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According to the NACE Standard MR 0715-88 sour environment definition for general purposes of carbon
and low alloy steel. The definition states that 0.05-Psia or equal to 0.34 kPa partial pressure H2S in gas
phase will cause Sulfide Stress Cracking (SCC) for Carbon steel and low-alloy steels at low temperature.
And for liquid phase, the total sulfur content is more than 0.5% is called sour.
H2S is the biggest caused of corrosion in pipelines of sour field. Hydrogen sulfide reacts with ferrous to
form a H2S film, but as this film get dissolved more and more ferrous will be available to get attacked by
H2S. The pipeline become thinner and thinner and finally become unsafe to use. Stress Sulfide Corrosion
occurs when metal is in exposed to H2S and water. And it will generate atomic hydrogen between grains
of the metal and reduces metal ductility. Damage result by H2S corrosion:
Figure 3.
Stress Oriented Stress Cracking (SOHIC)
NACE MR0175 and ISO 15156 defined SOHIC as staggered small cracks formed approximately
perpendicular to the principle stress (residual or applied) resulting in a “ladder-like” crack array linking
(sometimes small) pre-existing HIC Crack.
Figure 4.
H2S is the agent which can trigger the corrosion process to happen as below step:
H2S H+ + HS- (1st dissociation reaction)
HS- H+ + S2- (2nd dissociation reaction)
Fe Fe2+ + 2e- (Anodic/ oxidation reaction)
Fe2+ + S2- FeS (precipitation of FeS)
H+ + e- H0ads (Cathodic reaction/ adsorbed H-atom is adsorbed)
H0ads + H0ads H2 (Cathodic reaction/ hydrogen gas is formed)
Temperature effect
Rule of thumb:
Most of the cases, for every 10ºC increase of temperature, corrosion rate of metal will be doubled.
Such for example, when corrosion rate of a metal is 10 mpy at 30ºC, it will be expected rise to 20
mpy at 40ºC (Materials Tech Inst, 2008)
First, we have to define the partial pressure of H2S (ppH2S ) which is calculated as:
The partial pressure mentioned in Section 7.1.2 is the partial pressure of H2S in the gas phase in
equilibrium with the water in the production fluid. Annex C gives information on how to calculate
H2S partial pressure.
Notes:
X : mole fraction H2S in gas, % x 104 (parts per million by volume).
Y : Total absolute pressure, MPa
1 pH2S : 0.3 kPa
2 pH2S : 1 kPa
3 pH2S : 10 kPa
4 pH2S : 100 kPa
5 pH2S : 1000 kPa
Figure 2. Effect of temperature on corrosion rate of steel (pH2S = 1.2 MPa coexist with pCO2 =
1.0 MPa)
For Carbon Steel, the effect of H2S partial pressure can be seen in Figure 3 below.
Figure 3. SEM Images of the corrosion scales formed under different H2S partial pressure at
60ºC; (a) 0.15 MPa, (b) 0.3 MPa, (c) 1.0 MPa, (d) 1.5 MPa, (e) 2.0 MPa, (f) 2.5 MPa (Adapted
from Zhang et al, 2011)
As shown in Figure 3, it is clear for constant temperature circumstances, higher pressure implied
to system prone to initiate corrosion rate and exhibits smaller molecular scale upon metal surface.
Hence, high pressure operation could establish pitting corrosion on the metal surface. Figure 5
represents relationship between reacted S and Cl atoms with metals on different depth of pit.
“0” point,
bootom pit.
Figure 5. (a) SEM image of Pitting Corrosion upon Carbon Steel surface.
Figure 5 proved that higher pressure applied would make S and Cl atom to more reactive and
reacted to metal (Fe) surface by following reaction:
Figure 6. Reaction pathway of H2S Corrosion [Adapted from Sun et al, 2007]
H2S environment could construct amorphous ferrous sulfide, mackinawite, and cubic ferrous
sulfide. Among those mentioned, mackinawite allegedly first formation during reaction upon steel
surface by direct reaction {Sun et al, 2007].
Concentration Effect
Indeed, H2S influence on the protective ability of sulfide film formed. As the concentration
increases, film formed rather loose even at pH 3 – 5 does not contribute to the corrosion inhibiting
effect [Shoesmith et al, 1980].
References
Revie, RW. Uhlig, H.H. Corrosion and Corrosion Control An Introduction to Corrosion Science
and Engineering 4th Edition. A John Wiley & Sons, Inc., Publication. 2008. Hoboken.
Kim MJ, Lee DB. Corrosion of Fe-Al Alloys at 600 and 700ºC in a Gas Mixture of H2O, H2S,
N2. Korean J. Met. Mater. Vol. 53, No.6, pp. 406 – 411. DOI: 10.3365/KJMM.2015.53.6.406
Sun J, Sun C, Lin X, Cheng X, Liu H. Effect of Chromium on Corrosion Behavior of P110 Steels
in CO2-H2S Environment with High Pressure and High Temperature. Materials 2016, 9, 200;
doi:10.3390/ma9030200.
Guo, S.Q.; Xu, L.N.; Zhang, L.; Chang,W.; Lu, M.X. Corrosion of alloy steels containing 2%
chromium in CO2 environments. Corros. Sci. 2012, 63, 246–258
Chen, T.H.; Xu, L.N.; Lu, M.X.; Chang, W.; Zhang, L. Study on factors affecting low Cr alloy
steels in a CO2 corrosion. In CORROSION 2011; NACE International: Houston, TA, USA, 2011
Gao S, Jin P, Brown B, Young D, Nešić S, Singer M. Effect of High Temperature on the Aqueous
H2S Corrosion of Mild Steel. 2017 Poster Award Reseach Letters. NACE International.
dx.doi.org/10.5006/2523.