corrosion-in-oil-gas.ppt
DESCRIPTION
Corrosion in Oil and gasTRANSCRIPT
CORROSION AND
ITS PROTECTION IN OIL & GAS PRODUCTION
CORROSION IN OIL FILED : INTERNAL AND EXTERNAL THREATS
INTERNAL THREATS
WELL TREATMENT INFLUENCED
WATER CARRY OVER
UNDERDOSING DEMULSIFIER
INJECTION PUMP with LOW CAPACITY
UNDERDOSING CORROSION INHIBITOR
WATER SETTLE OUT
CORROSION CAUSES
5
Typical E&P process conditions• Temperature
– Typical E&P process temperatures range from -100ºC to >200ºC
– Corrosion rates increase with temperature
• Pressure – Pressure: up to 10,000psi– Increase partial pressure of
dissolved gases • Flowrate & flow regime
– High-flow: erosion and corrosion-erosion.
– Low-flow or stagnant conditions promote bacteria
6
Internal corrosion
Hydrocarbon phase • Not normally corrosive at
temperatures experienced in production systems
• Corrosivity depends on extent and distribution of the aqueous and hydrocarbon phases.
Aqueous phase • Responsible for corrosion• Corrosion exacerbated by acid
gases & organic acids• CO2, H2S and O2 are the most
aggressive species • Chlorides increase corrosion• Generally,
– ‘no water, no corrosion’
7
Internal (process-side) damage mechanisms
• H2S
• CO2
• Solids & velocity effects• Chlorides – pitting, stress corrosion cracking• Oxygen (crevice / under deposit / differential aeration)• Galvanic corrosion• Preferential weld corrosion (PWC)• Microbially induced corrosion (MIC)• Liquid metal embrittlement (LME)• Chemicals
TYPICAL REACTIONS
9
There is no species more corrosive on a concentration basis than oxygen!
Corroded seawater injection tubing
Dissolved gas - effect on corrosion
0
5
10
15
20
25
0 1 2 3 4 5 6 7 8
C
orro
sion
Rat
e of
Car
bon
Stee
l
O2
CO2
H2S
Dissolved Gas Concentration in Water Phase, ppm
0 1 2 3 4 5 6 7 8 0 100 200 300 400 500 600 700 800 0 50 100 150 200 250 300 350 400
O2
H2SCO2
10
H2S CORROSION
11
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
12
Wet H2S corrosion
• H2S is soluble in water
– Produces a weak acid and lowers the pHH2S 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
hydrogenH+ + e- HH + H H2
XAtomic
hydrogen - dangerous to
steels!!
13
Cracking in sour service
HHH
H
H
Higher Strength Steels YS > 500 MPa Low Strength Steels YS < 550 MPa
Applied Stress No Applied Stress
H2
H2
H2 H+
S2-Fe2+
H
H
FeS Film
Metal Matrix
14
Sulphide stress cracking (SSC) Key parameters:• pH and pH2S
– Domain diagrams for carbon steel• Material hardness
– High strength steels and areas of high hardness susceptible.
• Temperature– Maximum susceptibility at low
temperatures for carbon steels (15-25°C), higher for CRAs (5-70°C).
• Stress– Cracking promoted by high stress
levels e.g. residual welding
HAZ WELD HAZ
Hardness readings
15
Protection against SSC
• Avoid wetness• Minimise hardness
– Guidance on limits in ISO 15156
• Optimise microstructure and minimise residual stresses
Upgrade to CRAs• Martensitic and duplex stainless
steels have limited resistance• H2S limits for duplex and super-
duplex steels are complex– Function of temperature,
pH, chlorides, pH2S
• Nickel-base alloys such as 625 and 825 have high resistance
• Testing: NACE TM0177
16
ISO 15156 SSC zones for carbon steel
0.0034bara 0.05psia
Service
Domain
Max hardness (parent metal,
HAZ, weld metal)
0 No requirements
1 300HV
2 280HV
3 250HV root 275HV cap
17
SSC limits for selected CRAs
Alloy pH2S limit (bara)
13% Cr martensitic 0.008
22% Cr duplex 0.10
25% Cr super-duplex 0.25
Alloy 825 No limit
Alloy 625 No limit
18
HIC / SWC / blistering
• Laminar cracking in plane of inclusions or blistering (HIC).
• Transverse cracking between laminar cracks on different planes (SWC).
Step-wise cracking Blistering of CS plate
Hydrogen
blisters
19
Avoiding HIC / SWC
• Avoid plate steels (rolled)– otherwise qualify by HIC test
• Control impurities e.g. S, P• Uniform microstructure• Use internal coatings
– isolate steel from process fluid• Testing: NACE TM0284
Banded
Uniform
20
ISO 15156 (NACE MR0175)• ISO 15156 combination of
– NACE MR0175 and NACE testing requirements TM0177 & TM0284– European Federation of Corrosion Guidelines No.16 & 17
• Part 1: General principles for selecting crack-resistant materials• Part 2: Cracking resistant carbon & low-alloy steels & cast iron• Part 3: Cracking resistant corrosion resistant alloys (CRAs)• Covers all cracking mechanisms• Goes beyond application of the 0.05 psia pH2S threshold for sour service
• It is the equipment user’s responsibility to select suitable materials• HIC/SWC of flat rolled carbon steel products for environments containing even
trace amounts of H2S to be evaluated
• BP ETP: GP 06-20 Materials for Sour Service
21
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
22
CO2 CORROSION
23
CO2 - containing environments
• CO2 always present in produced fluids– Corrosive to carbon steel
when water present– Most CRAs have good
resistance to CO2 corrosion.
MechanismCO2 + H2O H2CO3
H2CO3 + e- HCO3- + H
2H H2
Fe Fe2+ + 2e-
Fe + H2O + CO2 FeCO3 + H2
24
Types of CO2 damage
Mesa corrosion
Localised weld corrosion
Flow-assisted-corrosion (CO2)
General & pitting corrosion
25
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
26
Factors in CO2 corrosion
• Main factors– pCO2, temperature, velocity, pH
- CO2 prediction model
Temperature, (ºC) pCO2
(bar)Carbon steel
corrosion rate (mm/yr)
130 0.6 7
75 0.6 6
149 30 >50
For an ideal gas mixture, the partial pressure is the pressure exerted by one component if it
alone occupied the volume. Total pressure is the sum of the partial
pressures of each gas component in the mixture
27
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
28
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
29
CO2 corrosion inhibition
• Filming type• Retention time• Continuous injection • Adsorption onto clean surfaces
Clean steel
30
CO2 + H2S corrosion – metal loss
• 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
CO2/H2S > 500 CO2 dominates
500 > CO2/H2S > 20 mixed CO2/H2S
20 > CO2/H2S > 0.05 H2S dominates
H2S + CO2 materials selection guide
Carbon/low alloy steels
Duplex SS
Nickel-based alloys
Partial pressure H2S (bar)
Parti
al p
ress
ure
CO2
(bar
) 13% Cr SS
32
EROSION & EROSION-CORROSION
33
Flow regimes
Liquid
Gas
Bubble (bubbly) flow
Stratified flow
GasLiquidAnnular flow
Churn flow
Gas
Liquid
GasLiq
uid
Plug flow
Wave (wavy) flow
Liquid
Gas
Slug flow
Mist (spray) flow
• Various multi-phase flow regimes possible;
− erosion characteristics
− distribution of phases
− carrier phase for solids
• Flow regimes with particles in the gas show higher erosion rates than those with particles in the liquid phase.
34
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
35
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 accumulate
– High pressure drop during washing of separators
• Sea water systems– High flow areas in water injection /
cooling systems
Trinidad
Algeria (duplex)
36
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
37
Erosion in a vessel• Sand allowed to accumulate in separator
– Wash nozzles embedded in sand• PCV not working properly
– High pressure / flowrate– Nozzle not erosion-resistant– Erosion of wash nozzle– Spray changed to a jet causing erosion
of shell• Local changes to operating procedures not
communicated– Frequency of sand washing– Risk not captured or assessed in RBI
Water spray
Water jet
38
Erosion of sandwash nozzle
Progressive nozzle
damage
39
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
40
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)
41
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
42
CORROSION IN SEAWATER
43
Raw seawater• Composition of raw seawater varies around the world
– Temperature, pH, salinity, dissolved oxygen, marine life • Very corrosive to unprotected carbon steel, other materials
susceptible to pitting and crevice corrosion• Select seawater resistant materials
– Super-duplex grades, 6Mo, CuNi, titanium• Consider galvanic corrosion
– Most seawater resistant grades of stainless steel and Ni-Cr-Mo alloys are compatible with each other in seawater.
• Seawater can cause SCC of 300-series, duplex grades and 6Mo
44
Pitting resistance of stainless steels
• Pitting Resistance Equivalent Number (PREw)
• Formula for comparing relative pitting resistance
• Applicable to stainless steels & Ni-Cr-Fe alloys
• Typically PREw ≥40 required for exposure to raw sea water <30ºC
• Alternatively, use titanium or GRE
Alloy PREw
13Cr 13
316ss 23
Alloy 825 28
22Cr duplex 33
25Cr super-duplex
40
Alloy 625 46
PREw = %Cr + 3.3x (%Mo + 0.5%W) + 16%N
45
Internal & external pitting
• Section of 3” 316L pipe fitting• Failed due to internal corrosion (pinhole leak)• Poor hydrotest practice - seawater left within spool
Internal pitting
46
Failure of a seawater pump cooling coil……
• 316 SS coil, raw seawater service, hypochlorite added• Shellside: lube oil up to 50°C• Tubeside: seawater inlet ~6°C, return ~18°C• Failed due to localised internal pitting
– 316 SS has low PREw• Material upgrade required
Internal surface of coil
External surface of coil
Indication on coil
47
Oxygen - concentration cells• Crevice corrosion
– O2 is consumed in the crevice and becomes the anode
– pH decreases in the crevice increasing attack
• Differential aeration cells– Air/water interfaces with attack below
the water line e.g. splash zone– Pipelines in soils containing different
amounts of oxygen• Under deposit corrosion
– Deposits of scale, sand or sludge– Produces differential concentration– SRBs thrive - H2S pitting
Crevice corrosion
under baffle
48
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
49
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
50
Galvanic corrosion - seal rings
• ETAP platform• Techlok joints in a firewater
piping system– Piping: super-duplex– Seal rings: 17-4PH
51
• 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
Dealloying of brass
52
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.
53
Example : CuNi-Super duplex
Apply a non-conducting internal coating on the more noble material.
Distance spool: solid, non-conducting material e.g. GRP
Distance spool: noble metal internally lined with an electrically non-conducting material such as rubber
54
Cathodic protection (CP) – what is it?• By connecting an external anode to the component to be protected and
passing a dc current, it becomes cathodic and does not corrode.– External anode may be a galvanic (sacrificial) anode, the current is
the result of the potential difference between the two metals– External anode may be an impressed current anode, current is
supplied from an external dc power source. • CP is mostly applied to coated, immersed and buried structures
– The coating is the primary protection, acting as a barrier between the metal and the environment
– CP protects steel at coating defects• Coating + CP is most practical and economic protection system.
– Primary principle in GP 06-31
55
Cathodic protection – how does it work?
ANODIC
MagnesiumZinc
AluminiumIron (steel)
CopperStainless steels
TitaniumGraphite
CATHODIC
Corrosion of steel by copper
plating
Cathodic protection of steel by zinc
plating
• CP works by making the component to be protected the cathode in an electrolytic cell
• When two metals are connected in an electrolyte, electrons flow from the anode to the cathode due difference in the electrical potential
56
Galvanic (sacrificial) CP• Aluminium anodes: require alloy additions to
become active e.g. Zn + In, high efficiency (>90%).– Typically used in seawater applications.
• Zinc anodes: ambient applications only. Alloyed with Al or Cd to improve efficiency.– Typically used on coated pipelines in seawater
• Magnesium anodes: large driving potential, alloyed with e.g. Al or Zn to reduce rapid activation, limited efficiency (50-60%)– Used in soils and other high-resistance
environments (risk of over-protection/rapid consumption in seawater).
Sacrificial anodes, new and wasted
(therefore working!)
57
Applications of internal CP
• Anodes in shell & tube seawater cooler water boxes
• Oil storage tanks (in water bottom)• Water tanks
•Stainless steel piping systems in warm/hot chlorinated seawater.
−To avoid high anode consumption rates, resistor controlled CP (RCP) systems should be considered.
−E.g. RCP + 25Cr super duplex piping instead of titanium or other higher-alloy CRA.
−Used on Greater Plutonio
58
Chloride stress corrosion cracking (SCC)
• Susceptibility varies considerably (no absolutes);– Material grade, strength, residual
stress, chlorides, oxygen and temperature
• 300-series austenitic stainless steels susceptible to at temps >50°C
• Highly-alloyed austenitic and duplex SS have improved resistance
• Nickel-base alloys with Ni ≥ 42% are highly resistant, e.g. 825
59
Chloride SCC (22Cr duplex vessel drain)
• 22Cr duplex drain ex-production separator
− heat-traced to 60°C (vessel temp up to 105°C)
• Internal chloride SCC (cracking in parent metal, HAZ and weld metal)
• Contributory factors:
− Susceptible material
− Local stress concentration (weld toe and lack of support)
− Environment (elevated temperature, chlorides).
60
Water injection systems (deaerated)Oxygen:• Trace amounts corrosive to carbon
steel. As a guide:– <20ppb O2 maintains general
corrosion rates <0.25mm/yr– Stricter limits often applied e.g.
<10ppb if 13Cr completionsMicrobial-induced Corrosion, MIC• SRB require anaerobic conditions
– deaerated water– conditions within and under
biofilms• SRB use sulphate in water in their
metabolisms to generate H2S
Fluid Velocity:• Areas of high fluid velocity or
turbulence and O2
– O2 from poor deaeration or air ingress
– susceptible areas include pump discharge piping, bends tees and reducers.
61
Mitigation & monitoring
• Deaeration and supplementary O2 scavenging– Monitor O2 concentrations on-line
(orbisphere) or colorimetric analysis– Maintain oxygen scavenger residual to
mop-up oxygen spikes.• Chlorination u/s of deaerator, biocide
applied into or d/s of deaerator• Effective biociding based on;
– Type, frequency, dosage, duration• Bacterial monitoring (sidestreams,
scrapings or bioprobes)• Corrosion monitoring
Leaking deaerator
Seawater injection tubing
62
Preferential weld corrosion (PWC)• The selective corrosion of weld zones (WM/HAZ)• Relevant factors include;
– Electrochemical properties of the materials and any corrosion cell forming around the weld joint
– Water phase liquid film thickness and conductivity– Temperature and tendency to form protective scale– Corrosion inhibitor effectiveness, (film formation, composition)– Weld joint metallurgy– Flow pattern and flow induced shear stress
• PWC rate of attack can be high, up to 12mm/yr observed
63
Preferential weld corrosion (1%Ni)Water Injection:• 1% Ni-containing welds
beneficial for avoiding PWC in WI systems.
• Weld cathodic to parent metal, protected by large area of parent metal.
Wet hydrocarbon service:• Lower conductivity, no benefit of
selecting ‘cathodic’ weld metal• Reliant on intrinsic corrosion resistance
of the weld metal• Require corrosion inhibitor for
protection (test against WM and PM)• Attack of weld metal promoted by
under-dosing of inhibitor (WM needs more inhibitor than PM)
Welds exposed to hydrocarbon service
64
Lomond drains - PWC
• TEG contactor scrubber drain pipework (hydrocarbon)
• Carbon steel parent metal• ~2%Ni deposited in weld metal• Groove along 6 o’clock position• Accelerated corrosion at the weld• Large number of isolations,
extensive inspection and repair
65
MIC & DEADLEG CORROSION
66
Microbially induced corrosion (MIC)
• Anaerobic environments often support development of biofilms.
• Sulphate reducing bacteria (SRB) thrive in anaerobic conditions
• SRB biofilms generate H2S
• FeS corrosion product cathodic to bare steel, increasing corrosion rate.
• MIC of carbon steel usually localized pitting under biofilm.
• Corrosion rates of 5-10 mm/yr seen• CRAs also susceptible
67
Bacterial growth factors• pH
MIC growth in pH 5-9.5 range• Temperature
SRB can grow in temps of 5-100°C. Optimum temp <45ºC.
• Sulphates– Necessary for SRB activity.– Growth restricted if <10 ppm
• Carbon source SRB growth restricted if organic
carbon (volatile fatty acids) not available (<20ppm)
• NitrogenImportant but at levels which
are difficult to detect• Flow
– Highest corrosion rates in stagnant conditions.
– Biofilms unstable at high flows.
68
Deadlegs – types & locations
• A deadleg is a section of pipework or vessel which contains hydrocarbon fluids and/or water under– stagnant conditions (permanent or intermittent)– or where there is no measurable flow.
• Permanent or physical deadlegs (long term stagnation by design)• Operational deadlegs (stagnant for operational reasons)• Unprotected mothballed items (plus those temporarily out of service)
69
Examples of deadlegs
70
Deadlegs – assessment factors• Consequence of failure• Location of pipework• Nutrients replenished by regularly opening /closing valves?• Is draining of pipework possible?• Is removal of deadleg possible?• Presence of SRBs, deposits, biocide?• Material of construction• Wall thickness• Fluid type (aqueous phase, sulphates, nutrients, oxygen ingress)• Temperature• Stagnant – permanent/intermittent• Prior history of corrosion
71
Example of deadleg corrosion
• Crude oil recycle cooler bypass• Scale-inhibited seawater left in line after leak test (of u/s valve)• Severe corrosion rate at and around pinhole.• Fortunately, a leak of water not crude.• Two week shutdown
Pin Hole leaksReleasing waterPin Hole leaksReleasing water
72
Root causes
110mm
80mm
Area of internal corrosion reading from 3.5 mm tapering out to average of 10.7mm
Area of internal corrosion 4.2 mm tapering out to average wall thickness of 10.0 mm
VIEW LOOKING WEST
Photo1
North
30mm
250mm
Corroded area approx 80mm x 110mm.
• Failure to identify the bypass line as an operational deadleg
• No deadleg register
• Failure to recognise introduction of new corrosion hazard
• No mitigation measures.
73
Mitigation & inspection
• Flush system of deposits and treat with biocide, nitrate
• Out of service items – Biocide treat or mothball procedure
• Use treated water – Hydrotest & washing
• Profile radiography or UT scanning– low points, bottom of vertical
sections etc.• Lowest parts of vessel bridle together
with any associated level gauges.
74
OTHER CORROSION MECHANISMS
75
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
76
Corrosion due to chemicals
• Carbon steel open drain pipework.
• Seepage of scale inhibitor (passing valve)
• Scale inhibitor pH <2.
• Chemical entered drains, not flushed
77
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
• Valve arrangement– Make self-draining– Enable quill removal
Main Flow
Injected Fluid
Impingement
78
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
79
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
• Mitigation:– PWHT all CS welds including repair and
internal/external attachment welds.– Use solid/clad stainless steel
• 304 SS or 316 SS
Intergranular cracking
Amine piping welds require
PWHT to avoid SCC
80
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
81
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
82
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
83
EXTERNAL CORROSION – SURFACE FACILITIES
84
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
85
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.
86
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.
87
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.
88
Piping, supports & clamps
89
Not just carbon steel
• 25Cr super-duplex (PREN ≥40)• Seawater service• 12 months exposure in tropical
climate• External corrosion along welds• Poor quality fabrication
90
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
91
Corrosion of bolts and fasteners
General corrosion Galvanic corrosion
Crevice corrosion Stress corrosion cracking
92
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
93
Corroded fasteners (seawater service)
Location of graphite gaskets
94
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
95
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
96
External cathodic protection
• Types of structures with external CP– Buried pipelines / structures /
piping / tanks– Floors of above-ground storage tanks– Submerged jetty structures
• Factors affecting corrosion– Extent of wetness– Oxygen – depends on depth– Resistivity of soil & presence of salts– Equipment temperature
97
Impressed current CP
• Adjustable dc source– Negative terminal
connected to the steel structure
– Positive terminal connected to the anodes
• Typically used on larger structures where galvanic anodes cannot economically deliver enough current.
98
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.
99
Insulation
• Typical insulation types;– Process– Personnel protection (PP)– Winterisation– Acoustic
• Challenge the need– Remove unnecessary
insulation– Replace PP with cages
‘Lobster-back’ joint
Mitred joint
Pre-formed bends
100
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
101
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
102
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
103
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
distinct lines along each side.• Scaling directly above lower
seam of insulation– location of water retention.
400x300x30mm
400x100x25mm
104
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.
105
Instrument tubing (316 SS and super-duplex)
316 SS tubing super-duplex tubing
316 SS (pitting/crevice corrosion) super-duplex (no pitting)
106
Crevice corrosion under clamps/supports
• Pitting and crevice corrosion of 316ss piping– Clamps– Plastic retaining blocks
107
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
108
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