Chapitre I Main corrosion phenomena encountered in oil and gas production

9 55

molybdenum contents offer enhanced corrosion resistance (Figure 1.37). For the most
severe conditions, stainless steel AISI 317L (UNS S31703) that contains over 3%
molybdenum exhibits the greatest resistance [50; 83; 90; 911.

100 I
50 -
-kl 20-
(u
-
$- 10
g
._ 5 -",9:"
-
.--
._ 2 - 1-3Cr
E - 4-6 Cr
v

a,
1
c
0.5 - 9Cr
.-In
5 0.2
.-
In
- 12Cr
g 0.1 -

s 0.05 - 18/8
S content: 0.6 wt%
0.02 -
0.01 I I I I I I

Figure 1.37
Comparison of corrosion resistance of the main steels for a crude of TAN = 2,
source [141].

1.13 CORROSION DURING THE FORMATION OF POLYTHIONIC ACIDS

1.13.1 Equipment concerned by polythionic acid corrosion

During shutdowns, polythionic acids may form on the equipment surface by reaction between
iron sulfides, water and oxygen. These acids may cause intergranular cracking of austenitic
stainless steels (AISI 300 series) and austenitic alloys [alloys 600 (UNS N06600) and 800
(UNS N08800)l. If the latter alloys have been sensitised, these cracks may propagate entirely
through the wall. This type of cracking mainly affects solid austenitic stainless steel equip-
ment or austenitic stainless steel cladding: weld overlay coatings are less sensitive.
Austenitic stainless steel equipment operating at temperatures between 400 "C and
8 15 "C and containing sulfur products is concerned. Furnace tubes, heat exchangers, pipes
in hydrotreatment and FCC plants and cokers, can be particularly affected.
56 Chapitre I Main corrosion phenomena encountered in oil and gas production

1.13.2 Mechanisms and parameters governing polythionic acid corrosion

Polythionic acids are formed during shutdowns, by reaction between iron sulfides, the atmo-
spheric oxygen and some liquid water (humidity) according to:
x FeS -t H 2 0 + (5 + x) 0 2 H2Sx06 + xFe0 (2 < x < 5)
These polythionic acids cause intergranular attack of sensitised stainless steels. Cracking
may propagate very quickly and cross the entire thickness of the wall within a few hours,
residual stresses inside the steel being sufficient for its propagation. External mechanical
stresses accelerate the crack propagation speed.
Some austenitic stainless steels are sensitised by prolonged periods at temperatures
between 400 "C and 8 15 "C, as shown on Figure 1.38 below for stainless steel AISI 304
[ 1041. Prolonged periods at these temperatures may cause precipitation of chromium car-
bides at the grain boundaries together with a reduction in chromium content in the zones
adjacent to this precipitation. The chromium-depleted zones become sensitive to intergranu-
lar corrosion phenomena (see paragraph 3.5.2 for further details).

1100 2012
- 1000 -

a
Coherent
0
S3
! 600 -
I
E

Time (h)

Figure 1.38
Stainless steel 304 sensitisation temperature ranges, source [ 1041.

1.13.3 Example of polythionic acid corrosion

Figure 1.39 is a photograph of the inside of a stainless steel AISI 32 1 (UNS S32 100) furnace
tube from a hydrodesulfurisation unit: cracks opening out onto this side are present, flame
side. Metallographic examination of a cross-section of the tube shown on Figure 1.40 clearly
indicates the intergranular path followed by this cracking. We observe precipitation of chro-
mium carbides at grain boundaries in this localised zone on the flame side, whereas
 Chapitre I Main corrosion phenomena encountered in oil and gas production 57

intergranular precipitation cannot be detected on the side opposite the flame. These furnace
tubes had been annealed but had not undergone a stabilisation treatment ( 2 to 4 hours
between 850 "C and 900 "C).

Figure 1.39
Cracking by polythionic acids of an austenitic stainless steel 321 furnace tube
from a hydrodesulfurisation unit.

Figure 1.40
Metallographic section of cracking by polythionic acids of an austenitic stainless
steel 321 furnace tube from a hydrodesulfurisation unit.
58 Chapitre I Moin corrosion phenomena encountered in oil and gas production
9

1A3.4 Prevention of polythionic acid corrosion

The main prevention methods concern the plant shutdown procedures andor the metallurgi-
cal choices.
- During unit shutdowns, neutralisation procedures can be implemented to eliminate the

polythionic acids by injecting alkaline solutions. Detailed information concerning

these procedures is provided in NACE recommendation RP 0 170 [ 161;
- Austenitic stainless steel grades stabilised with titanium AISI 321 (UNS S32100) or

niobium AISI 347 (UNS S34700) and stabilised austenitic alloy grades (alloys 825
(UNS N08825) and 625 (UNS N06625)) offer enhanced resistance to polythionic acid
corrosion. Chemical stabilisation treatment of 2 to 4 hours between 850 "C and 900 "C
increases the resistance of stabilised austenitic stainless steel (including the welded
zones) [39; 881;
- Austenitic stainless steel overlays, especially AISI 347 overlays (UNS S34700), offer

good corrosion resistance [107].

1.14 DECARBURISATION BY HIGH TEMPERATURE HYDROGEN ATTACK

1.14.1 Equipment concerned by high temperature hydrogen attack

Carbon and low alloy steel refining plants operating above 220 "C and under gaseous hydro-
gen pressure are subject to High Temperature Hydrogen Attack (HTHA), in particular
hydrotreatments, hydrocrackers, reformers and hydrogen production units [49].

1.14.2 Mechanisms and parameters governing high temperature hydrogen attack

Hydrogen recombines with the steel carbides (cementite Fe3C) to form methane, which
weakens the mechanical characteristics of the metal and may cause cracking (intergranular
cracking may develop since the methane cannot diffuse).
There are two types of high temperature hydrogen attack: surface decarburisation and
internal decarburisation.
High temperatures and low hydrogen partial pressures favour the first mode; the second
mode develops mainly at more moderate temperatures under high hydrogen partial pressures.
Suvface decarburisation: The generally accepted mechanism is based on migration of
carbon to the surface where it combines with hydrogen to form a gaseous compound. Unlike
internal decarburisation, surface decarburisation does not lead to the formation of microc-
racks, but reduces mechanical strength and increases ductility.
Internal decarburisation: Internal decarburisation is related to dissociation of molecular
hydrogen on the surface then diffusion of atomic hydrogen into the steel where it reacts with
carbon to form methane. The methane formed cannot diffuse out of the metal and tends to