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INTRODUCTION 3 AQUEOUS CO2 CORROSION OF MILD STEEL 2.1 2.2 3

CHEMISTRY OF CO2 SATURATED AQUEOUS SOLUTIONS EQUILIBRIUM CONSIDERATIONS 4 ELECTROCHEMISTRY OF MILD STEEL CORROSION IN CO2 SATURATED AQUEOUS SOLUTIONS Oxidation of iron 16 Reduction of hydronium ion 16 Reduction of carbonic acid Reduction of acetic acid Reduction of oxygen 22 Reduction of water 23 24 18 20 12

2.2.1 2.2.2 2.2.3 2.2.4 2.2.5 2.2.6 2.3 2.4 2.5 2.6

TRANSPORT PROCESSES IN CO2 CORROSION OF MILD STEEL CALCULATION OF MILD STEEL CO2 CORROSION RATE 27

SUCCESSES AND LIMITATIONS OF MODELING OF AQUEOUS CO2 CORROSION OF MILD STEEL 28 KEY FACTORS AFFECTING AQUEOUS CO2 CORROSION OF MILD STEEL 30 The effect of pH 30 31 The effect of CO2 partial pressure The effect of temperature The effect of flow 34 33

2.6.1 2.6.2 2.6.3 2.6.4 2.6.5 2.6.6 2.6.7 2.6.8 2.6.9 2.7 3

Effect of corrosion inhibition 38 The effect of organic acids Effect of glycol/methanol 39 40

Effect of condensation in wet gas flow 41 Non-ideal solutions and gases 41 42

LOCALIZED CO2 CORROSION OF MILD STEEL IN AQUEOUS SOLUTIONS 43

AQUEOUS H2S CORROSION OF MILD STEEL 3.1 3.2 3.3

CHEMISTRY OF H2S SATURATED AQUEOUS SOLUTIONS EQUILIBRIUM CONSIDERATIONS 44 MILD STEEL CORROSION IN H2S AND MIXED H2S/CO2/HAC SATURATED AQUEOUS SOLUTIONS CALCULATION OF MILD STEEL H2S CORROSION RATE 56 Pure H2S aqueous environment Mixed CO2/H2S Environments 56 60 61 62 53

3.3.1 3.3.2 3.3.3 3.4 3.5

Mixed CO2 / HAc / H 2 S Environments

LIMITATIONS OF MODELING OF AQUEOUS H2S CORROSION OF MILD STEEL KEY FACTORS AFFECTING AQUEOUS H2S CORROSION OF MILD STEEL 63

3.5.1 3.5.2 3.6 4 5

Effect of H2S partial pressure 63 Effect of time 68 72

LOCALIZED H2S CORROSION OF MILD STEEL IN AQUEOUS SOLUTIONS 73

NOMENCALTURE REFERENCES 82

1 INTRODUCTION
Astheoilandgasemergefromthegeologicalformationtheyarealwaysaccompanied by some water and varying amounts of acid gases: carbon dioxide, CO2 and hydrogensulfide, H 2 S .Thisisacorrosivecombinationwhichaffectstheintegrityof mildsteel.Evenifthishasbeenknownforover100years,yetaqueous CO2 and H 2 S corrosion of mild steel still represents a significant problem for the oil and gas industry.1 Although corrosion resistance alloys exist that are able to withstand this typeofcorrosion,mildsteelisstillthemostcosteffectiveconstructionmaterialused in thisindustry fortheseapplications.Allofthe pipelines, many wellsand much of theprocessingequipmentintheoilandgasindustryarebuiltoutofmildsteel.The cost of equipment failure due to internal CO2 / H 2 S corrosion is enormous, both in terms of direct costs such as: repair costs and lost production, as well as in indirect costssuchas:environmentalcost,impactonthedownstreamindustries,etc. Thetextbelowsummarizesthedegreeofunderstandingofthesocalledsweet CO2 corrosionandthesocalledsouror H 2 S corrosionofmildsteelexposedtoaqueous environments. It also casts the knowledge in the form of mathematical equations whenever possible. This should enable corrosion engineers and scientists to build entrylevelcorrosionsimulationandpredictionmodels.

2 AQUEOUS CO2 CORROSION OF MILD STEEL


Aqueous CO2 corrosion of carbon steel is an electrochemical process involving the anodic dissolution of iron and the cathodic evolution of hydrogen. The overall reactionis: 3


Fe + CO2 + H2O FeCO3 + H2

(1)

CO2 corrosion of mild steel is reasonably well understood. A number of chemical,

electrochemical and transport processes occur simultaneously. They are briefly describedbelow.

2.1 Chemistry of CO2 Saturated Aqueous Solutions Equilibrium Considerations


The CO2 gasissolubleinwater:
CO2 ( g ) CO2
K sol

(2)

For ideal gases and ideal solutions in equilibrium, Henrys law can be used to calculate the aqueous concentration of dissolved CO2 , cCO2 , given that the respective concentration in the gas phase (often expressed in terms of partial pressure, pCO2 ) is known:
H sol ( CO2 ) = 1 K sol ( CO2 ) = pCO2 cCO2

(3)

The CO2 solubility constant, K sol (CO2 ) , is a function of temperature, T f , and ionic strength, I :2

K sol ( CO2 ) =
4

14.5 ( 2.27 +5.65103 T f 8.0610 6 T f2 +0.075 I ) 10 1.00258

(4)

Ionicstrength, I ,canbecalculatedas:

I=

1 1 ci zi2 = 2 c1 z12 + c2 z 22 + ... 2 i

(5)

Theconcentrationof CO2 intheaqueousphaseisofthesameorderofmagnitudeas the one in the gas phase. For example at pCO2 =1 bar, at 25oC, the gaseous CO2 concentrationisapproximately4mol/l(kmol/m3)whileinthewateritisabout3mol/l. Since the solubility of CO2 decreases with temperature, at 100oC the respective concentrationsare:3.3mol/linthegasand1.1mol/linthewater. A rather small fraction (about one in five hundred) of the dissolved CO2 molecules hydratestomakeaweakcarbonicacid, H 2CO3 :

CO2 + H 2 O H 2 CO3

K hy

(6)

duetoarelativelyslowforward(hydration)rate.Assumingthattheconcentrationof waterremainsunchanged,theequilibriumconcentration c H 2CO3 isdeterminedby:


K hyd = c H 2CO3 cCO2

(7)

The equilibrium hydration/dehydration constant, K hyd = 2.58 10 3 , does not change muchacrossthetypicaltemperaturerangeofinterest(20100oC).3 Carbonic acid is considered to be weak because it only partially dissociates to producehydronium, H + ionsandbicarbonateion, HCO3 :
H 2 CO3 H + + HCO3
K ca

(8)

The HCO3 dissociatesfurthertogivesomemore H + andcarbonateion, CO32 :


HCO3 H + + CO32
K bi

(9)

Therespectiveequilibriumrelationscanbewrittenas:

K ca =
K bi =

c H + c HCO
3

c H 2CO3
c H + cCO 2
3

(10) (11)

c HCO
3

Theequilibriumconstantscanbecalculatedasfunctionsoftemperature, T f ,andionic strength, I ,as:2

K ca = 387.6 10
K bi = 10
6

6.41 1.594 10 3 T f + 8.52 10 6 T f2 3.07 10 5 p CO2 14.5 0.4772 I 0.5 + 0.118 I


3

10.61 4.97 10

T f + 1.331 10

T f2

2.624 10

p CO2 14.5 1.166 I

0.5

+ 0.3466 I

(12)
(13)

Thelowmolecularweightorganicacidsareprimarilysolubleinwaterandcanleadto corrosionofmildsteel.Highermolecularweightorganicacidsarenotwatersoluble but are typically soluble in the oil phase and pose a corrosion threat at higher temperatures in the refineries. Acetic acid CH3COOH (denoted as HAc in the text below)isthemostprevalentlowmolecularweightorganicacidfoundinbrines.Other acids typically foundinthe brine arepropionic,formic,etc.,howevertheir behavior and corrosiveness is very similar to that of HAc and therefore HAc can be used as a surrogateforalltheorganicacidsfoundinthebrine.HAcisaweakacid,howeverit isstrongerthan H 2CO3 (pKa4.76vs6.35at25C),anditisthemainsourceof H + ions whenthetwoacidconcentrationsaresimilar. Thedissociationofaqueous HAc :

HAc H + + Ac

(14)

is relativelyfast, butproceeds onlypartially i.e.aqueous HAc is alsoaweak acid, justlike H 2 CO3 discussedabove.ThepHi.e.theconcentrationofhydrogenions,[ H + ], determinesthedistributionoftheaceticspeciesinthesolution. The equilibrium constant associated with dissociation of HAc is a function of temperatureandcanbecalculatedas:

K HAc = 10

2 6.66104 0.0134916 TK + 2.37856 10 5 T K

(15)

The dissociation steps (8) and (9) are very fast compared to all other processes occurring simultaneously in corrosion of mild steel, thus preserving chemical equilibrium.However,the CO2 dissolutionreaction(2)andthehydrationreaction(6) aremuchslower.Whensuchchemicalreactionsproceedslowly,otherfasterprocesses (such as electrochemical reactions or diffusion) can lead to local nonequilibrium in thesolution. Either way, the occurrence of chemical reactions can significantly alter the rate of electrochemicalprocessesatthesurfaceandtherateofcorrosion.Thisisparticularly true when, due to high local concentrations of species, the solubility limit of salts is exceeded and precipitation of a surface layer occurs. In a precipitation process, heterogeneousnucleationoccursfirstonthesurfaceofthemetalorwithinthepores ofanexistinglayersincehomogenousnucleationinthebulkrequiresamuchhigher concentration of species. Nucleation is followed by crystalline layer growth. Under certain conditions surface layers can become very protective and reduce the rate of corrosion. In CO2 corrosionwhentheconcentrationsof Fe 2+ and CO32 ionsexceedthesolubility limit,theyformsolidferrouscarbonateaccordingto:

Fe 2+ + CO32 FeCO3 ( s )
wherethesolubilityproductconstantforferrouscarbonate K sp ( FeCO3 ) is:4 8

K sp ( FeCO3 )

(16)

K sp ( FeCO3 ) = 10

59.3498 0.041377 Tk

2.1963 + 24.5724 log Tk + 2.518 I 0.5 0.657 I Tk

(17)

Actually ferrous carbonate is frequently found in the aqueous solution at concentrations much higher than predicted by the equilibrium K sp ( FeCO3 ) . This is termed supersaturation and is a necessary condition before any substantial precipitationcanoccur.Theferrouscarbonatesupersaturation, SS ( FeCO3 ) isdefinedas:

SS ( FeCO3 ) =

cFe2+ cCO2
3

K sp ( FeCO3 )

(18)

The precipitation process can be seen as the process of the solution returning to equilibrium and is driven by the magnitude of supersaturation. The rate of precipitation( FeCO3 )isthereforeoftenexpressedas:

FeCO3 = k r ( FeCO3 )

A K sp ( FeCO3 ) SS( FeCO3 ) 1 V

(19)

where k r ( FeCO3 ) is a kinetics constant, which can be derived from the experimental resultsasafunctionoftemperature,usinganArrheniusstypeequation:5
k r ( FeCO3 ) = e
A( FeCO3 ) B( FeCO3 ) RTk

(20)

where A( FeCO3 ) =21.3and B( FeCO3 ) 64,851.4J/mol.

Images of a crystalline ferrous carbonate layer formed on a mild steel substrate are showninFigure.Theferrouscarbonatelayercanslowdownthecorrosionprocessby presenting a diffusion barrier for the species involved in the corrosion process and therebychangingtheconditionsatthesteelsurface.Theeffectiveprotectivenessofa solid ferrous carbonate layer depends on its porosity which hangs in the balance of theprecipitationrateandtheunderlyingcorrosionrate.Forhighprecipitationrates, and low corrosion rates, a dense and protective ferrous carbonate layer is obtained and vice versa, low precipitation rates and high corrosion rates lead to formation of porous unprotective ferrous carbonate layers. A nondimensional parameter termed scaling tendency ( ST ) can be used to quantify the relative rates of precipitation ( FeCO3 )andcorrosion( CR )expressedinthesamevolumetricunits:

ST =

FeCO3
CR

(21)

For ST <<1, porous and unprotective films are likely to form. Conversely, for ST 1, conditions become favourable for formation of dense, protective ferrous carbonate films.However,theuseofscalingtendencyisnotasstraightforwardasitappears,as itrequiressimultaneouscalculationof FeCO3 andcorrosion CR . Insomecasesothersaltscanbedetectedinthesurfacelayersthatformonmildsteel. In high temperature CO2 corrosion magnetite (Fe3O4) has been detected. In the presenceof oxygen aferricoxide hematite(Fe2O3)formswhich is very insolublebut offerslittleprotectionfromcorrosion.Finally,inthepresenceof H 2 S ,varioustypesof sulfidesformasdiscussedinaseparatechapterbelow. 10

ferrouscarbonate

mildsteel

Figure 1. A cross section and a top view of a ferrous carbonate layer formed on mild steel; 80oC, pH6.6, pCO2 =0.5 bar, stagnant conditions.
11

2.2 Electrochemistry of Mild Steel Corrosion in CO2 Saturated Aqueous Solutions


Theelectrochemicaldissolutionofironinawatersolution:

Fe Fe 2+ + 2e

(22)

is the dominant anodic reaction in CO2 corrosion. The reaction is pH dependent in acidicsolutionswithareactionorderwithrespecttoOHbetween1and2,decreasing toward 1 and 0 at pH >4, which is the typical range for CO2 corrosion. Measured Tafel slopes are typically 3080 mV. This subject, which is still somewhat controversialwithrespecttothemechanism,hasbeenreviewedforacidiccorrosion6,7 and CO2 solutions.8 Thepresenceof CO2 increasestherateofcorrosionofmildsteelinaqueoussolutions primarilybyincreasingtherateofthehydrogenevolutionreaction.Itiswellknown thatinstrongacids,whicharefullydissociated,therateofhydrogenevolutionoccurs accordingto:

2 H + + 2e H 2

(23)

and is, for the case of mild steel corrosion, limited by the rate at which H + ions are transported from the bulk solution to the steel surface (mass transfer limitation). In
CO2 solutionswheretypicallypH>4,thislimitingfluxwouldbesmallandthereforeit

is the presence of H 2CO3 which enables hydrogen evolution at a much higher rate.

12

ThusforpH>4thepresenceof CO2 leadstoamuchhighercorrosionratethanwould befoundinasolutionofastrongacidatthesamepH. This can be readily explained by considering that the homogenous dissociation of

H 2CO3 ,asgivenbyreaction(8),servesasanadditionalsourceof H + ions,whichare


subsequentlyadsorbedatthesteelsurfaceandreducedaccordingtoreaction(23).1A differentpathwayis alsopossible,wherethe H 2CO3 firstadsorbsatthesteelsurface followed by heterogeneous dissociation and reduction of the H + ion. This is often referredtoasdirectreductionofcarbonicacid9,10,11andiswrittenas:

2 H 2CO3 + 2e H 2 + 2 HCO3

(24)

Clearly the addition of reactions (8) and (23) gives reaction (24) proving that the overall reaction is the same and the distinction is only in the pathway, i.e in the sequence of reactions. The rate of reaction (24) is limited primarily by the slow hydrationstep(6)11, 12andinsomecasesbytheslow CO2 dissolutionreaction(2). It can be conceived that in CO2 solutions at pH>5 the direct reduction of the bicarbonateionbecomesimportant: 13

2 HCO3 + 2e H 2 + 2CO32

(25)

what seems plausible, as the concentration of HCO3 increases with pH and can exceed that of H 2CO3 as seen in Figure 2. However it is difficult to experimentally 13

distinguishtheeffectofthisparticularreactionpathwayforhydrogenevolutionfrom thetwopreviouslydiscussed((23and(24).Inadditionevidenceexistswhichsuggests thattherateofthisreactioniscomparativelylowandcanbeneglected.Forexample: asthepHincreases,theamountof HCO3 increasesaswell(seeFigure2),suggesting thatthecorrosionrateshouldfollowthesametrend,ifoneistobelievethatthedirect reduction of the bicarbonate ion (25) is a significant cathodic reaction. Experimental evidencedoesnotsupportthisscenarioandshowstheoppositetrend:thecorrosion rateactuallydecreaseswithanincreasingpH,evenifnoprotectiveferrouscarbonate layerforms. Aceticacidiswellknowntobeoneofthespeciesthatattacksmildsteel.Itwasclearly established that the main cause of mild steel corrosion is the undissociated (free) HAcandnottheacetateionAc.20Thereforethepresenceoforganicacidsisamajor corrosionconcernparticularlyatlowerpH,andparticularlyathightemperature. Beingaweaki.e.partiallydissociatedacid,HAccanbeseenasanadditionalsourceof H+,whicharethenadsorbedatthesteelsurfaceandreducedaccordingtothecathodic reaction(23).ItisalsopossiblethatHAcmoleculeitselfisadsorbedatthesteelsurface followed by the heterogeneous reduction of H+, which is often referred to as the directHAcreductionpathway:

2 HAc + 2e H 2 + 2 Ac

(26)

Although oxygen is not common corrosive specie in oil and gas pipeline system, it could invade the system by inappropriate operation or incomplete deoxidation of 14

waterchemicalsolutionsinjectedintothesystem.Therefore,oxygenislikelytoexist in oil and gas pipelines. Oxygen can contribute to corrosion process by an oxygen reductionreactionasshownbelow:

O2 + 2 H 2 O + 4e 4OH
Hydrogenevolutionbydirectreductionofwater:

(27)

2 H 2O + 2e H 2 + 2OH

(28)

isalwayspossible, butiscomparativelyveryslowandisimportantonlyat pCO2 <<0.1 barandpH>6.14, 15Thereforethisreactionisrarelyafactorinpractical CO2 corrosion situations. The various electrochemical processes described above can be quantified using the well established electrochemical theory. The rate of the electrochemical reactions, inkmol/(m2s),canbereadilyexpressedintermsofcurrentdensity, i inA/m2,since the two are directly related: for example during hydrogen evolution (23) for every kmolof H + onekmolofelectronsisused( n =1kmole/kmol),whileforeverykmolof irondissolved(22)twokmolesofelectronsareused( n =2kmole/kmol).Thereforeone canwrite:
i = nF

(29)

15

2.2.1 Oxidation of iron In corrosion of mild steel, the oxidation (dissolution) of iron (22) is the dominant anodic reaction. The anodic dissolution of iron at the corrosion potential (and up to 200 mV above) is under charge transfer control. Thus, pure Tafel behavior can be assumedclosetothecorrosionpotential:
Ecorr Erev ( Fe )

ia ( Fe ) = io ( Fe ) 10

ba ( Fe )

(30)

The temperature dependence of exchange current density of iron oxidation is a functionoftemperature:


H Fe

io ( Fe ) = i

ref o ( Fe )

1 1 ) Tc + 273.15 Tc , ref + 273.15

(31)

TheTafelslopeofthisreactionisgivenby:

ba ( Fe ) =

2.303 R (Tc + 273.15) 1.5 F

(32)

2.2.2 Reduction of hydronium ion Ingeneral,the H + reductionreaction(23)canbeeitherunderchargetransferormass transfer(diffusion)control,thereforeonecanwrite:

1 i c (H + )
16

1 i (H + )

1 i ( )
d lim H +

(33)

Thechargetransfercurrentdensitycanbecalculatedby:
E corr E
rev H +

i (H + ) = io (H + ) 10

c H +

(34)

The exchange current density io (H + ) is a function of pH and temperature. The pH dependenceis:

log io (H + ) pH

= 0 .5

(35)

Thetemperaturedependenceoftheexchangecurrentdensitycanbecalculatedviaan Arrheniustyperelation:

io (H + ) iorefH + ) (

=e

(H+ )

1 1 T c + 273 .15 T c , ref + 273 .15

(36)

Thereversiblepotentialfor H + reduction E rev (H + ) isafunctionoftemperatureandpH:


Erev (H + ) = 2.303 R (Tc + 273.15 ) pH F

(37)

ThecathodicTafelslope bc (H + ) iscalculatedas:

bc ( H + ) =
17

2.303 R (Tc + 273.15) 0.5 F

(38)


d Thelimitingmasstransfercurrentdensity i lim (H + ) isrelatedtotherateoftransportof

H + ionsformthebulkofthesolutionthroughtheboundarylayertothesteelsurface:

d ilim (H + ) = k m ( H + ) F c H +

(39)

wherethemasstransfercoefficient, k m ( H + ) canbecalculatedfromacorrelationofthe Sherwood,Reynolds,andSchmidtnumbersasexplainedinthefollowingsection. 2.2.3 Reduction of carbonic acid The carbonic acid reduction reaction (24) can be under charge transfer control or limitedbytheslowchemicalreactionhydrationstep(6),precedingit.11,12Therateof thisreactionintermsofcurrentdensityis:

1
ic ( H 2CO 3 )

1
i ( H 2CO 3 )

1
i
r lim ( H 2 CO 3 )

(40)

Thechargetransfercurrentdensity i ( H 2CO3 ) iscalculatedas:


i ( H 2CO3 ) = io ( H 2CO3 ) 10
Ecorr Erev ( H 2CO3 ) bc ( H 2CO3 )

(41)

The exchange current density io ( H 2CO3 ) depends on pH, H 2CO3 concentration, and temperature: 18

log io ( H 2CO 3 ) pH log io ( H 2CO 3 )

= 0 .5

(42) (43)

c H 2CO 3

= 1
H ( H 2CO 3 ) 1 1 Tc + 273 .15 R Tc , ref + 273 .15

io ( H 2 CO 3 ) iorefH 2 CO 3 ) (

=e

(44)

ThecathodicTafelslope bc ( H 2 CO3 ) is:

bc ( H 2CO3 ) =

2.303 R (Tc + 273.15) 0.5 F

(45)

Since the reduction of H 2CO3 and H + are equivalent thermodynamically, the reversiblepotentialfor H 2CO3 reduction E rev ( H 2CO3 ) iscalculatedas:
Erev ( H 2CO3 ) = 2.303 R (Tc + 273.15 ) pH F

(46)

r Thechemicalreactionlimitingcurrentdensity i lim ( H 2 CO 3 ) canbecalculatedfrom: 16

r ilim ( H 2 CO 3 ) = F cCO 2 f H 2 CO 3 f D H 2 CO 3 K hyd k hyd

(47)

Thediffusioncoefficientforcarbonicacid D H 2 CO 3 asafunctionoftemperaturecanbe calculatedusingEinsteinsrelation:

19

T + 273.15 H 2O , ref D = Dref c T + 273.15 H 2O c , ref

(48)

f Theforwardreactionrateforthe CO2 hydrationreaction k hyd iscalculatedas:

f hyd

= 10

169 . 2 53 . 0 log (T c + 273 . 15 )

11 , 715 T c + 273 . 15

(49)

Theflowfactor f H 2CO 3 is:

f H 2 CO 3 = coth H 2 CO 3
where

(50)

H CO =
2 3

m ( H CO ) r ( H CO )
2 3 2 3

(51)

and

m ( H CO ) =
2 3

DH 2CO3 k m ( H 2CO3 )

(52) (53)

r ( H CO ) =
2 3

DH 2CO3
b k hyd

The carbonic acid mass transfer coefficient k m ( H 2CO3 ) is discussed in the following section2.3. 2.2.4 Reduction of acetic acid The acetic acid reduction reaction (26) can be either under charge transfer or mass transfer(diffusion)control,thereforeaceticacidreductionratecanbecalculatedas: 20

1 ic ( HAc )

1 i ( HAc )

1 i
d lim ( HAc )

(54)

Thechargetransfercurrentdensityisgivenas:

i ( HAc ) = io ( HAc ) 10

E corr E rev ( HAc ) b c ( HAc )

(55)

The exchange current density of this reaction are functions of undissociated HAc concentrationandtemperature,whichcanbeobtainedfrom,

io ( HAc )

c ref = io ( HAc ) HAc c HAc,ref

0.5

1 1 H HAc Tc + 273.15 Tc ,ref + 273.15 R

(56)

Thereversiblepotential andTafelslope of this reaction are obtainedusingthe same equationsasthosefor H + reduction:


E rev ( HAc ) =

bc ( HAc ) =

2.303 R (Tc + 273.15) 0.5 F

2.303 R (Tc + 273.15 ) pH F

(57) (58)

d Themasstransferlimitingcurrentdensity ilim ( HAc ) isgivenby,

d ilim( HAc ) = km( HAc ) FcHAc

(59)

21

Again, the mass transfer coefficient k m ( HAc ) can be calculated using the correlation describedinthelatersection. 2.2.5 Reduction of oxygen Like H + and HAc , oxygen reduction can be either charge transfer control or mass transfercontrol,therefore,thecurrentdensityiscalculatedasthesumoftwoportions, chargetransfercurrentdensityand masstransfer limiting current density, as shown below:

1
ic (O2 )

1
i (O2 )

1
i
d lim (O2 )

(60)

Thechargetransfercurrentdensityofthisreactionisgivenby:

i (O2 ) = io (O2 ) 10

E corr Erev ( O2 ) bc ( O2 )

(61)

The exchange current density of oxygen reduction is a function of temperature, and canbecalculatedfrom:
ref io (O2 ) = io (O2 ) e H O2 1 1 Tc + 273.15 Tc , ref + 273.15 R

(62)

22

Thereversiblepotentialofthisreactiondoesnotchangesignificantlywithintherange oftemperatureandpHofinterest.Therefore,itistakentobeaconstantat0.5V. TheTafelslopeofthisreactionisgivenby:

bc(O ) =
2

2.303 R (Tc + 273.15) F


(63)

d Themasstransferlimitingcurrentdensity ilim (O 2 ) canbeobtainedfrom

d ilim,O2 = 4 k m (O2 ) F cO2

(64)

Again, mass transfer coefficient of oxygen can be obtained in the similar fashion as describedforotherspecies. It is worthy of mentioning here that due to the high reversible potential of oxygen reduction,thisreactionisalmostalwaysundermasstransfercontrolinthepotential regionofinterest. 2.2.6 Reduction of water Sincewatermoleculesarepresentinvirtuallyunlimitedquantitiesatthesteelsurface, itcanbeassumedthatthereductionrateof H 2O iscontrolledbythechargetransfer processand,hence,pureTafelbehavior: 23

ic ( H 2O ) = io ( H 2O ) 10

Ecorr Erev ( H 2O ) bc ( H 2O )

(65)

Sincethereductionof H 2O and H + areequivalentthermodynamically,theyhavethe samereversiblepotentialatagivenpH:


Erev ( H 2O ) = 2.303 R (Tc + 273.15 ) pH F

(66)

Theexchangecurrentdensityforwaterreduction io ( H 2O ) dependsontemperature:

io ( H 2O ) iorefH 2O ) (

=e

H ( H 2 O ) 1 1 Tc + 273 .15 Tc , ref + 273 .15 R

(67)

TheTafelslopefor H 2O reductionwasfoundtobethesameasthatfor H + reduction:

bc ( H 2O ) =

2.303 R (Tc + 273.15) 0.5 F

(68)

2.3 Transport Processes in CO2 Corrosion of Mild Steel


From the description of the electrochemical processes above it is clear that certain speciesinthesolutionareproducedatthemetalsurface(e.g. Fe 2+ )whileothersare depleted (e.g. H + ). The established concentration gradients lead to molecular diffusion of the species towards and away from the surface. In cases when the diffusion processes are much faster than the electrochemical processes, the 24

concentration change at the metal surface is small. Vice versa, when the diffusion is unabletokeepupwiththerateoftheelectrochemicalreactions,theconcentration of species at the metal surface can become very different from the ones in the bulk solution.Ontheotherhand,therateoftheelectrochemicalprocessesdependsonthe species concentrations at the surface. Therefore there exists a twoway coupling betweentheelectrochemicalprocessesatthemetalsurface(corrosion)andprocesses in the adjacent solution layer (i.e. diffusion in the boundary layer). The same is true for chemical reactions which interact with both the transport and electrochemical processesinacomplexway. Inmostpracticalsystemsthewatersolutionmoveswithrespecttothemetalsurface. Therefore, the effect of convection on transport processes cannot be ignored. Turbulent eddies can penetrate deep into the hydrodynamic boundary layer and significantlyaltertherateofspeciestransporttoand fromthesurface.Verycloseto thesurfacenoturbulencecanexistandthespeciesaretransportedsolelybydiffusion. Theeffectofturbulentflowiscapturedeasiestbyusingtheconceptofmasstransfer coefficient,describedbelow. In turbulent flow of dilute ideal solutions, a mass transfer coefficient k m for a given species ( H + , H 2CO3 , HAc , O2 etc.) can be calculated from a correlation, such as straightpipecorrelationofBergerandHau:25
Sh p = 0.0165 Re 0.86 Sc 0.33

(69)

orarotatingcylindercorrelationofEisenbergetal.:26 25


Shr = 0.0791 Re 0.7 Sc 0.356

(70)

oranyothersimilarcorrelationfortheflowgeometryathand.Itshouldbenotedthat mostofthemasstransfercorrelationsfoundintheliterature(includingthetwolisted above)aresuitedonlyforsinglephaseflow.Therefore,extensionofthisapproachto multiphaseflowsituationsneedstobedonewithcarefulconsideration. Overall, CO2 corrosionofmildsteelisnotverysensitivetoflow,atleastnotsowhen comparedtomildsteelcorrosioninstrongacids.Thisisduetothefactthatthemain corrosive species in CO2 corrosion is H 2CO3 , which can easily be depleted due to a slow chemical step which precedes it: the hydration reaction (6). Therefore the limiting rate of CO2 corrosion is primarily affected by the rate of this chemical reaction(47)whichisafunctionoftemperatureand CO2 partialpressureandnotvery sensitivetoflow.Ontheotherhand, HAc corrosionisprimarilylimitedbyhowfast onecantransport HAc tothesteelsurface.Incontrastwith CO2 corrosion,thereisno slowchemicalstepin HAc corrosionwhichprecedesitandisratelimiting.Therefore flow strongly affects the limiting rate of the cathodic reaction due the presence of organicacids,andplaysamoresignificantroleintheoverallcorrosionprocess. Clearlythereisaparallelargumentbetween CO2 and HAc corrosionwhichstemsin bothcasesfromthefactthatonefindsaweakacidintheaqueousphase,whichgives riseto higher corrosionratesthanwould beexpectedfromlooking atthepHalone. The main difference arises from the phase behaviour of the two solutions. In the 26

temperaturerangeofinterest, HAc canbefoundprimarilyintheaqueousphaseand thereforeitsbehaviourisnotsignificantlyaffectedbythepresenceofthe HAc vapor. With CO2 itistheopposite,i.e.thegaseous CO2 controlstheamountof CO2 dissolved and the amount of H 2 CO3 found in the solution. Therefore CO2 corrosion is significantlyaffectedbythepresenceofthegaseousphase.

2.4 Calculation of Mild Steel CO2 Corrosion Rate


Once the speciation of the aqueous CO2 solution (including the pH, H 2CO3 concentration,etc.)isresolved,usingthethermodynamicapproachoutlinedinsection 2.1, the corrosion rate of mild steel can be calculated by using the electrochemical theoryoutlinedinsection2.2.TheunknowncorrosionpotentialEcorrin(30),(34),(41), (55),(61)and(65)andcanbefoundfromthecurrent(charge)balanceequationatthe steelsurface:

ic (H + ) + ic ( H 2CO3 ) + ic ( HAc ) + ic (O2 ) + ic ( H 2O ) = ia ( Fe )

(71)

When the calculated value of E corr is now returned to (30), (34), (41), (55), (61) and (65),therateofeachindividualreactioncanbecomputed.Thisincludesthesocalled corrosioncurrentdensityobtainedfrom(30):

icorr = ia ( Fe )

(72)

Finallythesocalled CO2 corrosionrateisthenrecoveredbyusingFaradayslaw: 27

CR =

icorr M Fe Fe nF

(73)

Ifthe unit A/m2is usedforthecorrosion currentdensity icorr ,then conveniently the corrosionrateforironandsteelexpressedinmm/ytakesalmostthesamenumerical value,precisely: CR = 1.155 icorr .

2.5 Successes and limitations of modeling of aqueous CO2 corrosion of mild steel
Evidence that our basic understanding of the processes underlying CO2 corrosion of mild steel is reasonably sound can be found by comparing the predictions made by the mechanistic model outlined above with experimental values. In Figure 2 below onecanseethecomparisonofapotentiodynamicsweepobtainedintheexperiments and the one predicted by the model. Many other comparisons of the predicted and measured corrosion rates are given in the following section where the effect of key factorsin CO2 corrosionofmildsteelisdiscussed.

28

0 -0.1 -0.2 -0.3 E vs. SHE / V -0.4 E corr -0.5 -0.6 -0.7 -0.8 -0.9 -1 0.1 1 i / (A/m )
2

total cathodic model sweep experimental sweep

total anodic (Fe dissolution)

H2O reduction

H2CO3 reduction

H reduction

i corr

10

Figure 2. Potentiodynamic sweep, experimental vs. model; 20oC, pCO2 =1 bar, pH4, 2 m/s.
Regardless the relative progress we have made in understanding and modeling of aqueous CO2 corrosion of mild steel, many questions persist. One is the issue of localized CO2 corrosion which is still a topic of intense ongoing research. Effect of other factors such as steel metallurgy, organic acids, oxygen, multiphase flow and inhibitors are challenges that need further effort. Some of those are discussed in the followingsections.

29

2.6 Key Factors Affecting Aqueous CO2 Corrosion of Mild Steel


2.6.1 The effect of pH pH has a strong influence on the corrosion rate. Typical pH in CO2 saturated condensed water is about pH 4 while in buffered brines, one frequently encounters 5<pH<7. At pH 4 or below, direct reduction of H + ions, reaction (23), is important particularly at lower partial pressure of CO2 when the pH has a direct effect on the corrosion rate. However, the most important effect of pH is indirect and relates to how pH changes conditions for formation of ferrous carbonate layers. High pH results in a decreased solubility of ferrous carbonate and leads to an increased precipitation rate and a higher scaling tendency. The effect of various pH and supersaturations are shown in Figure 3. At lower supersaturations obtained at the lowerpH6,thecorrosionratedoesnotchangemuchwithtime,evenifsomeferrous carbonate precipitation occurs, reflecting the fact that a relatively porous, detached andunprotectivelayerisformed(lowscalingtendencyST).ThehigherpH6.6results in higher supersaturation, faster precipitation and formation of more protective ferrouscarbonate,reflectedbyarapiddecreaseofthecorrosionratewithtime.There are other indirect effects of pH, and by almost all accounts, higher pH leads to a reductionofthecorrosionrate,makingthepHstabilization(meaning:pHincrease) technique an attractive way of managing CO2 corrosion. The drawback of this techniqueisthatitcanleadtoexcessivescalingandcanberarelyusedwithformation watersystems.

30

Figure 3. Effect of ferrous carbonate supersaturation SS ( FeCO3 ) on corrosion rate obtained at a range of pH6.0-pH6.6, for 5 ppm< c Fe2+ < 50 ppm at T = 80oC, under stagnant conditions. Error bars represent minimum and maximum values obtained in repeated experiments. Data taken from Chokshi et al. 17
2.6.2 The effect of CO2 partial pressure In the case of scalefree CO2 corrosion, an increase of pCO2 , typically leads to an increase in the corrosion rate. The commonly accepted explanation is that with

pCO2 the concentration of H 2CO3 increases and accelerates the cathodic reaction,
equation (25), and ultimately the corrosion rate. The detrimental effect of pCO2 at a constant pH is illustrated in Figure 4. The model described above reasonably well capturesthistrenduptoapproximately pCO2 =10bar.

31

50 model 40

CR / (mm/y)

30 experimental 20

10

0 1 10 pCO2 / bar 100

Figure 4. The effect of CO2 partial pressure, pCO2 on bare steel corrosion rate, comparison of experimental results and model; 60oC, pH5, 1 m/s, 100 mm ID single-phase pipe flow.
However, when other conditions are favorable for formation of ferrous carbonate layers,increased PCO2 canhaveabeneficialeffect.AtahighpH,higher PCO2 leadsto an increase in bicarbonate and carbonate ion concentration and a higher supersaturation,whichacceleratesprecipitationand protectivelayerformation. The effectof PCO2 onthecorrosionrateinthepresenceofferrouscarbonateprecipitationis illustratedinFigure5whereinstratifiedwetgasflow,corrosionrateisreducedboth attopandbottomofthepipewiththeincreasepartialpressureof CO2 .

32

Figure 5. Experimental measurements of the corrosion rate at the top and bottom of the pipe in stratified gas-liquid flow showing the effect of CO2 partial pressure, pCO2 on formation of ferrous carbonate layer. Test conditions: 90oC, pH6, 100 mm ID, Vsg=10 m/s, Vsl=0.1 m/s,. Data taken from Sun and Nei18.
2.6.3 The effect of temperature Temperature accelerates all the processes involved in corrosion: electrochemical, chemical, transport, etc. One would expect then that the corrosion rate steadily increases with temperature, and this is the case at low pH when precipitation of ferrouscarbonateorotherprotectivelayersdoesnotoccur.Anexampleisshownin Figure 6. The situation changes markedly when solubility of ferrous carbonate is exceeded, typically at a higher pH. In that case, increased temperature accelerates rapidly the kinetics of precipitation and protective layer formation, decreasing the 33

corrosionrate.Thepeakinthecorrosionrateisusuallyseenbetween60oCand80oC depending on water chemistry and flow conditions. Many of empirical models are builttomimicthisbehaviorwithoutaccountingforthecomplicationeffectofpH.as showninFigure6(dottedline).

Figure 6. The effect of temperature on CO2 corrosion rate of mild steel; pH 4, pCO2 = 1bar, 100 mm ID single phase pipe flow. Points are experimental values and the solid line is the model. The red dotted line is a model simulation of the same conditions at pH6.6.
2.6.4 The effect of flow There are two main ways in which flow may affect CO2 corrosion which can be distinguished based on whether or not other conditions are conducive to protective layerformationornot.

34

In the case of corrosion where protective layers do not form (typically at low pH as foundincondensedwaterandintheabsenceofinhibitors),themainroleofturbulent flowistoenhancetransportofspeciestowardsandawayfromthemetalsurface.This mayleadtoanincreaseinthecorrosionrateasillustratedinFigure7.AtlowerpH4, the effect is much more pronounced as the dominant cathodic reaction is direct H + ionreduction(23),whichisundermasstransfercontrol(seeEquation(39)). When protective ferrous carbonate layers form (typically at higher pH in produced water)orwheninhibitorfilmsarepresentonthesteelsurface,theabovementioned effectofflowbecomesinsignificantasthemainresistancetocorrosionisnowinthe surface layer or inhibitor film. In this case, the effect of flow is to interfere with formationofprotectivesurfacelayersortoremovethemoncetheyareinplace,often leadingtoanincreasedriskoflocalizedattack. Thetwoflowacceleratedcorrosioneffectsdiscussedabovearefrequentlyaggravated byflowdisturbancessuchasvalves,constrictions,expansions,bends,etc.wherelocal increases of nearwall turbulence and wallshear stress are seen. However, flow can leadto onset of localized attack onlywhen giventhe rightset ofcircumstancesas discussedinaseparateheadingbelow. The effect of multiphase flow on CO2 corrosion is complicated by the different flow patterns that exist, most common being: stratified, slug and annularmist flow. In the liquid phase, water and oil can flow separated or mixed with either phase being continuouswiththeotherflowingasadispersedphase.Differentflowpatternslead to a variety of steel surface wetting mechanisms: stable water wetting, stable oil wetting,intermittentwetting,etc.,whichgreatlyaffectcorrosion.Inannularmistflow, 35

theliquiddropletsmoveathighvelocityandcanmayleadtoprotectivelayerdamage at points of impact such as bends, valves, tees, constrictions/expansions and other pipefitting.Slugflowcanleadtosignificantshortlivedfluctuationsinthewallshear stresswhichcanhelpremoveaprotectivesurfacelayerofferrouscarbonateoraffect aninhibitorfilm.

36

4 pH = 4 3 CR / (mm/y) 2 1 0 4 3 2 1 0 4 3 2 1 0 0 2 4 6 8 10 12 14 Velocity / (m/s) 0 pH = 6 2 4 6 8 10 12 14 Velocity / (m/s) 0 pH = 5 CR / (mm/y) 2 4 6 8 10 12 14 Velocity / (m/s)

CR / (mm/y)

Figure 7. Predicted and experimentally measured corrosion rates showing the effect of velocity in the absence of ferrous carbonate layers. Test conditions: 20oC, pCO2 = 1 bar, 15 mm ID singlephase pipe flow. Experimental data taken from Nei et al.19
37

2.6.5 Effect of corrosion inhibition Thetwomostcommonsourcesofcorrosioninhibitionneedtobeconsidered: a)inhibitionbyadditionofcorrosioninhibitorsand b)inhibitionbycomponentspresentinthecrudeoil. a)Corrosioninhibitors Describing the effect of corrosion inhibitors is not a straightforward task due to the enormouscomplexityofthesubject.Quantifyingthemandpredictingtheirbehavior isevenharder.Thereisaplethoraofapproachesintheopenliterature,varyingfrom the use of simple inhibitor factors and inhibition efficiencies to the application of complicated molecularmodeling techniques to describe inhibitor interactions with the steelsurfaceandferrouscarbonatelayer.Amiddleoftheroadapproachisbasedon the assumption that corrosion protection is achieved by surfacecoverage, i.e. that the inhibitoradsorbsontothesteelsurfaceandslowsdownoneormoreelectrochemical reactions by blocking. The degree of protection is assumed to be directly proportionaltothefractionofthesteelsurfaceblockedbytheinhibitor.Inthistypeof model one needs to establish a relationship between the surface coverage and the inhibitorconcentrationinthesolutioncinh.Thisismostcommonlydonebytheuseof adsorptionisotherms. b)Corrosioninhibitionbycrudeoil Ithasbeenknownforawhilethat CO2 corrosionratesseeninthefieldinthepresence ofcrudeoilaremuchlowerthenthoseobtainedinlaboratoryconditionswherecrude

38

oilwasnotusedorsyntheticcrudeoilwasused.Onecanidentifytwomaineffectsof crudeoilonthe CO2 corrosionrate. Thefirstisawettabilityeffectandrelatestoahydrodynamicconditionwherecrudeoil entrains the water and prevents it from wetting the steel surface (continuously or intermittently). Thesecondeffectiscorrosioninhibitionbycomponentsofthecrudeoilthatreachthe steel surface either by direct contact or by first partitioning into the water phase. Varioussurfaceactiveorganiccompoundsfoundincrudeoil(typicallyoxygen,sulfur andnitrogencontainingmolecules)havebeenidentifiedtodirectlyinhibitcorrosion ofmildsteelin CO2 solutions. 2.6.6 The effect of organic acids The effect of HAc is particularly pronounced at higher temperatures and low pH when the abundance of undissociated HAc can increase the CO2 corrosion rate dramatically as seen in Figure 8. Solid iron acetate does not precipitate in the pH range of interest since iron acetates solubility much higher than that of ferrous carbonate. There are some indications that the presence of organic acids impairs the protectivenessofferrouscarbonatelayers,howeverthemechanismisstillnotclear.

39

60 50 CR/ mm/y 40 30 20 10 0 1 10 100 1000

Undissociated aqueous HAc concentration / ppm

Figure 8. The effect of the concentration of undissociated acetic acid (HAc) on the CO2 corrosion rate, 60oC, pCO2 =0.8 bar, pH4, 12 mm OD rotating cylinder flow at 1000 rpm. Experimental data taken from Geroge and Nei et al.20
2.6.7 Effect of glycol/methanol Glycolandmethanolareoftenaddedtoflowingsystemsinordertopreventhydrates from forming. The quantities are often significant (50% of total liquid phase is not unusual). In the very few studies available it has been assumed that the main inhibitive effect of glycol/methanol on corrosion comes from dilution of the water phase, which leads to a decreased activity of water. However, there are many unanswered questions such as the changes in mechanisms of CO2 corrosion in water/glycolmixtureswhichhaveyettobediscovered. 40

2.6.8 Effect of condensation in wet gas flow Whentransportinghumidnaturalgas,duetothecoolingofthestream,condensation of water vapor occurs on the internal pipe wall. The condensed water is pure and, duetodissolved CO2 ,hastypicallyapH<4.Thisleadstothesocalledtopoftheline corrosion (TLC) scenario. If the rate of condensation is high, plenty of acidic water flows down the internal pipe walls leading to a very corrosive situation. If the condensationrateislow,thewaterfilmisnotrenewedandflowsdownveryslowly andthecorrosionprocesscanreleaseenough Fe 2+ toraisethelocalpHandsaturate the solution, leading to formation of protective ferrous carbonate layer. The layer is oftenprotective,howeverincidentsoflocalizedattackinTLCwerereported.21Either way,thestratifiedorstratifiedwavyflowregime,typicalforTLC,doesnotleadtoa good opportunity for inhibitors to reach the upper portion of the internal pipe wall andprotectit.AverylimitedrangeofcorrosionmanagementoptionsforTLCexists. Toqualitativelyandquantitativelydescribethephenomenonofcorrosionoccurringat the top of the line, a deep insight into the combined effect of the chemistry, hydrodynamics,thermodynamics,andheatandmasstransferinthecondensedwater is needed. A full description exceeds the scope of this review, and the interested readerisdirectedtoseesomerecentarticlespublishedonthistopic.21,22 2.6.9 Non-ideal solutions and gases Inmanycasesproducedwaterhasaveryhighdissolvedsolidscontent(>10wt%).At such high concentrations, the infinite dilution theory used above does not hold and corrections need to be made to account for solution nonideality. A simple way to account for the effect on nonideal homogenous water chemistry is to correct the 41

equilibriumconstantsbyusingtheconceptofionicstrengthasindicatedabove.This approachseemstoworkwellonlyformoderatelyconcentratedsolution(uptoafew wt%ofdissolvedsolids).Formoreconcentratedsolutionsamoreaccuratewayisto use activity coefficients as described by Anderko et al. 23 The effect of concentrated solutions on heterogeneous reactions such as precipitation of ferrous carbonate and other layers is still largely unknown. Furthermore, it is unclear how the highly concentratedsolutionsaffectsurfaceelectrochemistry.Someexperiencesuggeststhat corrosionratescanbedramaticallyreducedinveryconcentratedbrines,nevertheless amoresystematicstudyisneeded. At very high total pressure the gas/liquid equilibria cannot be accounted for by Henrys law. A simple correction can be made by using a fugacity coefficient which accounts for nonideality of the CO2 /natural gas mixture24 and can be obtained by solvingtheequationofstateforthegasmixture.

2.7 Localized CO2 Corrosion of Mild Steel in Aqueous Solutions


Asillustratedabove,significantprogresshasbeenachievedinunderstandinguniform
CO2 corrosion, without or with protective layers, and hence a successful uniform

corrosion models can be built. However, much less is known about localized CO2 corrosion.Itisthoughtthatoneofthemainfactorsthattriggerslocalizedattackis flow, tempered by other environmental variables such as pH, temperature, partial pressure of CO2 , etc. It seems that localized attack occurs when the conditions are suchthatpartiallyprotectiveferrouscarbonatelayerform.Itiswellknownthatwhen 42

fully protective ferrous carbonate forms low general corrosion rates are obtained and vice versa: when no protective layers form a high rate of general corrosion is seen. It is when the corrosive environment is in between, in the so called grey zone, that localized attack can be initiated most often by some extreme flow conditions. There are many combinations of environmental and metallurgical parameters that define the grey zone, making this sound like a difficult proposal. However, there is a single parameter which is easy to calculate: ferrous carbonate supersaturation, SS ( FeCO3 ) (seeEquation(18)above),whichcanbesuccessfullyusedas agooddelineatorforthegreyzoneandassuchasapredictorfortheprobabilityfor localized attack. When bulk ferrous carbonate supersaturation in the range 0.5< SS ( FeCO3 ) <2thereisariskoflocalizedattack.Thefurtherawaythesolutionisfrom theseboundaries,thelowertherisk.ThescalingtendencyST(seeEquation(21)above) isconceptuallyevenbettersuitedasapredictoroflocalizedcorrosionrisk,however itscalculationismuchmoredifficultanduncertainasitinvolvescalculationofboth theuniformcorrosionrateandtheprecipitationrate. Basedonmostlyanecdotalevidence(fieldexperience),thepresenceof H 2 S andHAc wasrelatedto onsetoflocalizedattack,howeverlittleisunderstoodabouthowand whenthismayhappen.

3 AQUEOUS H2S CORROSION OF MILD STEEL


Internal corrosion of mild steel in the presence of hydrogen sulfide ( H 2 S ) also represents a significant problem for the oil and gas industry2733. Increasingly more fields are being developed that in addition to CO2 have high concentrations of H 2 S . 43

In CO2 / H 2 S corrosionofmildsteel,bothferrouscarbonateandferroussulfidelayers canformonthesteelsurface.Studieshavedemonstratedthatsulfidelayerformation is one of the important factors governing the H 2 S corrosion rate. The sulfide layer growth depends primarily on the kinetics of the corrosion process as is described below. Despitetherelativeabundanceofexperimentaldataon H 2 S corrosionofsteel,most of the literature is still confusing and somewhat contradictory. Therefore the mechanism of H 2 S corrosion remains much less understood when compared to that of CO2 corrosion. This uncertainty makes it more difficult to develop a model to predictthecorrosionrateofmildsteelin H 2 S saturatedaqueoussolution.

3.1 Chemistry of H2S Saturated Aqueous Solutions Equilibrium Considerations


Similarlyto CO2 discussedabove,the H 2 S gasisalsosolubleinwater:

H 2 S( g ) H 2 S
where K H 2 S isthesolubilityconstantof H 2 S inmol/(lbar):
K sol ( H 2S ) = cH 2 S pH 2 S

K H 2S

(74)

(75)

andcanbefoundfrom:34 44

K sol ( H 2 S ) = 10

2 16719 634.27 + 0.2709T K 0.11132 10 3 T K 261.9 log TK TK

(76)

AsshowninFigure9,thesolubilityof H 2 S decreasewithtemperature,thesameasis observed for CO2 . However, for the same partial pressure and temperature, the concentration of dissolved H 2 S actually exceeds that in the gas phase as shown in Figure10.
0.20

species concentration / (mol/l)

0.15

0.10 H2S 0.05 CO2 0.00 0 20 40 T / oC 60 80 100

Figure 9. Solubility of H 2 S and CO2 as a function of temperature; 25oC, pH 2S =1 bar, pCO2 =1 bar.
Theaqueous H 2 S isanotherweakacidwhichpartlydissociatesintwosteps:
H 2 S H + + HS
K hs

(77)

45

HS H + + S 2

Kbs

(78)

where K hs isthedissociationconstantof H 2 S :
K hs = cH + cHS cH 2 S

(79)

andcanbecalculatedas:35

K hs = 10 (15.345 0.045676 TK + 5.9666 10


and K bs isthedissociationconstantof HS :

2 TK )

(80)

K bs =

c H + cS 2 cHS

(81)

Thereisverylargediscrepancyinthereportedvaluesfor K bs ,varyingfrom 1.0 1019 to 1.1 1012 kmol/m3 at room temperature (seven orders of magnitude). Hence it is suggested that the using K bs to calculate the concentration of sulfide species, cS 2 and further to predict the solubility product constants for ferrous sulfides should be avoided. Given the same gaseous concentrations of H 2 S and CO2 , one obtains a similar aqueousconcentrationofdissolved H 2 S and CO2 (seeFigure9)andtheresultingpH 46

iswithin0.1pHunit.Theequilibriumdistributionofsulfidespeciesasafunctionof pH for an open system is shown in Figure 10. The concentration of bisulfide ion,

cHS becomes significant only above pH4, while the concentration of the sulfide ion, cS 2 isnotevenshownasitisverylowandunreliabletocalculate.
1.E+00 1.E-01 species concentration / (mol/l) 1.E-02 1.E-03 H2S 1.E-04 1.E-05 1.E-06 1.E-07 2 3 4 pH 5 6 7 H2S(g) HS
-

Figure 10. Sulfide species concentrations as a function of pH for a H 2 S saturated aqueous solution at pH 2S =1 mbar, 25oC, 1wt%NaCl.
Many types of iron sulfides occur, such as amorphous ferrous sulfide (FeS), mackinawite (Fe1+xS), cubic ferrous sulfide (FeS), troilite (FeS), pyrrhotite (Fe1xS or FeS1+x), smythite (Fe3+xS4), greigite (Fe3S4) and pyrite (FeS2). Some of these are stoichiometricsuchascubicferroussulfide,troilite,greigiteand pyrite,whileothers arenot,suchasmackinawite,pyrrhotiteandsmythite.Thethermodynamicsofthese systems is very complicated; depending on environmental conditions and time, 47

transformation from one type of ferrous sulfide into the other occurs. Limited informationexistsonaqueoussolubilityofthevarioussulfides.Avoidingtheusageof the sulfide ion concentration, cS 2 ,one can writeageneralequationforprecipitation offerroussulfideas:

Fe 2+ + H 2 S

K sp ( FeS )

FeS( s ) + 2 H +

(82)

wherethesolubilityconstantforonetypeofferroussulfidemackinawiteisknown asafunctionoftemperature:36

mackin sp ( FeS )

= 10

2848.779 6.347 Tk

(83)

Forotherferroussulfidesonlythevaluesatroomtemperatureareknown,aslistedin Table1below.Itisconvenienttoshowthevariousferroussulfidesolubilitiesinterms ofanequilibriumconcentrationofthe Fe 2+ asafunctionofpHatagiven H 2 S partial pressure(concentration). An example is presented in Figure 11 where it can be seen thatthemuchlesssolublepyrrhotiteandtroilitearethermodynamicallymorestable formscomparedtomackinawiteandamorphousferroussulfide.Foratypicalferrous ionconcentrationof cFe2+ =1ppm,thesaturationwithrespecttotroiliteandpyrrhotite isreachedalready atpH5.4 while formackinawite itispH6and amorphousferrous sulfide pH6.7. Keeping in mind that the concentration of Fe2+ at a corroding steel surfacecaneasilybemuchhigherthaninthebulk(e.g.10ppmorevenhigher)and thatthepHisalsohigheratthesurfacethaninthebulk(typicallyabovepH6),using

48

Figure 11 one can expect a whole range of different ferrous sulfides to form on a corrodingsteelsurfaceatthis H 2 S concentrationatdifferentpointsintime. Images of a ferrous sulfide surface layer formed on mild steel after a week long exposure are shown in Figure 12. The layered structure of the sulfide is prominent anditcanbeidentifiedasmackinawite.Inlongerexposures,theferroussulfidelayer thickensandbecomeseventuallymoreprotective.Animageofaferroussulfidelayer afteramonthlongexposureisshowninFigure13.Thecompositionofthelayerisa mixture of mackinawite and pyrrhotite. Another layered composed of a mixture of ferrouscarbonateandferroussulfideisshowninFigure14. Table1.Solubilityproductconstantsforvariousferroussulfidesat25oC.37 Typeofferroussulfide Amorphous(FeS) Mackinawite(Fe1+xS) Pyrrhotite(Fe1xSorFeS1+x) Troilite(FeS) log K sp ( FeS ) 2.95 3.6 5.19 5.31

49

1.E+04

concentration / ppm
2+

1.E+03

1.E+02

Fe

1.E+01

1.E+00 3 3.5 4 4.5 5 5.5 6 6.5 7

pH

Figure 11. Solubility of various sulfides as a function of pH shown in terms of the equilibrium concentration of Fe2+ , pH 2S =1 mbar, 25oC, 1wt%NaCl.

50

ferroussulfide

mildsteel

Figure 12. A cross section and a top view of a ferrous sulfide layer formed on mild steel; 60oC, pH6, pCO2 =7.7 bar, pH 2S =0.25 mbar, 1 m/s single phase flow in a 100 mm ID pipe, 7 days exposure.

51

ferroussulfide

mildsteel

Figure 13. A cross section a ferrous sulfide layer formed on mild steel; 60oC, pH6, pCO2 =7.7 bar, pH 2S =0.25 mbar, 1 m/s single phase flow in a 100 mm ID pipe, 30 day exposure.

ferroussulfide ferrouscarbonate

mildsteel

Figure 14. A cross section a mixed ferrous carbonate and ferrous sulfide layer formed on mild steel; 60oC, pH6, pCO2 =7.7 bar, pH 2S =1.2 mbar, 1 m/s single phase flow in a 100 mm ID pipe, 25 day exposure.
52

3.2 Mild Steel Corrosion in H2S and mixed H2S/CO2/HAc Saturated Aqueous Solutions
Astheaqueous H 2 S isanotherweakacid,itcanbeseenasanadditionalreservoirof

H + ions according to reaction (77), in a similar way as H 2CO3 was discussed above.
Thereforestimulationofthehydrogenevolutionreactioncouldalsobeexpectedinthe presence of H 2 S . Using the analogy with CO2 corrosion, one must also allow the possibility of direct reduction of H 2 S , i.e. that the H 2 S molecule can be adsorbed at thesteelsurface,followedbyareductionofthe H + andoxidationofironinthesteel. Assolidferroussulfide(mackinawite)isalwaysfoundonthecorrodingsteelsurface inthepresenceof H 2 S ,onecanwritethecorrosionreactionas:

Fe( s ) + H 2 S FeS( s ) + H 2

(84)

This has been referred to as a solid state reaction pathway as both the initial and finalstateofFearesolid(s). Therefore it seems that corrosion of mild steel by H 2 S initially proceeds by adsorption of H 2 S to the steel surface followed by a very fast redox reaction at the steelsurfacetoformanadherentmackinawitefilm(muchlikeatarnish).Thisinitial mackinawitefilmisverythin(<<1m)butapparentlyratherdenseandactsasasolid statediffusionbarrierforthespeciesinvolvedinthecorrosionreaction.Thereforethis thin mackinawite film is one of the most important factors governing the corrosion ratein H 2 S corrosion.Italsostronglyaffectscorrosiondueto CO2 . 53

The thin mackinawite film continuously goes through a cyclic process of growth, internal stress growth, cracking and delamination, what generates an outer sulfide layer which thickens over time (typically >>1m) and forms an additional diffusion barrier.However,thisoutersulfidelayerisveryporousandratherlooselyattachedto thesteelsurface,overtimeitmaycrack,peelandspall,aprocessaggravatedbythe flow. The transformation of mackinawite into other forms of less soluble ferrous sulfide (pyrrhotite and troilite, see Figure 11) may happen over time. In addition, ferrous sulfide precipitation from the bulk is also possible. Among the various ferrous sulfides,mackinawiteistheprevalentferroussulfidethatformsincorrosionofmild steel at low H 2 S concentration and low temperature. At increased levels of H 2 S , mackinawite is less prevalent and pyrrhotite is the main corrosion product. At very high H 2 S concentrations, pyrite and even elemental sulfur appear. While thermodynamics of ferrous sulfides may favor other types of sulfide over mackinawite as the corrosion product, the rapid kinetics of mackinawite formation favors it as the initial corrosion product seen in most situations. Overall however, there is no clear relationship between the nature of the sulfide layer and the underlyingcorrosion process.It isgenerallythought thatalltypesof ferroussulfide layersoffersomedegreeofprotectionformildsteel. Inthepresenceofoxygenandatveryhigh H 2 S concentrations,elementalsulfurcan appearandcauseseverelocalizedcorrosion.Themostlikelypathwayforformationof elementalsulfurisasfollows: 54

when there is O2 present, some of the ferrous sulfide reacts with O2 and convertstoironoxideformingislandsofelementalsulfurvia:

4 FeS + 3O2 2 Fe2 O3 + 4S


or

(85)

3FeS + 3O2 Fe3 O4 + 3S

(86)

alternatively,atveryhigh H 2 S concentration,thefollowingreactioncanoccur togiveelementalsulfur:

H2S H2 + S

(87)

Localizedcorrosionbyelementalsulfurcanoccurdueto:

directreactionwiththeironinthesteel:

S + Fe FeS

(88)

orfirstleadstoformationofsulfuricacidvia:

4 S + 4 H 2 O 3H 2 S + H 2 SO 4
whichthenattacksthesteel.

(89)

55

A more indepth discussion about the corrosion mechanisms of mild steel involving elementalsulfurexceedsthescopeofthisreview.

3.3 Calculation of Mild Steel H2S Corrosion Rate


3.3.1 Pure H2S aqueous environment Duetothepresenceoftheinnermackinawitefilmandtheouterporoussulfidelayer, it is assumed that the corrosion rate of steel in H 2 S solutions is always under mass transfercontrol.Onecanthenwritethefluxof H 2 S dueto:

convectivediffusionthroughthemasstransferboundarylayer:

FluxH 2S = km ( H 2S ) cH 2S co ( H 2S )

(90)

moleculardiffusionthroughtheliquidintheporousoutersulfidelayer:

FluxH 2S =

DH 2S

os

(c

o ( H 2S )

ci ( H 2S )

(91)

solidstatediffusionthroughtheinnermackinawitefilm:

ci ( H 2 S ) Flux H 2 S = AH 2 S ln cs ( H S ) 2

(92)

In a steady state, the three fluxes are equal to each other and are equivalent to the corrosionrate: 56

CRH 2 S = FluxH 2 S M Fe Fe
furthercorrectedforappropriatecorrosionrateunit.

(93)

By eliminating the unknown interfacial concentrations co ( H 2 S ) and ci ( H 2 S ) from equations(90)to(92),thefollowingequationisobtainedfortheflux(corrosionrate) dueto H 2 S :

FluxH 2S = AH 2S

os 1 cH 2S FluxH 2S + DH S km ( H S ) 2 2 ln cs ( H 2 S )

(94)

This is an algebraic nonlinear equation with respect to FluxH 2 S which does not have anexplicitsolutionbutcanbesolvedbyusingasimplenumericalalgorithmsuchthe interval halving method or similar. These are available as readymade routines in spreadsheet applications or in any common computer programming language. The predictionfor FluxH 2 S dependsonanumberofconstantsusedinthemodelwhichcan be either found in handbooks (such as DH 2 S ), calculated from the established theory (e.g. k m ( H 2 S ) ) or are determined from experiments (e.g. AH 2 S , cs ( H 2 S ) ). The unknown thickness of the outer sulfide layer change with time and need to be calculated as describedbelow. It is assumed that the amount of layer retained on the metal surface at any point in timedependsonthebalanceof:

57

layer formation kinetics (as the layer is generated by spalling of the thin mackinawitefilmunderneathitandbyprecipitationfromthesolution),and

layer damage kinetics (as the layer is damaged by intrinsic or hydrodynamic stressesand/orbychemicaldissolution):

sulfide layer retention rate

SRR = SFR SDR { { {


sulfide layer formation rate sulfide layer damage rate

(95)

whereallthetermsareexpressedinkmol/(m2s).Inordertosimplifythecalculationsit can be assumed that in the typical range of application (4<pH<7), precipitation and dissolutionofferroussulfidelayerdonotplayasignificantrole,soitcanbewritten:

SRR = CR SDRm

(96)

Eveninstagnantconditionsabouthalfofthesulfidelayerthatformsislostfromthe steel surface due to intrinsic growth stresses by internal cracking and spalling, i.e.

SDRm 0.5 CR ,soonecanwritefinally:

SRR = 0.5 CR

(97)

i.e.abouthalfoftheironcorrodedisfoundonthesteelsurfaceintheformofferrous sulfide. More experimentation is required to determine how the mechanical layer damageisaffectedbyhydrodynamicforces.

58

Once the layer retention rate SRR is known, the change in mass of the outer sulfide layercanbeeasilycalculatedas:

mos = SRR M FeS A t

(98)

The porosity of the outer sulfide layer was determined to be very high ( 0.9 ) by comparing the weight of the layer with the crosssectional SEM images showing its thickness. On the other hand this layer has proven to be rather protective (i.e. impermeable to diffusion) which can only be explained by its low tortuosity arising fromitslayeredstructure.Bycomparingthemeasuredandcalculatedcorrosionrates in the presence of the outer sulfide layer, the tortuosity factor was calculated to be

= 0.003 .
Atimemarchingexplicitsolutionprocedurecouldnowbeestablishedwhere: 1. thecorrosionrate FluxH 2 S intheabsenceofoutersulfidelayercanbecalculated byusingequation(94),andassuming os = 0 , 2. theamountofsulfidelayer mos formedoveratimeinterval t iscalculatedby usingequation(98), 3. the new corrosion rate FluxH 2 S in the presence of sulfide layer can be recalculatedbyusingequation(94), 4. anewtimeinterval t issetandsteps2and3repeated. Atverylow H 2 S gasconcentrations(ppmwrange),thereisverylittledissolved H 2 S andthecorrosionrateisdirectlyaffectedbypH.Amackinawitelayerstillformsand 59

controls the corrosion rate, however the corrosion process is largely driven by the reduction of H + ions, rather than of H 2 S . In an analogy with the approach laid out above,thefollowingexpressionisobtainedforthefluxof H + ionscontrolledbythe presenceoftheferroussulfidelayers:

FluxH + = AH +

1 os + cH + FluxH + D + k + m( H ) H ln cs ( H + )

(99)

Theflux FluxH + isdirectlyrelatedtothecorrosionrateby H + ions:

CRH + = Flux H +

M Fe

Fe

(100)

furthercorrectedfortheappropriatecorrosionrateunit. By solving equations (94) and (99) sequentially in time, the total corrosion rate in mixedpure H 2 S aqueousenvironmentscanbecalculatedas:

CR = CRH 2S + CRH +
3.3.2 Mixed CO2/H2S Environments

(101)

For mild steel corrosion in CO2 / H 2 S containing environments, one can account for the effect of CO2 by following the same assumptions. A similar expression can be

60

obtained for the corrosion rate driven by the presence of CO2 and controlled by the presenceoftheferroussulfidelayers:

FluxCO2 = ACO2

os 1 cCO2 FluxCO2 + DCO k m (CO ) 2 2 ln cs ( CO2 )

(102)

Theflux Flux CO2 isequivalenttothecorrosionrateby CO2 :

CRCO2 = FluxCO2

M Fe

Fe

(103)

furthercorrectedforappropriatecorrosionrateunit. By solving equations (94), (99) and (102), the total corrosion rate in mixed CO2 / H 2 S environmentscanbecalculatedas:

CR = CR H 2 S + CR H + + CRCO2

(104)

3.3.3 Mixed CO2 / HAc / H 2 S Environments IF both HAc and CO2 exist in the H 2 S containing environment, the corrosion rate induced by the presence of HAc can be obtained in the similar fashion as those for
H 2 S and CO2 :

61

Flux HAc = AHAc

os 1 + c HAc Flux HAc D k HAc m ( HAc ) ln c s ( HAc )

(105)

Theflux Flux HAc isequivalenttothecorrosionrateby:

CRHAc = Flux HAc

M Fe

Fe

(106)

furthercorrectedforappropriatecorrosionrateunit. By solving equations (94), (99), (102) and (105), the total corrosion rate in mixed
CO2 / HAc / H 2 S environmentscanbecalculatedas:

CR = CRH 2 S + CRH + + CRCO2 + CRHAc

(107)

3.4 Limitations of modeling of aqueous H2S corrosion of mild steel


The calculation model presented above covers uniform H 2 S , CO2 / H 2 S and
CO2 / HAc / H 2 S corrosion.Therearenumerouslimitations:

Itdoesnotpredictlocalizedcorrosionineitherenvironment. While it covers a very broad range of H 2 S partial pressures it is not recommended to use this model below pH 2S =0.01 mbar or above pH 2S =10bar. Similarlimitsapplytothe CO2 partialpressure.Thisleavesaverybroadarea ofapplicabilityforthepresentmodel.

62

This H 2 S model does not account for any precipitation of ferrous sulfide, ferrous carbonate, or any other scale; therefore in cases where this is deemed important for corrosion, the model should be used with caution. The model also does not account for various transformations of sulfide layer from one typetoanotherwhichareknowntohappenovertime.

The present model does not account for dissolution of the sulfide layer that may occur at very low pH. Therefore the use of this model at pH<3 is not recommended. Similarly the model should be used with caution for pH>7 whereithasnotbeentested.

The model does not account for the effect of high chloride concentrations, oxygen,elementalsulfuroranyotherunspecifiedconditionwhichisknownto affect the corrosion rate and is not explicitly covered in the theoretical underpinningsofthepresentmodel.

Whilethiscalculationmodelisclearlynotinclusiveofalltheimportantprocessesin aqueous H 2 S corrosion of mild steel, it is believed that the main underlying assumptions about the formation and protective nature of a mackinawite layer are correct. The comparison of the performance of this model with experimental data is giveninthesectionbelowwhichcoversthemainfactorsaffecting CO2 / H 2 S corrosion ofmildsteel.

3.5 Key Factors Affecting Aqueous H2S Corrosion of Mild Steel


3.5.1 Effect of H2S partial pressure

63

Corrosionrateofmildsteelatextremelylow H 2 S partialpressuresisseeninFigure where in atmospheric glass cell experiments pH 2S ranged from 0.0013 0.32 mbar, corresponding to 1 250 ppmm in the gas phase at 1 bar CO2 . Clearly this is a CO2 dominatedcorrosionscenario( pCO2 / pH 2S ratioisintherange103106),howeverthe presence of H 2 S controls the corrosion rate. Even when present in such minute amounts, H 2 S reducesthepure CO2 ( H 2 S free)corrosionrateby3to10timesdueto formation of a thin mackinawite film. The model presented above successfully capturesthiseffectasshowninFigure15.

H2S gas concetration / ppmm 0


10 Corrosion rate / mm/y

50

100

150

200

250
mod. exp.

pure CO2 corrosion rate

0.1

0.01 0 0.1 0.2 0.3

H2S partial pressure/ mbar

Figure 15. The corrosion rate vs. partial pressure of H2S; experimental data (exp.) = points, model predictions (mod.) = lines; conditions: total pressure p=1 bar, pCO2 =1 bar, pH 2S = 0.0013 0.32 mbar, T=20oC, reaction time 24 hours, pH 5, 1000 rpm. For reference: pure CO2 corrosion rate is measured to be 1 mm/y. Data taken form Lee38.
64

At higher H 2 S partial pressures the same effect is observed as shown in Figure 16, which shows results from autoclave experiments conducted at a very high total pressure (p=138 bar) and a high CO2 partial pressure ( pCO2 =13.8 bar). When comparingthepredictionswiththeexperimentalresultsitcanbeseenthatthemodel underpredicts the observed rate of steel corrosion by approximately a factor of two. However,whenthisiscomparedwithapure CO2 ( H 2 S free)corrosionrateunderthe sameconditions(whichisnotreportedbutcanbepredictedatalmost20mm/y)the accuracyofthemodelcanbeconsideredasreasonable.Atthehighest pCO2 / pH 2S ratio of 3500 ( pCO2 =13.8 bar, pH 2S =40 mbar), CO2 accounts for approximately 70% of the corrosionrateand30%canbeascribedto H 2 S .Atthelowest pCO2 / pH 2S ratioof1180 ( pCO2 =13.8bar, pH 2S =116mbar), CO2 accountsforapproximately57%ofthecorrosion rateand43%canbeascribedto H 2 S .

65

H2S gas concetration / ppmm 0 20


pure CO2 corrosion rate

100

200

300

400

500

600

700
mod. exp.

Corrosion rate / mm/y

15

10

0 0 20 40 60 80 100 120 140

H2S partial pressure/ mbar

Figure 16. The corrosion rate vs. H2S partial pressure; experimental data (exp.) = points, model predictions (mod.) = lines; conditions: total pressure p=137.9 bar, pCO2 =13.8 bar, pH 2S = 40 120 mbar, T=50oC, experiment duration 3 days, pH 4.0 6.2, stagnant. Experimental data taken from Smith and Pacheco et al. 31
Corrosion rates of mild steel at very high partial pressures of H 2 S ( pH 2S =3 20 bar) and CO2 ( pCO2 =3 12.8 bar) for exposures lasting up to 4 days are shown in Figure 17. Thisisasituationwherethe H 2 S wasthedominantcorrosivespecies. Atthehighest

pCO2 / pH 2S ratioof1.8( pCO2 =5.3bar, pH 2S =3bar) H 2 S generatedapproximately86%of


thecorrosionrate.Atthelowest pCO2 / pH 2S ratioof0.2( pCO2 =4bar, pH 2S =20bar) H 2 S generated97%oftheoverallcorrosionrate.Itisalsonotedthatthemodelpredictions showthatthecorrosionrateinthefirstreactionhourisonaverage20mm/ywithan 66

initialcorrosionrateof 60mm/yanda final corrosion rate of 10mm/y.Concededly, the pitting corrosion rate was reported to be 30 mm/y in a field case with similar conditions, which is related to the very high, H 2 S driven corrosion seen at the beginningofexperimentsbeforeathickprotectiveferroussulfidefilmforms.

40 35
Corrosion rate / mm/y
Test A and B mod. Test C mod. Test D mod. Test E mod. Test F mod. Test A and B exp. Test C exp. Test D exp. Test E exp. Test F exp.

30 25 20 15 10 5 0 0 20

40

60

80

100

Time / hour

Figure 17. The corrosion rate vs. time; experimental data (exp.) = points, model predictions (mod.) = lines; Test A and B: p=8.3 bar, pCO2 =5.3 bar, pH 2S =3 bar, T=60oC, 71hours (A) and 91 hours (B); Test C: p=24 bar, pCO2 =4 bar, pH 2S =20 bar, T=70oC, 91 hours; Test D: p=15.7 bar, pCO2 =3.5 bar, pH 2S =12.2 bar, T=65oC, 69 hours; Test E: p=20.8 bar, pCO2 =12.8 bar, pH 2S =8 bar, T=65oC, 91 hours; Test F: p=7.2 bar, pCO2 =3 bar, pH 2S =4.2 bar, T=65oC, 63 hours; experimental data taken from Bich and Goerz40
67

5.0
exp. 1 exp. 2 exp. 3 mod. 1 mod. 2 mod. 3

Corrosion rate / mm/y

4.0 3.0 2.0 1.0 0.0 0 1 2 3 Velocity / m/s 4 5

Figure 18. The corrosion rate vs. velocity; experimental data (exp.) = points, model predictions (mod.) = lines; exp 1.: 19 days, p=40 bar, pCO2 =3.3 bar, pH 2S =10 bar, T=80oC, pH 3.1, v=1 5 m/s; exp 2.: 21 days, p=40 bar, pCO2 =3.3 bar, pH 2S =10 bar, T=25oC, pH 3.2, v=1 5 m/s; exp 3.: 10 days, p=40 bar, pCO2 =10 bar, pH 2S =30 bar, T=80oC, pH 2.9, v=1 5 m/s; experimental data taken from Omar et al.41
3.5.2 Effect of time Amarkeddecreaseofpure CO2 corrosionrateduetothepresenceof H 2 S withtime isseeninstratifiedpipeflowasshowninFigure19.Thisisclearlyamixed CO2 / H 2 S corrosion scenario. At a pCO2 / pH 2S ratio of 200 ( pCO2 =2 bar, pH 2S =4 mbar) the CO2 contributiontothecorrosionrateis75%withmostofthebalanceprovidedby H 2 S . At the pCO2 / pH 2S ratio of 28 ( pCO2 =2 bar, pH 2S =70 mbar) both CO2 and H 2 S account forapproximately50%oftheoverallcorrosionrate. 68

10 8 6 4 2 0 0 100 200 300 Time / hour 400


pure CO2 corrosion rate

Corrosion rate / mm/y

pH2S=0 mbar (exp.) pH2S=4 mbar (exp.) pH2S=70 mbar (exp.) pH2S=4 mbar (mod.) pH2S=70 mbar (mod.)

500

600

Figure 19. The corrosion rate vs. time; experimental data (exp.) = points, model predictions (mod.) = lines; conditions: total pressure p=3 bar, pCO2 =2 bar, pH 2S = 3 70 mbar, T=70oC, experiment duration 2 21 days, pH 4.2 4.9, liquid velocity 0.3 m/s. Experimental data taken from Singer et al. 39
Corrosion experiments at high temperature (120oC), high partial pressures of CO2 ( pCO2 =6.9 bar) and H 2 S ( pH 2S =1.384.14 bar)inexposures lastingupto 16 days are showninFigure20.Asteadilydecreasingcorrosionratewasobservedduetobuildup ofaprotectiveferroussulfidelayer.Theeffectof pH 2S increaseoncorrosionratewas very small and practically vanished over time. Both these effects were readily capturedbythemodelwithverygoodaccuracyasseeninFigure20.Inthiscasethe
H 2 S is the dominant corrosive species. At the highest pCO2 / pH 2S ratio of 5 ( pCO2 =6.9

bar, pH 2S =1.38 bar) H 2 S generated approximately 70% of the corrosion rate. At the

69

lowest pCO2 / pH 2S ratioof1.67( pCO2 =6.9bar, pH 2S =4.14bar) H 2 S generated82%ofthe overallcorrosionrate.

100
pure CO2 corrosion rate

pH2S=1.38 bar (exp.) pH2S=2.76 bar (exp.) pH2S=3.45 bar (exp.) pH2S=4.14 bar (exp.)

Corrosion rate / mm/y

10

pH2S=1.38 bar (mod.) pH2S=2.76 bar (mod.) pH2S=3.45 bar (mod.) pH2S=4.14 bar (mod.)

0 0 100 200 300 Time / hour

400

500

600

Figure 20. The corrosion rate vs. time; experimental data (exp.) = points, model predictions (mod.) = lines; conditions: total pressure p=7 bar, pCO2 =6.9 bar, pH 2S = 1.38 4.14 bar, T=120oC, experiment duration 1 16 days, pH 3.95 4.96, liquid velocity 10 m/s. Experimental data taken from Kvarekval et al.42
Thelongest H 2 S containingcorrosionexperimentswhicharepracticallyachievablein thelabareoftheorderofafewweeksoratbestafewmonths,whilepredictionsare meanttocoveraperiodofatleastafewdecades,inordertobemeaningful.Withthis in mind it is interesting to take the experimental conditions above ( pCO2 =6.9 bar,

pH 2S =3.45 bar, T=120oC, pH 4, v=10 m/s) and extend the simulation to 25 years. The
resultisshowninFigure21.Thecorrosionratewaspredictedtostartoutratherhigh 70

as observed in the experiments, however it was reduced to below 0.1 mm/y after 2 yearsandwasaslowas0.03mm/yafter25years.Theaveragecorrosionrateoverthis period was only 0.06 mm/y, which amounts to a wall thickness loss of only 1.5 mm overthe25years,anacceptableamountbyanypracticalaccount.Actuallymostofthe other conditionssimulatedhave shownthat rather low H 2 S uniformcorrosionrates are obtained for very long exposures, which agrees with general field experience as recently discussed by Boniset al.33Nevertheless, noquantitativelong term labdata arecurrentlyavailabletobackuptheselongtermpredictions.

10.00

pH2S=3.45 bar (mod.) pH2S=3.45 bar (exp)

Corrosion rate / mm/y

1.00

0.10

0.01 0.00

0.01

0.10

1.00

10.00

100.00

Time / year
Figure 21. Extension of corrosion prediction to a 25-year lifetime; experimental (points), predicted (lines); conditions: pCO2 =6.9 bar, pH 2S =3.45 bar, T=120oC, pH 4, liquid velocity 10 m/s; taken from Kvarekval et al. 42

71

3.6 Localized H2S Corrosion of Mild Steel in Aqueous Solutions


Localized H 2 S corrosion of mild steel is even less understood than its uniform counterpart. While it is not very common, anecdotal evidence exists that has linked localized H 2 S corrosion in aqueous environments to other factors such as: high chloridecontent,thepresenceofelementalsulfurandthetransformationofonetype ofsulfideintoanother.Intenseresearchofthesetopicsisongoingwithbreakthrough inunderstandingexpectedinthedecadetocome.

72

4 NOMENCALTURE
A
surfaceareaofthesteelinm2

A / V surfacetovolumeratioin1/m

A( FeCO3 ) constantintheArrheniustypeequationfor k r ( FeCO3 ) AH 2S solidstatediffusionkineticconstantfor H 2 S throughmackinawitefilm,

AH 2S = 2.0 10 5 mol/(m2s)

AH + solidstatediffusionkineticconstantfor H + throughmackinawitefilm,

AH + = 4.0 10 4 mol/(m2s)

AHAc solidstatediffusionkineticconstantfor HAc throughmackinawitefilm,

AHAc = 2.0 10 6 mol/(m2s)

ACO2 solidstatediffusionkineticconstantfor CO2 throughmackinawitefilm,

ACO2 = 2.0 106 mol/(m2s)

ba ( Fe ) anodicTafelslopefor Fe oxidationinV

bc (H + ) cathodicTafelslopefor H + ionreductioninV bc ( HAc ) cathodicTafelslopefor HAc ionreductioninV

bc ( H 2CO3 ) cathodicTafelslopefor H 2CO3 reductioninV bc (O2 ) cathodicTafelslopefor O2 reductioninV


bc ( H
2O ) cathodicTafelslopefor H 2 O reductioninV

B( FeCO3 ) constantintheArrheniustypeequationfor k r ( FeCO3 ) inkJ/kmol cCO2 bulkaqueousconcentrationof CO2 inkmol/m3 cCO2 bulkaqueousconcentrationof CO32 ionsinkmol/m3
3

73

cFe2+ bulkaqueousconcentrationof Fe 2+ ionsinkmol/m3 cH +


bulkaqueousconcentrationof H + ionsinkmol/m3

cs ( H + ) nearzeroconcentrationof H + underneath themackinawitefilmat the steel


surface,setto 1.0 10 7 inkmol/m3

c HAc bulkaqueousconcentrationofundissociated HAc inkmol/m3 c HAc ,ref bulkaqueousconcentrationof HAc underreferenceconditionsinkmol/m3 cO2 bulkaqueousconcentrationof O2 inkmol/m3 cs ( HAc ) nearzeroconcentrationof HAc underneaththemackinawitefilmatthesteel
surface,setto 1.0 10 7 inkmol/m3

cHCO bulkaqueousconcentrationof HCO3 ionsinkmol/m3


3

c H 2CO3 bulkaqueousconcentrationof H 2CO3 inkmol/m3 c H 2CO3 bulkaqueousconcentrationof H 2CO3 inkmol/m3 cH 2S bulkaqueousconcentrationof H 2 S inkmol/m3 cHS bulkaqueousconcentrationof HS ionsinkmol/m3 ci
bulkaqueousconcentrationofagivenaqueousspeciesinkmol/m3

ci ( H 2S ) aqueous concentration of H 2 S at the inner sulfide film/outer sulfide layer


interfaceinkmol/m3

cS 2

bulkaqueousconcentrationof S 2 ionsinkmol/m3

cs ( H 2S ) nearzero aqueous concentration of H 2 S underneath then mackinawite film


atthesteelsurface,setto 1.0 107 inkmol/m3

co ( H 2 S ) aqueous concentration of H 2 S at the outer sulfide layer/solution interface in


kmol/m3 74

cs ( CO2 ) aqueous concentration of CO2 underneath then mackinawite film at the steel
surface
CR d

corrosionrateinmm/y characteristicdimensionforagivenflowgeometryinm diameterofapipeinm diameterofarotatingcylinderinm

d p d c
D

diffusioncoefficientofagivenspeciesinm2/s

D H + aqueousdiffusioncoefficientfor H + inm2/s

Dref ( H + ) referenceaqueousdiffusioncoefficientfor H + ,

Dref ( H + ) = 9.31 109 ,inm2/sat25oC

DHAc aqueousdiffusioncoefficientfor HAc inm2/s


Dref ( HAc ) referenceaqueousdiffusioncoefficientfor HAc ,

Dref ( HAc ) = 5.0 10 10 ,inm2/sat25oC

D H 2 CO 3 aqueousdiffusioncoefficientof H 2CO3 inm2/s

Dref ( H 2CO3 ) referenceaqueousdiffusioncoefficientof H 2CO3 ,

Dref , H 2CO3 = 1.3 10 9 m2/sat25oC

DO2 aqueousdiffusioncoefficientfor O2 inm2/s Dref ( O2 ) referenceaqueousdiffusioncoefficientfor O2 ,

Dref (O2 ) = 2.0 10 9 ,inm2/sat25oC

DH 2 S aqueousdiffusioncoefficientfordissolved H 2 S inm2/s DCO2 aqueousdiffusioncoefficientfordissolved CO2 ,


75

DCO2 = 1.96 10 9 ,inm2/s

potentialinV

E corr corrosion(opencircuit)potentialinV
E rev ( Fe ) reversiblepotentialof Fe oxidation, E rev ( Fe ) =0.488V

Erev(H + ) reversiblepotentialfor H + ionreductioninV


Erev( HAc) reversiblepotentialfor HAc ionreductioninV

E rev ( H 2CO3 ) reversiblepotentialfor H 2CO3 reductioninV E rev (O2 ) reversiblepotentialfor O2 reductioninV


E rev ( H
2O )

reversiblepotentialfor H 2 O reductioninV

f H 2 CO 3 flowfactorforthechemicalreactionboundarylayer

Faradayconstant: F =96,485C/mole

Flux H 2 S fluxof H 2 S inkmol/(m2s)

FluxH + fluxof H + ionsinkmol/(m2s)


Flux HAc fluxof HAc ionsinkmol/(m2s) Flux CO2 fluxof CO2 inmol/(m2s) H sol ( CO2 ) Henrysconstantfordissolutionof CO2 inbar/(kmol/m3)
H Fe activationenthalpyfor Fe oxidation, H Fe =50kJ/mol
H (H + ) activationenthalpyfor H + ionreduction, H (H + ) =30kJ/mol
H ( HAc ) activationenthalpyfor HAc reduction, H ( HAc ) =55kJ/mol H ( H 2CO 3 ) activationenthalpyfor H 2CO3 reduction, H ( H 2CO 3 ) =57.5kJ/mol H (O2 ) activationenthalpyfor O2 reduction, H (O2 ) =10kJ/mol

H ( H 2O ) activationenthalpyfor H 2O reduction, H ( H 2O ) =30kJ/mol


76

currentdensityinA/m2

icorr corrosioncurrentdensityinA/m2 ia ( Fe ) anodiccurrentdensityofironoxidationinA/m2


ic (H + ) cathodiccurrentdensityfor H + ionreductioninA/m2 ic ( HAc ) cathodiccurrentdensityfor HAc reductioninA/m2
ic ( H 2CO3 ) cathodiccurrentdensityfor H 2CO3 reductioninA/m2

ic (O2 ) cathodiccurrentdensityfor O2 reductioninA/m2

ic ( H 2O ) cathodiccurrentdensityfor H 2 O reductioninA/m2
d i lim (H + ) masstransfer(diffusion)limitingcurrentdensityfor H + ionreductioninA/m2

d ilim ( HAc ) masstransfer(diffusion)limitingcurrentdensityfor HAc reductioninA/m2


r i lim ( H 2CO 3 ) chemicalreactionlimitingcurrentdensityfor H 2CO3 reductioninA/m2

d ilim (O 2 ) masstransfer(diffusion)limitingcurrentdensityfor O2 reductioninA/m2

io ( Fe ) exchangecurrentdensityofironoxidationinA/m2
io (H + ) exchangecurrentdensityfor H + ionreductioninA/m2 io ( HAc ) exchangecurrentdensityfor HAc ionreductioninA/m2
io ( H 2CO3 ) exchangecurrentdensityfor H 2CO3 reductioninA/m2 io (O2 ) exchangecurrentdensityfor O2 reductioninA/m2

io ( H 2O ) exchangecurrentdensityforwaterreductioninA/m2;
ref ref io ( Fe ) referenceexchangecurrentdensityof Fe oxidation, io ( Fe ) =1A/m2

ref io (H + ) referenceexchangecurrentdensityof H + oxidation,

77

ref io (H + ) =0.03A/m2at Tc , ref =25CandpH4

iorefH 2CO 3 ) referenceexchangecurrentdensityfor H 2CO3 reduction, (

iorefH 2 CO 3 ) =0.06A/m2at Tc , ref =25C,pH5,and cH 2CO3 ,ref =104kmol/m3 (

iorefHAc ) referenceexchangecurrentdensityfor HAc reduction, (

iorefHAc ) =0.1A/m2at Tc , ref =20Cand c HAc3 ,ref =103kmol/m3 (

iorefO2 ) referenceexchangecurrentdensityfor O2 reduction, (

iorefO2 ) =0.06A/m2at Tc , ref =25C (

ref io ( H 2O ) referenceexchangecurrentdensityfor H 2O reductioninA/m2,

ref io ( H 2O ) = 3 105 A/m2at Tc , ref =25oC

i (H + ) chargetransfercurrentdensityfor H + ionreductioninA/m2 i ( H 2CO3 ) chargetransfercurrentdensityfor H 2CO3 reductioninA/m2 i (O2 ) chargetransfercurrentdensityfor O2 reductioninA/m2

ionicstrengthinkmol/m3

b f b k hyd backwardreactionrateof H 2CO3 dehydrationreactionin1/s, k hyd = k hyd K hyd f k hyd forwardreactionrateforthe CO2 hydrationreactionin1/s

k m ( H + ) aqueousmasstransfercoefficientfor H + inm/s
k m ( H 2CO3 ) aqueousmasstransfercoefficientfor H 2CO3 inm/s

k m ( HAc ) aqueousmasstransfercoefficientfor HAc inm/s


k m ( O 2 ) aqueousmasstransfercoefficientfor O2 inm/s
k m ( H 2 S ) aqueousmasstransfercoefficientfor H 2 S inm/s k m ( CO 2 ) aqueousmasstransfercoefficientfor CO2 inm/s

78

k r ( FeCO3 ) kinetic constant in the ferrous carbonate precipitation rate equation


in1/(mols)
f b K hyd equilibriumhydrationconstantfor CO2 , K hyd = k hyd k hyd = 2 . 58 10 3

K bi K bs K ca K hs

equilibriumconstantfordissociationof HCO3 inkmol/m3 equilibriumconstantfordissociation HS inkmol/m3 equilibriumconstantfordissociationof H 2CO3 inkmol/m3 equilibriumconstantfordissociation H 2 S inkmol/m3

K sol ( H 2S ) solubilityconstantfordissolutionof H 2 S in(kmol/m3/bar) K sol (CO2 ) solubilityconstantfordissolutionof CO2 in(kmol/m3/bar) K sp ( FeCO3 ) solubilityproductconstantforferrouscarbonatein(kmol/m3)2
mackin K sp ( FeS ) solubilityproductconstantformackinawitein(kmol/m3)2

mos

massoftheoutersulfidelayerinkg

M Fe molecularmassofironinkg/kmolFe M FeS molecularmassofferroussulfideinkg/molFeS,


n

number of electrons used in reducing or oxidizing a given species in kmole/kmol

pCO2 partialpressureof CO2 inbar pH 2S partialpressureof H 2 S inbar

electrochemicalreactionrateinkmol/(m2s)

FeCO3 precipitationrateforironcarbonateinkmol/(m3s)

R
Re

universalgasconstant, R =8.314J/(molK) Reynoldsnumber, Re = v H 2O d H 2O

79

Sc Sh p

Schmidtnumberofagivenspecies, Sc = H 2O ( H 2O D ) Sherwoodnumberofagivenspeciesforastraightpipeflowgeometry, Sh p = k m d p D Sherwoodnumberofagivenspeciesforarotatingcylinderflowgeometry, Shr = k m d c D

Shr

SS ( FeCO3 ) supersaturationofironcarbonate
ST

scalingtendency temperatureinoC

Tc

Tc ,ref referencetemperature, Tc ,ref =25oC


Tf Tk
v

temperatureinoF temperatureinK watercharacteristicvelocityinm/s specieschargeofvariousaqueousspecies

zi

Greekcharacters

m ( H CO ) thicknessofthemasstransferlayerfor H 2CO3 inm


2 3

r ( H CO ) thicknessofthechemicalreactionlayerfor H 2CO3 inm


2 3

os
t
2

isthethicknessoftheoutersulfidelayerinm, os = mos / ( FeS A ) timeintervalins

H O waterdynamicviscosityin Pa s

H O, ref referencewaterdynamicviscosity Pa s atareferencetemperature,


2

80

H2O, ref = 1.002 10 4 Pa s at20oC

H CO ratioofthemasstransferlayerandchemicalreactionthicknessesfor H 2CO3
2 3

istheoutersulfidelayerporosity istheoutersulfidelayertortuosityfactor

H O densityofwaterinkg/m3 Fe densityofironinkg/m3 FeS densityofferroussulfideinkg/m3

81

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