H2S CORROSION

1
H2S CORROSION – METAL LOSS

 Formation of a thin protective FeS surface film often means general

corrosion rates are low on steels
 Main risk is localised pitting corrosion where film is damaged
 Pitting will be galvanically driven

2
WET H2S CORROSION

 H2S is soluble in water

 Produces a weak acid and lowers the pH

H2S  H+ + SH-
 At low concentrations, H2S helps form protective FeS film

 Main risk is localised pitting corrosion which can be rapid

 H2S also poisons combination of atomic hydrogen into molecular

hydrogen
H+ + e-  H
H + H  H2
Atomic hydrogen
- dangerous to
X steels!!

3
CRACKING IN SOUR SERVICE
H2 H+ Fe2+
S2-
H
FeS Film

Metal Matrix
H

Applied Stress No Applied Stress

Higher Strength Steels YS > 500 MPa Low Strength Steels YS < 550 MPa

H2
H H
HH H2
H
4
SULPHIDE STRESS CRACKING (SSC)
Key parameters:
 pH and pH2S
HAZ WELD HAZ
 Domain diagrams for carbon steel
 Material hardness
 High strength steels and areas of
high hardness susceptible.
 Temperature
 Maximum susceptibility at low Hardness
readings
temperatures for carbon steels (15-
25°C), higher for CRAs (5-70°C).
 Stress
 Cracking promoted by high stress
levels e.g. residual welding

5
PROTECTION AGAINST SSC

 Avoid wetness Upgrade to CRAs

 Minimise hardness  Martensitic and duplex
 Guidance on limits in stainless steels have limited
ISO 15156 resistance
 Optimise microstructure  H2S limits for duplex and super-
and minimise residual duplex steels are complex
stresses
 Function of temperature,
pH, chlorides, pH2S
 Nickel-base alloys such as 625
and 825 have high resistance
 Testing: NACE TM0177

6
DESIGNING FOR H2S SERVICE
 Materials requirements
 Reference ISO 15156 and GP 06-20

 pH2S and pH

 Temperature

 Chlorides

 Hardness limits

 Welding QA/QC (HIC)

 Maintain hardness limits

 HIC testing for plate products

7
CO2 CORROSION

8
CO2 - CONTAINING ENVIRONMENTS

 CO2 always present in produced

fluids
 Corrosive to carbon steel Mechanism
when water present
CO2 + H2O  H2CO3
 Most CRAs have good
H2CO3 + e- HCO3- + H
resistance to CO2 corrosion.
2H H2
Fe  Fe2+ + 2e-
Fe + H2O + CO2 FeCO3 + H2

9
TYPES OF CO2 DAMAGE

General & pitting corrosion Mesa corrosion

Flow-assisted-corrosion (CO2) Localised weld corrosion

10
CO2 CORROSION IN A PRODUCTION
FLOWLINE

• 6” CS production flowline (Magnus, 1983)

• 25mm thick, 90bar, 30°C, 2%CO2
• Heavily pitted pipe wall and welds (not
necessarily uniform corrosion)
• Didn’t fail – removed due to crevice
corrosion of hub sealing faces
11
FACTORS IN CO2 CORROSION
For an ideal gas mixture, the partial
 Main factors pressure is the pressure exerted by
 pCO2, temperature, velocity, pH one component if it alone occupied
the volume. Total pressure is the sum
- CO2 prediction model of the partial pressures of each gas
component in the mixture

Temperature, (ºC) pCO2 (bar) Carbon steel

corrosion rate
(mm/yr)
130 0.6 7
75 0.6 6

149 30 >50

12
EFFECT OF SAND ON CO2 CORROSION
 Produced sand can affect inhibitor efficiency
 Inhibitor adsorption loss

 Sand (and other solid) deposits give increased risk of localised corrosion;
 Prevent access of corrosion inhibitor to the metal

 Provide locations for bacteria proliferation

 Galvanic effects (area under deposit at more negative potential than

area immediately adjacent to deposit)
 Formation of concentration cells/gradients

13
MITIGATION OF CO2 CORROSION
 Internal CO2 corrosion of carbon steel needs to be managed
 Usually mitigate by chemical inhibitors

 Simple geometries only (mainly pipelines)

 Assume inhibitor availability (90-95%)

 Inhibited corrosion rate of 0.1mm/year

 Remaining time at full predicted corrosion rate

 Apply a corrosion allowance for the design life

 If calculated corrosion allowance >8mm use CRAs

14
CO2 CORROSION INHIBITION

 Filming type
 Retention time
 Continuous injection
 Adsorption onto clean surfaces

Clean steel

15
CO2 + H2S CORROSION – METAL LOSS
CO2/H2S > 500 CO2 dominates

500 > CO2/H2S > 20 mixed CO2/H2S

20 > CO2/H2S > 0.05 H2S dominates

 H2S corrosion (CO2/H2S < 20)

 Initial corrosion rate high

 Protective FeS film quickly slows down corrosion to low level

 The corrosion rate is much less than the Cassandra prediction

16
EROSION & EROSION-CORROSION

17
 FLOW REGIMES

• Various multi-phase flow Liq Ga

regimes possible; uid s
− erosion characteristics Bubble (bubbly) flow Plug flow

− distribution of phases Gas Gas

− carrier phase for solids Liq Liq
uid flow
Stratified uid flow
Wave (wavy)
• Flow regimes with
particles in the gas show
higher erosion rates than Gas Ga
Liq Liq
those with particles in the s
uid flow
Annular uidSlug flow
liquid phase.

Churn flow Mist (spray) flow

18
EROSION & EROSION-CORROSION

 Erosion
 Caused by high velocity impact
& cutting action of liquid
and/or solid particles
 Erosion failures can be rapid

 Erosion-corrosion
 Occurs in environments that
are both erosive and corrosive.
 Erosion and corrosion can be
independent or synergistic. Erosion of tungsten
carbide choke trim

19
TYPICAL VULNERABLE AREAS FOR
EROSION
 Areas wherever flow is restricted or
disturbed
 T-pieces, bends, chokes, valves, weld
beads
 Areas exposed to excessive flow rates
 Sand washing
 Washing infrequently allowing sand to
Trinidad accumulate
 High pressure drop during washing of
separators
 Sea water systems
 High flow areas in water injection /
cooling systems

Algeria (duplex)
20
EROSION IN PIPING

 Sand accumulation
 Build up of sand in a test
separator
 Pressure drop
 Large pressure drop across sand
drain pipework during washing
 Rapid failure
 Occurred within 2 minutes of
opening the drain

Erosion at bend

21
EROSION IN A VESSEL
 Sand allowed to accumulate in separator
 Wash nozzles embedded in sand

 PCV not working properly

 High pressure / flowrate Water
spray
 Nozzle not erosion-resistant

 Erosion of wash nozzle

 Spray changed to a jet causing erosion

of shell
 Local changes to operating procedures
not communicated Water
jet
 Frequency of sand washing

 Risk not captured or assessed in RBI

22
EROSION OF SANDWASH NOZZLE

Progressive nozzle damage

23
EROSION-CORROSION

 Occurs in environments that can be erosive and corrosive.

 Erosion and corrosion can either be:
 independent of each other;

 wastage equals sum of individual wastage rates

 synergistic;

 wastage rate > sum of individual rates

 localised protective film breakdown at bends, elbows

areas of turbulence

24
IMPINGEMENT

 Water speed or local turbulence damages or removes protective

film
 90-10 Cu-Ni susceptible to internal erosion-corrosion
(impingement) at velocities >3.5ms-1
 Water-swept pits (horse-shoe shaped)

25
CAVITATION

 Occurs at high fluid velocities

 Formation & collapse of vapour bubbles
in liquid flow on metal surface.
 No solids required
 Typical locations
 Pump impellers (rapid change in
pressure which damages films)
 Stirrers, hydraulic propellers
 Use erosion resistant materials
 Stellite, tungsten carbide

26
GALVANIC CORROSION

 Three conditions are required for galvanic corrosion;

 A conducting electrolyte (typically seawater).
 Two different metals in contact with the electrolyte.
 An electrical connection between the two metals.
 Relative positions within the electrochemical series (for given
electrolyte) provides driving potential and affects rate.
 Corrosion of base metal (anode) stimulated by contact with noble
metal (cathode).
 Relative area of anode and cathode can significantly affect
corrosion rate.
 Higher conductivity increases corrosion e.g. presence of salts

27
GALVANIC CORROSION – FIREWATER
PIPING
 Firewater – CuNi / super duplex
stainless steel connections.
 4”CuNi pipe with a 550mm
isolation spool (i.e. 5x OD)
 Leaks experienced on CuNi spools
at welds
 Same problems with CuNi / 6Mo

28
GALVANIC CORROSION - SEAL RINGS

 ETAP platform
 Techlok joints in a firewater
piping system
 Piping: super-duplex

 Seal rings: 17-4PH

29
DEALLOYING OF BRASS

 Brass tubesheet in seawater

service
 Brass is Cu-Zn alloy

 Cu is more noble than Zn

 Zn dissolves preferentially
leaving Cu behind
 Result
 Loss of strength

 Difficult to seal

 Remedy
 Add arsenic to the brass

30
MITIGATION OF GALVANIC CORROSION
 Avoid dissimilar materials in
seawater system designs
 MoC for later changes
 Avoid small anode/large
cathode
 Avoid graphite gaskets & seals
 Avoid connecting carbon steel
to titanium alloys
 Galvanic corrosion or
hydrogen charging of
titanium may occur
 Electrical isolation between
different alloy classes
 Install distance spools, separation
of at least 20x pipe diameters
 Solid non-conducting spool e.g.
GRP
 Line the noble metal internally
with an electrically non-
conducting material e.g. rubber
 Apply a non-conducting internal
coating on the more noble material.
Extend coating for 20 pipe
diameters.
31
Example : CuNi-Super duplex

Distance spool: solid, non-conducting material e.g. GRP

Distance spool: noble metal internally lined with an electrically non-

conducting material such as rubber

Apply a non-conducting internal coating on the more noble material.

32
OTHER CORROSION MECHANISMS

33
CORROSION DUE TO CHEMICALS
 Chemicals can be corrosive
 Carbon steel OK for non-corrosive chemical
piping, e.g. methanol
 Corrosive chemicals (e.g. concentrated
solutions of inhibitors and biocides) require
CRAs – vendor will specify
 316 SS is typical
 Notable exceptions:
 Hypochlorite: very corrosive, titanium or GRP
piping required
 Avoid titanium alloys in dry methanol service
due SCC SCC of a titanium seal
exposed to pure
methanol instead of
5% water content
34
CORROSION DUE TO CHEMICALS

• Carbon steel open drain pipework.

• Seepage of scale inhibitor (passing
valve)
• Scale inhibitor pH <2.
• Chemical entered drains, not flushed

35
INJECTION POINT ISSUES

 Inadequate mixing – corrosion

 Intermittent use
 switch off when not flowing
 Areas affected
 Impingement / turbulent
areas
 Bends and low points
 Use quill/other mixer
 Upgrade material
 Thicker schedule Injected Fluid
 Valve arrangement
 Make self-draining
 Enable quill removal
Main Flow Impingement

36
HIGH TEMPERATURE CORROSION

 Environments less common in E&P

 Flare tips, fired heaters, boilers
 Oxidation
 Oxidation significant >530°C
 Oxidation rate varies with temp, gas
composition and alloy Cr content
 Firetubes: usually CS, but Cr-Mo
alloys needed for high temps
 Flare tips: 310 SS, alloy 800H
 Other high temperature mechanisms
 sulphidation (H2S and SO2)
 carburizing, metal dusting, hot salt
 thermal fatigue and creep

37
AMINE STRESS CORROSION CRACKING

 Material: carbon/low-alloy steels

 Environment: aqueous amine systems
 Cracking due to residual stresses at/next
to non-PWHT’d weldments
 Cracking develops parallel to the weld
Intergranular cracking
 Mitigation:
 PWHT all CS welds including repair and
internal/external attachment welds.
 Use solid/clad stainless steel

 304 SS or 316 SS

Amine piping welds require

PWHT to avoid SCC
38
CORROSION IN GLYCOL SYSTEM
 Glycol usually regarded as benign
 Corrosion in glycol regeneration systems
usually due to;
 Acid gases absorbed by rich glycol or

 Organic acids from oxidation of glycol

and thermal decomposition products
 Condensation of low pH water giving
carbonic acid attack.
 Risk recognised in design
 On-skid: CRA piping & clad vessels

 However, off-skid piping mix of

regular CS and LTCS

39
CORROSION FATIGUE

 Combined action of cyclic tensile

stress and a corrosive environment
 Fatigue is caused by cyclic stressing
below the yield stress
 Cracks start at stress raisers
 Can occur due to vibration e.g.
smallbore nozzles & with heavy
valve attachments
 Presence of corrosive environment
exacerbates the problem
 Can lead to pitting, which acts as
stress concentrators

40
EXAMPLE OF CORROSION FATIGUE

 2” A106 GrB carbon steel piping

 Wet gas service, 1.2%CO2 and
160ppm H2S
 Operating @ 120°C and 70bar
 Elbow exposed to vibration (used in a
gas compression train)
 Crack located at 12 o'clock position
 Crack initiated internally

41
EXTERNAL CORROSION – SURFACE
FACILITIES

42
EXTERNAL CORROSION

 External corrosion of unprotected steel surfaces

 External corrosion of coated surfaces
 Corrosion under insulation (CUI)
 Corrosion under fireproofing (CUF)
 Pitting & crevice Corrosion
 Environmental cracking

43
WHERE DOES IT OCCUR?
 Bare steel surfaces
 At locations of coating breakdown
 Under deposits such as dirt, adhesive tape or nameplates
 Mating faces between pipe/pipe support saddles & clamps
 Isolated equipment not maintained or adequately mothballed
 Water sources include:
 sea spray and green water (FPSO or semi-sub)
 rain
 deluge water
 leaking process water
 condensation
 downwind of cooling towers.

44
WHAT DOES IT LOOK LIKE?

 Damage can be extensive or localised.

 Corrosion can be general attack, pitting or cracking.
 Seen as flaking, cracking, and blistering of coating with
corrosion of the substrate.

45
APPEARANCE

 Carbon/low alloy steels usually

covered in compact scale/thick scab
 Stainless steels have light stains on
the surface possibly with stained
water droplets and / or salts.
 Corroding copper alloys covered in
blue/green corrosion products.

46
PIPING, SUPPORTS & CLAMPS

47
NOT JUST CARBON STEEL

 25Cr super-duplex (PREN ≥40)

 Seawater service
 12 months exposure in tropical
climate
 External corrosion along welds
 Poor quality fabrication

48
CORROSION OF BOLTS AND FASTENERS
 Bolted joints
 Onshore and offshore: exposed to frequent wetting

 Low alloy bolts

 General or localised corrosion

 Galvanic corrosion in stainless steel flanges

 CRA bolts susceptible to pitting and/or SCC

 Crevice corrosion under bolt heads and nuts
 Hydrogen embrittlement possible
 Fatigue

49
CORROSION OF BOLTS AND FASTENERS

General corrosion Galvanic corrosion

Crevice corrosion Stress corrosion cracking 50

FLANGED CONNECTIONS
 Corrosion
 General surface corrosion
 Galvanic corrosion
 e.g. 316 SS / carbon steel
 Use of graphite gaskets
 Potential problems
 Failure of flanged connection due
to corroded fasteners
 Joint leak
 Corrective actions
 Change gasket/fastener materials
 Replace graphite gaskets with non-
asbestos or rubber material

51
CORRODED FASTENERS (SEAWATER
SERVICE)

Location of graphite gaskets

52
STRUCTURES / VALVES

 Valves
 Valve handles
 Chain-wheels
 Valve body
 Structures
 Stairways and walkways
 Gratings, ladders, handrails
 Cable trays and unistruts
 Threaded plugs
 Valve bodies, xmas trees,
piping
 Dissimilar metals

53
COATING DAMAGE AND BREAKDOWN
 Deterioration of coating with time
 All paints let water through - continuously wet areas will fail
 Poor original surface preparation / paint application
 Mechanical damage
 Small area of damage can lead to major corrosion

54
CORROSION UNDER INSULATION (CUI) AND
CORROSION UNDER FIREPROOFING (CUF)

 CUI
 Water seeps into insulation and
becomes trapped, results in
wetting and corrosion of the metal
 Carbon steel corrodes in the
presence of water due to the
availability of oxygen.
 CUF
 Same mechanism except water
gets behind the fireproofing.

55
INSULATION

 Typical insulation types;

 Process

 Personnel protection
(PP)
 Winterisation

 Acoustic
Mitred joint
 Challenge the need
 Remove unnecessary
insulation
 Replace PP with cages ‘Lobster-back’ joint

Pre-formed bends
56
CUI INCIDENT

 4” gas compression recycle line

 Operating pressure, 35bar
 3 bar pressure surge

 Temperature: 50ºC
 6.02mm nominal WT
 Rockwool insulation
 Extensive corrosion – rupture
 Unusual, burst rather than leaked

57
 CUI GAS LEAK
 2” fuel gas piping outside edge
of platform - exposed
 CS, heat-traced, Rockwool
 Operating @ 5bar, 45°C,
5.4mm NWT
 Failed during plant start-up
 External corrosion scale, CUI
 Focus on internal corrosion
 Previous survey found defect
in an adjacent line.
 Failed line in survey but not
failed area.
 Features selected from
onshore not site survey
58
PIPING CUI

• 4” CS hydrocarbon line
• 55°C, inlet to PSV (153 bar)
• Thermally-sprayed aluminium (TSA)
• CUI found, radiographed – ok to
refurbish.
• Found during needle-gunning
(paint removal)
• Max pit depth 10mm
• Insulation permanently removed

59
CUI ON PRESSURE VESSEL

 CS offshore vessel
 Operating at 85°C and 11 bar
 PFP coating (passive fire
protection)
 Extensive corrosion scabbing
on both sides of vessel.
 Scaling runs in two horizontal 400x300x30mm
distinct lines along each side.
 Scaling directly above lower
seam of insulation
 location of water retention.

400x100x25mm
60
EXTERNAL PITTING & CREVICE CORROSION

 Stainless steels in marine

environments (chlorides, O2)
 316L stainless steel
commonly used for instrument
tubing
 Particularly susceptible at
supports and fittings.
 Primary mitigation is materials
selection (higher PREw)
 Tungum, 6Mo, super-duplex

 Alternative mitigation methods

(coating, cleaning), not easy or
practical.

61
INSTRUMENT TUBING
(316 SS AND SUPER-DUPLEX)
316 SS tubing super-duplex tubing

316 SS (pitting/crevice corrosion) super-duplex (no pitting)

62
CREVICE CORROSION UNDER
CLAMPS/SUPPORTS

 Pitting and crevice

corrosion of 316ss piping
 Clamps

 Plastic retaining
blocks

63
EXTERNAL CHLORIDE STRESS CORROSION
CRACKING
 Mechanism same as internal chloride SCC however:
 Numerous variables influence susceptibility therefore guidance
differs
 Material, stress, chlorides, oxygen and temperature
 No absolute guidance available, seek expert advice

Chloride SCC is characterised

by trans-granular crack paths

64
EXTERNAL STRESS CORROSION CRACKING

 UK HSE:
 Coat 22Cr duplex >80°C
 NORSOK M-001 SCC temp limits:
 22Cr duplex >100°C
 25Cr super-duplex >110°C
 Recent testing has shown failures at 80°C
 now recommend 70°C as limit
 Reliant on external coatings to act as barrier
(isolate from environment)
 Beware solar heating - can raise external
temperature above threshold limits!
 SCC failure of 316L

65