Académique Documents
Professionnel Documents
Culture Documents
Harmen J. Bouwman
1. Wall Thinning
2. Stress Corrosion Cracking
3. High Temperature Degradation
2
1. Wall Thinning
1. Contents
1.1 Introduction
1.2 Main Degradation Mechanisms
1.3 Morphologies
1.4 Inspection
1.5 Reporting
3
1.1 Introduction
4
Two Main Types of Corrosion
5
Electro-Chemical Corrosion (Wet)
Oxygen
Medium
Fe2+
OH- O2 Reactions
Fe Fe2+ + 2e
e O2 + 2H2O + 4e 4OH-
Steel
Acid
HAc H+ + Ac-
Medium
H2
Fe2+
6
Electro-Chemical Corrosion (Wet)
Stability protective layer
Corrosion
Rate
Corrosion product
FeS strongly adherent
oHigh protection
FeCO3 weakly adherent
Time
oLow protection
Mechanical impact
Turbulence (velocity)
For fresh material the CR is very high Impingement
Protective layer is formed by the corrosion (erosion-corrosion)
process CR decreases = Global CR Composition electrolyte, e.g.
Global CR is dictated by the stability of the Cl- and CN- on FeS
protective layer.
7
Chemical Corrosion (Dry)
Direct reaction between metal and corrosive species: O2, H2S, HCl
Corrosive species, e.g.: Porous layer
O2, H2S, HCl
Diffusion of species thru Layer
Layer
Corrosion at interface Layer/Metal
Corrosion Rate
Difference between relative volume of Layer & Metal
Layer < Metal
Porous Layer No protection
Oxide > Metal
Non-porous/adherent layer possible Protection possible
Oxide >> Metal
Spalling of Layer Some protection possible
8
Chemical Corrosion (Dry)
Spalling
Layer
M e ta l
1 O ld L a y e r
N ew Layer
Layer M e ta l
4
M e ta l
2
S p a lle d
Layer Layer
N ew Layer
M e ta l
3 5
M e ta l
Oxidation rate
Linear
Weight Loss
Time
1.2 Main Degradation Mechanisms
10
Wall Thinning
Sulphidic Corrosion & NAC T2
H2S/H2 Corrosion T1
CUI T3
HCl Corrosion T4
Sour Water Corrosion T7
Amine Corrosion T8
Dew Point Corrosion T9N-1
Acid Dew Point Corrosion T9N-2
NH3-Salts T10
Oxidation T11
Metal Dusting T12N
High Temperature HCl/Cl2 Corrosion T13N
Localized Corrosion by entrained water M1N 11
Structure of presentations Thinning
Specifics
Description
Mechanism
Materials
Morphology
Examples
12
Sulphidic Corrosion: T2
Specifics
Chemical Corrosion / Dry / High Temperature
Process related
Typical Units : CDU, HVU, TGU.
Description
Sulphidic corrosion consumes a metal by the reaction between the
metal surface and sulphur compounds (mainly H2S & mercaptans) in
liquid or gaseous hydrocarbon streams at temperatures above 230 C.
13
Sulphidic Corrosion: T2
Mechanism
For CS the corrosion reaction
Outer
produces a layer of FeS on
layer
the surface of the metal. The
inner layer is fine grained, but
Inner the outer layer develops into a
layer porous amorphous structure.
Steel
The inner layer tends to be protective and slows down the corrosion rate.
Chromium steels and chromium-nickel steels produce tighter, finer-grained,
sulphide scales that can be very tenacious and therefore reduce the
corrosion rate much better.
Materials
Corrosion rate is approx. halved with each step up in %Cr:
CS 1Cr 2Cr 5Cr 9Cr 12Cr 18Cr8Ni
14
Sulphidic Corrosion: T2
Morphology
General Thinning : In general
Localised Thinning : Turbulence
Pitting : Observed in furnace tubes
15
Sulphidic Corrosion: T2
Examples
General Thinning in a partly insulated line
- Insulated
higher temp.
higher sulphidation rate
Non-insulated Insulated
16
Examples
Pitting in a furnace tube
17
Naphthenic Acid Corrosion: T2
Specifics
Chemical Corrosion / Dry / High Temperature
Process related
Typical Units : CDU, HVU, TGU.
Description
Naphthenic Acid corrosion consumes a metal by the reaction between
the metal surface and naphthenic acids (organic acids) in liquid or
gaseous hydrocarbon streams at temperatures above 230 C.
18
Naphthenic Acid Corrosion: T2
Mechanism
The corrosion reaction produces Fe-Naphthenates, which are soluble
in the oil phase and therefore a protective layer is not built up.
Materials
SS of the type 18Cr8Ni containing a sufficient level of Mo (> 2.5%)
provide sufficient resistance: 316 & 317
CS and Cr-steels provide limited resistance
19
Naphthenic Acid Corrosion: T2
Morphology
General Thinning
Localised Thinning : In general
Grooving (sharp edges)
Pitting (sharp edged)
20
Naphthenic Acid Corrosion: T2
Examples
21
Naphthenic Acid Corrosion: T2
Examples
22
Naphthenic Acid Corrosion: T2
Examples
23
Interaction Sulphidation - NAC: T2
24
H2S/H2 Corrosion: T1
Specifics
Chemical Corrosion / Dry / High Temperature
Process related
Typical Units : HTU, HDS, HCU
Description
H2S/H2-Corrosion consumes a metal by the reaction between the metal
surface and H2S in liquid or gaseous hydrocarbon streams containing
H2 at temperatures above 230C.
25
H2S/H2 Corrosion: T1
Mechanism
The inner layer tends to be protective and slows down the corrosion rate.
Chromium steels and chromium-nickel steels produce tighter, finer-grained,
sulphide scales that can be very tenacious and therefore reduce the corrosion
rate much better.
Materials
Cr-Steels up to 5% does not offer a benefit over CS.
When CS is not sufficient than SS of the type 18-8 is applied.
26
H2S/H2 Corrosion: T1
Morphology
Uniform Thinning : In general
27
Corrosion Under Insulation: T3
Specifics
Electro-Chemical Corrosion / Wet / Low Temperature
Non-Process related
Typical Units : All Units
Presence of wet insulation for streams with operating temperatures
in the following range: - 5 < T C < 150
Notes:
- Wet condition due to ingress of water due to damaged insulation
- Wet condition lowers metal below operating temperature
- Metal temperature rules the corrosion
Description
Corrosion Under Insulation consumes a metal by the reaction between
the metal surface and an O2-containing water phase.
Note:
Corrosion will be aggravated by water leachable salts in insulation,
e.g.: chlorides, sulphates & acids 28
Corrosion Under Insulation: T3
Mechanism
As for Electro-Chemical Corrosion, when O2 present.
Materials
Insulated CS & Cr-Steels
Morphology
Localized Thinning : In general
29
Corrosion Under Insulation: T3
Example
30
HCl Corrosion: T4
Specifics
Electro-Chemical Corrosion / Wet / Low Temperature
Process related
Typical Equipment : Overhead Atm. Dist. Column
Description
Hydrochloric Acid Corrosion consumes a metal by the reaction between
the metal surface and HCl in the water.
31
HCl Corrosion: T4
Mechanism
HCl H+ + Cl-
Medium
H2
Fe2+
Forming of HClaq
Presence of a water phase
Condensation of water in vapor stream
Water wash of vapor stream
32
HCl Corrosion: T4
Materials
Significant Corrosion rates for CS, when pH < 5
SS-type 18-8 is susceptible to pitting
CRAs: C-276, B2, 625, 825
Morphology
Uniform Thinning : In general
Localised Thinning : In case of Dew Point Corrosion
Pitting : SS-type 18-8
33
Sour Water Corrosion: T7
Specifics
Electro-Chemical Corrosion / Wet / Low Temperature
Process related
Typical Units : CDU, HVU, TGU, HTU, HDS, HCU, FCC
(almost all units containing H2S)
Description
Sour Water Corrosion consumes a metal by the reaction between the
metal surface and H2S in the water.
Note:
NH4HS will be formed, when also NH3 is present, which
generally will be case in refinery streams.
34
Sour Water Corrosion: T7
Mechanism
H2S H+ + HS-
Medium
Fe2+
Hads H+ Fe Fe2+ + 2e
2 H+ + 2e H2
Habs e
Steel
Hinterstitial
For CS the corrosion reaction produces a layer of FeS on the surface of the
metal. This layer is very tenacious and slows down the corrosion rate.
Materials
CS < 2% NH4HS
12Cr/18Cr8Ni 2 < %NH4HS < 8
CRA (e.g. 825) >8% NH4HS
35
Sour Water Corrosion: T7
Forming of Sour Water
Presence of a water phase
Condensation of water in vapor stream
Water wash of vapor stream
36
Sour Water Corrosion: T7
Morphology
Uniform Thinning : In general
Localised Thinning : Turbulence
: Condensed water
: Under deposits
Pitting (wide) : Under deposits (pH > 8 Precipitation of FeS)
Examples
Specifics
Electro-Chemical Corrosion / Wet / Low Temperature
Process related
Typical Equipment : Amine-Absorbers/-Regenerators
& associated equipment/piping
Description
Amine Corrosion consumes a metal by the reaction between the metal
surface and both the dissolved acids (in refineries mainly H2S) and the
amine degradation products.
Pure Amines are non-corrosive.
38
Amine Corrosion: T8
Mechanism
As for Sour Water Corrosion
Increased corrosion rates under following conditions
Turbulence
Flashing
Impingement
39
Amine Corrosion: T8
Morphology
Uniform Thinning : Low stream velocities
Localised Thinning : High stream velocities
: Flashing
: Impingement
Grooving : See localized thinning
Pitting : See localized thinning
Example
Specifics
Electro-Chemical Corrosion / Wet / Low Temperature
Process related
Typical Equipment : Overhead systems in CDU, HVU
: Effluent streams in HTs and HCU
: Process streams in SRU, TGU and Incinerators
: Sour Gas Lines
Description
Dew Point Corrosion consumes a metal by the reaction between the
metal surface and the dissolved acids (in refineries mainly H2S, CO2 and
HCl) in the condensed water.
Saturation temperature of the acid < water dew point
41
Dew Point Corrosion: T9N-1
Mechanism
As for Sour Water Corrosion
HAc H+ + Ac-
Medium
H2
Fe2+
Morphology
Localised Thinning
Pitting
Expected locations
Locations, where metal temperature falls below dew point for
water vapor
Low points and dead ends, where condensed water might collect
Full system, when low points/dead ends can not be identified
Wet spots in insulated & heat traced lines
Condensation is prevented by insulation & heat tracing
43
Acid Dew Point Corrosion: T9N-2
Specifics
Electro-Chemical Corrosion / Wet / Low Temperature
Both Process and Non-process related
Typical Equipment/Unit : Flue gasses in Boilers, Heaters & FCC-Regenerators
: Process streams in SRU & TGU
Description
Acid Dew Point Corrosion consumes a metal by the reaction between
the metal surface and the condensed acids (in refineries mainly SO2 &
SO3), which are diluted by condensed water.
Saturation temperature of the acid > water dew point.
The hygroscopic condensed acid will absorb water even below its dew
point.
44
Acid Dew Point Corrosion: T9N-2
Mechanism
As for HCl
HAc H+ + Ac-
Medium
H2
Fe2+
Morphology
Localised Thinning
Pitting
Expected locations
Locations, where metal temperature falls below temperature for
condensation
Wet spots in insulated & heat traced lines
Condensation is prevented by insulation & heat tracing
46
NH3-salt Corrosion: T10
Specifics
Electro-Chemical Corrosion / Wet / Low Temperature
Process related
Typical Equipment/Unit : Effluent streams in HTs and HCU
Description
NH3-salt Corrosion consumes a metal by the reaction between the
metal surface and the desublimated NH3-salts (NH4Cl, NH4F & NH4HS),
when wetted.
The hygroscopic salts will absorb water even below its dew point.
47
NH3-salt Corrosion: T10
Mechanism
As for HCl and Sour Water Corrosion
Morphology
Localised Thinning
Wide Pitting with sharp edges
Example
NH4F-salt Corrosion in a
Lube Oil HT REAC-line
48
High Temperature Oxidation: T11
Specifics
Chemical Corrosion / Dry / High Temperature
Non-process related
Typical Equipment : Boilers & Heaters
Description
High Temperature Oxidation consumes a metal by the reaction between
the metal surface and oxygen.
O2-content has no noticeable influence on the corrosion rate, when >1 %
49
High Temperature Oxidation: T11
Mechanism
Direct reaction between metal and O2
Materials
Material Tolerable temperature C
CS 565
9Cr 705
304/321/347 925
310 1150
50
High Temperature Oxidation: T11
Morphology
General Thinning
Localized Thinning
Example
51
Metal Dusting: T12N
Specifics
Chemical Corrosion / Dry / High Temperature
Process related
Typical Equipment : Heaters of CCR and HMU
Description
Metal Dusting consumes a metal (2Cr & 9Cr) by the reaction between
between the metal surface and carbon produced in a carburizing gas
phase.
52
Metal Dusting: T12N
Mechanism
Non-stable Fe3C Decomposes
Forming of free Carbon
Diffusion Fe3C 3Fe + C
2CO C + CO2
of C into Steel and Formation of Graphide
or
Formation of Fe3C and
C4H10 4C + 5H2
Removal of Metal
Fe Fe Fe
Carbon Layer Graphite
Fe3C
C C C Fe3C Fe3C
53
Metal Dusting: T12N
Morphology
Pitting
Example
Specifics
Chemical Corrosion / Dry / High Temperature
Process related
Typical Equipment : Regenerator of CCR
Description
High Temperature Chlorination consumes a metal by the reaction
between the metal surface and HCl/Cl2.
55
High Temperature Chlorination: T13N
Mechanism
Direct reaction between metal and HCl/Cl2.
Volatilisation of metallic chlorides
Materials
Tolerable temperature C
Material
Dry HCl Dry Cl2
CS 260 200
Alloy 400 230 430
Alloy B 450 540
Morphology
General Thinning
No scale smooth surface
56
Corrosion by Entrained Water: M1N
Specifics
Electro-Chemical Corrosion / Wet / Low Temperature
Process related
Typical Equipment : All Units
Description
Corrosion by entrained water consumes a metal by the reaction
between the metal surface and the corrosives in the entrained water
(often HH4HS).
Note: The entrained water must wet the metal surface, which will occur locally.
Mechanism
Electro-chemical corrosion as for sour water
57
Formation of Entrained Water
Spray Flow
Separator
59
Morphology
Localized uneven thinning
Aqueous Corrosion, where water settles out
oLow points and dead ends (low flow velocities), e.g.
Bottom of equipment items
Drains in piping
oFittings in piping
Localized Erosion-Corrosion
oCombination of spray flow (vapor phase) and fittings (geometry)
60
Effect of Erosion-Corrosion on Corrosion Rate
Corrosion Corrosion
Rate Rate
Time Velocity
For fresh material the CR is very high Impingement might destroy the
protective layer
Protective layer is formed by the
Entrained water droplets
corrosion process CR decreases
High gas velocity
Global CR is dictated by the stability
of the protective layer. Geometries prone for impingement
Step-wise increase of CR
61
19-1-2009 8:29
Inspection
Equipment by UT-Scanning based on intrusive VT
Piping up to dia. 10/12 by Profile Radiography
Piping above dia. 10/12 by UT-Scanning
62
1.3 Morphologies
63
Morphologies for Thinning
General Corrosion
Even
Even General
Uneven Unenven
General
Localized Corrosion Even
Even Localized
Uneven Unenven
Localized
Pitting
Wide Wide
Pitting
Medium Medium
Pitting
Narrow Narrow
Pitting
64
Definition Morphologies for Thinning(1)
General Corrosion
Loss of wall thickness progressing over a large part the surface of the
metal component in question.
Localized Corrosion
Loss of wall thickness progressing over a relatively small part the
surface of the metal component in question.
65
Definition Morphologies for Thinning(2)
Even Corrosion
Loss of wall thickness progressing at approx. the same rate
Uneven Corrosion
Loss of wall thickness progressing at different rates
66
Definition Morphologies for Thinning(3)
Wide pitting
Ratio depth/diameter > 1/3
Medium pitting
1/3 < Ratio depth/diameter < 3
Narrow pitting
Ratio depth/diameter > 3
67
Registration Inspection Findings for Thinning
Morphology Code Severity Extent Density/Number per Area
General even Gen Depth N.A. N.A.
General uneven Ugen Depth N.A. N.A.
Localized even Loc Depth Dia. Attacked Location locations/m2
Localized uneven Uloc Depth Dia. Attacked Location locations/m2
Wide Pitting Wpit Depth N.A. pits/dm2
Medium Pitting Mpit Depth N.A. pits/dm2
Narrow Pitting Npit Depth N.A. pits/dm2
69
Guidelines to define Component per Equipment Item
Heat Exchangers
Channel
Shell Side
Bundle
Air Coolers
Heads
Bundles
Vessel (Separator)
Lower Section, containing liquid
Upper Section, containing vapor
Medium Section subject to alternately liquid and vapor
(Boot)
71
Assessment Thinning of Equipment
Visual
Digital Photos to register Morphology
Gauging
Profile gauge
Pitting gauge
UT from outside to assess Thinning Corrosion Rates
UT : Measurement points (MP), using digital equipment
UT-A : Measurement points, using A-screens
UT-B : Line Scans
UT-C : Area Scans
UT-G : Grid Scans
Note:
Type of scan to be based on both morphology and extent of attacked area
72
Assessment Thinning of Equipment
Grid scans
Note:
73
Assessment Thinning of Equipment by UT
Reliability related to Morphology
Morphology UT UT-A UT-B UT-C UT-G
General Even
General Uneven
Localized Even
Localized Uneven
Wide Pitting
Medium Pitting
Narrow Pitting
Notes:
- UT is to be carried out from the outside. Therefore, areas with uneven
and/or localized corrosion observed during Internal Visual Inspection must be
marked at the outside.
- Both type and extend of UT should be related to both the extent and the
morphology of the attacked areas 74
Inspection Equipment on Thinning by UT during T/A
External inspection
UT on locations
defined on an equipment sketch
marked on the equipment item
Internal inspection
Discovery of areas with localized and/or uneven thinning
Digital Photos to register Morphology
Gauging to register inspection findings
Discovered areas
o To be defined on equipment sketch
o To be marked on outside of equipment item
UT-scanning for thinning of discovered areas from outside
75
Internal Inspection Equipment on Thinning during T/A
Start
Localized
and/or
Yes
uneven thinning
discovered
Uneven
General No
Thinning
Apply selected
scanning method
from the outside
76
77
1.5 Reporting
78
Reporting Findings
VI, supported by gauging
Format as defined in ITPs
Application of Registration Scheme
UT
Format as defined in ITPs
Equipment sketch defining locations
Table recording the results per location
Gauging and ET of tubes of bundles
Format as defined in ITPs
Sketch of bundle defining selected tubes
Table recording the results per examined tube
79
Reporting Findings
Format for VI, supported by gauging (example for vessels)
INSPECTION FINDINGS
Component Findings/Results
Shell Text one liners. According to Registration Inspection Findings for Thinning
Dished Ends Text one liners. According to Registration Inspection Findings for Thinning
Nozzles & joint faces Text one liners. According to Registration Inspection Findings for Thinning
Lining/Cladding Text one liners. According to Registration Inspection Findings for Thinning
Welds Text one liners. According to Registration Inspection Findings for Thinning
Vortex breaker Text one liners.
Coil Text one liners.
Baffles, demister, etc. Text one liners.
Level legs Text one liners.
Skirt saddles Text one liners.
Insulation Text one liners.
Insulation supports Text one liners.
Pressure Bolting Text one liners.
Holding down bolts Text one liners.
General All significant findings to be reported with reference to attached equipment sketch (key points) 80
Reporting Findings
N11
Format for UT
N37
46A 48A
46B 48B
N8
N17
N7
N35
45B
45A
N1
Tnom DCA MAT Feb. 2009 Next T/A
Body
mm mm mm Min. Max. Min. Max.
Btm dished end
Shell
Top dished end
81
Reporting Findings
Format for Tube-end Gauging
82
Reporting Findings
Format for ET
83
Retreivability Inspection Findings
84
Retreivability Inspection Findings
Examples
SW NE
Top
SE NW
Btm
85
2. Stress Corrosion Cracking (SCC)
2. Contents
2.1 Mechanism
2.2 Main types of SCC
2.3 Inspection
2.4 Reporting
86
2.1 Mechanism
87
Stress Corrosion Cracking (Wet)
Sequence of Events leading to SCC
Mechanisms
Brittle film rupture
Enobled layer
Passive film
Active path
Slip assisted dissolution
Hydrogen assisted cracking 88
Stress Corrosion Cracking
Models for Intergranular type of Cracking
90
Stress Corrosion Cracking
Caustic Cracking S2
Polythionic Stress Corrosion Cracking S3
Chloride Stress Corrosion Cracking S4
Amine Stress Corrosion Cracking S5
Wet H2S Cracking S1
Carb.-/Bi-Carb. Stress Corrosion Cracking S1-1
91
Structure of presentations Stres Corrosion Cracking
Specifics
Description
Examples
Description
Might occur when CS in the as-welded condition is exposed to a caustic
environment at (elevated) temperatures.
Notes:
1. Allowable temperature depends on caustic concentration
2. PWHT will extend the allowed operating temperature
From 70 to 110 C for 20% NaOH
3. Factors originating Caustic Cracking
Steam tracing
Steaming out
Temperature excursions 93
Caustic Cracking: S2
Materials
CS is commonly applied for caustic service
Ni-alloys are applied, when CS does not meet the
requirements anymore
94
Caustic Cracking: S2
Morphology
Microscopic : Intergranular cracking
Macroscopic : Cracking in weld region
Example
95
Polythionic Stress Corrosion Cracking (PA-SCC): S3
Specifics
Process related
Typical Equipment : HTs, HCU
Description
Might occur when sensitized stainless steel, which has operated in an
H2/H2S environment (reducing sulphidizing), is exposed to the
atmosphere (O2 & humidity).
96
Polythionic Stress Corrosion Cracking (PA-SCC): S3
Materials
Sensitized stainless steel plate material is susceptible to PASCC
347 has highest resistance to sensitization
Sensitization
Operation at temperatures > 400 C for 321/347
Due to fabrication, e.g. welding & PWHT of base metal (1Cr, 2Cr)
97
Polythionic Stress Corrosion Cracking (PA-SCC): S3
Morphology
Microcopic : Intergranular cracking
Macroscopic
Mud type cracking
Elongated cracking
Example
98
Intergranular Cracking
Polythionic Stress Corrosion Cracking (PA-SCC): S3
Examples
99
Chloride Stress Corrosion Cracking (Cl-SCC): S4
Specifics
Process related
Typical Equipment/Unit : CDU(Ovhd), HMU
(streams containing free water and chlorides)
Description
Might occur when stainless steel is exposed to an aqueous environment
above 50/60 C, containing Chlorides.
Presence of O2 enhances, whereas high pH reduces susceptibility
100
Chloride Stress Corrosion Cracking (Cl-SCC): S4
Materials
Susceptible materials are Stainless Steel of the type 18Cr8Ni
Up to 10 ppmw is tolerable in absence of O2
When O2 present than 1 ppmw might be sufficient
316 has highest resistance to Cl-SCC
At pH > 10 relatively high levels can be tolerated: up to 1000 ppmw
Relatively Resistant Materials
Super austenitic SS with Mo > 6%, e.g. 19hMo, 254SMO
Duplex Stainless Steels: DSS-2507 (difficult to weld)
Resistant Materials
Nickel Alloys with Ni% > 40,e.g. Monel 400, Incoloy 825, Inconel 625 and
Alloy C-276.
101
Chloride Stress Corrosion Cracking (Cl-SCC): S4
Morphology
Microscopic : Transgranular Branched Cracking
Macroscopic
Branched cracking
Crazy cracking
Example
102
Transgranular Branched cracking
Chloride Stress Corrosion Cracking (Cl-SCC): S4
Examples
Specifics
Process related
Typical Equipment/Unit : Amine Units, Absorbers in misc. Units
Description
Might occur when CS in the as-welded condition is exposed to an
aqueous lean amine solution.
Decreasing risk : MEA > DEA > MDEA > DIPA > SULFINOL
Notes:
1. Fresh amine solutions are not susceptible
2. Boundary between lean and fat (rich) solvent for gas loading
is 0.1 mol acid gas per mol amine
104
Amine Stress Corrosion Cracking (A-SCC): S5
Material
Common material is CS
Susceptible to A-SCC in the as-welded condition
PWHT prevents A-SCC
105
Amine Stress Corrosion Cracking (A-SCC): S5
Morphology
Microscopic : Intergranular Cracking
Macroscopic : In weld regions
Example
A-SCC in an elbow
Intergranular Cracking
106
Wet H2S-cracking: S1
Specifics
Process related
Typical Units : CDU, HVU, TGU, HTU, HDS, HCU, FCC
(almost all units containing H2S)
Description
Might occur when a susceptible steel is exposed to an aqueous
environment containing hydrogen sulphide, leading to hydrogen
charging
107
Wet H2S-cracking: S1
Mechanism
H2
Medium
Fe2+
e e Habs
Steel
Hinterstitial
H2S H+ + HS-
Fe2+
H+ Hads
e Habs
Steel
Hinterstitial
111
Wet H2S-cracking: S1
Examples
Sulphide Stress Cracking (SSC)
113
Wet H2S-cracking: S1
Examples
Hydrogen Induced Cracking (HIC)
114
Wet H2S-cracking: S1
Examples
Stress Oriented HIC (SOHIC)
Cracking in Weld
115
Wet H2S-cracking: S1
Examples
Stress Oriented HIC (SOHIC)
116
Wet H2S-cracking: S1
Inspection
SSC : As for SCC
HB : Visual
HIC & SOHIC : Combination of Special UT-techniques by Contractor
Normal wave, shear wave and ToFD
In general automated
117
Carbonate Stress Corrosion Cracking: S1-1
Specifics
Process related
Typical Units : FCC (units containing H2S and CO2)
Description
Might occur when CS/LAS is exposed to an environment of alkaline
sour water (pH>7.6), containing CO3=/HCO3-, when the material is in the
as-welded condition.
118
Carbonate Stress Corrosion Cracking: S1-1
Materials
CS and LAS in the PWHT-condition is resistant to Carb. SCC
Morphology
Microscopic : Intergranular cracking
Macroscopic : Cracking in weld region
119
Carbonate Stress Corrosion Cracking: S1-1
Example
Cracking at Stress Raiser
Penetration of Root Weld
Intergranular Cracking
120
2.3 Inspection
121
Assessment Cracking in Equipment
Surface breaking
Near side
MT or PT
oRegistration by digital photos
Far side
UT-shearwave, when examined from other side
Embedded
Combination of specialized UT-techniques
122
Registration Inspection Findings for Cracking
Density/Number per
Extent
Morphology Code Area
123
2.4 Reporting
124
Reporting Findings
See format for VI as defined in ITP
INSPECTION FINDINGS
Component Findings/Results
Text one liners. According to Registration Inspection Findings for Cracking
Shell
Reference to report, when applicable (HIC & SOHIC)
Text one liners. According to Registration Inspection Findings for Cracking
Dished Ends
Reference to report, when applicable (HIC & SOHIC)
Text one liners. According to Registration Inspection Findings for Cracking
Nozzles & joint faces
Reference to report, when applicable (HIC & SOHIC)
Lining/Cladding Text one liners. According to Registration Inspection Findings for Cracking
Welds Text one liners. According to Registration Inspection Findings for Cracking
Vortex breaker Text one liners.
Coil Text one liners.
Baffles, demister, etc. Text one liners.
Level legs Text one liners.
Skirt saddles Text one liners.
Insulation Text one liners.
Insulation supports Text one liners.
Pressure Bolting Text one liners.
Holding down bolts Text one liners. 125
General All significant findings to be reported with reference to attached equipment sketch (key points)
3. High Temperature Degradation Mechanisms
3. Contents
3.1 Types of HT Degradation
3.2 Reporting
126
3.1 Types of High Temperature Degradation
127
High Temperature Degradation
High Temperature Hydrogen Attack H1
Creep H2
Temper Embrittlement H3
Sigma-phase Embrittlerment H4
Sensitization H5N
Hydrogen Embrittlement H8N
128
Structure of presentations High Temperature Degradation
Specifics
Description
Mechanism
Materials
Morphology
Examples, when available
Inspection
129
High Temperature Hydrogen Attack (HTHA): H1
Specifics
Process related
Typical Units : CCR, HTs, HCU, Isomer, HMU
Description
Might occur when CS/LAS is exposed at high temperatures (> 240 ) to
an environment containing H2 (ppH2 > 7 bara)
130
High Temperature Hydrogen Attack (HTHA): H1
Mechanism
Atomic hydrogen diffuses into steel & reacts with carbides in the steel:
Fe3C + 4H 3Fe + CH4
Increased Resistance
No Hydrogen Attack !!
2.25%Cr-1Mo Steel
1%Cr-0.5Mo steel
Partial Pressure of H2
CS
Total Decarburization & Fissuring
Inspection
Advanced Ultrasonic Backscatter Techniques (AUBT)
to be carried out by a Contractor
133
Creep: H2
Specifics
Non-Process related
Typical Equipment : Heaters, HP-Steam Systems
Description
Time dependent deformation of materials under constant load at
elevated temperatures
Note:
Driving Force are the primary stresses: internal pressure and dead weight
134
Creep: H2
Mechanism
Development of failure
Original structure
Isolated cavities
Oriented cavaties
135
Creep: H2
Materials
Material Threshold temperature C
CS 410
1 Cr Mo 500
2 Cr 1 Mo 480
5 Cr Mo 470
9 Cr 1 Mo 515
304H 580
347H 595
136
Creep: H2
Morphology
137
Creep: H2
Inspection/Assessment
Dimensional measurements
Gouging deformation
Destructive techniques
Accelerated creep test on samples (cut-outs)
Non-Destructive techniques
Specialised UT (Conam)
Replica examination
Calculation of Usage Factor U
Based on actual operating conditions
Monitoring, when U > 0.6
138
Temper Embrittlement: H3
Specifics
Non-Process related
Typical Units : HTs & HCU (Rs & F/E-HEs)
Description(1)
Loss of ductility of low alloy CrMo-steels, when held within or cooled
slowly through a certain temperature range
Notes:
1. Temperature range : 370 575 oC
2. Most rapidly : 460 oC
3. Brittle at temperatures below 150 oC
139
Temper Embrittlement: H3
Description(2)
Energy
TTNew TTEmbrittled
Hammer
Ductile
10 mm
2 mm Tshift
New
Tshift Embrittled
Charpy Impact Testing Brittle
Required energy
to break the specimen
Test Temperature
140
Temper Embrittlement: H3
Mechanism
Segregation of impurity elements at the grain boundaries
Sb, P, Sn & As
Materials
Inspection
Not applicable
Mitigation
Limiting stresses at lower
Reactor failed after hydrotest temperatures
S/U S/D procedure
No hydrotest
142
Sigma-phase Embrittlement: H4
Specifics
Non-Process related
Typical Unit : FCC
Description
Loss of Ductility of Stainless Steels resulting from the precipitation of
Sigma-Phase (hard brittle phase containing about 50% Cr) at elevated
temperatures
Notes:
1. Temperature range : 540 924 oC
2. Most rapidly : 750 / 850 oC
143
Sigma-phase Embrittlement: H4
Mechanism
Precipitation of sigma-phase at grain boundaries or within grains
Growth into ferrite grains : few hrs
Growth within austenite grains : few thousand of hrs
Materials
Growth into ferrite grains
Weld metals of Stainless Steels of the type 18Cr8Ni
Stainless Steels with %Cr > 17 (DSS)
Growth within austenite grains
Stainless Steels of the 300-series with high %Cr, e.g. 310 (&HK40)
Alloy 800 less susceptible than 300-series of SS
144
Sigma-phase Embrittlement: H4
Morphology
145
Sigma-phase Embrittlement: H4
Inspection
Not applicable
Mitigation
Growth into ferrite grains
Ferrite < 7 % for weld metal SS type 18Cr8Ni
Growth within austenite grains
S/U S/D procedure
No chock loads
146
Sensitization: H5N
Specifics
Non-Process related
Typical Units : HTs, HCU
Description
Sensitisation refers to the precipitation of carbides at grain boundaries
of Stainless Steels of notably the 300-series, resulting in depletion of Cr
in the areas adjacent to the grain boundaries.
Notes:
1. Range for sensitisation : 425 870 oC
- Within minutes : 650 oC
- Within hours : 500 & 800 oC
- Within years : 425 & 870 oC
2. When the precipitation is relatively continuous, the depletion
leaves the steel susceptible to intergranular corrosion (e.g. PA-SCC).
147
Sensitization: H5N
Mechanism
Precipitation of carbides at grain boundaries
Difference in diffusion velocity of C and Cr
Solution Annealed 18-8 Stainless Steel Sensitised 18-8 Stainless Steel
Grain Cr-Carbides
boundaries
Cr-Depleted Zones
NormalStructure
%Cr
Grain
Boundary
X-Section over 18
Depleted Zone
Cr-Depleted
Zone
149
Sensitization: H5N
Morphology
150
Sensitization: H5N
Inspection
Not applicable
Testing
DOS-testing (Degree Of Sensitization)
Mitigation
Selection of grade of 18-8 SS
Low Carbon Grades
Chemical Stabilization
Heat treatment
Stabilizing
Homogenizing
151
Hydrogen Embrittlement: H8N
Specifics
Process related
Typical Units : CCR, HTs, HCU, Isomer, HMU
Description
Loss of ductility of CS and LAS when exposed at high temperatures to
an environment containing H2.
152
Hydrogen Embrittlement: H8N
Mechanism
Dissociation of molecular H2 into atomic H
Diffusion of H into the steel
Restricting plastic flow
Enhanced susceptibility to brittle fracture initiating at:
o Existing defects,
o Locations of stress concentration,
when exposed to temperatures below 150 C
Materials
CS
LAS: Mo, 1Cr, 1Cr, 2Cr
153
Hydrogen Embrittlement: H8N
Morphology
Inspection
Not applicable
154
Hydrogen Embrittlement: H8N
Inspection
Not applicable
Mitigation
Limitation of stresses (S/U-S/D Procedure)
o H-content > 3 ppm
Pressure < 1/3 Design value
Heating-/Cooling rate < 42 C/hr
155
3.2 Reporting
156
Reporting Findings
See format for VI as defined in ITP
INSPECTION FINDINGS
Component Findings/Results
Shell Text one liners. Reference to report, when applicable (HTHA & Creep)
Dished Ends Text one liners. Reference to report, when applicable (HTHA & Creep)
Nozzles & joint faces Text one liners. Reference to report, when applicable (HTHA & Creep)
Lining/Cladding Text one liners.
Welds Text one liners. Reference to report, when applicable (HTHA & Creep)
Vortex breaker Text one liners.
Coil Text one liners.
Baffles, demister, etc. Text one liners.
Level legs Text one liners.
Skirt saddles Text one liners.
Insulation Text one liners.
Insulation supports Text one liners.
Pressure Bolting Text one liners.
Holding down bolts Text one liners.
General All significant findings to be reported with reference to attached equipment sketch (key points) 157
End
158