Professional Documents
Culture Documents
Flavio Cif
Michele Scotto di Carlo
2
Mars G. Fontana
CONTENTS 3
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 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
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
n It requires an aqueous
environment which is
corrosive to at least one metal
and with a non negligible
conductivity
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
Insulation kit
GALVANIC CORROSION 20
GALVANIC CORROSION 21
GALVANIC CORROSION 22
PITTING CORROSION 23
UPSET
PITTING CORROSION 24
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
PITTING CORROSION 25
n CC requires an aggressive
environment (i.e. presence of
chloride)
n If temperature crevice
likelihood
UPSET
CREVICE CORROSION 29
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
CREVICE CORROSION 30
CREVICE CORROSION 31
UNDER DEPOSIT CORROSION 32
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
UNDER DEPOSIT CORROSION 34
AMMONIUM BISULFIDE
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
UNDER DEPOSIT CORROSION 35
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
UPSET
CHLORIDE STRESS CORROSION CRACKING 39
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
UPSET
SULPHIDE STRESS CRACKING 42
CONTROL:
For Refinery apply NACE MR0103
For upstream (oil and gas production) apply NACE MR0175
UPSET
CAUSTIC CRACKING 44
Cracking due to
exposition of CS to hot
caustic solution (i.e.
NaOH, KOH)
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
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)
MECHANISM:
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.
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
Refinery examples:
n hydrodesulfurizers
n hydrocrackers
n hydrogen reformers UPSET
n FCC
n Fired heaters (both external and internal)
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
UPSET
Influencing and control parameters:
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
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
CORROSION AND DEGRADATION
MECHANISMS
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
Oxidation issues
n O2 Concentration
n Alloy composition
n Metal temperature
Refinery examples:
n Heaters
n Boilers
CONTROL:
n Improve metallurgy
(with alloy containing
Cr, Ni, Si, Al)
Refinery examples:
n Topping and Vacuum (@ T >260C)
n HDS (hot heat exchangers, heaters and reactor)
n Sulphur Recovery Unit
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
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)
HIGH TEMPERATURE HYDROGEN ATTACK (HTHA) 83
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
Procurement
Joining techniques Availability time
Fabricability
Pre-fabrication
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 The materials:
Designation Type Metallurgy
n Typical conditions:
Acidic and saline water, high temperature
and low temperature, waste water,
demi water, organic acids.
n Main contaminants and corrodents:
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
Corrosion resistance
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.
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 In which conditions:
Seawater and desalinization plant, organic acid, in oxidizing and
mildly reducing wet environments.
TITANIUM ALLOYS 104
n Welding of titanium
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 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
Polymeric materials
In refinery
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
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 114
Reference electrodes
l Allows monitoring and verification
of corrosion for cathodically protected surfaces
CATHODIC PROTECTION 115
current generation
l an external DC current
source is necessary
reference electrodes
l the use is mandatory in
conjunction with current
control system
CATHODIC PROTECTION 116
n Design parameters
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
n DESALTER
n ATMOSPHERIC DISTILLATION UNIT
n VACUUM DISTILLATION UNIT
n AMINE UNIT
n HYDRODESULPHURIZATION UNIT
n SOUR WATER STRIPPER UNIT
DESALTER 120
TEMPERATURE
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
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
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
VACUUM DISTILLATION UNIT 131
METALLURGY
METALLURGY
METALLURGY
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
SOUR WATER STRIPPER 145
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)
SOUR WATER STRIPPER 147
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.