Damage Mechanisms: Causes and Prevention

Damage Mechanisms:
Causes and Prevention

Making optimal performance possible
Topsoe Academy™
March 16, 2017
Prevent damage and increase the lifetime of
your plant
2
What environments can cause degradation?
Alignment of expectations
• Discuss with the person next to you – 5 min

• Follow up in plenum
3
Agenda
• Material and mechanical properties
• Metals
• Carbon steels and low alloy steels
• Stainless steels
• Materials in hydrogen plants
• Desulfurization
• Reforming
• Waste heat boiler
• Shift, CO2 removal and Methanator
• Summary
4
Metals
5
Metals
Classification and use
Carbon steel:
Fe, C < 0.2%, Σ % all others < 2%
Fe, C < 0.2%, Cr > 10.5%, others Ni > 50%, Cr, Fe, others
Low alloy steel:
Fe, C < 0.2%, Cr < 10%, Ni < 8%
Carbon steel and low Stainless steel (SS) Nickel and other
alloy steel (CS & LAS) special alloys
• Ammonia converters • Methanol piping and • Burners
• Refractory lined reactors reactor • High temperatures
• Piping and tubing • Corrosive environments • Aqueous corrosive
environments
6
Metals
Classification and use
Carbon steel:
Fe, C < 0.2%, Σ % all others < 2%
Fe, C < 0.2%, Cr > 10.5%, others Ni > 50%, Cr, Fe, others
Low alloy steel:
Fe, C < 0.2%, Cr < 10%, Ni < 8%
Carbon steel and low Stainless steel (SS) Nickel and other
alloy steel (CS & LAS) special alloys
+ Cheap - Corrode + Good - Relative + Very good - Very high
+ Versatile easily corrosion high cost corrosion cost
resistance resistance
+ High
strength
7
Metals
Classification: No unified international definition according to composition
Topsoe classification Composition

Carbon Steel (CS) Σ % alloying elements < 2 %
(Bal is Fe, C< 0.2%)
(Low) Alloy Steel (LAS) Σ % alloying elements > 2
Stainless steel,
%, < 10 % Cr, << 8 % Ni CS & Low alloy steel Nickel Alloys, Monel Cupronickel
Stainless Steel (SS) Minimum 10.5 % Cr
Ni-Cr-Fe alloys Alloy 800, 800H, 800HT, EN: EuroNorm PED: Pressure
825, EAM: European Equipment
Nickel Alloys % Ni > 50% - 600, 601, 690, Approval of Directive)
693, 696, 602CA, 625 Materials 97/23/EF
Monel % Ni < 67%. Bal. Cu
Cupro-Nickel Cu + <30% Ni
Ti - alloys Ti + others
8
Metals
Two types of CS depending on solidification
• During solidification shrinkage takes place

Rimmed steel Killed steel
• If air/gasses are not removed before
solidification the resulting steel contains
small voids
• Air/gases can be removed by adding Al or Si

to the melt.
• If air/gasses are removed before

solidification the steel contains no voids.
9
Carbon steel and low alloy steel
Different properties depending on heat treatment
Normalized or annealed:
Ductile, soft and fairly strong
Ferrite and pearlite
Quenched:
Brittle, hard and strong
Martensite
Quenched & Tempered (Q&T):

Ductile, medium hard and strong
Tempered martensite
10
Normalizing
Annealing process:
• Exposure to elevated temperature Annealing
followed by cooling in air, to… temperature
• Improve yield strength (materials
• Recover toughness datasheet)
Temperature
Time
11
Normalizing – effect of cooling rate 0.13 % C
Cooling rate
[°C/min]
Hardness 1
values
100
sec 1000
min
hour
CCT-diagram for Ck35 steel

12
(0.35 %C, 0.25 % Si, 0.65 % Mn)
Quenched & Tempered
Quenching: Annealing followed by very

rapid cooling to increase
• Strength
• Hardness
Temperature
• Wear resistance Tempering
Quenching
Tempering: Follow up heat treatment at
intermediate temperatures to recover
RT
• Ductility
• Impact toughness Time
• Machinability
13
Stainless steels
Different properties depending on the Ni-content. Minimum 10.5% Cr
Ferritic SS/Martensitic SS (Ni < 1%)

(e.g. SS405, SS410)
Duplex SS (1% < Ni < 8%) (50/50

austenite/ferrite balance) (e.g. SS2205)
Austentic SS (Ni > 8%)

(e.g. SS304, SS304L, SS316)
Ni alloys are all austenitic (e.g. alloy 600)
14
Stainless steels and nickel alloys
Solution Annealing
• Exposure to elevated temperature

followed by cooling at specific rate, to…
Annealing Cooling rate
• Soften, increase ductility (materials
temperature
• Change microstructure (e.g. dissolve datasheet)
(materials
Temperature
precipitates)
datasheet)
• Remove strain hardening
Time
15
Metals
Thermal Expansion Coefficient
Property Definition Typical values

At 20°C, steels 7.7–8.0 g/cm3
Density r=m/V Ni alloys 8.9 g/cm3
Cu alloys 9.0 g/cm3
CS, LAS & ferritic SS steels: 10-12·10-6K-1
Thermal D L = a · Lo · DT
Nickel alloys: 14-17·10-6K-1
expansion L = Lo + D L = Lo [1 + a · DT]
Austenitic SS: 16-18·10-6K-1
Amount of energy to raise the
Specific heat temperature of one gram of a pure 0.5 J/(g K)
substance by one K
The rate at which heat flows within a
Thermal
body for a given temperature 30–50 W/(m K)
conductivity
difference
16
Mechanical properties
Tensile strength
Plastic deformation
Stress
Elastic deformation
17 Strain (deformation)
Tensile strength
• For CS and LAS the strength depends on the

Tensile C content
strength • The higher the C content, the larger the
amount of strong precipitates of Fe-carbides
Yield
strength
Stress
Toughness: Energy to fracture

Area under the curve
0.2% Strain (deformation)

18
Metals
Summary
• Material nomenclature depends on country and

standard.
• CS, LAS, SS and Ni alloys are used in Topsoe
equipment. SS
• The microstructure and mechanical properties of CS

& LAS depend on the heat treatment. CS and LAS
• Thermal expansion is smallest for CS, LAS & ferritic

SS, intermediate for Ni alloys and largest for SS. Nickel alloys
• Tensile testing gives information about mechanical

properties.
19
Agenda
• Metals
• Desulfurization
• Reforming
• Summary
20
Each plant section represents a different
environment and different risks
21
Process descriptions
Hydrogen and ammonia
• Hydrogen
Feed Desulfuri-
Reforming Shift PSA H2
zation
Steam
Oxygen
22
Desulfurization section
23
Desulfurization section
Hydrogenator and sulfur absorber – Typical conditions
CH4 + H2S + org. S + H2

36 bar g, 350°C
Reaction
RSH + H2 → H2S + RH
CH4 + H2S + H2
33.5 bar g, 345°C
Reaction
H2S + ZnO ↔ H2O + ZnS
CH4 + H2
32.5 bar g, 335°C Focus on hydrogen attack
24
Hydrogen attack
Ductile
fracture
in
absence
of H2
Brittle
fracture
in Hydrogen attack results
presence in loss of ductility and
of H2 toughness.
25
High temperature hydrogen attack (HTHA)
T > 200 °C (392 °F)
1. Adsorption of hydrogen molecules to the 3. Permeation of hydrogen atoms in the metal

metal surface
4. Formation of methane gas:
2. Dissociation of the adsorbed hydrogen C (alloy) + 4H → CH4
molecules to form H atoms
H H
H H
surface
H H
CH4
void
26
T > 200 °C (392 °F)

metal surface
4. Formation of methane gas:
2. Dissociation of the adsorbed hydrogen C (alloy) + 4H → CH4
Decarburization Fissuring Tesoro Refinery (2010)
Methane formation
results in
decarburization.
Methane upbuild in voids
and grain boundaries
results in cracking
27
T > 200 °C (392 °F) Material selection for prevention – API 941 (2016) Nelson curve
H2 partial pressure, MPa
Temperature, °C
Carbide formers (Cr,
2.25Cr1Mo-V
V, W, …) bind the C of
the alloy and thus
2.25Cr1Mo
hinder the formation
of CH4.
1.25Cr0.5Mo The higher the
CS (welded, PWHT) content of carbide
formers, the higher
CS (welded, no PWHT) HTHA resistance.
H2 partial pressure, psia
28
Low temperature hydrogen attack (LTHA)
T < 200 °C (392 °F)

metal surface
4. Formation of hydrogen gas:
2. Dissociation of the adsorbed hydrogen H + H → H2
H H
H H
surface
H H
H2
void
29
Rimmed Carbon Steel or Killed Carbon Steel
Rimmed steel Killed steel

• During solidification shrinkage takes place
• If air/gasses are not removed before

solidification the resulting steel contains
small voids
• If air/gasses are removed before

solidification the steel contains no voids
Killed steel has less cavities → Less permeation of H2
30
Prevention of hydrogen attack
Prevention of HTHA Prevention of LTHA

Ni > 50%, Cr, Fe, others
• Materials selection as per Nelson • Select alloys of lower strength

diagram (API 941) • Use hydrogen induced corrosion
• Alloying with carbide formers resistant (HIC) steels
(e.g. Cr, V and Mo) • Hardness requirement: Max 250
HV (22 HRC)
If Carbon Steel is selected, Killed Carbon Steel is preferable for hydrogen service
31
Desulfurization Section
Material in the desulfurization section is susceptible to

• High temperature hydrogen attack (HTHA)
• Low temperature hydrogen attack (LTHA)
Nelson
diagram
HTHA causes decarburization, fissuring and cracking (internal)
• Material selection according to API 941, Nelson Diagram
HTHA/LTHA
LTHA causes blistering, cracking and hydrogen embrittlement

Hydrogen
• Select low strength steels attack
• Limit hardness in welds to 250 HV
32
Agenda
• Metals
• Desulfurization
• Reforming
• Shift, Shift, CO2 removal and Methanator
• Summary
33
Steam reformer
34
Steam reformer
Typical conditions
Inlet conditions Outlet conditions (H2) Outlet conditions (NH3)

CO + CH4 + H2 + H2O + HC Focus will be on tube
CO + degradation
CO + H2 + H2O, ~7 mol % CH4H + H O, ~15 mol % CH
2 2 4
33 bar g, 540°C 31 bar g, 925°C 31 bar g, > 800°C
35
Steam reformer
• Conversion of HC’s into CO, CO2 and H2
Reaction
Reforming (general) CnHm + n H2O + Q → n CO + (n + ½ m) H2
Reforming (CH4) CH4 + H2O + Q ↔ CO + 3 H2
Shift CO + H2O ↔ CO2 + H2
36
Steam reformer
Reformer tubes
• The reformer tubes are made of Fe based

alloys with Cr and high Ni
• Cr and Ni (and other carbide formers) increase
strength and resistance to carburization
• Fabricated by centrifugal casting Centrifugal casting with columnar

• Impurities and gas are less dense and move structure
towards the inner diameter which is machined
after solidification
• Large grains provide high creep strength

Centrifugal casting with columnar structure
near the OD and equiaxed structure near
the ID
37
Tube degradation
General considerations
Typical design Typical service
Conditions
Pressure ~30 bar g 10-15% lower than design
Temperature ~1,000°C Min 15°C lower than design
Lifetime Typical 100,000 hours -
• Reformer tubes are designed to withstand the expected degradation

• Based on the combined effect of pressure and high temperature for ~100,000 hours
38
Tube degradation
• Within the design conditions some degradation is expected

High temperature
Carbide formation (thermal ageing)
and time
High temperature,
Creep
pressure and time
High CO at high
Carburization (more carbide formation)
temperatures
• Degradation not taken into account:

Temperature
Overheating (thermal damage)
above design
39
Tube degradation
Creep of alloys
Stress
T(K) > 0.5 · below
Time Creep
Tmelting yield
stress
• Creep is a permanent deformation
• Creep can be accelerated by:

• Through-wall stresses during start-up and shut-down
• High temperature excursions during operation or during start-up
• Conditions inside the tube (poisoning or crushing of catalyst  Hot bands)
40
Properties at high temperatures
• High temperatures can also affect the

strength of metals
• At a certain temperature the tensile strength
will drop and creep will occur
Creep
41
Properties at high temperatures – Creep strength
• Creep strength is defined as the time to

rupture at different temperatures and
different stress levels
• With time, deformation takes place and

results in rupture even at low stress levels
below the yield point (i.e. even in the elastic
region)
42
Properties at high temperatures – Creep strength
• Creep strength is defined as the time to rupture at different temperatures and different stress
levels
• At room and low temperatures, stress below the • At high temperatures, and with time, stresses even
yield stress limit of the material result in elastic below the yield stress limit of the material result in
deformation permanent plastic deformation – this is Creep
T (°K)<0.5*Tmelting T (°K)>0.5*Tmelting
a) b) a) b)
L+DL
L
L
DL
Elastic deformation
Permanent plastic deformation
43
Tube degradation
Creep accounted for in design
• Creep happens at T(K) > 0.5 · Tmelting

as a result of pressure and high
temperature
• Irreversible plastic deformation
• Happens at any stress level
• Time dependent
Creep strain
Primary Tertiary Rupture
Secondary
Instantaneous deformation
44
Time
Tube degradation
Creep not accounted for in design
Creep strain
• Certain parameters such as pressure and
temperature can accelerate creep 1 2 3
• The higher the temperature, the shorter the secondary
creep region → High temperature excursions decrease
the lifetime
• Similarly: Higher pressure → Shorter secondary creep T1 > T2 > T3
region → High pressure excursions decrease the lifetime Time
Creep strain
• Other effects:
• Expansion/contraction through wall stress during start- 1 2 3
up/shut-down
• Hot bands
P1 > P2 > P3
45
Time
Tube degradation
Creep damage classification
Class Structural and damage conditions
0 As received, without thermal service load
1 Creep exposed, without cavities
2a Advanced creep exposure, isolated cavities
More advanced creep exposure, numerous cavities without class 2a class 2b/3a
2b
preferred orientation
3a Creep damage, numerous oriented cavities
Advanced creep damage, chains of cavities and/or grain

3b
boundary separations
4 Advanced creep damage, microcracks
5 Large creep damage, macrocracks

class 3a/3b class 4
46
Tube degradation
Creep damage classification
Class Structural and damage conditions
0 As received, without thermal service load
1 Creep exposed, without cavities
2a Advanced creep exposure, isolated cavities
More advanced creep exposure, numerous cavities without

2b
preferred orientation
3a Creep damage, numerous oriented cavities
Advanced creep damage, chains of cavities and/or grain

3b
boundary separations Inner surface
4 Advanced creep damage, microcracks
5 Large creep damage, macrocracks
47
Tube degradation
Creep development
• Cracks originate in the bulk of the cross

section and propagate towards the inner
surface
Crack propagation
Inner surface
• The outer surface might look perfect but

the tube is close to final rupture
48
Tube degradation
Creep of alloys
Creep occurs due to plastic deformation
Creep occurs at high temperatures
The tensile stress applied can be lower

than the yield stress of the material
Creep is a permanent and irreversible

deformation and results in cracking
49
Tube degradation
Thermal aging
Material as cast Temperature WITHIN specifications

912°C/94900hrs/14MPa
50
Tube degradation
Thermal damage
Temperature WITHIN specifications Temperature ABOVE specifications

912°C/94900hrs/14MPa 982°C/65664hrs/12.3MPa
51
Tube degradation
Cumulative lifetime – API 530
• Operating above the tube design LMP = T (C + log t) x 10 -3

temperature can have severe consequences
• Effect on lifetime Where: LMP: Larson miller parameter
• Risk of rupture (provided by supplier)
T: Temperature in K
C: Material specific constant
• The tube design lifetime is provided by the (provided by supplier)
supplier
t: Time in hours
• If a tube has been operated above the ∆t

design lifetime in a known period it is Cumulative life = ෍ ∙ 100,000 hours
Tr
possible to calculate the effect on the total
lifetime Where: Δt: Time at the given temperature
Tr: Lifetime at the given temperature
52
Tube degradation
Cumulative lifetime – Example
• Example:
200 LMP = T (C + log t) x 10 -3
100 • Supplier information:

50 • C = 22.128
• The lifetime for this particular alloy if the stress
20 level is 20 MPa at different temperatures:
Stress MPa
10 T °C T °K Constant LMP Lifetime, h Lifetime, y

915 1188 22.128 32.5 169,396 19.3
925 1198 22.128 32.5 100,000 11.4
935 1208 22.128 32.5 56,670 6.5
0 1100 1373 22.128 32.5 34.9 0.004
53
10 20 30 40 50 60
LMP
Tube degradation
Cumulative lifetime – Calculation
∆t
• A reformer tube has been in operation for Cumulative life = ෍ ∙ 100,000 hours
little over five years Tr
• Design: 100,000 hours at 925°C Where: Δt: Time at the given temperature
• Service: 5 years at 925°C plus Tr: Lifetime at the given temperature
3 · 6 hours at 1,100°C
LMP = T (C + log t) x 10-3 Actual operating period
5 ∙ 365 ∙ 24 h + 3 ∙ 6 h = 43,818 h
T °C T °K Constant LMP Lifetime, h Lifetime, y
925 1198 22.128 32.5 100,000 11.4 Cumulative tube lifetime
1100 1373 22.128 32.5 34.9 0.004 43,800
+
18
∙ 100,000 h = 95,376 h
100,000 34.9
• LifetimeT = 925°C: 100,000 hours
• LifetimeT = 1100°C: 34,9 hours Remaining lifetime
100,000 h − 95,376 h = 4,624 h
54
Non-destructive tests
Three examples of different methods
Ultrasonic testing X-ray Eddy current

• Identification of defects and • Determine thickness or • Identify small cracks in or near
the depth of these composition of material the surface of the material
• Identify presence of defects
55
Replica
• Another non-destructive test is the replica

method where a copy of the surface is
created
• The first step is preparing the surface by

cleaning, grounding, polishing etc.
56
Replica

created

• Then a two component polymer is applied

to the surface and removed after
solidification
57
Replica

created

• Then a two component polymer is applied

to the surface and removed after
solidification
• This creates a “print” of the surface which is

then examined for damage
58
Destructive tests
• Destructive testing requires a physical piece

of the tube to be sent to a laboratory
• Both creep, thermal aging and thermal

damage are assessed
• Very important to know where to select the

sample for metallurgical examination
Section affected by the flame after leakage

59
Destructive tests
• Destructive testing requires a physical piece

of the tube to be sent to a laboratory
• Both creep, thermal aging and thermal

damage are assessed
• Very important to know where to select the

sample for metallurgical examination
Microscopy (LOM, ESEM, TEM)

Microhardness
X-ray diffraction
60
Steam reformer
Understanding tube aging and damage
• Reformer tubes are designed for a lifetime of

~100,000 hours
• Operating outside the design influences the lifetime
Degradation
• The design takes some degradation into account based on the
long term exposure to pressure and high temperatures:
• Creep (result of both temperature and pressure) Tube lifetime
• Thermal aging (within design temperatures)
Destructive
vs. non-
destructive
• Degradation not accounted for in design: tests
• Thermal damage (above design T) → Reduces lifte time significantly
• Both destructive and non-destructive tests are available

61
Secondary reformer
62
Secondary reformer
Typical conditions
Process air/oxygen
34 bar g, 550°C
Inlet conditions Intermediate conditions

CO + H2 + H2O, ~15 mol % CH4 CO + CO2 + N2 + H2 + H2O, < 0.5 mol % CH4
31 bar g, < 800°C 30 bar g, > 1,000°C
63
Secondary reformer
Catalyst bed Reactor shell Burner
Catalyst support Tiles Refractory
64
Secondary reformer
Refractory
• Often the refractory is constructed of

several layers
• High alumina hot face
• Bubble alumina refractory
• Cast insulating refractory
• Gunned/cast insulating refractory
• 75–80% of the reduction of the heat

transfer takes place in the layers of the
insulating castables
• The total lining thickness is 450-600 mm
65
Secondary reformer
Reactor shell
• Thermo indicative paint

• Used to quickly verify that the surface
temperature is not too high
• Change in color is irreversible
Up to
• Surface temperature is typically ~150°C 180°C
At 180-220°C
At 310-350°C
• Frequent visual inspection is required
• Monitoring done with IR cameras
66
Agenda
• Metals
• Desulfurization
• Reforming
• Shift, Shift, CO2 removal and Methanator
• Summary
67
Waste heat boiler
68
Waste Heat Boiler
CO + CO2 + N2 + H2 + H2O, < 0.5 mol % CH4 CO + CO2 + N2 + H2 + H2O, < 0.5 mol % CH4
30 bar g, > 1,000°C 30 bar g, 360°C
69
Waste Heat Boiler after the reformer
• The waste heat boiler is located downstream from the

reformer
• Example from an ammonia plant – Horizontal WHB at the
Secondary reformer outlet
• Conditions:
• Inlet temperature > 1,000°C
• Outlet temperature ~360°C
• Gas containing CO, CO2, H2, H2O, N2
• The conditions make the waste heat boiler prone for

metal dusting
70
Risk of Metal dusting
• Metal dusting is a disintegration of metal to

dust of metal and graphite, mostly as a
aggregate of pine particles (coke)
• Can also contain oxides and carbides,
depending on materials and conditions
• Occurs at temperatures of 400-850°C and a

carbon activity (aC) > 1, after a certain
period of time – Incubation time
71
Risk of Metal dusting
• Metal dusting is a disintegration of metal to • Metal dusting occurs many places in a plant
dust of metal and graphite, mostly as a
aggregate of pine particles (coke) Waste heat boiler
• Can also contain oxides and carbides,
depending on materials and conditions Steam superheater
• Occurs at temperatures of 400-850°C and a Secondary reformer, burner

carbon activity (aC) > 1, after a certain
period of time – Incubation time Convection reformer (HTCR)
Heat exchange reformer (HTER)
Heat exchanger
72
Metal dusting
Carbon formation
Carbon formation can be due to three reactions:

Reaction Carbon activity
CO PCO ∙ PH2
CO + H2  C + H2O a = K
reduction C 1
PH2O
P 2 CO
Boudouard 2 CO  C + CO2 aC = K 2
PCO2
PCH4
Methane CH4  C + 2 H2 aC = K 3
P 2 H2
73
Metal dusting (MD)
Carbon activity 10
Carbon activity
100
100
Carbon formation can be due to three reactions: Boudouard
Reaction Carbon activity
1 Metal dusting CO reduction
CO PCO ∙ PH2
CO + H2  C + H2O a = K
reduction C 1
PH2O 10
10
activity
P 2 CO
Boudouard 2 CO  C + CO2
activity
aC = K 2
0.1 PCO
2
CarbonCarbon
600 650 700 750 800 TB:850
738°C
PCH
Methane CH4  C + 2 H2 aC = K3 2 4 Temperature ( C)
P H2 1
1
Risk for MD at temperatures where carbon activity >1 TR: 713°C
0.1
0.1
600
600
650
650
700
700
750
750
800
800
850
850
74
Temperature, °C
Temperature ( C)
Metal dusting
Mechanism in stainless steel
C=O
Cr2O3
1. Formation of protective oxide layer
C=O
C=O
2. Deflect in the oxide layer where CO from the gas
can adsorb
3. C dissolves in the alloy and reacts with Cr to form
carbides, resulting in an expansion of the lattice Cr + C → Cr-carbides
(expanded austenite) C in solution
4. The metallic matrix becomes oversaturated with

C. This results in formation of graphite and the Graphite
release of free metallic particles
5. Coke grows catalytic by the reaction of the gas
with the free metallic particles Coke
75
Metal dusting
Scanning electron microscopy
Cross section of an attacked alloy: Carbon filaments with metallic

particles at their tips:
Metal dusting
pits
76
Metal dusting
Prevention
• Design – Keep out of critical temperature range
• Alloy selection
• Alloys where carbon has the slowest diffusion
• Alloys which form protective oxide scales
• Appropriate surface condition
• Appropriate grain size
• Coatings – Barriers for carbon diffusion and penetration
• Change of environment (sulfur additions)

• Interfere in the adsorption and diffusion mechanism
77
Metal dusting
Prevention
• Different alloy elements can help prevent metal dusting
Element Effect Resistance to

metal dusting
Cr, Al Promote formation of protective oxide ↑
Ni Decrease solubility and diffusivity of C ↑
Cu Supress CO dissociation ↑
Mo Promote formation of carbides ↓
• The surface condition also affects the affinity for metal dusting
• The more polished and smooth the surface, the higher the resistance
to metal dusting.
78
Metal dusting
Prevention
• Metal dusting can also be prevented by • Several types of coating exists:

coating • Vapor deposition (chemical or physical)
• Barrier for carbon-penetration • Chemical and electrochemical techniques
• Reservoir for scale formation promoters • Spraying (several types)
• Immersion (dip) coating
• The coating should have adequate
properties:
• Ductility
• Thermal expansion coefficient
• Adhesion
• Long term stability
79
Topsoe assistance
How can Topsoe help you – Metal dusting
• Many years of experience with detection

and prevention of metal dusting
80
Topsoe assistance
How can Topsoe help you – Metal dusting
Gas in
samples
• Many years of experience with detection
and prevention of metal dusting
• Where Topsoe differ from other companies:

• Metal dusting test-rig
Furnace
• Excel data records for risk of metal dusting
under different conditions
• A “white paper” to be handed out to clients
with open literature review of metal dusting
• Development of alloys in collaboration with
different suppliers
Gas out
Thermocouple
81
Summary
Secondary Reformer
• The secondary reformer operates at high
temperatures and several reactor internals,
such as target tiles, are required
Target tiles
Waste Heat Boiler

• Metal dusting occurs at a certain temperature interval (400-850°C) Coatings
when the carbon activity of the gas is > 1, after a certain period of
time – Incubation time
Metal
• Prevention of metal dusting can be achieved by changes in design, dusting
appropriate alloy selection, application of coatings or changes in
the environment
82
Agenda
• Metals
• Desulfurization
• Reforming
• Summary
83
Shift section, CO2 removal and Methanator
84
Shift section, CO2 removal and Methanator
Focus will be on CO2 & amine corrosion
Methanator
CO2 removal
Process
condensate
CO + CO2 + H2 + H2O, < 0.5 mol % CH4
210°C inlet - 330°C outlet (MTS)
85
Shift section
Reaction
Shift CO + H2O ↔ CO2 + H2 + Q
86
Carbonic acid corrosion
Risk if gas is not dry
• CO2 is a weakly acidic gas and becomes

Thermowell in CS
corrosive when dissolved in water
Reaction
Carbonic acid CO2 + H2O  H2CO3  H+ + HCO3-
dissolution
• The CO2 dissolution can result in a formation of Towards flow (wet gas)
a protective layer of Fe-carbonate
• Turbulent or very rapid flow can destroy the

carbonate layer and result in “flow accelerated
corrosion”
Opposite flow (wet gas)
87
Controlling factors
• Key controlling factors

• CO2 partial pressure
• Temperature
• Water dew point of gas
• Concentration of Fe2+ in condensate
• Flow velocity and type
• Scale formation – CO2

• Carbonate scale formation reduces corrosion
• Carbonate scale is unstable < ~60-70°C
• At higher temperatures carbonate scale
reduces corrosion rate
88
Prevention
• In order to prevent carbonic acid corrosion the

proper material should be selected
• Carbon steel and low alloy steel are not resistant

• Stainless steel shall be selected.
Uniform CO2 corrosion on Localized ‘Mesa’ CO2

carbon steel corrosion on carbon steel
89
CO2 removal
BASF amine unit
• In the CO2 removal amines are added

to react with the CO2
• Amines are not corrosive

• Corrosive components: Amine
degradation products = Heat stable
salts and dissolved CO2
90
CO2 removal
BASF amine unit
• In the CO2 removal amines are added Degradation

to react with the CO2
Cracking Due to:
Hydrogen
Alkaline (amine)
• Amines are not corrosive
Corrosion Due to:
• Corrosive components: Amine
• CO2
degradation products = Heat stable
salts and dissolved CO2 • Heat stable salts
Corrosiveness of amine solution

Related to amount and type of degradation product
Most MEA
Medium DEA, DGA, DIPA
Less MDEA
91
Summary – Shift, CO2 removal and Methanator
• Risk of carbonic acid corrosion in the Shift & CO2

removal
• CS & LAS are not resistant to carbonic acid. If CS or LAS
selected, add V in the stream which result in the
formation of a protective film in the CS or LAS alloy. Protection
• SS is resistant to carbonic acid
Corrosion
• Material selection for methanator according to API
941, Nelson diagram due to the presence of H2
Carbonic
acid
92
Ammonia loop
93
Ammonia loop
CH4 + N2 + H2
230°C
NH3
460°C
94
Ammonia synthesis converter
• Conversion of N2 and H2 S-300 converter:

into NH3
• Iron based catalyst
Reaction
Ammonia N2 + 3 H2 ↔ 2 NH3
synthesis +Q
95
Nitridation of low alloy steel
1. NH3 is adsorbed 3. N reacts with Cr, Mo, V to form metal

2. N and H atoms enter the metal 4. Carbides are converted to nitride → release of
C → formation of CH4
H
H N H H
H N H
surface
The formation of nitrides result in

H H N increased hardness
H CrN The formation of CH4 results in HTHA
CH4 C C-CrN
void
96
Plant data
• Nitridation depth = 1 mm
• Material: 2.25Cr1Mo
• ~ 0.5 years at T = 465 °C
• 3.7 years at T = 410 °C
• Nitridation depth = 0.4 mm

• ~ 0.2 years at T = 465 °C
• 1.4 years at 410 °C
97
Base metal versus welds
Few mm
H2 H2
NH3 NH3
Outer
Outer
Inner
Inner
Outer
Base metal – low stress level Weld – high stress level
Topsoe experiments show no effect of PWHT Stresses in the welds will accelerate
nitridation of CS & LAS by a factor of 3 – 5
on the depth of nitridation for welds.
98
Nitridation stainless steel and nickel
• NH3 is adsorbed
• N atoms enters the metal
• Hard and brittle layer of

nitrides develop at the
surface Sample of perforated plate in SS304
after 24 years’ exposure in an ammonia
converter at ca. 500 °C.
Example of longitudinal cracks in a 22-year
old interbed heat exchanger
99
Nitridation of stainless steel
Plant data
• Nitridation depth = 1 mm
• ~ 0.5 years at T = 465 °C
• 3.7 years at T = 410 °C
• Nitridation depth = 0.4 mm

• Material: 2.25Cr1Mo 465 °C
• ~ 0.2 years at T = 465 °C
• 1.4 years at 410 °C
• Material: Stainless steel
• >12 years at T = 465 °C
100
Nitridation
Effect of nickel
Ni reduces the solubility

and diffusion rate of N
Time: 29164 hours

NH3: 5-6 mole%
101
Nitridation
Material selection
Carbon Steels & Low Stainless Steels Nickel alloys (alloy 600)
Alloy Steels
Service temperature Service temperature Service temperature
< ca. 380°C < ca. 490°C > ca. 490°C
Higher Ni content Higher resistance

102
Loop steam super heater and loop boiler
• Process side:
Loop boiler
• Nitriding and HTHA
• Steam side (super heater):

• Stress Corrosion Cracking (wet steam)
• Water side (loop boiler):

• Stress corrosion cracking
• Caustic corrosion
• Phosphate hide-out
103
Water side corrosion mechanism and effect of pH
Reaction
Water side 3 Fe + 4 H2O → Fe3O4 + 4 H2
Corrosion
Topsoe recommendation of pH:
8.5
12.7 Low pressure boiler (68-136 bar):
• pH = 10 ± 0.2
High pressure boiler:
• pH = 10-11
Measured at 25°C
Carbon steel at 310°C
104
Caustic corrosion
1. Porous deposit forms at the surface if the tube

due to e.g. improper water chemistry
in high flux areas

Steam blanketing
2. Boiler water diffuses through the porous
deposit.
Protective Fe3O4
3. Water evaporates leaving a concentrated

Deposit NaOH solution below the deposit
4. The Fe3O4 layer is dissolved at high pH (>13)
5. Active corrosion of the metal occurs
6. Corrosion stops when deposit is removed or
caustic concentration is back to normal
Hot gas Hot gas

• Steam blanketing may also result in caustic
corrosion
105
Caustic corrosion
1. Porous deposit forms at the surface if the tube

due to e.g. improper water chemistry
2. Boiler water diffuses through the porous
deposit.
3. Water evaporates leaving a concentrated
NaOH solution below the deposit
4. The Fe3O4 layer is dissolved at high pH (>13)
5. Active corrosion of the metal occurs
6. Corrosion stops when deposit is removed or
caustic concentration is back to normal
• Steam blanketing may also result in caustic

corrosion
106
Phosphate hideout
Normal situation Situation with Phosphor hideout
107
Phosphate hideout
1. At high load/ high heat transfer:

• Phosphate forms a precipitate together with Fe-oxide and sodium
• The pH increases as phosphate content decreases
2. Low load/ reduction of high heat flux:

• The precipitate dissolves, whereby the phosphate content increases
• The pH decreases as the phosphate content increases
Mitigation strategies:
• Congruent phosphate treatment: Mixture of tri-sodium and di-sodium phosphate
• Tri-sodium phosphate and to use lower levels of phosphate
108
Ammonia synthesis loop
• Nitridation
• Nitriding occurs as nitrogen atoms enter the material
• Results in hardening of the material surface
• Nitriding rates depend on the temperature and the Steam
superheater
ammonia content
& WHB
• Carbon steels can be used up to 380°C, stainless steels up
to 490°C and alloy 600 for higher temperatures Boiler
corrosion
• Water side corrosion

Nitridation
• Caustic corrosion
• Steam blanketing or deposit
• Phosphate hideout:
• Phosphate and pH fluctuates with load
• Stress corrosion cracking
109
Stress corrosion cracking
110
• Typical susceptible materials include: Three parameters must be present

• Steel/alloy surfaces protected by a surface film
• Oxides, hydroxydes, sulfides, sulfates and carbonates
• Surfaces covered by salt deposits
• Sensitized steel/alloys Susceptible
material
SCC
Tensile Corrosive
stresses environment
111
Susceptible material – Film rupture model
• Before deformation: • After deformation:
Protective film Attack at exposed bare metal
112
Susceptible material
• Stress corrosion cracking can occur

• Intergranular Intergranular Transgranular
• Transgranular fracture fracture
• Distinguishable using microscopy Scanning

electron
micrograph
Light
optical
micrograph
113
Tensile stresses
• Tensile stresses can occur during

fabrication:
• Cold work
• Bending
• Welding
• Tensile stresses can also occur during

service
• The minimum stress level needed to start

cracking can be far below the yields
strength
• Stresses can be external or residual
114
Corrosive environment = Wet environment
• Stress corrosion cracking only affects specific material environment combinations

Material Environment Temp. Material Environment Temp.
Caustic solutions > 80°C Ni-base alloys Deaerated, hydrogenated ≥ 250/280°C
< 25-30% Cr water
Carbonates-bicarbonates ≥ RT
Carbon steels Sensitized Aerated “pure” water ≥ 60/100°C
Nitrates ≥ 50/60°C stainless
Solutions containing reactive ≥ RT
Liquid ammonia RT steels and Ni-
sulfur species (polythionic
base alloys
Near neutral dilute aerated ≥ 60/100°C acids, thiosulfates etc.)
chloride solutions Cu alloys Ammoniacal solutions RT
Austenitic
stainless Very acidic chloride solutions ≥ RT Al alloys Chloride environments RT
steels Chloride env. containing H2S ≥ RT Ti alloys Alcoholic chloride solutions RT
Caustic solutions ≥ 80/120°C Zr alloys Gaseous iodine and RT
Ni-base alloys Caustic environments ≥ 100/200°C dissolved iodide
115
Example – Chloride induced SCC
Corrosive environment
• Chloride concentration
• Temperature
• pH
• Dissolved oxygen
Tensile stresses
• Level of stress
Susceptible material Minimal risk of chloride SCC for 300

series SS at metal temperatures < 50°C
• Steel/alloy sensitization
116
Prevention
• Corrosive environment → Change environment

• Reduce concentration of critical compound (e.g.
chlorides)
• Avoid water condensation/ water carry-over
• Reduce temperature
• Tensile stresses → Reduce stress level

• Change of design (stress concentrations)
• Minimize residual stress by e.g. PWHT
• Susceptible material → Choose more resistant/

immune steel/alloy Alloys with Ni > 45 wt % are immune to
• Test in boiling 42% magnesium chloride Chloride SCC
117
• SCC is the result of three parameters:

• Corrosive environment: Usually aquatic, condensation,
carry-over or bulk solution
• Tensile stresses: Small stresses below the macroscopic Tensile stresses
yield stress
• Susceptible material: Metals with films (passivating layers,
Prevention
tarnish films etc.) and sensitized alloys
Stress corrosion
• To prevent SCC one or more of the three parameters cracking
must be eliminated/ changed
118
Summary
Materials in hydrogen and ammonia plants
Metals Desulfurization Reforming
• CS & LAS, SS, Ni based • H2 rich environment • Creep and thermal aging
alloys • HTHA and LTHA (Nelson • Metal dusting in WHB
diagram)
119
Summary
Materials in hydrogen and ammonia plants
Ammonia synthesis Stress corrosion

cracking
• Nitriding • Tensile stresses
• HTHA • Susceptible material
• Water side corrosion • Corrosive environment
120
Topsoe Academy™
Thank you for your attention
March 16, 2017

Damage Mechanisms: Causes and Prevention

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Damage Mechanisms: Causes and Prevention

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Damage Mechanisms:

Causes and Prevention

• Discuss with the person next to you – 5 min

Topsoe classification Composition

• During solidification shrinkage takes place

• Air/gases can be removed by adding Al or Si

• If air/gasses are removed before

Quenched & Tempered (Q&T):

CCT-diagram for Ck35 steel

Quenching: Annealing followed by very

Ferritic SS/Martensitic SS (Ni < 1%)

Duplex SS (1% < Ni < 8%) (50/50

Austentic SS (Ni > 8%)

• Exposure to elevated temperature

Property Definition Typical values

• For CS and LAS the strength depends on the

Toughness: Energy to fracture

0.2% Strain (deformation)

• Material nomenclature depends on country and

• The microstructure and mechanical properties of CS

• Thermal expansion is smallest for CS, LAS & ferritic

• Tensile testing gives information about mechanical

CH4 + H2S + org. S + H2

1. Adsorption of hydrogen molecules to the 3. Permeation of hydrogen atoms in the metal

1. Adsorption of hydrogen molecules to the 3. Permeation of hydrogen atoms in the metal

Decarburization Fissuring Tesoro Refinery (2010)

H2 partial pressure, MPa

1. Adsorption of hydrogen molecules to the 3. Permeation of hydrogen atoms in the metal

Rimmed steel Killed steel

• If air/gasses are not removed before

• If air/gasses are removed before

Killed steel has less cavities → Less permeation of H2

Prevention of HTHA Prevention of LTHA

• Materials selection as per Nelson • Select alloys of lower strength

Material in the desulfurization section is susceptible to

LTHA causes blistering, cracking and hydrogen embrittlement

Inlet conditions Outlet conditions (H2) Outlet conditions (NH3)

33 bar g, 540°C 31 bar g, 925°C 31 bar g, > 800°C

• Conversion of HC’s into CO, CO2 and H2

• The reformer tubes are made of Fe based

• Fabricated by centrifugal casting Centrifugal casting with columnar

• Large grains provide high creep strength

Typical design Typical service

• Reformer tubes are designed to withstand the expected degradation

• Within the design conditions some degradation is expected

• Degradation not taken into account:

• Creep is a permanent deformation

• Creep can be accelerated by:

• High temperatures can also affect the

• Creep strength is defined as the time to

• With time, deformation takes place and

• Creep happens at T(K) > 0.5 · Tmelting

Class Structural and damage conditions

0 As received, without thermal service load

1 Creep exposed, without cavities

2a Advanced creep exposure, isolated cavities

3a Creep damage, numerous oriented cavities

Advanced creep damage, chains of cavities and/or grain

4 Advanced creep damage, microcracks

5 Large creep damage, macrocracks

Class Structural and damage conditions

0 As received, without thermal service load

1 Creep exposed, without cavities

2a Advanced creep exposure, isolated cavities