ValidationofScaleSoftPitzer

CalciteSI,densityandsimplified
bariteSIprediction
December2008

Outlineofpresentation
y ComparenewPitzer coefficientsforcarbonates
(FrankMillero,Geochimica etCosmochimica Acta 71
(2007)4655)vs.thatinSSPforCalciteSIprediction.
y ReviseddensitycalculationinSSP.
y AsimplifiedequationtocalculatebariteSIand
precipitation.
y OtherimprovementsinSSPV.13.

CarbonatePitzer Coefficients
Currently used in SSP, He and Morse, 1993

New Pitzer coefficients by Millero et al., 2007

Applicable range: 0-250 C, 0-5 M I

CompareActivityCoefficients
0.8
0.6
0.4
0.2

1 M NaCl

0.0

40

gHCO3 Millero
gCO3 Millero

gCO2aq SSP

actiivty Coefficients

actiivty Coefficients

gCO2aq Millero

140

240

340

1.000
0.100
0.010
0.001
40

Temperature

1.2
1.0
0.8
0.6
0.4
0.2
0.0

140

240
Temperature

140

240

gHCO3 Millero
gCO3 Millero

gCO2 SSP

5 M NaCl
40

1 M NaCl

340

Temperature

340

actiivty
Coefficients

actiivty Coefficients

gCO2aq Millero

gHCO3 SSP
gCO3 SSP

gHCO3 SSP
gCO3 SSP

1.E+00
1.E-01
1.E-02
1.E-03
1.E-045 M NaCl
1.E-05
40
140

240

Temperature

340

1 M NaCl, 14.9 mg/L, Ca, 610 mg/L, alkalinity, 2% CO2

Hes Coefficient (SSP)
T

(F)

(psia)

Milleros Coefficient

Calcite

Calcite

pH

SI

pH

SI

32

15

7.34

1.12

7.33

1.13

84

1,124

7.09

0.96

7.08

0.97

136

2,234

7.00

0.80

7.01

0.80

187

3,343

7.02

0.61

7.04

0.57

239

4,453

7.08

0.40

7.13

0.31

291

5,562

7.16

0.18

7.23

0.04

343

6,672

7.20

0.02

7.28

0.19

394

7,781

7.19

0.15

7.26

0.36

446

8,891

7.11

0.19

7.18

0.42

498

10,000

6.94

0.01

7.00

0.23

CalciteSolubilityData
T(C) I(m)

SSP

Millero

Ref.

Mean

Std
Error

Mean

Std
Error

60
203

16.24

0.03

0.062

0.092

0.220

Ellis1963
Wolf1989

4204

13

0.006

0.021

0.009

0.054

BCC

Conclusion: calcite SI is more accurately predicted by

SSP. Therefore, no updates are recommended for
carbonate Pitzer coefficients.

OverallqualityofSSPSIprediction
ScaleType

I(m)

T( F )

P(psi)

SI S.D.

Calcitea

0 6.24

32 554

14.7 174

0.047 0.121

30

Barite

0 5.0

75 203

14.7 14,417

0.013
0.147
Halite
6.097 10.4 32 572
14.71,244
0.003
0.041
Gypsum
0 6.08
32 230
14.7 50
0.036
0.144
Anhydrite
0 6.30
122
14.7
0.087
0.081
Celestite
0 4
68 306 14.7 7,409
0.137
0.156
SummaryEstimatedRangeofSSPApplicability
AllScalesb

0 10

32 400

14.7
15,000/20,
000

0.013 0.14

36
13
18
7
19

123

DensitycalculationinSSP
y InearlyversionofSSP,densityiscalculatedbyan
empiricalequationbetweenTDSanddensitybased
NaCl data.
brine(g/ml)=0.9991+0.6358x106 TDS(mg/l)
r2=0.9995
y Thiscanbepotentialsourceoferrorunderextreme
conditions,e.g.,saturatedCa(HCO3)2,ZnBr2
weightingfluid,etc.
y Densityistheoreticallyrelatedtopartialmolal
volumes,etc.,andcanbecalculatedviaPitzer theory.

NewDensityCalculation
UsePitzeractivitycoefficientschangewithrespectto
pressuretoestimateexcessmolarvolumeofthesolution:
i
)R T
P
1000 + m i MWi

Viex = log(
=

1000 / H 2O + (Vi0 + Viex ) m i

SSPPredictedDensityvs.CRCHandbookValues(25C)
Compound

Conc.(M)

CRCHandbook

SSP

Aceticacid

6.255

1.043

1.049

NaAcetate

4.243

1.160

1.170

KCl

3.742

1.168

1.162

NaCl

5.326

1.197

1.185

MgCl2 6H2O

4.021

1.276

1.287

BaCl2

1.597

1.279

1.282

MgSO47H2O

2.799

1.296

1.262

CaCl2 2H2O

5.03

1.395

1.420

HCl

6.022

1.098

1.097

NaBr

5.495

1.414

1.421

SrCl2

2.293

1.298

1.303

H2SO4

5.313

1.303

1.288

KHCO3

2.801

1.169

1.181

K2CO3

4.093

1.414

1.473

NaHCO3

0.743

1.043

1.042

Na2CO3

1.638

1.157

1.170

Calculated density

1.5
1.4
1.3
1.2
y = 1.005x
R2 = 0.977

1.1
1.0
1.0

1.1

1.2

1.3

1.4

Density from Handbook

1.5

Calculated TDS (g/L)

Calculatedvs.MeasureddensityandTDS
650
600
550
500
450
400
350
300
250
200

y = 0.998x
R2 = 0.999

200 300 400 500 600

TDS from Handbook (g/L)

SSPDensityvs.ObservedData
13.0
y = 0.9981x
R2 = 0.9998

SSP calc density (lb/gal)

12.5
12.0
11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
8.0

9.0

10.0

11.0

Benchmark density (lb/gal)

12.0

13.0

SimplifiedequationforbariteSI
andprecipitation
y

Purpose:Toproduceasimple,explicit,andclosed
formalgebraicequationtocalculatebariteSIand
precipitationatanyT,PandIonicstrength.
y Approach:
y

GeneratealargesetofvaluesfromSSPoverawide
rangeofconditions:I=0.025.5m,T=40400F,P=
14.715000psi,TBa =00.5m,andTSO4=00.5m.
Nonlinearcurvefittingasemiempiricalequationto
thedata.

Background
Ion Activity Product
SI Log10

K sp (T, P)

a Ba 2+ a SO 24
m Ba mSO 4 Ba 2+ SO 24
SI Barite = Log10
= Log10

K
K
sp ,Barite

sp , Barite
= Log10 {m Ba m SO 4 } + Log10 { Ba 2+ SO 2 } Log10 {K sp ,Barite }
4

Pitzer ActivityCoefficient
Pitzer theory is based on the excess function approach.
The excess free energy is assumed to be a virial (power
series) expansion of binary and ternary interactions of
species with a leading term of a Debye-Huckel type.

G Excess
Pitzer / RT
composition.
ln( ofMeT,)P,=I and
are functions
n Me
T ,P ,n j

= z 2Me F(I) + m a (2B Mea + ZC Mea ) + m c (2 Mec + m a Meca )

a

+ m a m a ' Meaa ' + z Me m c m a C ca + 2 m n nMe

a < a'

The constants B Mea , C Mea , Mec , Meca , Meaa ' , C ca , and nMe
are functions of T, P, I and composition

Mainconsideration
y Properrepresentationofionpair,orcomplex,formation
betweenBa,Mg,Sr orCaandsulfateintheclosedform
equation.
y Pitzer theoryaddressesthisbytheBtermthatimplicitly
includesionpairformationintheactivitycoefficients.
ThereforetheactivitycoefficientisafunctionofT,P,I,
M2+/SO4 ratios.
y FromthisvantageweusedawiderangeofM2+/SO4 ratios
anddeterminetheeffectofionpairformationonactivity
coefficients.
Ba 2+ = Ba 2+ ,due to T, P,TDS Ba 2+ ,due to complex formation

m Ba free
2+
= Ba 2+ ,due to T, P,TDS f
m Ba

f SO 2 =
4

+
f Ba 2 + =

mSO 2

4 free

mSO

- (1 + K MeSO 4 m Me - K MeSO4 mSO 4 )

2 K MeSO 4 mSO 4

+ ((1 + K MeSO 4 m Me - K MeSO4 mSO 4 ) 2 + 4 K MeSO 4 mSO 4 ) 0.5

2 K MeSO 4 mSO 4

m Ba 2 + free
m Ba

1
1 + K BaSO 4 m SO 2

4 free

1
1 + K MeSO 4 m SO 4 f SO 4

log10 ( Ba SO 4 ) = a 0 + log10 (f Ba f SO 4 ) (-2.0329/(1 + I 0.5 )

+ 3.9678/(1 + I 0.5 ) 2 19.0838 e 1.3822*TR + 4.8149/TR - 0.0273 PR )
where
a 0 = -1.1501 - 73.4997/(1 + I 0.5 ) + 0.8337/(1 + I 0.5 ) 2
- 0.5417 e 2.8949TR + 79.6205 /(TR0.0647 (1 + I 0.5 )) 0.0647 PR
- 0.0188 PR / log(TR ) + 0.012 PR I

ChangesinSIandBa Conc.vs.Seawater
fraction
ConstantSIConstantBa Conc.

3.0

600

2.5
2.0

1.0

1.0-1.5

Barite SI

0.0

1.5-2.0

400

0.5-1.0
0.0-0.5

300

-0.5-0.0
-1.0--0.5

-0.5

-1.5

-2.0--1.5

200

3000
6000
100

9000

0.1

Demobrineat340F

0.3

18000

Sea water fraction

0.4
0.5
0.6
0.7
0.8
0.9
1

15000

0.2

1
0.8

0.6

0.4

0.2

18000

)
si

i)

15000

12000

(p

s
(p

12000

-2.0
P

9000

6000

3000

-1.0

-1.5--1.0

Sea w ater fraction

Remaining Ba2+ in solution, mg/l

1.5

2.0-2.5

0.5

500

2.5-3.0

500-600
400-500
300-400
200-300
100-200
0-100

NewfeaturesinSSP
y Newinhibitorneedcalculationforgypsumandanhydrite.
y Optionforcalculatingthescalingtendencyofacondensedor
dilutedbrine.
y Optionforcalculatingsaturationratiovs.saturationindex.
y OptionforuserinputT,P.
y Tenrowsofwhatif calculation.
_________________________________________________________
y Updatecosolventactivitycoefficients.
y Newinhibitorneedcalculationforbariteinthepresenceand
absenceofhydrateinhibitors.
y UpdatedhalitepKsp.
y Miscellaneouscorrectionsonmixingroutine,density,etc.

Conclusions
y SSPSIcalculationhasbeenvalidatedwithexperimentaldataup
to200C.
y Pitzer carbonatecoefficientsofMillero isnotrecommendedfor
SSP.
y SSPincorporatesthermodynamicallyrigorousdensity
calculationforhighsolidbrine.
y DensitycalculationvalidatetheaccuracyofSSPactivity
coefficients.
y Aclosedformbariumandsulfateactivitycoefficientcalculator
hasbeenderived.
y NumerousnewfeatureshavebeenaddedtoSSP,whichwillbe
demonstratedattomorrowsworkshop.