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Nace and Its Applicability - 10.12.09

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18 views

Nace and Its Applicability - 10.12.09

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PrashantGaurav
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© © All Rights Reserved
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NACE & ITS APPLICABILITY

•MECHANICAL PROPERTIES OF METALS


•HEAT TREATMENT PROCESSES
•NACE MR-0103 (REFINERY SERVICES)
•NACE MR-0175 (OIL & GAS SERVICES)
•HYDROGEN INDUCED CRACKING
•LESSONS LEARNT
MECHANICAL PROPERTIES OF METAL
HARDNESS
• Hardness is the resistance to plastic deformation
& a measure of plastic deformation
• Hardness scales: Rockwell, Brinnel &Vickers etc

• ROCKWELL C HARDNESS (HRC)- based on


penetration only
• BRINNEL SCALE (HB): load/ surface area of
indentation
• Vickers: load/surface area of indentation
• (for conversion refer ASTM E 140)
HEAT TREATMENT – softening process
HEAT TREATMENT PROCESSES
• ANNEALING
• TEMPERING
• NORMALIZING
• HARDENING
Heat treatment for steels
PURPOSE OF HEAT TREATMENT
• TO ACHIEVE DESIRED MECHANICAL PROPERTY
BY:
GRAIN SIZE REFINEMENT
CONTROLLING DISLOCATION DISTRIBUTION &
DENSITY
PHASE TRANSFORMATION
STRENGTHENING BY GRAIN SIZE
REDUCTION
STRENGTHENING BY GRAIN SIZE
REDUCTION
SOLID SOLUTION STRENGTHENING
STRAIN OR WORK HARDENING
STRAIN OR WORK HARDENING
COLD WORKING
DISADVANTAGES OF COLD FORMING
ANNEALING & RECRYSTALLIZATION
Refinery services

NACE MR 0103
STRESS CORROSION CRACKING
• Interaction of corrosion and stress may lead
failure
• 3 required conditions:
a) Susceptible material
b)Environment that causes SSC for that material
c) Sufficient tensile stress to induce SSC
FACTORS AFFECTING SSC
• CHEMICAL COMPOSITION, STRENGTH (AS
INDICATED BY HARDNESS), HEAT TREATMENT &
MICROSTRUCTURE
• TOTAL TENSILE STRESS (APPLIED + RESIDUAL)
• HYDROGEN FLUX GENERATED DUE TO PRESENCE
OF H2O, H2S CONCENTRATION, pH, and others
viz. cyanide and bisulphide ion concentration
• TEMPERATURE
• TIME
MATERIAL HARDNESS & SSC
• AFFECTED BY CHEMICAL COMPOSITION, HEAT
TREATMENT & MICROSTRUCTURE
• MATERIALS WITH HIGH HARDNESS ARE MORE
SUSCEPTIBLE TO SSC
• ALSO INCREASES WITH TENSILE STRESS
• HIGH RESIDUAL STRESS AT WELDS INCREASES
SSC SUSCEPTIBILITY
• CONTROL OF WELDMENT HARDNESS WITH OR
WITHOUT REDUCTION IN RESIDUAL STRESSES
PREVENTS SSC
ENVIRONMENTAL CONDITIONS FOR
SSC
Free water and
1. > 50 ppmw H2S in free water, or
2. Free water pH <4 & some dissolved H2S, or
3. Free water pH > 7.6 and 20 ppmw dissolved
HCN & some dissolved H2S in water
4. >0.0003 Mpa abs. (0.05 psia) partial pressure
of H2S with gas phase
DIFFERENCES WITH OIL & GAS
ENVIRONMENT
• Wet streams of Oil & Gas may also contain CO2 ,
hence pH lower (unlike refinery services does not
go beyond 7)
• Presence of Chloride ( which is significantly lower
in refinery sour services)
• pH2S is 0.07 MPa (10 psia) ( which is higher than
0.0003MPa i.e. 0.05 psia for refinery)
FERROUS MATERIAL- CS & ALLOY
STEEL
• CARBON STEEL: C <2% % Mn NOT <0.25% with no
alloying element other than Mn, Si, Cu + only
incidental quantity of element other than C, Mn,
Si, Cu, S & P
• ALLOY STEEL: C <2.5% % Mn NOT <0.25% with
specified quantities of one or more alloying
element other than Mn, Si, Cu + Cr > or = 10%
ACCEPTIBILITY OF CS & ALLOY STEEL IN
SOUR SERVICES
• No intentional addition of Pb, Selenium or S to
improve machinability
• Must be thermally relieved after cold forming
• Minimum stress relief temp. 593 Deg C
• Hardness after stress relieving < 200 HBW 9for P-
No. 1 material, refer ASME boiler & pressure
vessel code Section IX.
• Other Carbon Steels : 22 HRC (237 HBW) Max.
• P-Numbered alloy steels 225 – 248 HBW Max.
• Other alloy steels: 22 HRC (237 HBW) Max.
HEAT TREATMENT OF CS & ALLOY
STEELS
MUST USE ONE OF THE FOLLOWING;
I) HOT-ROLLED (CS ONLY)
II)ANNEALED
III)NORMALIZED
IV)NORMALIZED & TEMPERED
V)NORMALIZED, AUSTENITIZED, QUENCHED &
TEMPERED OR
VI)AUSTENITIZED, QUENCHED AND TEMPERED
OIL & GAS SERVICES

NACE MR 0175
SOUR SERVICE-DEFINITION
SOUR GAS
• TOTAL PRESS.: ≥0.4 MPa I.E. 4 Kg/CM2 AND
• PARTIAL PRESS. OF H2S : ≥ 0.0003 Mpa (22.25
MM Hg
SOUR OIL OR MULTIPHASES
• Standard material has performed satisfactorily for
crude oil systems
WHEN
1. MAX. GOR : 5000 SCF/BBL
2. MAX H2S IN GAS : 15%
3. MAX p (H2S) : 0.07 Mpa (0.0003 Mpa)
4.MAX. OP. PRESS. : 1.8 MPa (265 PSIA) (0.4MPa)
Why? Inhibitive effect of oil & low op. Pressure.
When op. Press. Exceeds 1.8 mpa follow the guidelines
under sour gas.
Relevant figures for sour gas are indicated in red within
parenthesis.
EFFECT OF HYDROGEN

BLISTERING, EMBRITTLEMENT,
DECARBURISATION
EFFECT OF HYDROGEN ON MATERIAL

• 1. COLD EMBRITTLEMENT-when liquid


hydrogen is stored. Cryogenic temperature
reduces ductility, least for FCC & marked in BCC
materials. Metals that work successfully at low
temp. are Al & its alloys, Cu & its alloys, Ni & its
alloys, Stable Austenitic steels
• 2. HYDROGEN EMBRITTLEMENT-Applies to
Hydrogen & Hydrogenated gases like H2S.
Effect of Hydrogen

Hydrogen can degrade metals by:


• hydrogen blistering;
• hydrogen embrittlement;
• decarburization;
• hydrogen attack.
Hydrogen blister
Cross section of a carbon steel plate
removed from a petroleum process stream
showing a large hydrogen blister. Exposure
time: 2 years.

Hydrogen enters the lattice of a metal,


diffuses to voids, creates high internal
stresses  blisters . . .
H-embrittlement
Similar to blistering . . . hydrogen enters metal
lattice . . .BUT . . .interaction with metal lattice
different. High-strength (and more brittle)
steels are susceptible.
H-embrittlement different from SCC in nature of
cracks . . . stress-corrosion cracks usually
propagate anodically;
Difference
Mechanism of H blistering
The mechanism of hydrogen uptake by metals must involve
ATOMIC HYDROGEN - molecular hydrogen cannot diffuse
through metal lattices.

BUT . . . molecular hydrogen may absorb and dissociate on metal


surfaces.
Decarburization
High temperature process - C or carbide in steels can
react with gaseous hydrogen . . .
C + 2H2  CH4
Note that the reaction can occur with atomic H in the
metal lattice . . .
C + 4H  CH4
May crack the steel from high internal pressure.
May cause loss of strength as C disappears.
Prevention of blistering
– use steels with few or no voids;
– use coatings;
– use inhibitors;
– remove impurities that can promote hydrogen
evolution . . . S2- (particularly bad), As, CN-, etc.;
– use different materials (Ni-base alloys have low
diffusion rates for hydrogen).
Prevention of Embrittlement

– reduce corrosion rate (inhibitors, coatings, etc.);


– change electroplating process to minimize H effects
(voltage, current density, bath composition, etc.);
– bake material to remove H;
– minimize residual stresses;
– use less susceptible material;
– maintain clean conditions during welding.
MECHANISMS
MOST IMPORTANT & WELL STUDIED PROCESSES OF
ENVIRONMENTAL DEGRADATION OF METALS. THREE
GENERAL MECHANISM ARE:
• 1. FORMATION OF HYDRIDE PHASE
• 2. HYDROGEN ENHANCED LOCAL PLASTICITY
• 3. HYDROGEN INDUCED GRAIN BOUNDARY
WEAKENING
• THERE IS OVERWHELMING EVIDENCE THAT HELP IS A
FUNDAMENTAL CONTRIBUTOR TO H-EMBRITTLEMENT.
• (REFER “HYDROGEN ENHANCED LOCAL PLASTICITY IN
ALUMINIUM – AB INITIO STUDY BY GANG LU ET. AL,
PHYSICAL REVIEW LETTERS, AUG. 2001
STEPS TO FAILURE IN HIC
Step-1: External stress produces local
concentration of tensile stress at crack and
hydrogen diffuses to crack tip as H prefers to
stay at slightly enlarged interstitial spaces
Step-2: This hydrogen generates dislocation and
enhances dislocation mobility and results in
plastic deformation in front of crack causing
thinning and softening
Step-3: Allow crack to propagate at lower stress
value
Preventive measures
• Selection of material: Austenitic SS are more
compatible than Ferritic alloys, but use of Austenitic
SS is cost prohibitive
• API RP 941 : Provides guidelines for selecting CS or
low alloy steel which are resistant to H-attack even at
high temperature & pressure (RG to cover later in
this presentation)
• HIC and Temperature: High temperature forms H-
atoms which easily diffuses and reacts with C (both
surface & internal ) leading to cracking.
An Experience On Hydrogen
Service Requirements In MSQ
•HYDROGEN SERVICE REQUIREMENT MENTIONED

IN PMS (ANNEXURE – B)
“Hydrogen service defined as service in contact with
hydrogen or gaseous mixtures containing hydrogen
in which the partial pressure of hydrogen is 5 bar
(abs), (58 psig) or more”.
AXEN’S GENERAL STATEMENT ABOUT
MATERIALS OF CONSTRUCTION
•In services containing hydrogen, materials are selected based on
their resistance to high temperature hydrogen attack. Hydrogen
attack can occur at temperature above about 220 deg. C.
•Material recommendation is based on the Nelson curves (refer
to API RP 941: “Steels for Hydrogen Service at Elevated
Temperatures and
Pressures in Petroleum Refineries and Petrochemical Plants”) for
hydrogen resistance.
•API RP 941 are based largely upon empirical experience, safety
margin of 28 deg. C (50 deg. F) and 3.4 bar (50psi) below the
relevant curves (respectively for maximum Operating
Temperature and Maximum Operating Hydrogen Partial
Pressure) are typically used when selecting steels.
CONCLUSION
• Hydrogen service requirement for the Piping lines of MSQ Unit has been
categories as per the following 03 Categories.

S.No. H2 Concentration Partial Pressure


Temperature

1. (Category A) Irrespective of conc. >=5 Bar >=220 Deg.


C

2. (Category B) > 90% Irrespective of irrespective


of
Pressure
temperature
3. (Category C) <90% >=5 Bar <220 Deg.
C
THANKS

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