,.

Perfor mance SEPTEMBER 2 004 h ttp://mp . nace . or g

P f
passive oxide fi lm by synergistic acdon
between chlorides and H
1
S.
1
At rhis writ-
ing, no well-prmen guideli nes exisr for
er 0 rmance 0 applying ss in wet sour gas-conraini ng
Austenitic Stainless
Steels in Wet Sour
Gas Part 2
V IRENDRA SINGH, GASCO
This article discusses seven failures on austenitic
steels in a sour gas processing plant. It presents
data compilation, analysis, and conclusions from these
failures and those covered in Part 1 (August 2004 MP) from
three other plants. The plants were built over a period of
time with changing material selection criteria. The
failures have all occurred in similar process units of the
condensate recovery and vapor compression sections,
where different plant designers used austenitic stainless
steels (types 304 and 316L [UN8 830400 and UN8 831603]).
Chloride-assisted stress corrosion cracking caused the

46 MATERIALS PERFORMANCE SrptrmLa 2004
mi l recenrly, it was wide-
ly belie,ed rhat rhe crack-
ing of austenitic srainless
steel (SS) in wet sour
gas-conrni ni ng chlorides
was caused by chloride-
assisted srrcss cor rosion
cracking (CSCC) at f.worablc rcmpcra-
rurcs. A rcccnr srudy on corrosion-resis-
ranr alloys. however, shows rhat CSCC
type of en\'ironmenrall y as-
sisted cracking (EAC)- is driven either
by enhanced 1-1 adsorptio n or hydrogen
sul fi de (1-1
1
5)-enhanced brenkdown of rhe
chlorides.
Case Studies
A total of 13 failures at four gas plants
have been identified as cases of EAC on
austenit ic SS. Surprisingly, all of the fail-
ures occurred on types 304, 404L, and
3 16L SS (UNS 530400, UNS 530403,
and UNS 53 1603, respecd,cly) and are
from rhe condensate swbilizarion and
vapor compression secrion of t he sour gas
planes. ll1e faci li ties are shown on si mpli-
fied process Row diagrams alo ng wit h
operating paramerers and analytical data.
l n\' esci gari ve fi ndings are ghcn case-by-
case along wirh applicable clara.
Parr I of t his arricle, which appeared
in the August 2004 issue of MP (p. 52),
discussed Cases I through 4 ar Pl ant I
and Cases 5 and 6 at Plants 2 and 3. Part
2 co\'ers Cases 7 t hrough 13 ar Plant 4. It
also includes clara compilation, analysis,
and conclusions for all 13 milures.
CASE STUDIES FROM PLANT 4
Figure I ill ustrates a simplified process
A ow diagram of rhe condensare srabiliza-
rio n and vapor compression secrion of
Planr 4. The planr was builr ro process
sour associated gas. l11c cri tical equip-
menr was made from clad or solid all oy
825 (UNS N08825). Solid or clad rype
3 16 L SS was used for the ,apor compres-
sor sucrion and inrer-scage drums, air
coolers, and pi ping.
Cttse7
A leak was noticed on rhc I 0-in. (25.4-
cm) N PS rype 3 16 L SS air cooler ourler
piping co the inrer-stage knock-our (KO)
d rum, as shown in t he process Row dia-
gram (Figure I). l11e gas in rhe pipe was
laden wirh condensed wcr liquid from the
air cooler. ll1c leak was clamped. Radio-
graphic inspection of nearby weld joims
showed fi ne cracks trans,erse ro rhe girrh
welds. A few days larer, another leak was
obser\'ed on t he next weld and ir was also
clamped pending inspection and proper
Performance SEPTEMBER 2004 http://mp.nace.org
proper repairs. Both of t he leaks were
confined O rhe roe of rhe weld. Periodic
monitoring analys is from the suction
scrubbers and inter-stage drum showed
the presence of chlorides (Figure l).
A metallographic smdy on the failed
pipe spool was rhen conducted (Figure 2),
which revealed the presence of multiple
cracks that were transverse (perpendicu-
lar) ro rhe weld in various locations of the
circumferenrial burr weld. A shorr section,
remo,ed trans,erse O the weld area, re-
vealed rhe presence of more than si:< vis-
ible macro cracks, branching in nature,
rhat emanated from rhc inside surfuce of
rhe joinr. 1l1e micro-examination, ar low
and high magnification, revealed rhe pres-
ence of multiple classical branched CSCC
emanating from the inside surfuce of rhe
joinr in rhe area of the weld. A hardness
FIGURE 1
lAgend -- Alloy 825
0\V = Oily wntor - - Alloy 825 dod C
B = bJIJ:(g),C:!(; -- SS 316
Q =Chlorides - - SS 316 clod CS
check showed <200 Hardness, Vickers Process flow diagram showing items that failed from EAC in Plant 4.
(HV
10
). 1l1e meml composition of the
pipe and wcld-meml was confirmed O be
FIGURE2
r .
hd
. ---;-. ' tc a con ttton
As polished
Micrograph s howing the classical stress
corrosion cracks observed in the weld metal
at low and high magnification
micro section
showing cracks
in weld metal
(shown by arrows)
EAC on the type 316L SS piping from air cooler to KO drum in Plant 4.
FIGURE3
Photograph of compressor suction strainers showing EAC of type 316
ss .
2004 MATERIALS PERFORMANCE 47


Performance SEPTEMBER 2004 http: //mp .nace.org
Materals Selectio, & Design
FIGURE4
-
........
Cases 10, 11,
nnd 12
--- .......
1he compressor
suction and inrer-
srage vessels were
made of carbon
steels (CS) clad with
0 '") '
l . -
.
type 316L SS imer-
nally. All the nozzle
weld connections
wirh shell and
Cracks in type 316L SS weld overlay in Stage 1 suction scrubber.
domes were inter-
nally weld o,erlaid
wi rh rype 316L SS.
These vessels had
undergone post-
type 316L SS. Corrosion deposits on
the inside surface of the elbow were
analyzed quantitatively, revealing a sig-
nificant amount of sulfide (12.1 o/o) and
chlorides (2.0%).
Cnscs 8 nud 9
1he strainers from Stages l and 2 on
the compressor inlet pipi ng were found
robe badly damaged (Figure 1). Material
identification confirmed rhar bmh strain-
ers were made of type 316L SS. Damage
on the Srage 2 strai ner was more extensive
than on the Stage J strainer (Figure 3).
The cracking resembled that of Cases 2
and 3 in Plant 1 (sec August 2004 MP).
FIGURE 5
100,000

C)
10,000
C)

co;
0
(')
0
0
1,000

100
10
weld heat treatment
as per rhe design and f.1bricarion code for
the shell thickness.
1he fluid in the vessels was wet sour
gas, and anr condensable liquid was
knocked down from rhe gas after compres-
sion. A ,isual inspection of the surmces
showed some oil y spots rhat were cleaned
and checked with dye penetrant. It re-
vealed numerous cracks in the weld over-
laid sections (Figure 4). 1l1ese were con-
sidered the cases of EAC, and no further
ilwestigarion was carried out.
Case 13
1he first-stage air cooler{Figure 1) was
made of type 316L SS seamless tubes and
g

...
0
C)
0
0
...
0
0
0
0
10
0
g
g
MR0175-
2003,
Cl < 50
MR0175- IS0-15156-3, IS0-15156-3, NORSOK NORSOK-
M001,
Cl < 5%
NORSOK
M001,
Cl <5%
2003, Temp Temp M001,
Temp < so < soc Cl < 1%
< soc
Environment limits for type 316 SS as recommended by international standards.
48 MATERIALS PERFORMANCE 5ipumba 2004
type 316L SS header boxes. 1he fluid was
the same wet gas as in the previous case.
1he gas was cooled down by exch;mging
hear with air and any condensable liquid
was dropped our. Hydrostatic resting with
demineralized water showed profuse leaks
from the tube ro the tube sheer weld joilu.
Close inspection revealed leaks from 27
rubes in the bottom row. No further in-
vestigation was carried our as the nature
of rhe cracking suggested it was a case
ofEAC.
Review of of
Austenitic SS in Sour Gas
It was established long ago that the
presence of chlorides in wet gas can cause
CSCC on SS under f.,,orable tempera-
ture conditions. It was established much
later that rhe presence ofH
2
S could assist
in SCC. T hese cases of cracking arc
grouped as EAC. EAC is driven either by
H !$-enhanced H absorption or H:S-
enhanced breakdown of the passive oxide
fi lm by synergistic action between chlo-
rides and H!S.
1
No well-proven guideline
is yet available for
material selection of
corrosion-resistant alloys
in sour gas-containing
chlorides.
EAC f.1il ures generally are catastroph-
ic and difficult to reproduce in laboratory
smdies. Hence no well-proven guideline
is yer a\'ailable for material selection of
corrosion-resistant alloys (CRAs) in sour
gas-containing chlorides. Another impor-
ranr consideration has been the nonavail-
ability of realistic water chemistry of
various streams ar the plant design stage.
The estimated chloride content is seldom
correct because chloride content may \'ary
considerably based on dynamic downhole
conditions. Furthermore, materials selec-
tion depends on the experience and con-
Perfo rmance SEPTEMBER 20 04 h ttp: //mp.na c e.org
fidence level of che corrosion engineer
associated with plant design.
Four documents are frequently cited
in reference to CR.A applications in sour
environments:
NACE Standard MRO 175J lim the
chemical compositions of materials
(UNS numbers) and recommends
hardness (strength) limitations along
with environmental limits.
European Federation of Corrosion
Publication- 17J offers guidance o n
evaluating EAC susceptibility.
ISO 15 156-3
4
provides require-
ments and recommendations for marc-
rial qualification and selection.
FIGURE6
Failures at Chlorides < 50 mg/L
10,000
!'i "'
! ,a

!

l imit of
f!.
pH,S < 3,500 mbor
i
,..-
1,000 - - - - -- - -
r: . -.-
- - -- -- . - --
--
NORSOK Umlt of
pH,S < 100 mbor
$

'

..,
6
. - . ;:.
y
;:.
100 - -
. - . -
-- . - -
-
rE
,..
fi fi
r-
...

r-


,.a

n o

p.


r--
10
ll a ppH,s, mba rial
DTemp. c
a Chloride,
1
I I
Case 1 Case 2 Case 3 Case4 Case 7 Case 8 Case 9 Case11 Case 12 Case 13
Norwegian specifi cation N 0 RSO K Operating parameters of the failed equipment <50 mg/l of chlorides.
M-OO P pro\"ides etwiro n mental re-
strictions for use of CRAs.
Figure 5 compares recommended lim-
iting emironmems for type 316 SS (UNS
S3 1600) in a sour emironmenr.
Review of Analytical Data
of Failures
A practical approach was made ro col-
Ieee and veri fY operating data for the op-
erating plants. Results from rest runs,
subsequent 1-year plant operation data,
and rhe periodic sample analysis resul ts
(laboratory) were collected and \"erified.
Typical data are listed on rhe respecrive
process Row diagrams. 1l1e pressure and
temperature ,alues are rhe typical average
values. 1l1c listed mo niroring results for
pH arc rhc lowest laboratory results and
arc not in situ values. 1l1crc has been
much ,ariacion in chloride content, and
t he maximum values are listed on rhe
diagrams. 1l1e listed partial pressu re of
1-1 JS was t he calcubred value from peri-
odic laboratory analyses of gas on rhe
nearest test poi m in the stream. 1l1c re-
sults were grouped toget her in the respec-
tive corrosion circuits to review rhe envi-
ronment for individual equi pment and
piping.
1l1e clara in Figures 6 through 8 are
plorrcd graphicall y in respect to H
1
S par-
tial pressure, chloride content, and rem-
peramrc-rhe three most cri tical emi ron-
menml conditions for EAC. Comments
FIGURE 7
Fallllntl at Tamp. < 80"C
10,000
----- -- - ------ - - -- -
J
NACE/ISO limit of
pH,S < 3,500 mbar
C> C>
... ...
when Cl < 50 mg/L
... ...
N

J - - - - ! r -
,...-
;;g
C>
. - . ;:. . - . . - .
< 10,000 mg
1,000
....
"'
.,., .,.,
,:::..
....
"' "'
.-
;:..
--
..=.
- -. - --- -. -
...
!i;
"'
Q)

.....
"'
!i;
"' "' "'
In
- r- r-
-
- ... r- - ....
"'
..,
100

N N

....
r-
-
N
N N
r-
r- r-
n n
I 10
0 ppH,S, mbarlal I
[J Temp. c
0 Chloride, mg/ L
I
II _ll_ _l j_j_
Case 1 Case 2 Case 3 Case 4 Case 8 Case 9 Case 10 Case 12
Operating parameters of the failed equipment <60"C.
arc added ro compare the clara with rhc
limiting values fro m NACE. ISO, o r
NORSOK specifications. 1l1e fi ndings arc
discussed as fo llows.
FAILURES BELOW 50 MG/L OF
CHLORIDES IN THE STREAM
Figure 6 displays a roral of I 0 cases out
of 13 chat showed fi1ilurc where chloride
comcnt was below 50 mg/L in rhe fluid
stream, with rhe following fi ndings:
1luee failures-Cases 7. II , and
13-could be am ibwcd ro a higher
operating rcmpcmrure abme t he 60"C
limit as per NACE/ISO. Bur one of
them-Case 13-was also higher rhan
rhe 120"C limir as per NORSOK.
Four failures-Cases 2, 3, 8, and
9-could be att r ibuted to cold
working.
s,ptrmlur 2004 MATERIAlS PERFORMANCE 49
('
Performance SEPTEMBER 2004 http://mp.nace.org
aterials Selection L Design
FIGURES
Failures at Temp. < 60' C, pH
2
S < 1000 mbar and Chloride < 50 mg/ L
1,000 - - - - 1
limit of
,!..
pH,S < 3,500 mbar
J_
NORSOK limit of
pH,S < 100 mbar


,::....
100 - -- -- ----
- - -- -
--- - --- -
-.---.-.


"' "' 1

r...:....
I

rl--

"'
I

10 - -- - - --- - j
0 ppH,S, mbarlal
[]Temp. c
0 Chloride, mg/L
I
I
I
1
Case 1 Case 2 Case 3 Case 4
Operating parameters of equipment that failed >60C.
The remaining rhree cases fuiled with-
in the 3,500-mbar limit of H
2
S as per
NACE/ISO bur abo,e the 100-mbar
limit as per NORSOK specifications.
FAILURES AT TEMPERATURES
BELOW60C
Figure 7 displays a coral of eight cases
our of 13 that failed below 6oc wich rhe
following findings:
Four of the failures-Cases 2, 3, 8,
and 9- could be amibured to cold
forming.
All of the remaining four cases have
fail ed ac H
2
5 le,els higher chan rhe
recommended H
2
S limit of 100 mbar
(for chlorides< 1 %) as per NORSOK
specificat ions.
Case I 0 could be :mribuced co
ppH
2
S abo\'e I ,000 mbar as per
NACEIJSO in the sour gas having
chlorides abO\e rhe limit of 50 mg/L.
FAILURES AT TEMPERATURES
BELOW 60C, H
2
S < 1,000 MBAR,
AND CHLORIDE < 50 MG/L
Figure 8 displays che four cases our of
13 rim f.1i led wi thin che lim irs ofNACE/
ISO in respect to temperature, H
2
5,
and chloride content with the following
findings:
Two fi1i lures, Cases 2 and 3. could
be amibucable co cold working.
50 MATERIALS PERFORMANCE SrptrmLrr 1004
The remaining rwo cases had H
2
S
levels much above che I 00-mbar limits
of NORSOK specifications for chlo-
ride levels of< I o/o.
Conclusions
The findings presented in chis ani-
de establ ish that the seemingly insig-
nificant amounc of chlorides in wet
sour gas is definitely sufficient co cause
EAC of austeni tic SS when then: is a
risk of condensing water. Such is rhc
case in the condensate scabilizarion
and vapor compression section of con-
densate reco\'ery uni ts in a sour gas
processing plane.
1he author's analysis suggests char
synergistic action between chloride
and H
2
S may exist. 1l1e action may
ha,c c.1uscd f.1ilures co occur below
che recommended le\'els of
and H!S.
The present environment li mits
lisred in NACEIISO specifications co
protect rype 316 SS material from
EAC in sour gas-concaining chlorides
were found co be inadequate. Surpris-
ingly, all cases off.1ilures conformed co
NORSOK specifications, except Case
13 being above che 12oc limit.
Using austenitic SS in wee sour gas
senices as listed above is nor recom-
mt:ndcd. Alloys 825, C-4 (UNS
N06455), or C-276 (UNS N10276)
are preferable as they showed satisfac-
tory plant performance in rhe cases
described in this art icle.
The auchor suggests that NACE
re\'iew the environmenc limits for aus-
tenitic SS in view of che planr failures
discussed.
Acknowledgments
The author would like t o thank
GASCO management for giving permis-
sion m publish chis article and his col-
leagues in Inspection, Process, and Main-
tenance, who extended their support in
adding pertinent informacion co this ar-
ticle. The views expressed in this article are
personal opinions of che author and have
no bearing or responsi bi li ry of any nature
should chey pro\'e to be erroneous.
References
1. P. R. Rhode>. "EJI\ironniCJH-A>. <isccd Cr-Jck-
ing of Corrosion-Rcsiscanc Allor s in Oil and Gas
Production En\'ironmcncs: A Rcicw," Corrosion
57, 11 (2001).
1. NACE S1a nd:t rd MR01 75-2003. "Meals
for Sulphide Sncss Crncking and S1ress Corrosion
Cr.cking Rc.i>lancc in Sour Oilfield Eniro111ncm''
(Houscon, TX: NACE. 1003).
3. European Federmion of Corrosion Publica
don- 17, "Corrosion Rcsisc:t nc Allors for Oil and
Ga. l'roduc1ion: Guidance on Genernl Requirements
and Tcs1 lvlc1hods for H"S Scnicc" (l ondon. U.K.:
EFC).
4. ISO 15156-3, ''l'erroleum and Na1urnl G:tS
lndusnics-1\l:t!crial for Usc in H,S Comaining En
ironmcm in Oil and G:ts Produc1ion- P:m 3: Cmck-
ing Rcsis1am CRt\s (CorrosionRcsimm Allo)'S) and
01hcr Alloys" (Genc\':1, Swittcrland: ISO).
5. Norwcgklll Technology Centre Petroleum
S1andardis:uion. NORSOK M-OO I: Materials sclc.:-
lion. Rc . . (Nonvar : No. 2002).
VIRENDRA SINGH is Senior Metallurgical En-
gineer with GASCO, Projects Engineering. PO
Box 665, AbuDhabi, U.A.E. He has more than
33 years of experience in the oil and gas indus
tries in plant integrity, inspection, maintenance,
corrosion, and engineering disciplines from
wellhead to oil and gas production, oil refiner
ies, gas processing, and petrochemical plants
in India. l'raq, Kuwait, Qatar. and the U.A.E. He
holds a B.S. in metallurgical engineering. He
is a NACE Corrosion Specialist, CP Specialist,
and board member of the NACE U.A.E
Chapter. lVP