Corrosión +important

Review
Key issues ielaled lo modelling ol inleinal

coiiosion ol oil and gas ielines A ieview
Sidjan esic
*
Insiiiuie for Corrosion and Auliiphase Technology, Ohio Unitersiiy,
342 esi Siaie Sireei, ihens, OH 45701, US
Received 20 DecemLei 2005; acceled 5 1une 2007
AvailaLle online 14 1uly 2007
Abstract
Tle slale-ol-lle-ail in modelling ol inleinal coiiosion ol oil and gas ielines made liom caiLon
ioleclive scales and scales, lemeialuie, ow, sleel, inliLilion, walei condensalion, glycolfmellanol
and localized allacl. Vaiious mallemalical modelling slialegies aie discussed.
2007 !lseviei Ilo. All iiglls ieseiveo.
Keywords. A. Acelic acid; A. H
2
S; B. CO
2
coiiosion; B. Review; B. Walei welling
Contents
1. !nlioduclion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4309
2. Tle Laclgiound. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4311
2.1. Lleclioclemisliy ol CO
2
coiiosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4311
2.1.1. Anodic ieaclion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4311
2.1.2. Callodic ieaclions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4313
2.2. Lllecl ol walei clemisliy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4314
2.2.1. Pioleclive scales . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4316
2.2.2. Tle ellecl ol H . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4318
2.2.3. Tle ellecl ol CO
2
ailial iessuie . . . . . . . . . . . . . . . . . . . . . . . . . . . 4319
0010-938X/$ - see lionl mallei 2007 Llseviei Ild. All iiglls ieseived.
doi:10.1016/j.coisci.2007.06.006
*
Tel.: 1 740 593 9945; lax: 1 740 593 9949.
E-nail address. nesicolio.edu
Available online at www.sciencedirect.com
Coiiosion Science 49 (2007) 43084338
www.elseviei.com/locale/coisci
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2.2.4. Tle ellecl ol HAc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4320
2.2.5. on-ideal Lelavioui . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4322
2.3. Tle ellecl ol lemeialuie. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4322
2.4. Tle ellecl ol llow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4322
2.4.1. Mullilase llow. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4324
2.5. Tle ellecl ol sleel lye . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4324
2.6. Lllecl ol coiiosion inliLilion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4325
2.6.1. Coiiosion inliLilois . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4325
2.6.2. Coiiosion inliLilion Ly ciude oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4325
2.7. Lllecl ol condensalion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4325
2.8. Lllecl ol glycolfmellanol. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4326
2.9. Iocalized allacl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4326
3. Tle mallemalical models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4327
3.1. Meclanislic models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4328
3.1.1. Tle Leginnings. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4328
3.1.2. Lleclioclemical models. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4329
3.1.3. Tiansoil Lased eleclioclemical models . . . . . . . . . . . . . . . . . . . . . . . 4331
3.2. Semi-emiiical models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4332
3.3. Lmiiical models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4333
4. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4334
Releiences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4336
1. Introduction
Building models ol lysico-clemical iocesses las many uioses. Tley aie ol lel lo
an engineei in indusliy as mucl as lo a ieseaiclei in a laLoialoiy. Models (slould) ieecl
a way ol llinling, a way ol maling sense ol all lle accumulaled inloimalion, a way ol
seeing low il all nls logellei (oi does nol), and lasl Lul nol leasl aie a lool lo iedicl wlal
may laen in lle luluie. Models aie lools llal can assisl engineeis in maling decisions
ielaled lo design, oeialions and conliol.
ol all models aie endless iows ol comlex equalions. Qualilalive, lysico-clemical
models aie wlal we ollen ielei lo as e\planaiions, and lley aie lle laidesl ones lo come
Ly. !l somelling can Le exlained lle iesl ol lle modelling iocess is usually a mallema-
lical exeicise.
!n lle lexl Lelow, lle slale-ol-lle-ail in modelling ol inleinal coiiosion ol oil and
gas ielines made liom caiLon sleel is ieviewed. Tlis aiea ol coiiosion is ollen
ieleiied lo simly as ``caiLon dioxide coiiosion``, even il il liequenlly involves ollei
coiiosive secies sucl as lydiogen sullide, oiganic acid, elc. Tle ieview Lelow locuses
iimaiily on lysico-clemical modelling ol sweel (CO
2
) coiiosion, wlile a discussion ol
soui coiiosion (due lo H
2
S) exceed lle scoe ol llis aei. Tle aei ieecls low
mucl lle aulloi Lelieves we undersiand aLoul lle comlex iocesses undeilying CO
2
veiled inlo mallemalical equalions aie oullined in lle second ail ol lle aei. Many
ol lle delails aLoul lle equalions as well as mosl ol lle numeiical and iogiamming
asecls ol modelling aie omilled and lle inleiesled ieadei is ieleiied lo lle oiiginal
uLlicalions.
S. Nesic / Corrosion Science 49 (2007) 43084338 4309
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Nomenclature
f1 suilace aiea-lo-volume ialio, 1fm
b
a
, b
c
anodic and callodic Talel sloe, Vfdecade
c
j
concenlialion ol secies j, lmolfm
3
c
i
and c
concenlialions ol ieaclanls and ioducls, lmolfm

3
CR coiiosion iale, mmfy
CO
2
|
L
Lull concenlialion ol dissolved caiLon dioxide, molfm
3
d diolel diamelei, m
D
2
fs, ie diamelei, m
D
ell
)
D
m
)
D
l
)
j, in m
2
fs
D
m
)
j, in m
2
fs
D
l
)
2
fs
E
iev
ieveisiLle olenlial, V
1 !aiaday conslanl (96,490 Cfequiv.)
f coiieclion lacloi, conslanl in !iumlin model, liiclion lacloi
H
|
s
, H
|
L
suilace and Lull lydiogen ion concenlialion, molfm
3
HAc|
s
, HAc|
L
suilace and Lull liee acelic acid concenlialion, molfm
3
i cuiienl densily, Afm
2
i
a
anodic cuiienl densily, Afm
2
i
c
callodic cuiienl densily, Afm
2
i
cl
claige lianslei comonenl ol lle lolal cuiienl densily, Afm
2
i
o
exclange cuiienl densily, Afm
2
i
lim
limiling cuiienl densily, Afm
2
i
d
lim
2
i
i
lim
clemical ieaclion limiling cuiienl densily, Afm
2
k
m
k
l
and k
L
loiwaid and Laclwaid ieaclion iale conslanls
k
l
lyd
loiwaid ieaclion iale loi lle CO
2
lydialion ieaclion, 1fs
K
afd
equiliLiium conslanl loi inliLiloi adsoilionfdesoilion
K
lyd
equiliLiium conslanl loi lle CO
2
lydialion ieaclion
K
s
soluLilily limil
A molai mass, lgflmol
p
CO2
ailial iessuie ol caiLon dioxide gas, Lai
F univeisal gas conslanl (8.3143 1f(mol K))
F
j
souice oi sinl ol secies j due lo clemical ieaclions, lmolfm
3
s
R
!eCO
3
ieciilalion iale ol iion caiLonale, mmfy
Fe tlf Reynolds numLei
i lemeialuie, C, oi lime, s
S sueisaluialion
ST scaling lendency
T aLsolule lemeialuie, K
t velocily, mfs
U
c
sueincial velocily ol lle conlinuous lase, mfs
1
coi
coiiosion iale, mmfy
4310 S. Nesic / Corrosion Science 49 (2007) 43084338
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Tle lollowing loics will Le coveied in lle lexl Lelow:
Lleclioclemisliy ol CO
2
coiiosion.
CO
2
walei clemisliy including loimalion ol ioleclive scales and scales.
Iocalized allacl.
Mallemalical modelling slialegies.
2. The background
2.1. Elecirochenisiry of CO
2
corrosion
Aqueous CO
2
coiiosion ol caiLon sleel is an eleclioclemical iocess involving lle ano-
dic dissolulion ol iion and lle callodic evolulion ol lydiogen. Tle oveiall ieaclion is:
!e CO
2
H
2
O !eCO
3
H
2
1
Tle eleclioclemical ieaclions aie ollen accomanied Ly lle loimalion ol scales sucl as
!eCO
3
(andfoi !e
3
O
4
ailiculaily al liglei lemeialuie), wlicl can Le ioleclive oi non-
ioleclive deending on lle condilions undei wlicl lley aie loimed.
2.1.1. nodic reaciion
Tle anodic dissolulion loi iion in acid solulions:
!e !e 2e 2
las Leen sludied exlensively will seveial mulli-sle meclanisms suggesled lo exlain lle
vaiious exeiimenlal iesulls. Tle ieaclion is H deendenl in acidic solulions will a
We
o
o
DU
2
c
WeLei numLei
\ salial cooidinale, m
oiosily ol lle scale, walei cul
E E
iev
oveiolenlial, V
viscosily, lgf(m s)
densily, lgfm
3
o
oil densily, lgfm
3
mixluie densily, lgfm

3
ialio Lelween lle lliclness ol lle mass lianslei and clemical ieaclion
Loundaiy layei
ie inclinalion, degiees
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ieaclion oidei will iesecl lo OH Lelween 1 and 2, decieasing lowaid 1 and 0 al H 4.
Measuied Talel sloes aie lyically 3040 mV. Tlis suLjecl, wlicl is conlioveisial will
iesecl lo lle meclanism, is ieviewed in delail Ly Diazic 1| and Ioienz and Heuslei
2|. Tle anodic dissolulion in aqueous CO
2
solulions las, unlil iecenlly 3|, nol Leen
lle suLjecl ol delailed meclanislic sludies.
Tle meclanism lound Ly Bocliis el al. 4| (BDD) in sliong acids:
!e H
2
O !eOH H e
!eOH
ids
!e OH e 3
!eOH H !e H
2
O
wlicl iedicls a Talel sloe ol 2FTf31 40 mV al 25 C and a ieaclion oidei will iesecl
lo OH equal lo one, las liequenlly Leen assumed lo aly in CO
2
solulions. !l was ovei-
looled llal lle exeiimenlal iesulls iesenled Ly Bocliis el al. 4| slow llal lle H
deendency decieases iaidly aLove H 4 and llal is exaclly lle aiea ol CO
2
coiiosion
wleie il was suLsequenlly (aL)used 58|.
Huilen el al. 9|
Ly CO
2
in aqueous sall solulions, Lul llal CO
2
slimulales iion dissolulion in lle inleime-
diale ieassive slale. Tley ieoiled a Talel sloe ol ca. 30 mV al 25 C and a nisl oidei
deendency.
Giay el al. 7,8|
sleel coiiosion in aqueous CO
2
solulions and lleii ``modelled`` Talel conslanls loi anodic
iion dissolulion incieased liom 50 lo 120 mV in lle H iange 210 wleieas lle exclange
cuiienl densily (i
o
) values weie ielalively indeendenl ol H. Tley also ieoiled llal lle
anodic olaiizalion cuive in lle iegion neai lle coiiosion olenlial was signincanlly
incieased Ly lle iesence ol dissolved CO
2
al H 610. !l was also lound llal lle Talel
conslanls loi lle anodic dissolulion ol iion deiived liom lle sludy weie iooilional
lo lle aLsolule lemeialuie T, and llal lle i
o
values in lle iesence and aLsence ol
CO
2
weie iooilional lo 1fT u lo 60 C, aLove wlicl lemeialuie lle deendency
was suLslanlially decieased. Tle lallei is ioLaLly due lo loimalion ol ioleclive iion cai-
Lonale layeis wlicl clanged lle linelics ol lle iocess.
Tle de Waaid and Milliams 5| model loi aqueous CO
2
coiiosion assumed llal lle
BDD meclanism alied. Tley oLlained similai Talel sloes 3040 mV in lle aLsence
and iesence ol CO
2
and no clange in lle osilion ol lle Talel sloe. Davies and Buislein
10| suggesled llal lle loimalion ol lle comlex !e CO
3
2
2
duiing lle coiiosion ol iion in
LicaiLonale solulion goveins lle anodic Lelavioui ol iion in lle aclive iegion.
Videm 11| lound llal lle anodic dissolulion in aCl solulion, al p
CO
2
1 Lai, in lle
aclive iegion lad a ieaclion deendency will iesecl lo OH equal lo 1 al H 4.2. Al
liglei H values lle dissolulion was indeendenl ol H. Al H 4.3 lle iesence ol CO
2
cenlialion ol lle LicaiLonale ions.
!n a moie iecenl sludy, esic el al. 3| lave ieoiled llal lle anodic dissolulion ol iion
2
lulion in CO
2
solulions comaied lo sliong acids, aie due lo a caiLonic secies acling as a
Since H
2
CO
3
and dissolved CO
2
aie lle only caiLonic secies wlose concenlialions do nol
deend on H, and since lle concenlialion ol CO
2
is lai liglei ol lle lwo, il was assumed
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lle ligand !e
I
!eCO
2
is loimed as an adsoiLed secies al lle elecliode suilace. Seveial
delailed mulli-sle models weie iesenled lo exlain lle vaiious nndings. Tle lollowing
meclanism was ioosed lo exlain lle exeiimenlal iesulls al H 5:
!e CO
2
!e
I
!e
I
H
2
O !e
I
OH
ad
H e
!e
I
OH
ad
ids
!e
I
OH
ad
e
!e
I
OH
ad
H
2
O !e
I
OH
2ad
H
!e
I
OH
2ad
!e
I
OH
2sol
!e
I
OH
2sol
2H !e
2
CO
2
2H
2
O
4
2.1.2. Caihodic reaciions
Tle iesence ol CO
2
incieases lle iale ol coiiosion ol iion in aqueous solulions Ly
incieasing lle iale ol lle lydiogen evolulion ieaclion. !n sliong acids, wlicl aie com-
lelely dissocialed, lle iale ol lydiogen evolulion cannol exceed lle iale al wlicl H
ions
can Le liansoiled lo lle suilace liom lle Lull solulion. !n solulions will a H 4 llis
mass lianslei conliolled limiling cuiienl is small and lle iesence ol H
2
CO
3
enaLles
lydiogen evolulion al a mucl liglei iale. Tlus al a given H lle iesence ol CO
2
leads
lo a mucl liglei coiiosion iale llan would Le lound in a solulion ol a sliong acid.
Desile moie llan lliee decades ol inlense ieseaicl, il is slill nol lnown will aLsolule cei-
lainly wlellei H
2
CO
3
is ieduced diieclly (as assumed Ly many woileis in lle neld)
5,7,12| oi lle nnal sle in lle ieaclion lollows lle dissocialion ol lle H
2
CO
3
13|. Many
lave assumed llal lle lwo ieaclions aie indeendenl and lle nel callodic cuiienl is lle
sum ol lle cuiienls loi lle lwo ieaclions 7| (see !ig. 1):
-1.1
-1
-0.9
-0.8
-0.7
-0.6
-0.5
-0.4
0.01 0.1 1 10 100
i / (A/m
2
)
experiment - pipe sample
experiment - rotating cylinder
model - Fe oxydation
model - H + reduction
model - H
2
CO
3
reduction
model sweep
!ig. 1. Piedicled and measuied olenliodynamic swees illuslialing lle lwo callodic ieaclions undeilying CO
2
coiiosion. Tesl condilions: H 4, 20 C, P
CO2
1 Lai, 2 mfs, c
!e
2 2 m. Model ol esic el al. 21| was used.
Lxeiimenlal dala lalen liom esic el al. 69|.
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2H 2e H
2
5
2H
2
CO
3
2e H
2
2HCO
3
6
Tle limiling cuiienls loi lydiogen evolulion in aqueous CO
2
solulions do nol iesond
lo clanges in lle solulion ow iale in a mannei llal would Le execled loi a wlolly mass
lianslei conliolled ieaclion, and lle liglei lle H lle less lle iesonse lo ow iale
clanges. Tlis las Leen exlained on lle Lasis llal lle ielenislmenl ol lle H
2
CO
3
is con-
liolled Ly lle slow lydialion ol dissolved CO
2
. Sclmill and Rollman 6| weie lle nisl lo
oLseive lle clemical ieaclion comonenl ol lle limiling cuiienl, suggesling a leleioge-
inum and iion, lomogeneous conliol is now acceled 12|.
Hydiogen evolulion liom lle diiecl ieduclion ol walei wlicl occuis al lowei olenlials
Lecomes imoilanl 14,15| al H 5 and veiy low ailial iessuies ol CO
2
2H
2
O 2e H
2
2OH 7
Giay el al. 8| lave suggesled llal in CO
2
solulions al liglei H lle diiecl ieduclion ol
lle LicaiLonale ion Lecomes imoilanl:
2HCO
3
2e H
2
2CO
2
3
8
due lo lle incieasing concenlialions ol LicaiLonale will incieasing H. Wlile aealing,
ollei lwo (Lqs. (5) and (6)). !ndeed il las Leen oLseived llal lle coiiosion iales sleadily
deciease will H in lle iange 4 H 7 wlile lle concenlialion ol LicaiLonale ion slea-
dily incieases, Liinging lle signincance ol ieaclion (8) inlo queslion.
2
coiiosion is lle walei
clemisliy. Tle secialion can vaiy liom veiy simle, will only a lew caiLonic secies
iesenl, as is lle case will condensed walei in gas ielines, lo veiy comlex will numei-
ous secies lound, loi examle, in loimalion walei emeiging logellei will ciude oil. !n
lle lallei case lle icluie can Le comlicaled luillei Ly lle iesence ol secies llal ai-
lilion inlo lle walei liom lle oil lase. !n some cases lle concenlialion ol dissolved salls
can Le veiy ligl (10 wl) maling lle solulion non-ideal. A lisl ol lyical dissolved
secies lound in loimalion walei is given in TaLle 1.
Coiiosion ol mild sleel in oilneld Liines is ielaled lo lle iesence ol dissolved gases:
CO
2
in lle nisl lace and in some inslances H
2
S. !n many cases oiganic acids aie iesenl
and in ailiculai acelic acid
1
(HAc) llal can aggiavale lle coiiosion ioLlem luillei, as
will Le discussed Lelow. Dissolved CO
2
lydiales lo loim caiLonic acid, wlicl dissociales
lo give a lydiogen ion and a LicaiLonale ion, wlicl dissociales again lo give anollei
lydiogen ion and a caiLonale ion. Similai laens will dissolved H
2
S wlicl also goes
lliougl lwo dissocialion sles and acelic acid wlicl dissociales in one sle. A lisl ol mosl
common clemical ieaclions llal need lo Le accounled loi in Liine clemisliy is given in
TaLle 2. Vaiious salls can ieciilale il lleii soluLilily is exceeded, lle mosl imoilanl
1
Acelic acid is commonly used as `ìeiesenlalive`` loi all ollei walei soluLle oiganic acids wlicl aie lound in
2
coiiosion ol mild sleel is well undeislood.
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Leing iion caiLonale !eCO
3
, and vaiious lyes ol scale lyically iicl in calcium (CaCO
3
,
CaSO
4
\ndeislanding Liine clemisliy is an imoilanl iecondilion loi iedicling CO
2
coiio-
sion. Secialion can Le deleimined Ly solving a sel ol equalions loi lle clemical equiliLiia
comlemenled will lle eleclioneulialily equalion. !oi lle case ol ideal (dilule) solulions,
in lle aLsence ol comlex loimalion, lle sel ol equiliLiia equalions lo Le solved is lisled in
TaLle 2. Two main scenaiios can Le encounleied in lle calculalion iocess:
wlen H is accuialely lnown (wlal is inliequenl in lle neld Lul common in lle laL),
leading lo a simle ioceduie wleie lle secialion calculalion is veiy sliaigllloiwaid;
wlen lle H is unlnown and lle LicaiLonale HCO
3
conlenl is lnown liom lilialion
(lyical loi lle neld). !n lle lallei case lle calculalion is only sligllly moie involved as
one las lo solve a cuLic equalion lo oLlain lle H.
TaLle 1
Secies lyically lound in oilneld Liines
CO
2
Dissolved caiLon dioxide
H
2
CO
3
CaiLonic acid
HCO
3
BicaiLonale ion
CO
2
3
CaiLonale ion
H
Hydiogen ion
OH Hydioxide ion
!e
2
!ion ion
Cl Clloiide ion
a
Sodium ion
K
Polassium
Ca
2
Calcium ion
Mg
2
Magnesium ion
Ba
2
Baiium ion
Si
2
Slionlium ion
CH
3
COOH (HAc) Acelic acid
CH
3
COO (Ac ) Acelale ion
HSO
4
Bisullale ion
SO
2
4
Sullale ion
TaLle 2
Clemical ieaclions lyical loi oilfgas neld Liines and lleii equiliLiium conslanls
Reaclion LquiliLiium conslanl
Dissolulion ol caiLondioxide CO
2
(g) CO
2
K
sol
C
CO2
P
CO2
Walei dissocialion H
2
O
Kl wa
KL wa
H OH K
wa
C
H
C
OH
CaiLondioxide lydialion CO
2
H
2
O
Kl lv
KL ly
H
2
CO
3
K
ly
C
H2CO3
C
CO2
CaiLonic acid dissocialion H
2
CO
3
Kl ca
KL ca
H HCO
3
K
ca
C
H
C
HCO
3
C
H2CO3
BicaiLonale anion dissocialion HCO
3
Kl Li
KL Li
H CO
2
3
K
Li
C
H
C
CO
2
3
CHCO
3
Acelic acid dissocialion HAc
Kl ac
KL ac
H Ac KHAc C
H
CAc CHAc
Hydiogen sullale anion dissocialion HSO
4
Kl HSO
4
KL HSO
4
H SO
2
4
K
HSO
4
C
H
C
SO
2
4
C
HSO
4
Values loi vaiious conslanls aie ieadily availaLle elsewleie 17|.
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Tleie is one imoilanl olenlial souice ol eiioi associaled will lle second, indiiecl
mellod ol calculaling lle H. Due lo lle lacl llal HAc was ollen nol included in clemical
analyses ol Liines, laige eiiois in H calculalion weie made wlen acelale concenlialion
was mislalenly ``lumed inlo`` LicaiLonale. A simle examle can illusliale lle oinl.
Iel us imagine llal al 80 C, 1 Lai CO
2
, lilialion analysis indicales HCO
3
0 013 M
in lle Liine. Bacl-calculalion gives H 6.3. Tlis is a ielalively ligl H, wlicl in comLi-
nalion will lle ligl lemeialuie could lead lo ioleclive iion caiLonale scale loimalion.
Aclually will viilually any leiious ion iesenl in lle Liine sueisaluialion will iesecl lo
iion caiLonale is aclieved (e.g. loi !e
2
1 m, iion caiLonale sueisaluialion is
aioximalely 15, i.e. lle amounl ol dissolved iion caiLonale is 15 limes liglei llen al
equiliLiium). ow lel us assume llal mosl ol lle measuied LicaiLonale is aclually acelale
(HCO
3
0 003 M, Ac 0.010 M). Tlis coiiesonds lo aioximalely 60 m ol undis-
socialed (``liee``) acelic acid in solulion, a ielly common value loi many nelds. Bacl-
calculalion gives H 5.6 wlicl is a laige discieancy wlen comaied lo H 6.3. Tle
solulion is now undeisaluialed will iesecl lo iion caiLonale and ioleclive scales aie
nol lilely lo loim, i.e. mucl liglei coiiosion iales could Le execled. Tlis examle cleaily
indicales llal caielul analyses, wlicl dislinguisl HCO
3
liom Ac , aie needed in oidei lo
ioeily calculale lle H in lle neld.
2.2.1. Proieciite scales
Wlen lle soluLilily ol a sall is exceeded, il will ieciilale wlal could lead lo loimalion
ol a ioleclive scale. Tle mosl common lye ol scale encounleied in CO
2
coiiosion is iion
caiLonale.
!e
2
CO
2
3
!eCO
3
9
Wlen iion caiLonale ieciilales al lle sleel suilace, il can slow down lle coiiosion
iocess Ly:
coveiing (inliLiling) a oilion ol lle sleel suilace.

!ion caiLonale scale giowll and ils iolecliveness deend iimaiily (Lul nol exclu-
sively) on lle ieciilalion iale. As lle sleel suilace coiiodes undei lle scale, coiiosion
conlinuously undeimines lle scale. As voids aie ciealed, lley aie nlled u Ly lle ongoing
ieciilalion, elc. Wlen lle iale ol ieciilalion al lle sleel suilace exceeds lle iale ol
coiiosion (scale undeimining) dense ioleclive scales loimsomelimes veiy llin
( 1 m) Lul slill ioleclive. Vice veisa, wlen lle coiiosion iocess undeimines lle newly
loimed scale laslei llan ieciilalion can nll in lle voids, a oious and unioleclive scale
loims - wlicl can Le somelimes veiy llicl ( 100 m) and slill unioleclive.
imoilanl one is walei clemisliy, discussed Lelow. !n oidei lo oLlain aieciaLle levels
ol ieciilalion, sueisaluialion will iesecl lo iion caiLonale las lo Le exceeded. Al
ioom lemeialuie, lle iocess ol ieciilalion is veiy slow and unioleclive scales aie
usually oLlained, even al veiy ligl sueisaluialions. Conveisely, al ligl lemeialuie
(e.g. 60 C) ieciilalion ioceeds iaidly and dense and veiy ioleclive scales can Le
loimed even al low sueisaluialion. Aclually, ligl sueisaluialion cannol Le suslained
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loi long al ligl lemeialuie as lle acceleialed ieciilalion iocess will lend lo iaidly
ieluin lle solulion lo lleimodynamic equiliLiium.
An examle ol an iion caiLonale ioleclive scale is slown in !ig. 2. A dense scale is
seen 46 m in lliclness. Tle coiiesonding coiiosion iale lisloiy is slown in !ig. 3.
\ndei ligl sueisaluialion lle coiiosion iale was ieduced iaidly as ioleclive iion cai-
Lonale scales loimed.
!ig. 2. SLM image ol a cioss seclion ol a sleel secimen including an iion caiLonale scale. Lxosed loi 10 l al
T 80 C, H 6.6, P
CO
2
0 54 Lai, c
!e
2 250 m, t 1 mfs. Tle coiiosion iale lisloiy is slown in !ig. 3.
Talen liom esic and Iee 53|.
0
1
2
3
4
5
6
0 2 4 6 8 10 12
Time / hr
OU V3.0
LPR
ioleclive scale loimalion. Tesl condilions: 80 C, H 6.6, P
CO2
0 54 Lai, c
!e
2 250 m, t 1 mfs. Dala
lalen liom esic and Iee 53|. SLM image ol lle coiioded sleel suilace cioss seclion slown in !ig. 2. Coiiosion
iales weie measuied Ly lineai olaiizalion iesislance O\ V 3.0 is lle model ol esic el al. 21|.
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ieview.
!l was slown ieviously Loll exeiimenlally and comulalionally 16| llal H las a
sliong inuence on lle coiiosion iale. Tyical H in CO
2
saluialed condensed walei is
Al H 4 oi Lelow, diiecl ieduclion ol H
ions, Lq. (5), is imoilanl ailiculaily al

lowei ailial iessuie ol CO
2
(see !ig. 4).
condilions loi loimalion ol iion caiLonale scales. Higl H iesulls in a decieased soluLilily
ol iion caiLonale and leads lo an incieased ieciilalion iale and liglei scaling lendency.
To illusliale llis, lle exeiimenlal iesulls liom Clolsli el al. 18| loi vaiious H and
sueisaluialions aie slown in !ig. 5. Al lowei sueisaluialions oLlained al H6 lle coi-
iosion iale does nol clange mucl will lime, even il some iion caiLonale ieciilalion
occuis, ieecling lle lacl llal a ielalively oious, delacled and unioleclive scale is
loimed. Tle liglei H6.6 iesulls in liglei sueisaluialion, laslei ieciilalion and loi-
malion ol moie ioleclive scales, ieecled Ly a iaid deciease ol lle coiiosion iale will
lime.
fHAc incieases will
H maling lle acelic acid less ol a coiiosion ioLlem, ligl H leads lo loimalion ol ollei
lyes ol scales, elc. By almosl all accounls, liglei H leads lo a ieduclion ol lle coiiosion
iale, maling lle ``H slaLilizalion`` (meaning H inciease) leclnique an alliaclive way ol
managing CO
2
coiiosion. Tle diawLacl ol llis leclnique is llal il can lead lo excessive
scaling and can Le iaiely used will loimalion walei syslems.
0
1
2
3
4
5
6
4 5 6
pH
LPR
OU V3.0
caiLonale scales. Tesl condilions: 20 C, P
CO2
1 Lai, 1 mfs, c
!e
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pariial pressure
!n lle case ol scale-liee CO
2
coiiosion, an inciease ol CO
2
ailial iessuie P
CO
2
ly-
ically leads lo an inciease in lle coiiosion iale. Tle commonly acceled exlanalion is
llal will P
CO
2
lle concenlialion ol H
2
CO
3
incieases and acceleiales lle callodic ieaclion,
Lq. (6) P
CO
2
is illuslialed in !ig. 6. How-
evei, wlen ollei condilions aie lavouiaLle loi loimalion ol iion caiLonale scales,
incieased P
CO
2
P
CO
2
leads lo an inciease
5 m c
!e
2 50 m al T 80 C, undei slagnanl condilions. Liioi Lais ieiesenl minimum and maximum
values oLlained in ieealed exeiimenls. Dala lalen liom Clolsli el al. 18|.
0
5
10
15
20
25
30
35
40
3 10 20
CO
2
PartiaI Pressure / bar
LPR
WL
OU V3.0
Electrochemical
4
4
4
5
4
4
2
ailial iessuie P
CO
2
.
Tesl condilions: 60 C, H5, 1 mfs. Dala lalen liom Wang el al. 26|. Coiiosion iales weie measuied Loll Ly
lineai olaiizalion iesislance (IPR) and weigll loss (WI). Liioi Lais denole maximum and minimum values and
lle nguie aLove lle Lais is lle numLei ol ieealed exeiimenls. O\ V 3.0 is lle model ol esic el al. 21|,
eleclioclemical model comes liom Geoige el al. 28|.
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in LicaiLonale and caiLonale ion concenlialion and a liglei sueisaluialion, wlicl accel-
P
CO
2
on lle coiiosion iale in lle
iesence ol iion caiLonale ieciilalion is illuslialed in !ig. 7 wleie in slialined ow coi-
iosion iale is ieduced Loll al lo and Lollom ol lle ie will lle inciease ailial iessuie
ol CO
2
.
HAc is a weal acid, lowevei il is sliongei llan caiLonic acid (K
a
4.76 vs 6.35 al
25 C), and il is lle main souice ol lydiogen ions wlen lle lwo acid concenlialions aie
similai. Some undeislanding ol lle iole ol HAc in CO
2
coiiosion comes liom neld exe-
iience as ielaled lo lle so-called To-ol-Iine-Coiiosion (TIC) 22|. Hedges and McVeigl
23| ieoiled a mild inciease in lle callodic ieaclion in lle iesence ol HAc alllougl lleii
iesulls weie nol lully conclusive. Gaisany el al. 24| uLlisled woil using vollammeliy lo
disc elecliode (RDL) on scale-liee suilaces. Tleii vollammogiams slow lwo waves, wlicl
aie alliiLuled lo lydiogen ion ieduclion (Lq. (5)) and a new callodic ieaclion HAc
ieduclion (!ig. 8):
2HAc 2e H
2
2Ac 10
Tley aigue llal since HAc dissocialion can occui veiy quiclly il is nol ossiLle lo dis-
linguisl lle ieduclion ol lydiogen ions liom diiecl HAc ieduclion al lle elecliode sui-
lace. Sun el al. 25|
HAc on lle callodic and anodic ieaclions using a iolaling cylindei elecliode (RCL) nnd-
26| and Geoige el al. 27| lave
!ig. 7. Lxeiimenlal measuiemenls ol lle coiiosion iale al lle lo and Lollom ol lle ie in mullilase
2
ailial iessuie, P
CO2
on loimalion ol iion caiLonale scale. Tesl
condilions: 90 C, 1
sg
10 mfs, 1
sl
0.1 mfs. Dala lalen liom Sun and esic 43|.
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iecenlly uLlisled an exlensive sludy ol HAc coiiosion and concluded llal HAc is ailic-
ulaily laimlul in ils undissocialed slale. Geoige el al. 28| lave ioosed models ol CO
2
f
HAc coiiosion slowing lle sliong inuence ol velocily on lle HAc conliiLulion lo lle
aluies and low H wlen lle aLundance ol undissocialed HAc can inciease lle CO
2
coi-
iosion iale diamalically as seen in !ig. 9.
Tleoielically solid iion acelale could ieciilale via:
!e
2
2Ac !e(Ac)
2
11
0.00
0.20
0.40
0.60
0.80
1.00
1.20
0 50 100
H
2
S concentration / ppm
20C
60C
80C
2
S on lle CO
2
coiiosion iale; m ieleis lo lle H
2
S concenlialion in lle
gas lase. Dala lalen liom Iee and esic 70|.
0
10
20
30
40
50
60
70
80
0 10 100 1000 5000
HAc + Ac
-
Concentration / ppm
LPR
WL
OU V3.0
Electrochemical
60 C, H 4, 0.5 mfs. Dala lalen liom Geoige el al. 28|. Coiiosion iales weie measuied Loll Ly lineai
olaiizalion iesislance (IPR) and weigll loss (WI). O\ V 3.0 is lle model ol esic el al. 21|. Lleclioclemical
model comes liom Geoige el al. 28|.
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lowevei, iion acelale`s soluLilily is so mucl liglei llan iion caiLonale`s, llal ioleclive
scale loimalion Ly iion acelale does nol ieadily occui. !l las Leen seculaled llal lle ies-
ence ol oiganic acids imaiis lle iolecliveness ol iion caiLonale nlms, lowevei a iecenl
delailed sludy las cleaily ioven llal llis could Le ielaled lo a ieduclion in H in lle ies-
29|. Tleie is no evidence
llal oiganic acids clange lle soluLilily ol iion caiLonale, lowevei, llis woil is slill ongo-
ing and uLlicalion ol lle lalesl iesulls is execled in lle neai luluie.
2.2.5. Non-ideal behatiour
!n many cases ioduced walei las a veiy ligl dissolved solids conlenl (10 wl). Al
sucl ligl concenlialions, lle innnile dilulion lleoiy does nol lold and coiieclions need
on non-ideal lomogenous walei clemisliy is lo coiiecl lle equiliLiium conslanls desciiLed
in TaLle 2, Ly using lle concel ol ionic sliengll. Tlis aioacl seems lo woil well only loi
modeialely concenlialed solulion (u lo a lew wl ol dissolved solids). !oi moie concen-
el al. 44|.
iion caiLonale and ollei scales is slill laigely unlnown. !uilleimoie, il is uncleai low lle
llal coiiosion iales can Le diamalically ieduced in veiy concenlialed Liines, neveilleless
a moie syslemalic sludy is needed.
Al veiy ligl lolal iessuie lle gasfliquid equiliLiia cannol Le accounled loi Ly Heniy`s
non-idealily ol lle CO
2
fnaluial gas mixluie 32| and can Le oLlained Ly solving lle equa-
lion ol slale loi lle gas mixluie.
Temeialuie acceleiales all lle iocesses involved in coiiosion: eleclioclemical, clemi-
cal, liansoil, elc. One would execl llen llal lle coiiosion iale sleadily incieases will lem-
eialuie, and llis is lle case al low H wlen ieciilalion ol iion caiLonale oi ollei
ioleclive scales does nol occui. An examle is slown in !ig. 10. Tle silualion clanges
mailedly wlen soluLilily ol iion caiLonale (oi anollei sall) is exceeded, lyically al a liglei
H. !n llal case, incieased lemeialuie acceleiales iaidly lle linelics ol ieciilalion and
ioleclive scale loimalion, decieasing lle coiiosion iale. Tle eal in lle coiiosion iale is
usually seen Lelween 60 C and 80 C deending on walei clemisliy and ow condilions.
Many ol emiiical models aie Luill lo mimic llis Lelavioui and some aie discussed Lelow.
2
coiiosion wlicl can Le dislin-
guisled Lased on wlellei oi nol ollei condilions aie conducive lo ioleclive scale loima-
lion oi nol.
!n lle case ol coiiosion wleie ioleclive scales do nol loim (lyically al low H as
lound in condensed walei and in lle aLsence ol inliLilois), lle main iole ol luiLulenl
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ow is lo enlance liansoil ol secies lowaids and away liom lle melal suilace. Tlis
may lead lo an inciease in lle coiiosion iale as illuslialed in !ig. 11.
Conveisely, wlen ioleclive iion caiLonale scales loim (lyically al liglei H in io-
duced walei) oi wlen inliLiloi nlms aie iesenl on lle sleel suilace, lle aLove-men-
loimalion ol suilace scalesfnlms oi lo iemove llem once lley aie in lace, leading lo an
incieased coiiosion iale.
0
1
2
3
4
5
6
1 2 4 6 10
VeIocity / m/s
LPR
OU V3.0
iion caiLonale scales. Tesl condilions: 20 C, P
CO2
1 Lai, c
!e
0
5
10
15
20
25
30
35
40
22 40 60
Temperature / C
LPR
WL
OU V3.0
Electrochemical
condilions: H 4, P
CO2
1 Lai, c
!e
2 5 m, 100 m acelic secies (HAc Ac ) t 0.5 mfs. Dala lalen liom
Wang el al. 26|. Coiiosion iales weie measuied Loll Ly lineai olaiizalion iesislance (IPR) and weigll loss
(WI). O\ V 3.0 is lle model ol esic el al. 21|. Lleclioclemical model comes liom Geoige el al. 28|.
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ow disluiLances sucl as valves, consliiclions, exansions, Lends, elc. wleie local
incieases ol neai-wall luiLulence and wall-sleai sliess aie seen. !n addilion, mullilase
ow, and in ailiculai unsleady slug ow, can lead lo signincanl sloil lived uclualions
in lle wall-sleai sliess wlicl can iemove a ioleclive suilace scale ol iion caiLonale oi
ol ciicumslances as discussed in a seaiale leading Lelow.
2.4.1. Auliiphase fow
2
coiiosion
since many ol lle ielines and owlines caiiying oil and gas aie oeialing undei lwo-
siraiifed, slug and annular ow. !n lle liquid lase, walei and oil can ow seaialed oi
mixed will eillei lase Leing conlinuous will lle ollei owing as a diseised lase. Dil-
leienl ow alleins lead lo a vaiiely ol sleel suilace welling meclanisms wlicl gieally
!n lle aLsence ol ioleclive scales mullilase ow can lead lo veiy ligl uclualing
aled will llis aie even laigei uclualions ol lle suilace sleai sliess wlicl can lead lo
iemoval ol ioleclive scale andfoi inliLilois. Pols 30| las ioosed llal lle mass lianslei
iale in mullilase ow can Le modelled Ly using a slandaid mullilase ow simulaloi
couled will a single-lase ow mass lianslei coiielalion and lle lydiaulic diamelei con-
cel. 1eson el al. 31| suggesled llal lle !ioude numLei is imoilanl loi claiacleiizing
2
coiiosion, ailiculaily in slug ow. Recenlly, esic
el al. 21| lave slown an inlegialed CO
2
coiiosionfmullilase ow model wlicl enaLles:
ow allein iediclion;
calculalion ol lle associaled lydiodynamic ioeilies ielevanl loi coiiosion, sucl as:
walei layei velocily, lliclness, elc.;
iediclion ol walei enliainmenlfwelling.
lle coiiosion iale is a loic llal exceeds lle scoe ol llis aei will lle delails lound else-
wleie 21|.
Mosl ol lle sludies ol CO
2
coiiosion locus on a single mild sleel: de Waaid el al. 33|
looled al lle noimalised D! Sl52 sleel. esic el al. 15| lave sludied iedominanlly lle
X65 low caiLon sleel, wlile lle model ol Giay el al. 8| was Lased on exeiimenls will lle
ioduclion casing sleel.
esic el al. 15|, in lleii eleclioclemical model, lave idenlined exclange cuiienl den-
33| gioued all
lle lesled sleels in lwo calegoiies: (a) noimalised sleels and (L) quencled and lemeied
ielalion will lle exeiimenlal dala.
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All lle aLove alies lo lle CO
2
comosilion on ioleclive scale loimalion, mesa allacl and adsoilion ol inliLilois is
even moie comlicaled. !oi examle, il is lnown llal a ligl Ci conlenl can Le Lenencial
loi loimalion ol ioleclive scales Lul deliimenlal loi eiloimance ol ceilain coiiosion
Tle lwo mosl common souices ol coiiosion inliLilion need lo Le consideied:
(a) inliLilion Ly addilion ol coiiosion inliLilois and
(L) inliLilion Ly comonenls iesenl in lle ciude oil.
2.6.1. Corrosion inhibiiors
lelloia ol aioacles in lle oen lileialuie, vaiying liom lle use ol simle inhibiior fac-
iors and lo lle alicalion ol comlicaled nolecular nodelling lecl-
niques lo desciiLe inliLiloi inleiaclions will lle sleel suilace and iion caiLonale scale. A
middle-ol-lle-ioad aioacl is Lased on lle assumlion llal coiiosion ioleclion is
aclieved Ly surface coterage, i.e. llal lle inliLiloi adsoiLs onlo lle sleel suilace and
slows down one oi moie eleclioclemical ieaclions. Tle degiee ol ioleclion is assumed
lo Le diieclly iooilional lo lle liaclion ol lle sleel suilace coveied Ly lle inliLiloi.
!n llis lye ol model one needs lo eslaLlisl a ielalionsli Lelween lle suilace coveiage
and lle inliLiloi concenlialion in lle solulion c
inl
. Tlis is mosl commonly done Ly
lle use ol adsoilion isolleims. !l las Leen slown 34| llal lle !iumlin isolleim can
2.6.2. Corrosion inhibiiion by crude oil
!l las Leen lnown loi a wlile llal CO
2
coiiosion iales seen in lle neld in lle iesence
ol ciude oil aie mucl lowei llen llose oLlained in laLoialoiy condilions wleie ciude oil
on lle CO
2
coiiosion iale.
Tle nisl is a weiiabiliiy
enliains lle walei and ievenls il liom welling lle sleel suilace (conlinuously oi inleimil-
38|.
corrosion inhibiiion Ly ceilain comonenls ol lle ciude oil llal
ieacl lle sleel suilace eillei Ly diiecl conlacl oi Ly nisl aililioning inlo lle walei lase.
coiiosion. !n a iecenl delailed sludy 3537| on lle suLjecl, lle degiee ol inliLilion was
quanlilalively ielaled lo lle clemical comosilion ol lle ciude oil and secincally lo
lle concenlialion ol saluiales, aiomalics, iesins, aslallenes, niliogen and sullui.
Wlen liansoiling naluial gas, due lo cooling ol lle uid, condensalion ol walei
vaoui occuis on lle inleinal ie wall. Tle condensed walei is uie and, due lo dissolved
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CO
2
, las lyically a H 4. Tlis leads lo lle so-called iop-of-ihe-line corrosion (TIC) sce-
naiio. !l lle iale ol condensalion is ligl, lenly ol acidic walei ows down lle inleinal
ie walls leading lo a veiy coiiosive silualion. !l lle condensalion iale is low, lle walei
nlm is nol ienewed and ows down veiy slowly and lle coiiosion iocess can ielease
enougl 1e
2
lo iaise lle local H and saluiale lle solulion, leading lo loimalion ol io-
leclive iion caiLonale scale. Tle scale is ollen ioleclive, lowevei incidenls ol localized
allacl in TIC weie ieoiled 22|. Lillei way, lle slialined oi slialined-wavy ow iegime,
lyical loi TIC, does nol lead lo a good ooilunily loi inliLilois lo ieacl lle uei oi-
lion ol lle inleinal ie wall and iolecl il. A veiy limiled iange ol coiiosion managemenl
olions loi TIC exisls.
To qualilalively and quanlilalively desciiLe lle lenomenon ol coiiosion occuiiing al
mics, lleimodynamics, and leal and mass lianslei in lle condensed walei is needed. A
lull desciilion exceeds lle scoe ol llis ieview, and lle inleiesled ieadei is diiecled lo
see some iecenl ailicles uLlisled on llis loic 22,39|.
Glycol and mellanol aie ollen added lo owing syslems in oidei lo ievenl lydiales
liom loiming. Tle quanlilies aie ollen signincanl (50 ol lolal liquid lase is nol unu-
ol glycolfmellanol on coiiosion comes liom dilulion ol lle walei lase, wlicl leads lo a
decieased aclivily ol walei. Howevei, lleie aie many unansweied queslions sucl as lle
clanges in meclanisms ol CO
2
coiiosion in waleifglycol mixluies wlicl lave yel lo Le
discoveied.
2.9. 1ocali:ed aiiack
As illuslialed aLove, signincanl iogiess las Leen aclieved in undeislanding uniloim
CO
2
coiiosion, willoul oi will ioleclive scales, and lence some successlul uniloim coi-
iosion models lave Leen Luill and will Le discussed Lelow. Howevei, mucl less allenlion
las Leen given lo localized CO
2
coiiosion and il is slill nol well undeislood. !n a landlul
ol iecenl sludies, ow las Leen ioosed as lle main lacloi liiggeiing localized allacl.
!oi examle, Gunallun 40| ioosed a localized coiiosion iediclion model wlicl
alies a luiLulence lacloi lo modily a geneial coiiosion iale iediclion. Sclmill el al.
41| develoed a ioLaLilislic model loi lle iediclion ol ow induced localized coiiosion.
!l is lnown llal lleie aie ollei enviionmenlal laclois, sucl as H, lemeialuie, ailial
iessuie ol CO
2
, elc. llal conliiLule lo occuiience ol localized allacl on caiLon sleel,
and lleieloie a moie geneial model llal could lale llis inlo accounl needs lo Le ul
loiwaid.
Recenlly, a numLei ol indeendenl sludies 42,43| lave suggesled llal localized allacl
can occui wlen lle condilions aie sucl llal ailially ioleclive scales loim. !l is well
lnown llal wlen lully ioleclive scales loim, low coiiosion iales aie oLlained and vice
veisa wlen no ioleclive scales loim a ligl iale ol geneial coiiosion is seen. !l is wlen
lle coiiosive enviionmenl is in Lelween, in lle so-called ``giey zone``, llal localized allacl
is inilialed due lo lle sloclaslic naluie ol lle iocesses undeilying coiiosion. Tleie aie
many lydiodynamic, (eleclio)clemical and melalluigical aiamelei comLinalions llal lall
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iecenlly Leen slown llal lleie is a single aiamelei sucl as sueisaluialion llal can suc-
cesslully desciiLe llis Lelavioui. Sun and esic 43| ioved exeiimenlally llal sueisal-
uialion can Le used as a good iedicloi ol lle ioLaLilily loi localized allacl (see !ig. 12).
Tlis aioacl las iecenlly Leen inlegialed inlo lle exisling quanlilalive CO
2
coiiosion
iediclion models 21|.
Based on moslly anecdolal evidence (neld exeiience), lle iesence ol H
2
S and HAc
was ielaled lo onsel ol localized allacl, lowevei lillle is undeislood aLoul low and wlen
llis may laen.
3. The mathematical models
2
coiiosion aie used nowadays Ly engineeis
in lle oil and gas indusliy. Some aie desciiLed in lle oen lileialuie, olleis aie ioiielaiy
models. Tle lallei aie lyically a vaiialion ol uLlicly availaLle models oi aie duLious
emiiical coiielalions Lased on iaclical exeiience. yLoig 45| las iecenlly ieviewed
lle eiloimance ol a ieiesenlalive samle ol CO
2
coiiosion iediclion models Ly comai-
ing llem lo a neld dalaLase. Comlemenling llal eiloimance-Lased ieview, lle iesenl
comlex iocesses undeilying CO
2
coiiosion. !ndeed, insiglllul commenls could leie Le
limiling lle iesenl ieview iimaiily lo lle models desciiLed in lle oen lileialuie.
!n oidei lo classily lle CO
2
coiiosion models lley lave aiLiliaiily Leen gioued inlo
lliee Lioad calegoiies Lased on low nimly lley aie giounded in lleoiy.
0
2
4
6
8
10
0.0001 0.001 0.01 0.1 1 10 100 1000
SoIution super-saturation IeveI
C1018, begining
C1018, end
X65, begining
X65, end
saturation line
Deeper pits
Shallower
pits
slowing llal lle mosl seveie illing is oLlained loi ielalively small sueisaluialion wlen ailially ioleclive
nlms aie loimed. Dala lalen liom long leim exeiimenls Ly Sun and esic 43|, wleie lle oen symLols denole
sueisaluialion al lle Leginning ol lle exeiimenls and ied-nlled symLols denole end ol exeiimenls.
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Aechanisiic nodels: llese models desciiLe lle meclanisms ol lle undeilying ieaclions
and lave a sliong lleoielical Laclgiound. Mosl ol lle conslanls aeaiing in llis lye ol
models lave a cleai lysical meaning. Many ol lle conslanls aie easily lound in lle lil-
eialuie, wlile some lave slill lo Le oLlained Ly comaiing lle iediclions will availaLle
exeiimenls. Wlen caliLialed will a ieliaLle (and nol necessaiily laige) exeiimenlal dala-
Lase llis lye ol models enaLle accuiale and lysically iealislic inierpolaiion (iediclion
willin lle Lounds ol caliLialing aiameleis), as well as good e\irapolaiion iediclions.
!l is easy lo add new lnowledge lo llese models will minimal modincalion ol lle exisling
model sliucluie and willoul laving lo iecaliLiale all lle model conslanls.
Seni-enpirical nodels: llese models aie only ailly Lased on nim lleoielical lyoll-
lnowledge is availaLle in a way llal lle addilional lenomena aie desciiLed will emii-
ical lunclions. Some ol lle conslanls aeaiing in llese models lave a cleai lysical
and ieliaLle exeiimenlal dalaLase llese models can enaLle good inleiolalion iedic-
lions. Howevei, exliaolalion can lead lo unieliaLle and somelimes lysically uniealislic
laclois andfoi Ly doing a ailial iecaliLialion ol lle model conslanls.
Enpirical nodels. llese models lave veiy lillle oi no lleoielical Laclgiound. Mosl con-
slanls used in llem lave no lysical meaning lley aie jusl Lesl-nl aiameleis lo lle
availaLle exeiimenlal iesulls. Wlen caliLialed will a veiy laige and ieliaLle exeiimenlal
dalaLase, llese models can give good inleiolalion. Howevei, any exliaolalion leads lo
unieliaLle iesulls as lleie aie no assuiances llal lle aiLiliaiy emiiical coiielalions lold
oulside lleii caliLialion domain. Addilion ol any new lnowledge lo llese models is iallei
lois can Le added will a laige degiee ol unceilainly ielaled lo lleii inleiaclion will lle
exisling emiiical conslanls.
3.1. Aechanisiic nodels
3.1.1. The beginnings
Since CO
2
coiiosion is an eleclioclemical lenomenon il is nol suiiising llal a num-
Lei ol aullois slailed oul will mallemalical modelling ol coiiosion Ly desciiLing lle
eleclioclemical iocesses occuiiing al lle melal suilace. Alllougl lleie is no disule
aLoul lle lacl llal lle suilace eleclioclemisliy is an imoilanl lacloi in lle oveiall io-
cess, il was and slill is aigued Ly scelics llal lle iale limiling sle is ollen elsewleie in lle
iocess (e.g. in mass liansoil lliougl a suilace scale) and llal delailed and ollen veiy
comlex modelling ol lle eleclioclemical iocesses is ol limiled value.
One ol lle nisl and mosl widely used meclanislic models is lle one ioosed Ly de
Waaid and Milliams 5,46| in 1973. Based on lle assumlion ol diiecl ieduclion ol
H
2
CO
3
(as iesenled ieviously in lle lexl) and lleii own glass cell exeiimenls, lle
aullois iesenled a coiielalion loi lle coiiosion iale wlicl is a lunclion ol lle and
lemeialuie
log J
coi
7 96
2320
t 273
5 55 10
3
t 0 67logp
CO
2
12
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Tle 0.67 lacloi in lionl ol P
CO
2
was oLlained Ly assuming llal lle H is a lunclion ol
P
CO
2
only; llal is: all lle H
ions in solulion come liom dissocialion ol caiLonic acid.

Wlile llis assumlion lolds loi uiefcondensed waleiCO
2
solulions, lle iesence ol
ollei secies wlicl aie noimally iesenl wlen sleel coiiodes in Liines, means llal llis
is no longei liue. Tle lemeialuie lunclion in (12) was oLlained Ly assuming an Aile-
nius-lye deendence loi a claige lianslei conliolled iocess. !n lleii deiivalion, lle
aullois assumed llal lle anodic iocess ol iion dissolulion ioceeds via a H-deendenl
BDD meclanism 4|. !l is lnown loday llal llis assumlion does nol lold 3,11,15|. As
new exeiimenlal dala emeiged, new model conslanls weie deleimined 32,33| e.g. liom
exeiimenls ol Dugslad el al. 59| willoul clanging lle oiiginal ``Lase equalion``. Tle
scoe ol de Waaid and Milliams 46| model was ievised on seveial occasions 32,33| lo
exlend ils validily inlo aieas wleie ioleclive scales loim, lo accounl loi ligl H in
Liines, velocily, walei welling, glycol, elc. Howevei, llis was done Ly using coiieclion lac-
lois (mullilieis lo lle oiiginal Lq. (12)) wlicl violale lle assumlions undei wlicl lle
oiiginal equalion was deiived. Tlis necessaiily lool lle oiiginal meclanislic modelling
slialegy inlo lle aiea ol semi-emiiical modelling wlicl is discussed in lle lollowing sec-
lion. Desile all lle lleoielical sloilcomings, lle model ol de Waaid and Milliams 46|
slood as one ol lle imoilanl ieleience oinls loi CO
2
coiiosion ieseaicl ovei lle asl
lwo decades and in ils mosl iecenlly ievised loim 33|, is slill used as an inloimal indusliial
slandaid.
3.1.2. Elecirochenical nodels
Almosl lwo decades lalei Giay el al. 7,8| iesenled a moie comlele eleclioclemical
model as a ail ol lleii exeiimenlal sludy ol CO
2
meclanisms. A numLei ol meclanisms
loi lle eleclioclemical ieaclions occuiiing al lle melal suilace weie adoled liom lle lil-
eialuie and included inlo an oveiall model. Tle model conslanls weie deleimined liom
lleii own glass cell exeiimenls and ow cell exeiimenls (loi liglei lemeialuies). !n
ils scoe and aioacl llis was a ``Lieallliougl`` sludy in lle neld ol CO
2
coiiosion
modelling. Tle aullois amLiliously allemled lo covei an uniealislically Lioad uniealislic
iange ol aiameleis (e.g. H 211, i 25125 C) will a iallei simle lleoielical liame-
woil wlicl inevilaLly lead oveisimlincalions and omissions ol some ley lenomena
sucl as scale loimalion elc. Desile ils undouLled olenlial, suiiisingly lew ieseaicleis
in lle neld lave conlinued along llis lleoielical all.
One ol lle iaie lollow-u sludies is lle one Ly esic el al. 15| wleie lle aullois also
iesenled an eleclioclemical model ol CO
2
coiiosion. Plysical conslanls aeaiing in lle
model weie deleimined liom lle lileialuie, oi wlen missing, lound liom numeious iolal-
ing cylindei glass cell exeiimenls. Mosl ol lle exeiimenlal oLseivalions and lysical
conslanls lound in llis sludy connimed lle nndings ol Giay el al. 7,8|. Tle iediclions
made will lle model weie successlully comaied will indeendenl ie-ow glass-loo
exeiimenls demonslialing lle aLilily ol meclanislic models loi exliaolalion. Tle
aullois also comaied lleii iediclions will lwo ollei oulai models al lle lime: lle
semi-emiiical models ol de Waaid el al. 32| and lle emiiical model ol Dugslad el al.
59| (iesenled Lelow) oLlaining ieasonaLle agieemenl.
!n a similai develomenl, Andeilo el al. 44| lave conlinued will lle eleclioclemical
modelling aioacl comLining il will advanced walei clemisliy models. Recenlly Geoige
el al. 28| lave iesenled an exlension ol esic el al. 15| eleclioclemical model wlicl
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!n all ol lle eleclioclemical models menlioned aLove lle callodic cuiienl i
c
is lound
as:
1
i
c
1
i
cl
1
i
lim
13
wleie lle nisl leim ieecls lle claige lianslei conliolled cuiienl:
i
cl
i
o
10
bc
14
wlile lle second leim is lle limiling cuiienl. !n lle case ol H
ieduclion, lle limiling cui-

ienl comes liom lle mass lianslei limilalion loi H
ieduclion:
i
d
lim H
k
m
! H
L
15
and in lle case ol H
2
CO
3
ieduclion lle limiling cuiienl is a consequence ol a slow CO
2
lydialion sle and can Le lound as 47|:
i
r
lim H
2
CO
3
! CO
2
L
D
H
2
CO
3
K
lyd
k
l
lyd
0 5
16
esic el al. 48| lalei ioosed a lleoielical ow mulliliei f loi llis exiession wlicl is
layei is ol lle same oidei ol magnilude as lle ieaclion layei loi H
2
CO
3
lydialion (al
lowei lemeialuies and liglei velocilies).
) coll 17
Paiamelei
Geoige el al. 28| lave slown llal lle limiling cuiienl loi HAc ieduclion is mass lians-
lei limiling and las lle same loim as lle one loi lydiogen ion ieduclion:
i
d
lim HAc
k
m
F HAc
L
18
wleie k
m L
is lle Lull concenlialion
ol HAc.
!oi lle case ol diiecl H
2
O ieduclion lleie is no limiling cuiienl. !oi lle anodic disso-
lulion ol iion uie Talel Lelavioui was assumed close lo lle coiiosion olenlial and lle
anodic cuiienl is:
i
a
i
o !e
10
ba
19
Tle coiiosion olenlial and cuiienl was llen lound liom lle equalily:
i
c
i
a
20
Tle coiiosion iale, CR, can Le calculaled simly liom lle anodic (coiiosion) cuiienl i
a
.
All lle models ol llis lye can Le ciilicised on lle giounds llal wlile lley desciiLed in
delail lle eleclioclemical iocesses occuiiing on lle melal suilace, lle liealmenl ol lle
liansoil iocesses and clemical iocesses in lle Loundaiy layei was oveisimlined. Tlis
is ailiculaily imoilanl wlen a ieliaLle iediclion ol ioleclive scale loimalion is sougll.
Tleieloie a new geneialion ol coiiosion models emeiged wleie lle liansoil and lle
clemical asecls ol CO
2
coiiosion weie imioved.
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3.1.3. Transpori based elecirochenical nodels
Tuigoose el al. 49| weie lle nisl lo ave lle way loi a moie iealislic way ol desciiLing
lle liansoil iocesses in lle Loundaiy layei loi lle case ol CO
2
coiiosion. Wlile lley
suLsequenl sludies ol Pols 30| and olleis 21,17|. Tlis new couled liansoilfeleclio-
clemical aioacl is long eslaLlisled in ollei aieas ol eleclioclemisliy 50| and cievice
coiiosion 51|, and ils essenlial logic is Liiey desciiLed Lelow loi lle case ol CO
2
coiiosion.
!n coiiosion, ceilain secies in lle solulion aie `ìoduced`` al lle sleel suilace (e.g.
!e
2
) wlile olleis aie deleled (e.g. H
) Ly lle eleclioclemical ieaclions. Tlis leads lo

Tle concenlialion ol eacl secies is goveined Ly a secies conseivalion (mass Lalance)
equalion. A univeisal one-dimensional loim ol lle equalion wlicl desciiLes liansoil
loi secies j in lle iesence ol clemical ieaclions, wlicl is valid Loll loi lle liquid Lound-
aiy layei and lle oious scale, is:
c
)
t
accumulalion
1 5
D
ell
)
c
)
x
nel llux
R
)
souice oi sinl due lo clemical ieaclions
21
TuiLulenl conveclion is aioximaled Ly
deleimine exlicilly. Llecliomigialion las Leen neglecled as ils conliiLulion lo lle oveiall
ux ol secies in liee coiiosion is small.
One liansoil equalion ol lle loim (21) can Le wiillen loi eacl secies in lle solulion
(loi a lisl see TaLle 1). Tle iesulling sel ol equalions is solved simullaneously in sace and
ai ihe sieel surface: ux ol secies as deleimined liom lle iale ol lle eleclioclemical
ieaclions given Ly Lqs. (14) and (19);
in ihe bulk : equiliLiium concenlialions ol secies as oLlained Ly solving lle sel ol equi-
liLiia lisled in TaLle 2.
As lle liansoil equalion (21) is liansienl, inilial condilions need lo Le denned. Tyi-
cally a Laie melal suilace will lle solulion in clemical equiliLiium is used as lle inilial
coveied will a ie-exisling mill scale, elc.
Once lle sel ol equalions is solved loi any given lime sle, lle coiiosion iale, CR, can
Le simly calculaled as lle ux ol !e
2
ions al lle melal suilace.
A vaiiely ol clemical ieaclions accomanies lle CO
2
lle suilace concenlialions ol secies, clemical ieaclions can signincanlly allei lle iale
ol eleclioclemical iocesses al lle sleel suilace and lle iale ol coiiosion. Tlis is ailic-
ulaily liue wlen, due lo ligl local concenlialions ol secies, lle soluLilily limil is
exceeded and ieciilalion ol suilace scales occuis.
Tle iale ol a lomogeneous clemical ieaclion (slown in TaLle 2) can Le calculaled,
assuming ideal solulions, as:
R
)
k
l
nr
r 1
c
r
k
L
np
p 1
c
p
22
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Tle iale ol ieciilalion ol iion caiLonale R
!eCO
3 s
can Le desciiLed as:
R
!eCO
3 s
A
J
) 1 K
s
) S 23
Sueisaluialion is denned as:
S
c
!e
2 c
CO
2
3
K
s
24
Tle linelic exiession loi iion caiLonale ieciilalion as ioosed Ly 1olnson and
Tomson 52| oi Van Hunnil el al. 42| can Le used leie loi f(S). !ion caiLonale scale
giowll deends iimaiily on lle ieciilalion iale, R
!eCO
3
as well as lle iale ol undeimin-
ing goveined Ly lle coiiosion iale. Tlis can Le exiessed as a mass Lalance equalion loi
solid iion caiLonale in leims ol lle volumeliic scale oiosily :
t
lilm oiosily clange
M
!eCO
3 s
!eCO
3 s
R
!eCO
3 s
ieciilalion
CR
x
undeimining
25
Solulion ol llis equalion simullaneously will lle liansoil equalion (21) and lle eleclio-
clemical equalion (20) enaLles diiecl calculalions ol oiosily, lliclness as well as lle io-
leclive ioeilies ol iion caiLonale scales. !oi moie delails see esic al al. 53|.
Ollei simlei vaiialions ol liansoil Lased models ol CO
2
coiiosion exisl. !oi examle
Dalayan el al. 54,55|
liansoil equalion (21) and neglecled lle linelics ol clemical ieaclions. Acloui el al. 56|
lave used a similai model lo simulale il ioagalion ol caiLon sleel in CO
2
enviionmenls
undei liglly luiLulenl condilions.
Tle liansoil Lased models oullined aLove can Le ieadily and logically linled lo ow
models and in ailiculai mullilase ow models. One ol lle moie comlele allemls was
iecenlly iesenled Ly esic el al. 21|. Tley lave iesenled an inlegialed CO
2
coiiosionf
mullilase ow model wleie meclanislic mellods weie desciiLed loi iedicling vaiious
ow iegimes (e.g. slug, slialined, annulai) as well as lle loi calculaling ley lydiodynamic
aiameleis in mullilase ow sucl as walei layei lliclness and velocily, wall sleai sliess,
oil and gas ielines is ielaled lo walei wellingfenliainmenl. Rules ol llumL oi emiiical
lunclions weie used in lle asl (discussed in lle seclion Lelow). Tle new model ol esic
el al. 21| Luilds on a well eslaLlisled lydiodynamic lleoiy ol Biaunei 57| and Bainea
58|. A ciileiion loi loiming slaLle walei-in-oil diseised ow was deiived as lle means
ol calculaling lle ciilical velocily loi walei enliainmenl willin lle liquid layei. Two main
lysical ioeilies, na\inun droplei si:e ielaled lo Lieal-u and coalescence and criiical
droplei si:e ielaled lo sellling and seaialion, weie comaied lo deduce llis ciileiion.
3.2. Seni-enpirical nodels
By lai lle mosl commonly used and lle Lesl-lnown model ol CO
2
coiiosion is lle
semi-emiiical model ol de Waaid and collaLoialois 32,33|. !ollowing lle inilial land-
mail sludy 5| wlicl iesulled in a meclanislic model, de Waaid made `ìmiovemenls``
lo lle oiiginal model moslly Ly iecaliLialing lle model conslanls againsl lle emeiging,
moie ieliaLle, exeiimenls (e.g. Dugslad el al. 59|) and Ly adding numeious coiieclion
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laclois lo lle oiiginal coiielalion (12)
cussed Lelow. Ollei semi-emiiical models can Le lound in lle lileialuie 60,61|. Howevei,
lley can Le seen mosl ollen as vaiialions ol lle de Waaid models, wleie lle exeiimenlal
!n lle woil ol de Waaid and Iolz 32|
scales was modelled via a parallel resisiance model:
1
J
coi
1
J
i
1
J
m
26
wleie lle nisl leim on lle iigll land side ieiesenls lle iale ol eleclioclemical iocesses,
wlile lle second denoles mass lianslei. !l is inleiesling llal llis equalion wlicl is io-
osed lollowing a simle elecliical ciicuil analogy aclually iesemLles lle callodic Lq.
(13) wlicl is deiived diieclly liom eleclioclemical lleoiy. Tlis exlains lle success wlicl
lle iesislance model lad in aioximaling lle exeiimenlal iesulls, comaied will lle
oiiginal Lq. (12)
As lle oiiginal Lq. (12) was deiived exclusively loi uiefcondensed walei (low H)
lacloi loi ioleclive scales 32|. Tle lallei was oLlained Ly doing a mulli-dimensional
iegiession on lle ligl lemeialuie CO
2
coiiosion exeiimenls ol !leda el al. 62|. Tle
ioLlem will llis aioacl is llal lle inilial lleoielical coiielalion (12) wlicl was Leing
``coiiecled`` is valid only undei uie claige lianslei conliol condilions. Piesence ol io-
leclive scales ollen imlies mass lianslei conliol ol lle coiiosion iocess llus iendeiing
lle ievious claige-lianslei Lased coiielalion invalid.
!n lle woil ol de Waaid and Iolz 32| lle iesence ol lle oil lase was accounled loi
lliougl a so-called walei-welling lacloi. !iom lle oiiginal exeiimenls ol Wicls and !ia-
sei 63|, a Linaiy iediclion lacloi was exliacled suggesling llal oil-welling will occui only
loi walei culs (conlenls) less llan 30 and velocilies laigei llan 1 mfs wlen all walei can
Le enliained in lle oil lase. Tlis is a ciude ciileiion llal neglecls many ley laclois sucl
as: lle ioeilies ol lle oil and walei lases, lle ow iegime and lle ow geomeliy. !ui-
lleimoie, neld exeiience suggesls llal in some cases coiiosion was oLlained al walei culs
as low as 2, in olleis no coiiosion was oLlained loi walei culs as ligl as 50.
de Waaid el al. 64| in 2001 and 2003 udaled lle oiiginal de Waaid and Iolz 32|
emiiical coiieclion lacloi loi walei welling liom 1993 and ioosed a new emiiical lac-
loi using an analysis Lased on lle emulsion Liealoinl aioacl. A linl Lelween AP!
giavily, emulsion slaLilily and walei welling ol sleel Ly an oilwalei mixluie was consid-
eied Ly laling inlo accounl lle clanges in inleilacial lensions in an oilwaleisleel syslem.
Tlis was a majoi sle loiwaid liom lle oiiginal model, lowevei, wlile agieeing ieason-
aLly well will lle secinc ool ol neld cases used loi ils caliLialion, lle new model
iemained an emiiical coiielalion Luill on limiled neld dala will an unceilain olenlial
elei, oil densily, oil viscosily and syslem lemeialuie on lle ciilical velocily ol lle owing
oil lase iequiied loi enliainmenl.
3.3. Enpirical nodels
One ol lle mosl liequenlly encounleied emiiical models is lle one Ly Dugslad el al.
59| wlicl is Lased on lle same exeiimenlal dalaLase as lle model ol de Waaid el al. 33|.
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Tle inilial aioacl ol Dugslad el al. 59| was lo deleimine a lemeialuie-deendenl
``Lasic equalion`` (a Lesl-nl olynomial lunclion) and llen mullily il Ly lle coiieclion
laclois loi p
CO
2
, H, velocily (sleai sliess) and sleel Ci conlenl. Tle Lasic equalion las
ale ioleclive scales. Tle coiieclion lacloi loi ow was denned as a comLined owei-lawf
exonenlial lunclion ol lle wall-sleai sliess, an aioacl similai lo Lnid el al. 60|. Tle
H and p
CO
2
coiieclion laclois iesemLle llose used Ly de Waaid and Iolz 32|. Tlis sim-
le emiiical model is al lle coie ol lle so-called ORSOK model wlicl las Leen unciil-
ically and widely used due lo lle lacl llal il is ``slandaidized`` and lieely availaLle al
lll:ffwww.slandaid.no.
Anollei examle ol an emiiical CO
2
coiiosion model is lle lineai mullile iegiession
model slown Ly Adams el al. 65|. !l is douLllul llal a lineai model (even il il is mullivai-
iaLle) can desciiLe well lle liglly nonlineai iocesses occuiiing in CO
2
coiiosion.
Moie iecenlly, esic el al. 66| lave iesenled a liglly nonlineai emiiical CO
2
coiio-
sion model Lased on neuial nelwoils () using lle exeiimenlal dalaLase ol Dugslad
el al. 59| loi caliLialion. Tle coiielalion was develoed Ly using a ``Lacl ioagalion``
neuial nelwoil comLined will a genelic algoiillm 67,68|. Geneially, neuial nelwoils
develo a suilaLle analylical model. Duiing lle liaining, lle nelwoil oeiales inleiac-
lively will a genelic algoiillm. Genelic algoiillms aie sloclaslic seaicl lools loi deleimi-
nalion ol lle nllesl ioLlem solulion accoiding lo some ie-denned ciileiia. Tle uiose
ol lle genelic algoiillm, is lo acceleiale lle nelwoil liaining Ly deleiminalion ol lle mosl
ieiesenlalive sequence ol liaining alleins liom lle liaining dala sel. Tle nllesl liaining
sequence geneiales lle minimal liaining eiioi. Tle model demonslialed sueiioi ei-
loimance wlen caliLialed will lle Dugslad el al. 59| dalaLase wlen comaied lo lle
emiiical model ol Dugslad el al. 59|, lle semi-emiiical model ol de Waaid el al. 33|
and lle meclanislic eleclioclemical model ol esic el al. 15|.
Desile llis aaienl advanlage ovei ollei lyes ol modelling, lle ley ioLlem will
lle and ollei lully emiiical models is llal lley aie ``Llacl Loxes`` i.e. lleii iediclion
ndence oulside lleii caliLialion iange (loi exliaolalion). Adding new lnowledge is
ledious and usually iequiies iecaliLialion ol lle enliie model will all lle dala.
4. Conclusions
\ndeislanding inleinal coiiosion in oil and gas ielines made liom caiLon sleel (CO
2
coiiosion) las come a long way ovei lle asl lew decades. Tle inuence ol lle many
imoilanl eleclioclemical, clemical, lydiodynamic and melalluigical aiameleis las
Leen uncoveied, will some majoi clallenges lying alead.
Lleclioclemisliy ol mild sleel dissolulion in CO
2
solulions las laigely Leen undeislood
and modelled, will lle oulslanding issues iimaiily ielaled lo ollei enviionmenls (H
2
S
Key meclanisms leading lo loimalion ol iion caiLonale scales lave Leen idenlined.
elilion ol ieciilalion and coiiosion can lead lo Loll ioleclive and unioleclive sui-
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slill laigely unlnown.
2
coiiosion is well eslaLlisled and successlully modelled, Loll al
low H lyical loi condensed walei as well as liglei H wlen ioleclive scales loim.
!n almosl all cases liglei H leads lo lowei coiiosion iales.
2
coiiosion is an issue llal was lai-
gely ignoied unlil iecenlly. Howevei, majoi advancemenls in undeislanding ol lle iole
ol HAc lave Leen made in lle asl lew yeais will a lew oen issues iemaining, iimai-
CO
2
coiiosion, las Leen claiined. Al low H wlen ioleclive scales do nol loim, lem-
eialuie acceleiales coiiosion and vice veisa wlen condilions aie lavouiaLle loi iion
caiLonale lo loim, lemeialuie leads lo laslei ieciilalion and ollen lo lowei coiio-
sion iales.
ow on CO
2
on ioleclive scalefinliLiloi iemoval needs luillei invesligalion.
!l las Leen slown llal vaiious mild sleels lave aioximalely lle same Lelavioui
wlen il comes lo scale-liee CO
2
as well as inliLiloi eiloimance is an oen issue.
PioLlems ielaled lo iediclion ol coiiosion conliol Ly inliLilion iemain, ailiculaily
wlen il comes lo lle eiloimance ol inliLilois in slug ow, in lle iesence ol suilace
scalesfscales, H
2
S oi HAc.
2
coiiosion ol inliLilois iesenl
in lle ciude oil las Leen inilialed, will a moie dedicaled lollow-u needed llal will
covei a Lioadei iange ol ciude oils.
(TIC) allacl was advanced signincanlly ovei lle asl decade. Remaining clallenges
2
2
coiiosion
exisls. Moie lundamenlal woil is needed Leloie any meaninglul modelling can Le
aclieved.
Iocalized allacl, Leing lle mosl dangeious lye ol CO
2
lo iedicl. Wlile many laclois ianging liom melalluigical, lydiodynamic lo (elec-
lio)clemical can inuence lle onsel ol localized coiiosion, il aeais llal mucl ol
lle evidence oinls lowaids exislence ol a ``giey zone`` wleie localized allacl is moie
lilely lo occui. Tle ``giey zone`` seems lo Le associaled will lle loimalion ol ailially
ioleclive scales.
Vaiious mallemalical modelling slialegies can Le used lo caluie oui undeislanding ol
CO
2
coiiosion.
Aechanisiic nodels aie lle mosl diiecl lianslalion ol oui lnowledge ol lle undeily-
ing iocesses inlo mallemalical lunclions. Tley aie lle laidesl ones lo consliucl
and lave lle laigesl olenlial lo lel engineeis in vaiious slages ol lle design, oei-
alions and conliol oeialions.
Seni-enpirical nodels, wlicl lave a limiled amounl ol inLuill undeislanding, iely
on coiieclion laclois lo eiloim well. Tlese laclois come in lle loim ol aiLiliaiy
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lunclions develoed on saise exeiimenlal dalaLases and lave duLious inleiac-
lions. Wlile Leing signincanlly easiei lo develo llan meclanislic models, lle caa-
Lilily ol semi-emiiical models lo exliaolale is queslionaLle.
Enpirical nodels consisling ol aiLiliaiy mallemalical lunclions ol vaiying comlex-
ily, can lave ieasonaLle oi even excellenl inleiolalion caaLililies Lul lave lo Le
liealed will ulmosl caulion wlen used lo iedicl oulside lley caliLialion iange.
References
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Key issues ielaled lo modelling ol inleinal

concenlialions ol ieaclanls and ioducls, lmolfm

mixluie densily, lgfm

coveiing (inliLiling) a oilion ol lle sleel suilace.

ions, Lq. (5), is imoilanl ailiculaily al

ions in solulion come liom dissocialion ol caiLonic acid.

ieduclion, lle limiling cui-

) Ly lle eleclioclemical ieaclions. Tlis leads lo

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