rates
• UOP guidance is to select alloy material if
Kp >0.4

Specific Low Temp.
Oct, 01 112
Dew Point Corrosion

Specific Low Temp.
Oct, 01 113
Dew Point Corrosion
• Normally the temperature at which liquid
water forms from vapor
• Often also used as the temperature at which
solids precipitate from vapor
– Ammonium bisulfide
– Ammonium chloride

Specific Low Temp.
Oct, 01 114
Dew Point Corrosion
• First drop of liquid water contains dissolved
gases in equilibrium with gas phase
– Solutions can be very concentrated
• Sublimation of gas to solid may cause
extensive fouling

Specific Low Temp.
Oct, 01 115
Refinery Example
• Condensation of hydrochloric acid
– HCl(g) + H2O ==> H3O+ + Cl-
– First drop of water will be a saturated solution
• pH will be in the negative range
– Crude column overhead
– FCC main column overhead
• Chlorides from distillation column, catalyst
• Water from stripping steam in reactor, main column
Specific Low Temp.
Oct, 01 116
Solution
• Ammonia addition to neutralize HCl in the
gas phase
– NH3 + HCl <==> NH4Cl

Specific Low Temp.
Oct, 01 117
New Problem
• NH4Cl sublimes to a solid and fouls the
system

Specific Low Temp.
Oct, 01 118
New Solution
• NH4Cl is water soluble
• Water wash will remove foulant

Specific Low Temp.
Oct, 01 119
New Problem
• Ammonium chloride solutions are corrosive
– NH4Cl + H2O <==> NH4+ + Cl- + H2O
– NH4+ continues to react
– NH4+ + H2O <==> NH3 + H3O+
• Reaching a neutral pH requires substantial
excess ammonia

Specific Low Temp.
Oct, 01 120
The Worst Problem
• Wet ammonium chloride
– Not enough water to dissolve but enough to
make corrosive
– Foulant
– Under Deposit corrosion
• If you are going to water wash - do it well

Specific Low Temp.
Oct, 01 121
Operational Guidelines
• Desalt well < 2lb salt/1000bbl
• Caustic injection
– 2-3% NaOH, <4lb 1000bbl, <300F
• Automate pH control
– Aim for 6 - 6.5 in crude units, 7-9 FCCs
• Continuous water wash
– At least 10% free water
Specific Low Temp.
Oct, 01 122
Specific High Temperature
Corrosion Mechanisms of
Interest in Refineries

Specific High Temp.
Oct 2003 1
Topics
• Oxidation
• Carburization
• Metal Dusting
• Sulfidation
• Hydrogen
• Liquid Metal
• Naphthenic Acid
Specific High Temp.
Oct 2003 2
Specific Mechanisms
• The corrosion problems addressed in this

section are of specific concern in refineries
• Some problems discussed are a general
class while others are quite specific

Specific High Temp.
Oct 2003 3
Specific Mechanisms
• This section will attempt to provide specific
corrosion conditions and control actions
which may be taken
• Many of these corrosion problems are found
in more than one unit
– Generally the causes and controls are similar
– Differences will be pointed out

Specific High Temp.
Oct 2003 4
Oxidation

Oxidation
July, 02 1
Topics
• Oxidation issues
• Refinery examples
• Control techniques
• References

Oxidation
July, 02 2
Oxidation Issues

Oxidation
July, 02 3
Oxidation
• Most common high temperature corrosion
• Air is not the same as combustion
atmospheres
– Combustion most common
– Air most studied

Oxidation
July, 02 4
Oxidation Issues
• Oxygen concentration
• Alloy composition
• Temperature

Oxidation
July, 02 5
Oxygen Concentration
• Oxygen must exceed thermodynamic values
• After oxygen sufficient, little effect on
corrosion rate. Corrosion rate function of
scale thickness
• Oxygen may be from CO/CO2, H2/H2O
equilibria
– 2CO + O2 <==> 2CO2
– 2H2 + O2 <==> 2H2O
Oxidation
July, 02 6
Oxygen Scales
• Scale composition varies with
– alloy composition
– position in scale
– temperature

Oxidation
July, 02 7
Oxygen Scales
O2
O2-
Fe2O3
Fe2+ Fe3+ Fe3O4 O2-
Fe2+ FeO Fe2+ Fe3+
Fe
Above 570C Below 570C

Oxidation
July, 02 8
Scale Chem and Corrosion Rate
Parabolic rate constant 1.E-06
FeO/Fe3O4/Fe2O3 (Fe)
1.E-07 Fe-Cr oxide/FeO/Fe3O4/Fe2O3

(Fe-2Cr)
1.E-08 (Fe,Cr)O3/Fe2O3 (Fe-9Cr)
FeFe (2-n) CrnO4(internal)/
1.E-09 Cr2O3/Fe3O4/Fe2O3
(Fe-16 Cr)
1.E-10
Cr2O3 (Fe-28Cr)
1.E-11
0 10 20 30 40 50 60 70 80
Wt % Cr

Oxidation
July, 02 9
Oxidation Rates of Alloys (Air)
1 = Carbon Steel
1 2 3 4 2 = 1 Cr - 1 /2 Mo
100 3 = 2 Cr - 1 /2 Mo
4 = 5 Cr - 1 /2 Mo
5 = 7 Cr - 1 /2 Mo
6 = 5 Cr - 1 /2 Mo - 1 1 /2 Si
7 = 9 Cr - 1 Mo
8 = TP 304 Stainless Steel
9 = TP 309/310 Stainless Steel
10 5
6
7
8
1.0
9
0.1
1000 1100 1200 1300 1400 1500 1600 1700
Temperature, ºF

Oxidation
July, 02 10
Metal Temperature, a Key Issue
• Metal temperature, not process temperature
or flame temperature is critical
• In fired heaters if heat transfer drops metal
temperatures rise
– Watch for coking or fouling
• Decreases heat transfer
• Increases firing rate

Oxidation
July, 02 11
Refinery Examples

Oxidation
July, 02 12
Refinery Examples
• Fired heaters

Oxidation
July, 02 13
Control Techniques

Oxidation
July, 02 14
Control Techniques
• Decrease temperature
• Increase alloy
– Cr, Ni, Al, Si
• Control environmental contaminants
– Metals, e.g. V, in fuel
– Sulfur

Oxidation
July, 02 15
Carburization

Carb., Coke, Metal Dust
Oct 2003 1
Topics
• Carburization Issues
• Refinery Examples
• Control Techniques

Oct 2003 2
Carburization Issues

Oct 2003 3
Carburization
• Ingress of carbon into metal
• Occurs when carbon activity in the
environment is greater than in the metal
• Identical to carburization heat treatment
– Increased strength, Decreased ductility
• Kinetic and thermodynamic issues
• Consider ≈500C, bigger issue 1000C
Oct 2003 4
Carbon Activity
• Governed by several equilibria

– CO + H2 <==> C + H2O
– 2CO <==> C + 2H2O
– CH4 <==> C + 2H2
• Water and hydrogen reduce tendency to
carburize

Oct 2003 5
Carburization
• Causes the formation of carbides in grain
boundaries (primarily) and grains
• Factors affecting carburization
– Temperature
– C diffusion rate
– Alloy (diffusion rate and existence of scale)
– C solubility
– C activity gradient
Oct 2003 6
Carburization Resistance
• Complex
– Without scale follows parabolic rate law
• Diffusion of C through metal
– With scale much slower
• Cr, Ni, Si affect rate
– Formation of scales
– Diffusion of C
Oct 2003 7
Material Selection
• Select specifically for environment and

temperature
– Both affect which oxides will be stable
– Stable oxide highly desirable

Oct 2003 8
Refinery Examples

Oct 2003 9
Refinery Examples
• Furnace tubes (in general)

• Ethylene pyrolysis tubes
• Ethylene and Olefin plant pigtails

Oct 2003 10
Control Techniques

Oct 2003 11
Control Techniques
• Keep temperature low
• Select best metallurgy for conditions
• Maintain conditions
– Temperature and environment
• Maintain oxide scale
• Maintain sulfide scale
– See section of sulfidation
Oct 2003 12
Metal Dusting

Oct 2003 1
Topics
• Metal Dusting Issues

• Refinery Examples
• Control Techniques

Oct 2003 2
Metal Dusting Issues

Oct 2003 3
Metal Dusting
• Pitting, thinning and wastage of metal

• Fine powder residue
– Metals, Carbides, Oxides
• Area beneath pits will be carburized

Oct 2003 4
Metal Dusting Environments
• 480 to 900oC (900 to 1650oF)

• Occurs first in “no flow” locations
• CO, H2 environments
– Water in environment should reduce tendency
for dusting but sometimes makes it worse

Oct 2003 5
Carbon Adsorption
Environment
H-H H H H H
H-H O O
C-O
C-O C
C
Metal

Oct 2003 6
Metal Dusting Mechanism
• Mechanism not fully understood
– Carburization form Fe3C
– C diffusion in Fe3C is slow, graphite forms on
surface
– Fe3C decomposes
• Graphite grows into metal
• Iron “particles” diffuse out through graphite,
catalyze coke formation
Oct 2003 7
Metal Dusting Mechanism
• Many alternate mechanisms e.g.

– Formation of chromium carbides depletes Cr in
solution. Remaining Fe Ni matrix may be
easily corroded by environment

Oct 2003 8
Materials Affected
• Carbon steel
• Cr Mo steel
• Stainless steel
• Iron based alloys
• Nickel based alloys

Oct 2003 9
Refinery Examples

Oct 2003 10
Refinery Examples
• Synthesis gas reactors

• Butane dehydrogenation
• Reformers (petroleum, methanol, ammonia)

Oct 2003 11
Control Techniques

Oct 2003 12
Control Techniques
• Find a resistant alloy

• Minimize carbon activity (if possible)
• Minimize “dead spots”
• Sulfur addition?
• Complete SiO2, Cr2O3, or Al2O3 scales help
– Kinetics of scale formation at low end of temp
range may be a problem
Oct 2003 13
Sulfidation

2003 ENGINEERING DESIGN SEMINAR – LIMITED DISTRIBUTION: This material is UOP LLC technical information of a confidential nature
for use only by personnel within your organization requiring the information. The material shall not be reproduced in any manner or distributed for
Sulfidation
any purpose whatsoever except by written permission of UOP LLC and except as authorized under agreements with UOP LLC.
July, 02 1
Topics
• Definitions
• Thermodynamics
• Kinetics
• Prediction tools

Sulfidation
July, 02 2
Definitions

Sulfidation
July, 02 3
Sulfidation
• Use care in discussing. Means different

things to different people
– Injection of S to form a protective scale
– Formation of S rich scale
– Loss of metal grains from the surface of metal
due to intergranular corrosion
– Penetration of S along grain boundaries

Sulfidation
July, 02 4
Sulfidation
• The interaction of sulfur and metal, even for
the purpose of forming a protective sulfide
scale is corrosive and some metal is lost
• Sulfide scales separate metal from
environment and eliminate metal catalyzed
coking
• Sulfide scales resist diffusion of carbon and
reduce carburization
Sulfidation
July, 02 5
Thermodynamics

Sulfidation
July, 02 6
Thermodynamics
Log PH2O/PH2 and PCO2/PCO
-10 -8 -6 -4 -2 0 2 4 6 8
o
Fe eS
2O 3
Cr r2 S
-4
F
O
Ni iS
3
C
N
O
Log PS2 Atm
Cr2S3
-8 FeS NiS
CrS Ni
Cr S Fe
3
2O
Cr
FeO
-12
NiO
Fe
Ni
CrS
Cr
Cr2O3
Cr
-16
-36 -32 -28 -24 -20 -16 -12 -8 -4 0

Log P02 Atm

Sulfidation
July, 02 7
Life Expectancy Based on Scale
CrS
Sulfidation
Limited Life
Log PS2
Cr Cr2O3
Resistant Generally
Resistant
Log PO2

Sulfidation
July, 02 8
Scale Composition
• Varies with environment and alloy
composition
• Want single layer, chromium rich adherent
scale
• Often get multiple layer, less than fully
adherent scale

Sulfidation
July, 02 9
Kinetics

Sulfidation
July, 02 10
Sulfidation Kinetics
• Faster than oxidation

• Normally parabolic
– Diffusion of metal ions through scale
– S does not diffuse inward
• Thick scales spall off
– Linear (very fast) kinetics

Sulfidation
July, 02 11
Breakaway Corrosion
• Preexisting oxide scale or oxygen/sulfur

environment
• Patchy sulfide scales form inside and
outside of oxide
• Sulfur penetration along grain boundaries
• Corrosion rate initially moderate.
Dramatically accelerates after incubation.
Sulfidation
July, 02 12
Prediction Tools

Sulfidation
July, 02 13
Sulfur Corrosion Rates
• Two sets of corrosion curves

• McConomy (API)
– Based on total sulfur
– UOP uses variation of this set of curves
• Couper Gorman
– Based on hydrogen/hydrogen sulfide

Sulfidation
July, 02 14
Hot H2S Corrosion
10 10
Carbon Corrosion
Rate
Steel mpy
1 50 Corrosion 1 4
30 3
20 Rate
Mole % H2S
Mole % H2S
40 2
10 25 mpy 1
1 3 5 15 .6
2 0.1 .4
0.1
.2
0.01 0.01
No Corrosion
No Corrosion
18 8 Stainless
0.001 0.001
400 600 800 1000 400 600 800 1000
Temperature F Temperature F

Sulfidation
July, 02 15
High Temp Sulfur Corrosion

Sulfidation
July, 02 16
High Temperature Hydrogen

Hydrogen
July, 02 1
Topics
• Mechanism

Hydrogen
July, 02 2
Mechanism

Hydrogen
July, 02 3
Hydrogen
• At high temperatures H2 dissociates on the

metal surface to form 2 H0
• H0 can diffuse through metal (just the same
as at low temperature only faster)
• Causes two problems
– Hydrogen attack
– Hydrogen embrittlement
Hydrogen
July, 02 4
Hydrogen Attack
• Above 232oC (450oF) Hydrogen will

decarburize carbon and low alloy steels
– Reduces mechanical properties
• 4H + C ==> CH4
• Methane can’t diffuse - acts like low temp
hydrogen blister

Hydrogen
July, 02 5
Hydrogen Attack
• Extent of hydrogen attack determined by

available carbon
• Chromium carbides more stable than iron
carbides
– Resist reaction of hydrogen to form methane
• As temperature increases, more chromium
is required to resist hydrogen attack
Hydrogen
July, 02 6
Nelson Curve (API-971)
1400
External Decarburization Internal Decarburization
1300
1200 6 Cr-0.5 Mo
1100
1000 3 Cr-1Mo or 2.25 Cr-1Mo-V
900 2.25 Cr-0.5 Mo
1 Cr
800
700 1 or 1.25 Cr-0.5 Mo
600
500 Carbon Steel
400
0 500 1000 1500 2000 2500 3000
Hydrogen Pressure (psia)

Hydrogen
July, 02 7
Carbon 1/2 Moly
• Used to be specific zone of acceptability on
Nelson curves
• Later found to be no better than carbon steel
• UOP position
– Should be replaced
– If not, thorough and frequent inspection
• Cracks random and grow quickly, inspection not
really practical
Hydrogen
July, 02 8
• Hydrogen solubility greater at high temps
• If hydrogen rich metal cooled too quickly,
supersaturates
– Ductility dramatically reduced
– Normally appears only below 149oC (300oF)
• Cooling rates between 28-56oC/hr (50-
100oF) normally acceptable
Hydrogen
July, 02 9
Refinery Examples

Hydrogen
July, 02 10
Refinery Examples
• Hydrotreaters
• Hydrocrackers

Hydrogen
July, 02 11
Control Techniques

Hydrogen
July, 02 12
Control Techniques
• Select proper alloys

• Monitor metal temperatures
– Fouling and changes in throughput will affect
metal temperature and hydrogen attack
• Control cooling rates

Hydrogen
July, 02 13
Liquid Metal Embrittlement

nature for use only by personnel within your organization requiring the information. The material shall not be reproduced in any manner or Liq. Metal Embrittlement
July, 02 1
Topics
• Mechanisms

July, 02 2
Mechanisms

July, 02 3
• Related to stress corrosion cracking

• Certain combinations big problem
– Others no problem
• Cracking is essentially instantaneous

July, 02 4
• Not the same as liquid metal corrosion

• Generally little solubility of the two
materials in either solid or liquid forms
• Generally no intermetallic compounds
• Theory is adsorbed metal weakens base
metal bonds and allows crack to propagate
with lower than normal stress
July, 02 5
Refinery Examples

July, 02 6
Refinery Examples
• Mercury
– Aluminum/water
– 302, 304, 321, 347
– Copper and many brasses
– Nickel
– Monel
– Alloy 600
– Titanium
July, 02 7
Refinery Examples
• Zinc (galvanizing, primers)

– Austenitic stainless steel
• Cracks are instant and very severe
– Ferritic steels
• Some slow degradation of properties

July, 02 8
Control Techniques

July, 02 9
Control Techniques
• Avoid liquid metal and base metal contact
– Oxide scales good unless ruptured
• Consider fire scenario
– Zinc paints should not be used on stainless
– Don’t grind galvanized steel near stainless (dust
will melt in a fire and embrittle
• Consider welding
– Don’t weld galvanized to stainless
July, 02 10
Naphthenic Acids

nature for use only by personnel within your organization requiring the information. The material shall not be reproduced in any manner or Naphthenic Acid
July, 02 1
Topics
• Corrosion conditions

July, 02 2
Corrosion Conditions

July, 02 3
Naphthenic Acids
• Class of acids
O
– Not a single acid
=
-R-C-O-H
• MW varies greatly
– Normally heavy R = Hydrocarbon
chain
1 or more 5 or 6
member rings

July, 02 4
Naphthenic Acid Corrosion
• Direct reaction between metal and acid
– Water and ionization not required
• Corrosive temperature range 450-750oF
– Max 520-535oF
• Leaves metal bare (no scale)
• Sharp ridges and grooves
• Sulfur scale reduces corrosion
July, 02 5
Corrosion Prediction
• TAN best method readily available

– Not very good
– Acids other than Naphthenic acids part of TAN
• Other acids don’t corrode by same method
– <0.5 TAN normally considered OK
• Works part of the time

July, 02 6
Corrosion Prediction
• For different crudes

– Ratio of naphthenic acids to other acids varies
– Molecular weight of naphthenic acids varies
• For crudes with only naphthenic acids and
only a narrow range of molecular weights
even a very low TAN will give high
corrosion in one cut
July, 02 7
Sulfur Corrosion vs Naphthenic
Acid Corrosion
• Sulfur corrosion
– Shallow scoops
– Scale
– Resolved by 410 metallurgy
• Naphthenic acid
– Sharp ridges
– Bare metal
– Not resolved by 410 metallurgy
July, 02 8
Refinery Examples

July, 02 9
Refinery Examples
• Primarily crude units and vacuum units

– Areas where temperatures are between 450-750oF
• Feed heaters and piping of downstream units
– Same temperature range
– Naphthenic acids destroyed by catalysts and
temperatures over 750oF

July, 02 10
Control Techniques

July, 02 11
Control Techniques
• Blend crudes to reduce TAN

– Not perfect solution but best available
– Check acid in individual cuts
• Use 317 ss in areas subject to naphthenic
acid corrosion

July, 02 12

(UOP) Corrosion and Fouling PDF

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Introduction to Low

Corrosion and Fouling

• Provide the student with a basis for

• Start from a point of everyday familiarity

Corrosion and Fouling

• Corrosion Definitions • Concentration Cells

Corrosion and Fouling

Corrosion and Fouling

Corrosion and Fouling

• Many possible definitions

• Low temp corrosion

• All corrosion is electrochemistry

Corrosion and Fouling

• Ca(OH)2 and Mg(OH)2 are weak bases

Corrosion and Fouling

Corrosion and Fouling

• Essentially all low temperature corrosion is

Corrosion and Fouling

Corrosion and Fouling

Corrosion and Fouling

– Equation is not important - concept is

Flow of Electrons - Not Just the

Corrosion and Fouling

• The rate of corrosion is proportional to the

• Consider almost dead car battery

• The higher the current the lower the voltage

• Actually the higher the current the lower the

• Consider the copper zinc cell again

Corrosion and Fouling

Corrosion and Fouling

• Ammeter has no resistance

• If potential was also measured would voltage

Corrosion and Fouling

-0.4 Potential and

Corrosion and Fouling

Where making conditions worse

Corrosion and Fouling

• Some alloy/environments form film which

• Produces counterintuitive corrosion results

Corrosion and Fouling

• Will DILUTE nitric acid corrode iron?

Corrosion and Fouling

Corrosion and Fouling

• Will iron corrode in concentrated nitric

Corrosion and Fouling

Corrosion and Fouling

• Will iron that has been in concentrated

Corrosion and Fouling

Corrosion and Fouling

• If the dilute acid is shaken, will the iron

Corrosion and Fouling

Corrosion and Fouling

Corrosion and Fouling

• Potential/current relationship for copper

• Potential/current relationship for zinc

• Lines cross at corrosion potential/current

-0.4 Potential and

Corrosion and Fouling

• For active passive metal like iron, potential

Corrosion and Fouling

Corrosion and Fouling

• Corrosion potential/current is still the