Material Selection Corrosion Control PDF

CORROSION MECHANISMS
MATERIAL SELECTION AND

CORROSION CONTROL
IN REFINERY
Flavio Cif
Michele Scotto di Carlo
2
Corrosion is defined as the destruction or

deterioration of a material because of
reaction with its environment
Mars G. Fontana
CONTENTS 3
n CORROSION AND DEGRADATION MECHANISMS

CORROSION PROCESSES KINETIC
LOW TEMPERATURE DEGRADATION MECHANISMS
l GENERAL CORROSION
CO2 corrosion
Wet hydrogen sulfide corrosion
l GALVANIC CORROSION
l PITTING CORROSION
l CREVICE CORROSION
l UNDER DEPOSIT CORROSION
l STRESS CORROSION CRACKING
Chloride stress corrosion cracking (CSCC)
Sulfide stress cracking (SSC)
Alkaline stress corrosion cracking (ASCC)
Caustic cracking
Amine cracking
Cracking in H2O-CO-CO 2 systems
CONTENTS 4
LOW TEMPERATURE CORROSION MECHANISMS (CONTINUE)

l SENSITIZATION AND WELD DECAY CORROSION (INTEGRANULAR)
Sensitization
Weld Decay
knife line attack
Polythionic Acid Stress corrosion Cracking (PASSC)
l EROSION CORROSION
l MICROBIOLOGICALLY INDUCED CORROSION
l CORROSION UNDER INSULATION
l HYDROGEN DAMAGE
HIGH TEMPERATURE CORROSION MECHANISMS

l NAPHTENIC ACID CORROSION
l HIGH TEMPERATURE OXIDATION
l SULFIDATION
l HIGH TEMPERATURE HYDROGEN DAMAGE
CONTENTS 5
n MATERIALS AND CORROSION PROTECTION

MATERIAL SELECTION GUIDELINE
CARBON STEEL
LOW ALLOYED STEELS
STAINLESS STEELS
COPPER ALLOYS
NICKEL ALLOYS
TITANIUM ALLOYS
POLIMERIC MATERIALS
CATHODIC PROTECTION
n MATERIAL SELECTION AND CORROSION CONTROL

IN REFINERY UNITS
DESALTER
ATMOSPHERIC DISTILLATION UNIT
VACUUM DISTILLATION UNIT
AMINE UNIT
HYDRODESULPHURIZATION UNIT
SOUR WATER STRIPPER UNIT
CORROSION AND DEGRADATION
MECHANISMS
General criteria
CORROSION KINETICS 7
n STATIONARY KINETICS
Steady corrosion rate which often allows:
corrosion rate prediction trough laboratory tests, bibliographic data
and estimation models.
Monitoring on stream and off stream
Upset conditions are not decisive on corrosion process
R corr
n INCUBATION PERIOD KINETICS

It presents an incubation period which closes
with high corrosion rate (cracking).
Stationary
upset conditions are decisive. Incubation period

The incubation period may be very short (h!!!)
ti Time
The corrosion process once started (t > ti) continues up to the
rupture independently from the incubation conditions persistence.
Whenever upset conditions are decisive for the described
corrosion mechanism they will be clearly highlighted with
UPSET
LOW/HIGH TEMPERATURE CORROSION 8
LOW TEMPERATURE CORROSION

n Temperature < 260C
n Aqueous phase and presence of ionic species
HIGH TEMPERATURE CORROSION

n Temperature > 260C
n Aqueous phase not necessary
MECHANISMS
Low temperature corrosion mechanisms

LOW TEMPERATURE DEGRADATION MECHANISMS 10
n GENERAL CORROSION
n GALVANIC CORROSION
n PITTING CORROSION
n CREVICE CORROSION
n UNDER DEPOSIT CORROSION
n STRESS CORROSION CRACKING
n SENSITIZATION AND WELD DECAY CORROSION
(INTEGRANULAR CORROSION)
n EROSION CORROSION
n MICROBIOLOGICALLY INDUCED CORROSION
n CORROSION UNDER INSULATION
n HYDROGEN DAMAGE
GENERALIZED CORROSION AT LOW TEMPERATURE 11
n ANODE location where metal

dissolution takes place (i.e.
FeFe2+ )
n CATHODE: location where O2, H+

or metal reduction takes place
(i.e. Fe3+ Fe2+)
n No specific location for anode

and cathode
n Anode and cathode move with

time
n Can be monitored, measured and

predicted
Can be uniform or not
CONTROL:
n Select proper metallurgy
n Corrosion allowance (function of
corrosion rate and required lifetime)
n Inhibitor
n Cathodic Protection
n Monitoring
Some metal-environment combinations
known to results in general corrosion:
CS - dilute mineral acid Corrosion rate of various alloys in
CS - CO2 and/or H2S in aqueous phase boiling mixtures of 50% acetic acid
and varying proportions of formic acid.
CS - seawater Test time 1+3+3 days. (by SANDVIK)
SS - organic acid at high T (i.e. 100- 200 C)
Ti - concentrated sulfuric acid
GENERALIZED CORROSION AT LOW TEMPERATURE- CO2 13
An example of generalized corrosion at low temperature is CO2

corrosion on carbon steel.
Requires a presence of aqueous phase and its due to the low pH.
It can be tentatively predicted using a software

Its a function of:
n PCO2
n Temperature
n System Fluid dynamics
(influences scale stability )
n Presence of H2S and/or organic acid
n O2 content
CONTROL: it can be controlled with CS + CA up to corrosion rate (CR)

0.6mm/y. For higher CR upgrade metallurgy to 304 (316 not necessary)
GENERALIZED CORROSION AT LOW TEMPERATURE - H2S 14
Another example of generalized

corrosion at low temperature on
carbon steel is Wet Hydrogen
Sulphide corrosion. (Note:
includes also risk of SSC and
hydrogen damage).
It requires a presence of aqueous
phase and its due to the low pH
and to the reaction between S and
Fe (formation of FeS scale)
The stability of FeS scale is
influenced by pH and presence of
contaminants (i.e. CN-)
The temperature rise increase CR
CR is hardly predictable NOTE: CR is influenced also by pH, fine
metal composition, presence of
contaminants (i.e. CN), etc... (by NACE)
GENERALIZED CORROSION AT LOW TEMPERATURE - H2S 15
H (atomic) can diffuse into the

metal causing: Graph
n cracking by
UOP
n blistering
n embrittlement
(see also SSC and
Hydrogen damage)
CONTROL: Wet H2S general corrosion can be controlled with CS + CA

up to corrosion rate (CR) 0.6mm/y. For higher CR upgrade metallurgy
to SS
The phenomenology related to hydrogen attack are taken into account
requiring HIC resistant specs (composition + test NACE TM 0284).
Note: consider as valid alternative SS cladding instead of CS HIC
resistant
GALVANIC CORROSION 17
n Preferential corrosion of one

metal of two or more
electrically connected
dissimilar
n It requires an aqueous
environment which is
corrosive to at least one metal
and with a non negligible
conductivity
n Its related to the V between

the metals in the considered
environment (i.e. see galvanic
series in seawater).
ALL the following parameter have to be verified to evaluate risk of

galvanic corrosion
n Verify the allowable V:
if it is not significant (i.e. the coupled metals are close in the
galvanic series measured in the considered environment) dont
worry about CG
n Verify the medium corrosivity:
if the fluid is not aggressive towards at least one of two coupled
metals (i.e CS - SS in neutral deoxygenated water) CG is not a
problem
n Verify the fluid conductivity:
if it is very low (i.e. demi water of hydrocarbons) CG are not an
issue
n Verify cathodic/anodic areas:
if the cathodic area is << of anodic area (dont forget to consider
lining!!) galvanic corrosion can be tolerated (i.e. SS bolting on
CS flange)
CONTROL:
).
n Ratio cathodic/anodic areas (if the ratio increase the CR
n Control environment (i.e. pH , remove O2... )
n Use of coating (either on both surfaces or on cathodic surface,
NEVER only on anodic surface)
n Use insulation kit to break electrical continuity
n Cathodic Protection
Metal coupling that can generate GC

(the first is attached):
CS-SS CS-Copper alloy CS-Ti
CS-Hastelloy SS-Ti SS - Hastelloy
Insulation kit
PITTING CORROSION 23
n PITTING: form of extremely

localized attack that results in hole
in the metal. One of the most
dangerous and insidious form of
corrosion.
n It causes equipment to fail because
of perforation with only a small
weight loss
n Normally occurs in active/passive
metals (i.e. SS series 300) in
passive state
n Requires depassivating species
(i.e. chloride or other halides )
n Worse problem at low velocity and
high T
n Hard to detect and/or predict
UPSET
CONTROL:
n avoid metal/environment
combination susceptible to
pitting
n check environmental
conditions especially
[Cl-] o [X-]
Temperature
O2
Minimum fluid velocity
Critical pitting temperatures (CPT) for SAF 2205,
A parameter to evaluate pitting AISI 304 and AISI 316 at varying concentrations of
resistance of SS is PREN (pitting sodium chloride (potentiostatic determination at
+300 mV SCE), pH6.0 (by SANDVIK)
resistance equivalents number):
PREN = Cr + 3.3 Mo + 16N
UPSET
Examples of metals susceptible

to pitting in chlorides
environment:
n SS (Ferritic, Austenitic,
Duplex)
n Fe-Ni-Cr Alloy (Incoloy)
n Aluminum Alloy
n Copper Alloy UPSET
Immune Very resistant Resistant Acceptable Not Acceptable

Ti 90/10 Cu/Ni 70/30 Cu/Ni Monel SS series 400
Alloy C Admiralty brass Tin 316 (+ CP) 304
Alloy 625 Al bronze Alloy 825 Nickel
Alloy 20
Pitting resistance in seawater

CREVICE CORROSION 28
Selective corrosion in crevice
n CC requires a stagnant zone

where its possible to develop
different conditions from bulk
(inhibitor, oxygen, pH, Cl-)
n CC requires an aggressive
environment (i.e. presence of
chloride)
n If temperature crevice
likelihood
UPSET
CONTROL:
n Use materials less sensitive to pitting (the corrosion mechanisms
are similar therefore a material resistant to pitting corrosion is also
resistant to crevice corrosion. See slide 99)
n avoid stagnant zone
n dont use threaded connections
n control O2 content
Some materials susceptible to CC:
SS
Ni alloy
Ti UPSET
Preferentially locations for CC:
n Flanged connection
n Tube/Tubesheet connection
n Threaded connections
n Plate Heat Exchangers
UNDER DEPOSIT CORROSION 32
Corrosion enhanced by the

presence of scales (can be
aggressive i.e NH4Cl or not)
Under deposit corrosion results
from difference between local and
bulk environment (i.e oxygen, pH,
presence of aggressive ions Cl. See
also crevice and pitting corrosion)
If chloride are present H+ drawn
under deposits (pH drops below 4
increasing corrosion rates)
Most common materials are
subjected to UDC including CS,
austenitic SS, nickel alloy (Inconel
625, Hastelloy and Ti are very
resistant)
Refinery examples:
any location in which scaling and/or
fouling occur especially if chloride or
oxygen are present
CONTROL TECHNIQUES
n treat the source of the problem (i.e.
corrosion or fouling)
n design equipment to minimize
deposition. Metallurgy may solve
corrosion problem but not performance
loss
n antifoulant may be helpful
AMMONIUM BISULFIDE
n frost from gas to solid at a temperature depending on NH3 H2S

concentration
n Is corrosive vs CS but not vs SS or higher alloy
n Causes very rapid fouling
Refinery examples
n REACs (hydrotreaters/hydrocrackers)
n Crude unit overhead
n FCC (overhead in separator section)
CONTROL
n wash water
use continuous washing (20%min water not vaporized)
inject upstream of ammonium bisulfide dew point
n Use balanced piping for REACs
n Upgrade metallurgy
AMMONIUM CHLORIDE
n frost from gas to solid at a temperature depending on NH3 HCl
concentration
n Is corrosive vs CS and SS. Ti and Inconel 625 may offer sufficient
protection
n Causes very rapid fouling
REFINERY EXAMPLES
n Crude unit overhead
n hydrotreaters (REACs, overhead in separator section)
n Catalytic reformer (REAC, separator, stabilizer, recycle gas
compressor)
n FCC (overhead in separator section)
CONTROL
n wash water
use continuous washing (20%min water not vaporized)
inject upstream of ammonium chloride dew point
n Use balanced piping for REACs
n Upgrade metallurgy (expensive solution)
STRESS CORROSION CRACKING 36
Cracking corrosive process that requires the simultaneous

presence of:
n Material in passive state susceptible to attack

nAggressive environment
nstress state
residual (i.e. welds) UPSET
applied (i.e. bends)
Table from ASM Vol 13 Corrosion

Main type of SCC
n Chloride stress corrosion cracking (CSCC)

n Sulphide stress cracking (SSC)
n Alkaline stress corrosion cracking (ASCC)
n Polythionic Acid Stress Corrosion Cracking (PASSC)
n Cracking in H2O-CO-CO2 system
UPSET
CHLORIDE STRESS CORROSION CRACKING 39
Material susceptible to CSCC
n austenitic SS, duplex , ferritic

(sensibilized)
n Fe-Cr-Ni alloy (Incoloy)
n Copper alloy
n Bronze/Brasses
n Aluminum
n Cobalt alloy (i.e. Stellite)
View of chloride stress corrosion cracking in a 316
stainless steel chemical processing piping system.
Chloride stress corrosion cracking in austenitic
UPSET stainless steel is characterized by the multi-
branched "lightning bolt" transgranular crack
pattern. (Mag: 300X)
CHLORIDE STRESS CORROSION CRACKING 40
For SCC Ni content is

fundamental
SS serie 300
CONTROL:
n limit O2 content
threshold value)
n limit stress (
n Control temperature
n Control pH
N.B. H2S lowers CSCC limits
SCC resistance in oxygen-bearing (abt. 8 ppm)
UPSET neutral chloride solutions. Testing time 1000
hours. Applied stress equal to proof strength at
testing temperature. (by SANDVIK)
SULPHIDE STRESS CRACKING 41
SSC is defined as cracking of a metal under

the combined action of tensile stress and
corrosion in the presence of water and H2S
SSC is a form of hydrogen stress cracking
resulting from absorption of atomic hydrogen
that is produced by the sulfide corrosion
reaction on the metal surface
SSC is influenced by:
n Chemical composition (P,S,Mn), hardness,
metal thermal treatment
nTotal tensile stress (applied plus residual)
n Hydrogen flux (function of [H2S], pH, CN-,
etc..)
n Time (Note: short term conditions i.e.
shutdowns can be sufficient) H2S SSC Cracks in a 17-4 pH
n Temperature (increase H 2S dissociation stainless steel
and H diffusion)
UPSET
SULPHIDE STRESS CRACKING 42
Some environmental conditions known to cause SSC are those

containing free water (in liquid phase) and:
n >50 ppmw dissolved H2S in the free water or
n free water pH<4 and some dissolved H2S present or
n free water pH>7,6 and 20ppmw dissolved HCN in the water and
some dissolved H 2S present
n >0.0003 MPa absolute partial pressure H2S in the gas in processes
with a gas phase
CONTROL:
For Refinery apply NACE MR0103
For upstream (oil and gas production) apply NACE MR0175
Note: Pay attention to thermodynamic model used in the simulators

and to hypothesis to calculate % H2S in free water
UPSET
ALKALINE CRACKING 43
cracking in caustic environment

carbonate cracking
cracking in amine environment
Main materials involved:

n Carbon steel
n Low alloy steel
n Stainless steel
n Copper alloy
UPSET
CAUSTIC CRACKING 44
Cracking due to
exposition of CS to hot
caustic solution (i.e.
NaOH, KOH)
CONTROL: use the

materials indicated on
Caustic Soda Service
Graph (see also SR) by
NACE
Note: If for the service

austenitic SS has been
specified, check
chloride concentration
and T max.
UPSET
Caustic Soda Service Graph by NACE
AMINE CRACKING 50
Cracking caused by amine (mainly due to dissolved CO2 e H2S).

Amine cracking happens preferentially in the heat affected zone (HAZ).
Lean amine is not corrosive vs CS and it shows less probability to
cause cracking.
MEA is more aggressive than DEA o MDEA
If temperature cracking likelihood (consider also short term
condition, i.e. Steam out)
CONTROL:
SR (included PWHT) in accordance with API 945 (595 C < T <
649C, min holding time 1h)
hardness < 200HRB
SR is suggested, function of used amine, at the following operating T:
nMEA : all operating T
nDEA: T > 60C
nMDEA : T> 82C UPSET
CRACKING IN CO-CO2-H2O SYSTEMS 51
It can happen in pressure system with the simultaneous presence of

CO-CO2-H2O
n low T (maximum risk in the range 20-60C)
n minimum CO and CO2 pressure required
CONTROL: Check environmental conditions (T, water, PCO & PCO2)
Use SS (12 Cr o 304; 316 not necessary)
Range of SCC susceptibility
1400
CO partial pressure (kPa)
1200
1000
800
600
400
200
0
0 200 400 600 800 1000 1200 1400 1600 1800
CO2 partial pressure (kPa)
Published data SASOL Mossgas

SENSITIZATION ISSUES (INTERGRANULAR CORROSION) 52
Main degradation forms related:

n Sensitization
n Weld decay
n Knife line attack
n Polythionic acid stress corrosion
cracking
MECHANISM:
1) A high temperature exposure

allows the reaction between
Cr and C.
2) Cr carbides precipitates at grain

boundaries.
3) Cr depletion in areas surrounding

to grain boundaries. (when Cr
below 12% the steel is no more SS
and corrode like CS).
SENSITIZATION AND WELD DECAY 53
Sensitization
n is not a corrosion mechanism but the Cr depletion may generate
intergranular attack.
n May occur rapidly due to: weld, heat treatment and operating
temperature.
n The sensitization range (temperature and time) is related to the
material.
Heat affected zone (HAZ)

Weld decay
n The Cr depletion is related to the
heating in areas surrounding the weld.
n Varies with welding conditions
n varies with distance form the weld
Knife line attack

n Same mechanism of weld decay
n on chemically stabilized material
SENSITIZATION CONTROL TECHNIQUES 54
Sensitization control
n Materials selection:
normal and high carbon grades: Carbon content 0,03 % - 0,10
l Ferrous (i.e. 304/316) and Ni-Cr alloys
Subjected to sensitization.
low carbon grades: below 0,03 %
l i.e. 304L, 316 L, Hastelloy C-276
Do not sensitize under welding conditions but are
subjected to sensitization under operating conditions
Chemically stabilized material (Nb or Ti)
l I.e. 321, 347, Incoloy 801, 825, alloy G, Inconel 625
Ni and Ti form carbides avoiding Cr depletion.
Thermal treatment (stabilization) avoids
sensitization over long term exposure.
l Stabilization heat treatment should be recommended
n Procedure mistakes
Cleaning with oily rag before welding introduces C
PWHT in the sensitizing time-temperature range
INTERGRANULAR CORROSION 55
POLYTHIONIC ACID STRESS CORROSION CRACKING (PASCC) 56
Intergranular corrosion and cracking

caused by the simultaneous presence
of:
n Sulfide scale
n Sensitized material
n Oxygen
n Stress (residual or applied)
n Water
n Polythionic Acids (H2SxOy) form
(usually during shut down) for reaction
of sulfide scale with H2O e O2
Main material subjected to sensitization:

Polythionic acid stress corrosion cracking of
n Austenitic or Ni alloy (also low carbon type 310 stainless steel. The item was
or stabilized) operating at high T (i.e. 370 exposed to sulfur containing natural gas in a
continuous flare
C < T < 815C for 304/316)
n Austenitic or Ni alloy (not stabilized)
welded UPSET
POLYTHIONIC ACID STRESS CORROSION CRACKING (PASCC) 57
Refinery examples:
n hydrodesulfurizers
n hydrocrackers
n hydrogen reformers UPSET
n FCC
n Fired heaters (both external and internal)
CONTROL: follow guideline NACE RP0170
n Exclusion of oxygen (air) and water by using a dry nitrogen purge

n Alkaline washing with soda ash. Avoid washing of zone that cant
be drained
n Exclusion of water by using a dry purge with a dew point lower
than -15C
CORROSION UNDER INSULATION 58
For further information on CUI see NACE RP 0198

HYDROGEN DAMAGE 59
Atomic hydrogen even produced by low temperature corrosion

phenomena may diffuse through metal surface causing hydrogen
damage.
Hydrogen damage is recognized under various forms:
n Blistering
n Hydrogen Induced Cracking (HIC)
n Stress Oriented Hydrogen Induced Cracking (SOHIC)
n Hydrogen Embrittlement
n High Temperature Hydrogen Attack
UPSET
BLISTERING-HIC-SOHIC 60
Main steps of blistering and HIC

n Atomic hydrogen diffuses inside the
metal bulk
n Inside the metal atomic hydrogen
meets the voids (rolling defects) and
inclusions (MnS) and re-combines in
molecular hydrogen (H2)
n Gradually, molecular hydrogen
collected in voids and inclusions
increases the pressure reaching up
to 10 GPa.
n The elevated pressure evidenced by
surface blistering may lead to local
(stepwise) and complete rupture of
the plate.
n SOHIC is related to residual stresses
presents in the metal.
UPSET
UPSET
Influencing and control parameters:
n Chemical composition of the process fluids (presence H2O,

pH, H2S, CN, As, Sb)
n Voids and inclusions presence
n Metal chemical composition and thermal treatments.
n Residual stresses (only for SOHIC)
n Construction and welding and test procedure according

standards. (NACE MR 0175, NACE 0103, NACE TM0284, API
945)
HYDROGEN EMBRITTLEMENT 63
Embrittlement caused by the

hydrogen diffusion through the
metals.
Possible Hydrogen sources:
n General corrosion
n Galvanic corrosion
n Overprotection of cathodic
protection.
Influencing factors:
n Enhanced by CN, As, Sb
presence.
n May occur on CS, alloyed steels,
nickel alloys, Titanium (T > 71 C)
Copper alloys are considered
immune
UPSET
HYDROGEN DAMAGE 64
Critical areas:
Rich section of amine units.
Sour water stripper.
Hydrodesolfurization units. UPSET
FCC units.
Hydrogen damage control:
n Appropriate material selection
Reduction the allowable metal inclusions (S, Mn and P content).
Ca and rare earth addition (shape control of residual inclusions).
Steel HIC resistance according NACE TM0284.
n Optimization of process conditions (i.e. H2O, pH)
n Construction and welding according standard (i.e. NACE MR0175
NACE 0103).
n Correct cathodic protection design and operation.
n Use of insulation kit for different metals in electrical contact.
EROSION-CORROSION 65
Degradation mechanism
accelerated by flow conditions of a
corrosive fluid in contact with metal
surface
Mechanism:
Corrosive fluid reacting with metal
creates a film scale
Fluid removes mechanically the
scale exposing uncorroded metal
Typical corrosion rates in seawater mdd

Material 1ft/sec 4 ft/sec 27 ft/sec
CS 34 72 254
Ad. Brass 2 20 170
70-30 Cu Ni (0.05% Fe) 2 - 199
70-30 Cu Ni (0.5% Fe) <1 <1 39
Factors influencing erosion-

corrosion:
n Velocity and fluid turbulence
n Temperature
n Multiphase flow
n Suspended solid
n Galvanic effect (i.e.: CS-SS and
CS-CuNi in seawater)
CONTROL:
n Material Selection or lining (i.e. Cu-Ni 66-30-2-2 instead of Cu-
Ni 70/30).
n Check allowable velocity
n Localized preventive measures (i.e. ferrule on tubes inlet).
n Change environment (i.e. inhibitor, filtering, temperature).
68
MICROBIOLOGICAL INDUCED CORROSION (MIC) 69
MIC refers to corrosion

influenced by the presence
and activities of
microorganisms and/or their
metabolites
Microorganism (i.e. fungi,
bacteria or algae) can be
aerobic or anaerobic
Generally MIC shows jeopardized attack on CS, localized on SS (i.e.

pitting)
Microorganisms growth is influenced by pH, temperature and food
availability (peak between 30 e 40 C)
Stagnant zone increase attack severity
MICROBIOLOGICAL INDUCED CORROSION (MIC) 70
Refinery examples:
n Cooling water systems
n Water layer in tanks
n Following hydrotesting
CONTROL:
n Use Biocide addition
n High thick Coating (i.e. coal tar)
n Cathodic Protection (+950 mV)
n High quality hydrotest water
n Avoid wet dead legs
71
MECHANISMS
High temperature corrosion mechanisms

HIGH TEMPERATURE CORROSION MECHANISMS 73
n NAPHTENIC ACID CORROSION

n HIGH TEMPERATURE OXIDATION
n SULFIDATION
n HIGH TEMPERATURE HYDROGEN DAMAGE
NAPHTENIC ACID CORROSION 74
Generalized corrosion at high T (230-

400 C) caused by naphtenic acids for
crude with TAN > 0.5 (ASTM D 974
T.A.N. as mg KOH/g) or TAN > 0.35 for
some licensor.
several type of naphtenic acids
Naphtenic acids are very aggressive especially close to their boiling

points (thus can attack selectively some locations of the unit )
n Metallurgy: CS and Cr alloy (i.e. 5 - 9 - 12Cr o 304/316 std) are
readily attacked
n Sulfur content: especially at low fluid velocity, sulfur can mitigate
corrosive attack
n Velocity: high velocity (>2.7 m/s) increases corrosion rate
NAPHTENIC ACID CORROSION 75
Refinery examples:
n Heaters and Transfer Line in CDU
n Diesel section of CDU column (pump-around)
n Atmospheric column residue
n Vacuum column residue
n Gas oil section of VDU
CONTROL:
n N.B. Check TAN for each cut with operating temperature in the
range 260 - 400C
n Stainless steel 317 o 316 with Mo 2.5%min
n Monitoring + inhibitor (only for short run)
n Use blending to reduce TAN
n Neutralization with NaOH (pay attention on caustic embrittlement)
HIGH TEMPERATURE OXIDATION 76
Generalized corrosion caused by

direct oxidation of base material
(liquid water not required)
Oxidation issues
n O2 Concentration
n Alloy composition
n Metal temperature
The source of O2 can be also

steam or CO2
The scale composition

influences CR
Microstructure of iron oxides formed on iron by
high-temperature oxidation in air
HIGH TEMPERATURE OXIDATION 77
Refinery examples:
n Heaters
n Boilers
CONTROL:
n Improve metallurgy
(with alloy containing
Cr, Ni, Si, Al)
Control environmental conditions, especially:

n Sulfur (Increase corrosion rate)
n metals (i.e. V which causes V2O5 formation) in fuel
n Temperature (if scale thermal exchange
and lifetime
)
SULPHIDATION 78
Reaction between Sulfur and metal or alloy at high temperature.

Can cause generalized corrosion @ T>260 C
CR is influenced mainly by T and %S (or H2S)
Refinery examples:
n Topping and Vacuum (@ T >260C)
n HDS (hot heat exchangers, heaters and reactor)
n Sulphur Recovery Unit
%Cr is fundamental to resist to sulfidation attack. Generally low

chrome alloy are used with %Cr higher and higher (1.25-2.25-5-7-9
Cr) up to stainless steel (as 12Cr like 405 and 410) or austenitic
(304 or 316)
SULPHIDATION 79
CONTROL:
Use appropriate metallurgy considering CR calculated by available
curves (function of metal T, alloy composition and %S for Mc Conomy
or H2S for Couper Gorman)
n Mc Conomy (API) based on total sulfur content:
SULPHIDATION 80
CONTROL:
Use Couper Gorman for fluid containing high H2 and H2S concentration
(see also Nelson curves on API 941 for HTHA)
Available for several material (i.e. CS, low Cr alloy and SS)
Couper Gorman Curves for carbon steel and 18-8 stainless steel
HIGH TEMPERATURE HYDROGEN ATTACK (HTHA) 81
High temperature hydrogen can attack

steels in two ways :
n Surface decarburization (slight,
localized reduction in strength and
hardness and an increase in ductility)
n Internal decarburization and fissuring

(CH4 formation and high localized
stresses which lead to the formation of
fissures, cracks or blister in the steel)
Factors influencing HTHA:

n Temperature Hydrogen attack corrosion and cracking
on the ID of an 1800 psig carbon steel
n H2 pressure boiler tube.
n Stress (i.e. welds)
incubation period)
n Time (
CONTROL:
Use Cr-Mo alloy instead of CS (reduces
the amount of available carbide)
SS are practically immune from HTHA
For CS and Cr-Mo alloy refer to API 941
Note:
C-0.5Mo, usually, is not allowed in
H2 service
Solids deposition and hydrogen attack
Cladding should not be considered corrosion at the ID weld in an 1800 psig
as material resistant to HTHA carbon steel boiler tube. The arrow
marks the direction of flow. (~1X)
(therefore also base material have
to be resistant)
Nelson curves (API 941)

N.B. Add safety margin, below the relevant curve,when selecting steels (11 C min)
STATISTIC RELEVANCE OF CORROSION FAILURES 84
nCorrosion causes the 55%

of the failures in chemical Types of corrosion failures (duPont)
plants (the remaining 45% of others corrosion
6%
the failures are related to
General
mechanical reasons). 27%
Stress Corr.
n General corrosion and SCC Cracking
24%
show the higher occurrence
in corrosion failures (in sum
they account 51%). High temperature
Crevice corrosion
n Crevice corrosion causes 2% 2%
Erosion-corrosion
only 2% of the failures while Weld corrosion
5% 7%
pitting the 14%. Corrosion fatigue

3%
Pitting Intergranular
nThe sum of Intergranular 14% 10%
and weld corrosion is

relevant (15%).
Il campo della corrosione con molta aderenza
paragonabile a quello della medicina. Per I materiali, la
corrosione indubbiamente la pi insidiosa delle cause di
decadimento e di morte e al corrosionista si presenta il
compito in genere assai arduo, di diagnosticare il male, di
stabilirne le cause, di prevenirlo ove possibile altrimenti di
reprimerlo o contenerlo in limiti accettabili [A questo
scopo il corrosionista deve] pazientemente costruirsi il
suo atlante di anatomia patologica dei materiali esposti ai
pi svariati ambianti aggressivi, edificare il corpus della sua
diagnostica, sviluppare una sempre pi efficace
farmacologia anticorrosionistica.
Roberto Piontelli, 1961

CORROSION CONTROL
Selection criteria, material properties

and cathodic protection
MATERIALS AND CORROSION PROTECTION 87
n CONDITION ASSESMENT AND MATERIAL SELECTION

n CARBON STEEL
n LOW ALLOYED STEELS
n STAINLESS STEELS
n COPPER ALLOYS
n NICKEL ALLOYS
n TITANIUM ALLOYS
n POLIMERIC MAERIALS
n CATHODIC PROTECTION
MATERIAL SELECTION 88
Phase sequence Scope of corrosion activities
1. Process Conditions assessment

development
2. Material selection Ensure the required service life time
3. Process and Costs decrease

material optimization Improve the reliability of the unit
4. Engineering, Ver. corrosion protection measures i.e. CP

Procurement, Control galvanic corrosion
Construction Control erosion corrosion
On Stream Inspection
1. CONDITIONS ASSESSMENT 89
Contaminants
Environment type and corrodents
(water/oil content) TDS & -
TSS Cl , H2S, CN-, NH 3
Oxidizers Temperature
O2, Cl2, Fe3+, Cu2+ (local)
Pressure
Fire hazard Marine environment Chemical
composition
Physical Fluid dynamic
External conditions
Underground Conditions
Thermal insulation Condensation
Atmospheric env. and dew point
(local)
Chemical
composition Upset conditions Thermodynamic
Physical Solid
Thermodynamic Precipitation
Phase settling
Time extension Probability
2. MATERIAL SELECTION 90
Conditions Life Time

experience in similar units
Strength
Density
Heat treating
Experience
and literature Corrosion
allowance
Material sel. in similar
service within the prj Metallurgy Costs
Corrosion
protection
Galvanic couplings
Material
Procurement
Joining techniques Availability time
Fabricability
Pre-fabrication
Construction dimensions Spare parts Fittings

3. PROCESS AND MATERIAL OPTIMIZATION 91
Exam of the whole unit
Conditions Material
assessment selection
Process Engineer
Corrosion Engineer
Process
development
Scope
Decrease the project costs
Avoid over and under specification
Improve the reliability of the unit
CARBON STEEL 92
n The material
Chemical composition based on Fe and C, can be adjusted to
improve the resistance to specific degradation mechanism (i.e. HIC)
n Typical conditions:
By far the most common material used up to 400C
in refineries due primarily to a combination of
strength, availability, low cost, and resistance to fire.
n Main contaminants and corrodents:

Halides (chlorides), sulfides, ammines, dry ammonia, carbonates,
CO2+H2O+CO, cyanides, Hydroxides, nitrates, CO2+H2O, acids,
oxygenated demi water.
n The degradation mechanisms to be verified:

General corrosion, stress corrosion cracking, crevice, under
deposit, under insulation, galvanic attack, hydrogen damage,
erosion corrosion, high temperature damage (almost all).
CARBON STEEL 93
Specific corrosion protection measures.

n Design according to soda chart, Mc Conomy, Couper Gorman,
Nelson where applicable.
n Selection of inhibitors (i.e. acidic water, cooling water, boiling
water).
n Cathodic protection to control general, galvanic, MIC and crevice
corrosion.
n Anodic protection to control general corrosion.
n Polymeric lining (epoxy, PTFE, GRP, rubber)
to control corrosion at low temperature.
n PWHT to control SCC.
n Electrical insulation from others metals to control
galvanic corrosion.
n Water injection to control under deposit corrosion.
LOW ALLOYED STEEL 94
Chemical Composition Max Temperature C

The materials:
0,5% Mo 500
n Typical conditions: 1% Cr 0,5% Mo 600
1,25% Cr 0,5% Mo 600
For high temperature 2,25% Cr 1% Mo 625
service, or hydrogen and 5% Cr 0,5% Mo 650
sulfidant atmosphere.
9% Cr 1% Mo 650
n Present the same contaminants and corrodents of Carbon steel.

As per CS. Specifically Hydrogen high temperature damage and
high temperature sulfidation.
n Corrosion prevention measures:
Design according Nelson diagram, Couper Gorman and Mc
Conomy to realize correct selection and evaluation of corrosion
allowance.
STAINLESS STEEL 95
n The materials:
Designation Type Metallurgy
12-13 Cr 405, 410, 410 S Martensitic, Ferritic
18 Cr 8 Ni 304, 304L, 321, 347 Austenitic
18 Cr 10 Ni Mo 316, 316 Ti Austenitic
22 Cr 5 Ni Mo N S31803 (2205) Duplex
25 Cr 7 Ni Mo N S32750 (2507) Super Duplex
20 Cr 18 Ni 6 Mo Cu N S31254 (254 SMo) Super Austenitic
20 Cr 24 Ni 6,5 Mo (Al-6X) Nickel alloy
n Typical conditions:
Acidic and saline water, high temperature
and low temperature, waste water,
demi water, organic acids.
Halides (chlorides), hydroxides (wet and dry), sulfurous acid (on
austenitic), organic acids, Hydrogen sulfide and (by external
side) Vanadium, molten zinc and molten aluminum.
STAINLESS STEEL 96

General corrosion, Pitting, SCC, crevice, galvanic, MIC, erosion
corrosion, weld decay, liquid metal embrittlement.
n Corrosion protection measures:
Design taking into account the resistance of the different alloys

in considered environment.
Selection of inhibitors.
Thermal treatments to control SCC and intergranular corrosion
cracking.
Chemical cleaning (against PASCC) and passivation.
Electrical insulation from others metals to control galvanic
corrosion.
FERRITIC AND MARTENSITIC STAINLESS STEELS 97
n 11-13% Chrome (type 405 and 410 S)

Primarily used for clad lining
n 11-13% Chrome (type 410)

ferritic or martensitic stainless steel extensively applied for
standard trim on process valves, pump impellers, vessel trays, tray
components and exchanger tubes.
Corrosion resistance
excellent resistance to sulfur at high temperature.

good resistance to hydrogen sulfide at low concentrations and
intermediate temperatures.
AUSTENITIC STAINLESS STEEL 98
Variables influencing the behavior of austenitic stainless steels

in salted water:
n Temperature:
50 C is accepted as the minimum temperature for the
occurrence of stress corrosion cracking and pitting in slightly
salted water (100-200 ppm).
n Chloride content:
In stress relieved structures, the maximum allowed chloride
content to avoid pitting and crevice (below 50C) is related to
the alloy
Type Cl-
304 100 ppm
316 300 ppm
(these limits can be lower for some Licensor i.e. 50 ppm for UOP)
AUSTENITIC STAINLESS STEEL 99
n Metallurgy
selection is realized considering critical temperature which is
the minimum temperature at which pitting or crevice may
occur in ferric chloride solution.
CSCC occurrence have to be considered separately.
COPPER ALLOYS 100
n The materials
Alloy type Main composition
Aluminium bronze 92% Cu, 8% Al
Aluminium brass 77% Cu, 21% Zn, 2% Al, 0.04% As
Admiralty 71% Cu, 28% Zn, 1% Sn, 0.04% As
90-10 Cu-Ni 10% Ni, 1% Fe, Cu rem.
70-30 Cu-Ni 30% Ni, 1% Fe, Cu rem.
66-30-2-2 Cu-Ni 30% Ni, 2% Fe, 2 %Mn, Cu rem.
n The typical applications
Seawater exchangers, water pipes,

brackish water equipment.
COPPER ALLOYS 101
Maximum seawater velocities for continuos flow conditions

nMain degradation m/sec (ref.:BS MA 18)
mechanisms
Erosion corrosion and
impingement attack, stress
corrosion cracking (in
presence of 1 ppm of
ammonia), selective leaching
(Immune to hydrogen
damage, and prevent
biofouling)
nCorrosion protection
measures
correct design according
standards (BS MA18 in the
graph).
Check ammonia presence
(UPSET conditions)
Erosion ferrules (in Teflon or
special Cu Ni alloys Cr
modified)
TITANIUM ALLOYS 102
The materials
n Titanium is a reactive metal and as the other materials of the
group forms spontaneously a superficial oxide film which
ensure protection from the environment.
n The corrosion resistance is related to the stability and the

continuity of the oxide layer (on-off corrosion behavior).
n The reactive metal group is formed by (increasing by

corrosion resistance): Titanium, Zirconium, Niobium and
Tantalum. The corrosion behavior of these materials shows a
large amount of similarities.
ASTM grade Composition
Gr 1,2,3,4 unalloyed (O and N content)
Gr 7, 11 0.2 Pd
Gr 12 0.8 Ni 0.3 Mo
Gr 16, 17 0.04 Pd
TITANIUM ALLOYS 103
n In which conditions:
Seawater and desalinization plant, organic acid, in oxidizing and
mildly reducing wet environments.
TITANIUM ALLOYS 104

Wet Fluorides (and halides in high concentration), methanol plus halides,
nitric acid fuming, nitrogen tetroxide, gaseous water free halides,
chlorinated solvents, concentrated reducing acids.
n Degradation mechanism to be verified
General corrosion, pitting, crevice, SCC, catastrophic oxidation, galvanic*,
hydrogen embrittlement.
TITANIUM ALLOYS 105
n Welding of titanium
1) The weld of Chemically Pure and Pd alloys (ASTM gr. 1, 2, 3,

4, 7, 11, 16, and 17) shows the same corrosion resistance
as the bulk material.
2) Like all reactive metals at high temperature reacts strongly

with atmospheric oxygen.
3) Can be welded with GTAW or GMAW (same equipment used

for SS 316 or nickel alloys).
4) Argon or helium have to be be used to protect the weld

in welding chamber (shop) or welding shoes (construction
site).
5) The weld quality verified easily for acceptance

Visual examination of as weld surface
hardness measurement is highly sensitive to oxygen pickup
NICKEL ALLOYS 106
n Materials
Alloy type Main composition
Incoloy 800 33% Ni, 21% Cr, 40%Fe, 0.1% C, 1% Al+Ti
Incoloy 825 43% Ni, 22% Cr, 3% Mo, 2% Cu, 0.04% C, Fe Bal
Inconel 625 43% Ni, 22% Cr, 9% Mo, 3.5% Nb, 0.04% C
Inconel 600 76% Ni, 16% Cr, 8% Fe, 0,2 Cu, 0.08 C
Inconel 601 60% Ni, 23% Cr, 16% Fe, 1% Al Cu, 0.1 C
Hastelloy C-276 57% Ni, 15% Cr, 16% Mo, 1% Fe, 0.02% C
Monel 400 66% Ni, 31% Cu, 1.4% Fe, 0.15% C
n Advantages:
Very resistant (as a function of specified type) to many
environments
In aggressive reducing environments are mandatory selection
n Disadvantages:
High cost (GdP will be not so happy!!! )
Possible availability problems for some alloy
NICKEL ALLOYS 107
TYPICAL ENVIRONMENTS
n Hastelloy C/C276, Inconel 625
High resistance to acid (both oxidizing and reducing)
excellent resistance in chloride and/or H2S environment
High resistance vs underdeposit corrosion
n Inconel 601, Incoloy 800

High temperature resistance
n Incoloy 825
High resistance in chloride and/or H2S environment (lower than
Hastelloy C-Inconel 625)
High resistance vs underdeposit corrosion (but can fail with NH 4Cl)
n Monel
High resistance to hot alkalis
High resistance to acid (especially HF)
POLYMERIC MATERIALS 108
n High molecular weight organic materials that can be formed into

useful shapes.
n Can be used for piping and equipment (thermosetters and
thermoplastics) or for gaskets (elastomers)
Polymeric materials
In refinery
Thermoplastics Thermosetters Elastomers

PE Glass fiber epoxy resin Viton (Flueelastomers)
PTFE Glass fiber vynil ester ep. resin Kalrez (perfluoelestomers)
PVC Glass fiber Poly ester ep. resin NBR
THERMOPLASTICS 109
n Are characterized by the softening with Main Materials:

the increase of temperature and return Polyethylene (PE)
to their original hardness when cooled Polypropylene (PP)
Polyvinyl chloride (PVC-CPVC)
(most are weldable). Polyvinylidene Fluoride (PVDF)
n Degradation mechanisms are different Teflon (PTFE)
from metals:
Swelling, softening, loss of mechanical
properties, hardening and discoloration
(no electrochemical mechanisms
involved). Degradation may be caused
by heat, solar exposure and UV.
n For correct material selection and
design are necessary: life time,
temperature (!), environment and
pressure.
n Main couple material-environment are:
PE(or PP)-water, PVC-mineral acids,
PVDF-acids (at higher pressure and
temperature).
THERMOPLASTICS 110
n Advantages
Excellent chemical resistance to
water environment,
l PTFE can withstand practically all
refinery environments below 200C
Easy welding and installation (not
for all)
No protection required in
underground service
n Disadvantages
Rapid decrease of properties with
the temperature increase.
Chemical resistance to
hydrocarbons
Not suitable in fire hazard area
THERMOSETTERS 111
n Are characterized by the thermal Main matrix Materials:

degradation when exposed to Epoxy resin
heating. Vinyl ester epoxy resin
Phenolic resin
n Thermosetters are generally used

as matrix for composite material.
Glass is generally used as fiber.
n Same degradation mechanism of

thermoplastic:
Swelling, softening, loss of
mechanical properties, hardening
and discoloration. Higher
resistance than thermoplastics.
THERMOSETTERS 112
Main applications are:

Firewater, cooling water, high
pressure water lines (special types up
to 280 Bar), sewer.
Advantages
Excellent chemical resistance to
aqueous environment
No protection required in
underground service
Disadvantages
Installation difficulties
Design and installation know how
Not suitable in fire hazard area
Sensitivity to vibrations and
mechanical stresses
CATHODIC PROTECTION 113
n History
In 1824 Sir Humphrey Davy discovered that is possible to protect the
copper of royal ships from marine corrosion by electrically coupling it
with iron.
n Basic Principle
The metal dissolution is reduced trough the application of cathodic
current that may originates from:
the corrosion of a less noble metal (sacrificial cathodic protection)
the conductive anode and V (current impressed cathodic
protection)
n Scope of CP applications:
Protect from wet and soil
corrosion coated steel.
Allow the use of carbon
steel avoiding the material
upgrade.
Minimize the cost of CS
coating maintenance.
Cathodic protection techniques
n Sacrificial cathodic protection

Use of anodic metal
l Magnesium (t< 40C)
l Zinc (t < 40C)
l Aluminum
(Cl- > 1000 ppm or t > 40C)
Anode connection with cathode

l direct (economical)
l trough a electrical resistance
(improve the control and avoid
under and over protection)
Reference electrodes
l Allows monitoring and verification
of corrosion for cathodically protected surfaces
Cathodic protection techniques
n Impressed current cathodic protection

anode material
l Ti Mixed metal oxide coated
l High silicon iron
l Ceramic electrodes
current generation
l an external DC current
source is necessary
reference electrodes
l the use is mandatory in
conjunction with current
control system
n Design parameters
Temperature (important for anode selection)

pH
Chemical composition (Cl- and ions content)
Conductivity (high conductivity = aggressive condition)
Redox potential (i.e. oxygen content or other oxidizer presence)
Dimensions of the metal surface in contact with conductive
electrolyte.
(important! Water level on separators and oil tank internals)
n With the parameters is possible to design the system:
which technique (sacrificial or impressed)

anode selection (Al, Mg, Zn, Ti or Fe-Si-Cr)
anode quantity (related to the required current)
anode distribution (related to the disposition of the surface to
protect)
current system design (only for impressed current)
Insulation kits and resistance bonds disposition
n Typical applications
Underground and submerged steel surfaces (may be
required by law).
l Bottom tanks
l Underground and submerged Pipelines
l Jacket on offshore structures
l underground and submerged steel reinforced concrete
structures
Low temperature corrosion on the process side (cost

evaluation).
l Water tanks
is preferable to cathodically protect internally lined surfaces
l Water boxes (channels) of Thermal exchangers
CP avoids cladding in Cu-Ni alloys in seawater exchangers
l Water-oil separators
CP avoids the use of stainless steel or ensure lower
maintenance of internal lining
CORROSION CONTROL IN
REFINERY UNITS
MATERIAL SELECTION AND CORROSION CONTROL IN REFINERY UNITS 119
n DESALTER
n ATMOSPHERIC DISTILLATION UNIT
n VACUUM DISTILLATION UNIT
n AMINE UNIT
n HYDRODESULPHURIZATION UNIT
n SOUR WATER STRIPPER UNIT
DESALTER 120
THE DESALTER CAN BE THE SOURCE OR THE SOLUTION OF

REFINERYS PROBLEMS
DESALTER 121
TIPICAL CORROSION AND FOULING PROBLEMS
n Corrosion of water outlet lines (brine)
n Fouling of inlet heat exchangers (generally due to oxygen

and excessive temperature)
n Remaining problems with desalter arent problems in the

desalter itself (affect efficiency and downstream corrosion)
DESALTER - OPERATING GUIDELINES 122
n Principal variables (by UOP)

wash water (4-10%)
Settling time (30-45min)
Temperature (90-150C, high enough to dissolve sediments
and salts)
Desalting chemicals (0.25 - 1 pint for 1000 barrels)
Alternating electric field
Valve
P (7-15 psig)
Level
n TARGET: DESALT TO LESS THAN 2 LBS/THOUSAND BARREL (PTB)
n Stripped Water should be used as wash water

DESALTER - OPERATING GUIDELINES 123
TEMPERATURE
n Increasing temperature reduces viscosity and reduces settling time
n Increasing temperature increases water solubility and water

(including dissolved salt) carry over
n Keep inlet heat exchangers below 150 C

Reduce corrosion rates in exchangers
Reduce fouling in exchangers (minimizing salt precipitation)
ATMOSPHERIC DISTILLATION UNIT 124
TYPICAL CORROSION AND

FOULING PROBLEMS
n HCl corrosion in the OVHD

system
Ammonium Chloride
Ammonium Bisulfide
n High temperature sulfur
corrosion
n Naphtenic acid corrosion
n Asphaltine/wax/polymer
fouling
n PASCC (300 series SS)
n Wet hydrogen sulphide
METALLURGY
Use Chrome alloy (solid or lining for high Cr %) for sulfur
resistance (according to McConomy curves) es. 1.25 Cr, 2.25Cr, 5
Cr, 9Cr, 12Cr in the bottom section of CDU tower and in the hot
side of the heating train
n Use Monel for HCl resistance in the top section of tower (for
cladding and trays) and in the OVHD accumulator if
condensation is expected
n Use 90-10 Cu-Ni for Chloride resistance in the desalter brine
n If Naphtenic acid are an issue (Note: check TAN number in cuts)
ALL 5 - 9 - 12Cr change to 317 or 316 with 2.5% min Mo (see
also T and TAN)
Carbon steel in gas oil cut may also change to 317 or 316 with
2.5% min Mo
Must guard against PASCC of austenitic SS
ATMOSPHERIC DISTILLATION UNIT - MSD 127
NOTE: The indicated selection is not a guideline; it indicates only a

possible choice among several solutions as a function of process
conditions, corrosion mechanisms involved, lifetime and Prj requirements
ATMOSPHERIC DISTILLATION UNIT - OPERATING GUIDELINES 128
CAUSTIC INJECTION
n Inject caustic if necessary to reduce chlorides in OVHD or to
reduce TAN
Use fresh 2-3% caustic
Inject no more than 4 PTB
Inject to crude no hotter than 150 C
Inject at least 5 feet upstream of equipment
and as close to desalter downstream
as possible
Inject using a quill
TAIL WATER pH Injection Quills

n Operate between pH 5.5- 6.5 in tail water
n Use a online pH meter
n Automate control of corrosion inhibitor injection
n Keep pH meter clean (filming amine, used as inhibitor, can dirty the
instrument)
ATMOSPHERIC DISTILLATION UNIT - OPERATING GUIDELINES 129
WASH WATER IN OVERHEAD SYSTEM

n 20% of injected water not vaporized
n water quality not critical, can recirculate
DEW POINT
n Run top of tower above dew point
Watch for shock condensation at point of recycle water inlet
CORROSION INHIBITOR
n Use corrosion inhibitor in the overhead line
n May need to inject neutralizer and film former separately
VACUUM DISTILLATION UNIT 130
TYPICAL CORROSION AND

FOULING PROBLEMS
n H2S, CO2 corrosion in the

OVHD system
n High temperature sulfur
corrosion wherever
temperature exceeds 260C
n Naphtenic acid corrosion
especially in heater outlet
and transfer piping
n Asphaltine/wax fouling
n Polythionic acid SCC (300
series SS)
METALLURGY
n Problem: traces of H2S, CO2, HCl in OVHD system

SOLUTION: use MONEL mesh for demister
n Problem: traces of corrodents in Vacuum ejector

SOLUTION: use 316 internals
n Problem: high temperature sulphur corrosion in bottom section of

tower and in the heating train
SOLUTION: use chrome alloy (solid or lining for high Cr %)
according to McConomy curves
n Problem: Naphtenic acid corrosion (for cuts with TAN>0.5)

ALL 5 - 9 - 12Cr change to 317 or 316 with 2.5% min Mo
n Problem: Polythionic acid SCC for sensitized material

follow the recommendation listed in NACE RP 0170
VACUUM DISTILLATION UNIT - MSD 133

AMINE UNIT 134
AMINE UNIT 135
TYPICAL CORROSION AND FOULING PROBLEMS

n Tendency for corrosion varies with amine used, concentration and
loading
n Acid gas corrosion
H2S, CO2
Letdown valve into stripper
Overhead of stripper
n Heat stable amine salts (stronger than H2S)
Not stripped by heat in stripper
Inorganics (Cl-,SO4=, CN -, SO2)
l Contaminants in feed
Organics (formic, acetic, oxalic)
l Feed+oxygen
l Pump seals, make up water
Areas: stripper bottom, reboiler, hot lean amine pipe
n Thermal degradation of amines
forms corrosive, acid species (especially in presence of oxygen)
AMINE UNIT 136
METALLURGY
n Problem: Amine stress corrosion cracking and hydrogen damage

SOLUTION: PWHT (see also amine SCC) and use killed carbon
steel
n Problem: Acid gas corrosion (Letdown valve/piping into stripper

and Overhead of stripper)
SOLUTION: use SS (304 or 316)
n Problem: H2S, CO2in OVHD system

SOLUTION: use SS for tube condenser and OVHD accumulator
(or CS HIC resistant)
n Problem: sour water in the reflux pump

SOLUTION: use SS or duplex (as suggested by API 610)
AMINE UNIT - MSD 137

AMINE UNIT - OPERATING GUIDELINE 138
n Limit amine temperature to 130 F

Reboiler steam less than 4.5 bar
n Avoid acid gas flashing
Upgrade metallurgy if
unavoidable
n Keep out oxygen from the system
n Control fluids velocity
n Filter
Typically 10-20 m (smaller may help, i.e. 2 in series 15
m-5
m)
Partially filtration (10-15%) may be sufficient
Carbon filter to remove hydrocarbon and reduce fouling
n Problems come from operating at maximum
Amine concentration
Circulation rate
Rich amine loading
HYDROTREATER 139
HYDROTREATER 140

n Rust from tankage
oxygen in tank/transport
Plugs reactor bed
n High temperature sulphur attack (sulphidation)
n High temperature hydrogen attack (HTHA)
n ammonium chloride in hydrogen recycle gas
n ammonium bisulphide
Reactor Effluent Air Cooler (REAC)
n PASCC
HYDROTREATER 141
METALLURGY
n Problem: Sulphidation and HTHA on reactor feed (generally from

heater), reactor and effluent piping and exchangers
SOLUTION: use Austenitic SS (321 or 347). Use Chrome alloy for
base material in case of cladded solution
n Problem: Ammonium chloride, Ammonium bisulfide, wet H 2S on

REAC, piping and accumulator
SOLUTION: use wash water and/or upgrade material to Incoloy
825, Inconel 625 or Ti. Austenitic 316 may be good to clad water
phase on accumulator. CS is also possible with stringent
velocity limits and monitoring
n Problem: Polythionic acid SCC for sensitized material

follow the recommendation listed in NACE RP 0170
HYDROTREATER - MSD 142

HYDROTREATER - OPERATING GUIDELINE 143
n Oxygen in feed (rust in tanks and polymerization fouling)

Gas blanket tankage
l Nitrogen best
l Natural gas may have air in it
l Fuel gas good
Better bypass tankage section
n Wash water
can be continuous (better)
or discontinuous
Use balanced exchanger
20% of injected water not vaporized
Velocity between 2.5 and 6m/s
(9 for alloy)
Foul water < 8% NH4HS
SOUR WATER STRIPPER 144

n ammonium chloride
n ammonium bisulphide
Reactor Effluent Air Cooler (REAC)
n Hydrogen damage
METALLURGY
n Problem: Sulfide Stress Cracking
SOLUTION: Apply requirements of NACE MR0103 where
necessary
n Problem: Ammonium chloride, Ammonium bisulfide, wet H 2S on
REAC, piping and accumulator and reflux pump. Erosion corrosion
on pump
SOLUTION:
l Use intermittent wash water on REAC and upgrade material to Ti.
l Use SS pipe (304 or 316 if chloride are expected) Maintain stream
velocity below 15 m/s on piping.
l Austenitic 316 may be good to clad accumulator
l Use Hastelloy C (or alloy 20) on reflux pump to withstand corrosion
and erosion-corrosion
n Problem: Hydrogen damage on feed surge drum
SOLUTION: Use CS HIC resistant or CS SS cladded or lined CS
(+CP)
METALLURGY
n Problem: Wet H2S Corrosion, Acid gas on tube bottom feed
exchanger, stripping column upper portion and inlet (after valve)
SOLUTION: Use solid SS (304 or 316 if chloride are expected) or
cladding solution.
n Problem: Galvanic corrosion exchanger, stripping column upper

portion and inlet (after valve)
SOLUTION: Use solid SS (304 or 316 if chloride are expected) or
cladding solution.
n Problem: Ammonium chloride, Ammonium bisulfide, wet H 2S

Erosion corrosion on charge sour water pump
SOLUTION:
l Use Duplex or Superduplex SS to withstand corrosion and erosion-
corrosion
SOUR WATER STRIPPER - MSD 148


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CORROSION MECHANISMS

MATERIAL SELECTION AND

Corrosion is defined as the destruction or

n CORROSION AND DEGRADATION MECHANISMS

LOW TEMPERATURE CORROSION MECHANISMS (CONTINUE)

HIGH TEMPERATURE CORROSION MECHANISMS

n MATERIALS AND CORROSION PROTECTION

n MATERIAL SELECTION AND CORROSION CONTROL

n INCUBATION PERIOD KINETICS

upset conditions are decisive. Incubation period

LOW TEMPERATURE CORROSION

HIGH TEMPERATURE CORROSION

Low temperature corrosion mechanisms

n ANODE location where metal

n CATHODE: location where O2, H+

n No specific location for anode

n Anode and cathode move with

n Can be monitored, measured and

Can be uniform or not

An example of generalized corrosion at low temperature is CO2

It can be tentatively predicted using a software

CONTROL: it can be controlled with CS + CA up to corrosion rate (CR)

Another example of generalized

H (atomic) can diffuse into the

CONTROL: Wet H2S general corrosion can be controlled with CS + CA

n Preferential corrosion of one

n Its related to the V between

ALL the following parameter have to be verified to evaluate risk of

Metal coupling that can generate GC

n PITTING: form of extremely

Examples of metals susceptible

Immune Very resistant Resistant Acceptable Not Acceptable

Pitting resistance in seawater

Selective corrosion in crevice

n CC requires a stagnant zone

Corrosion enhanced by the

n frost from gas to solid at a temperature depending on NH3 H2S

Cracking corrosive process that requires the simultaneous

n Material in passive state susceptible to attack

Table from ASM Vol 13 Corrosion

Main type of SCC

n Chloride stress corrosion cracking (CSCC)

Material susceptible to CSCC

n austenitic SS, duplex , ferritic

For SCC Ni content is

SSC is defined as cracking of a metal under

Some environmental conditions known to cause SSC are those

Note: Pay attention to thermodynamic model used in the simulators

cracking in caustic environment

Main materials involved:

CONTROL: use the

Note: If for the service

Cracking caused by amine (mainly due to dissolved CO2 e H2S).

It can happen in pressure system with the simultaneous presence of

Published data SASOL Mossgas

Main degradation forms related:

1) A high temperature exposure

2) Cr carbides precipitates at grain

3) Cr depletion in areas surrounding

Heat affected zone (HAZ)

Knife line attack

Intergranular corrosion and cracking

Main material subjected to sensitization:

CONTROL: follow guideline NACE RP0170