4 - Thermodynamics of Mineral Scale Prediction: Ken Sorbie

4 – Thermodynamics of Mineral
Scale Prediction
Ken Sorbie
Shell, Houston, 10-12 December 2013

Plan of Presentation
• Simple scale prediction models for insoluble salts
• Theory and data for carbonate scale prediction

• Numerical example calculating CaCO3 precipitation
• Validation and comparison of scale prediction

codes
• North Sea field example - carbonate scale
• Further complications in scale prediction
• Summary and Conclusions

Section 3: Slide 2 of 76
• Simple scale prediction models for insoluble

salts


codes
• Summary and Conclusions Section 3: Slide 3 of 76

Simple scale model for barite - BaSO4
Basic idea of a scale prediction model

Ba2+ + SO42-  BaSO4(s)
BaCl2 Na2SO4
Can take various approaches to modelling
the equilibrium chemical reaction
••• •
• ••••• •

Ba2+ + SO42-  BaSO4(s)
BaCl2 Na2SO4
Can take various approaches e.g. ...
- minimisation of Gibb’s free energy (i) •• •
•
• ••••• •
G   BaSO4  Ba2  Ba2  SO2  SO2  0

4 4
- “mass action” equilibrium const. approach

(we will follow this here)

Ba2+ + SO42-  BaSO4(s)
BaCl2 Na2SO4
where
[ Ba 2 ][ SO42 ]
K  •• •
[ BaSO4( s ) ] •
• ••••• •
K sp  K .[ BaSO4( s ) ]  [ Ba 2 ][SO42 ]  K sp (T , P )
Ksp is the solubility product of BaSO4
Thermodynamic Equilibrium Constants at 25°C
VERY
INSOLUBLE
(from Ostvold and Kaasa , Adv. in Oilfield Scaling Conf., 28-29 Jan., 1998) Section 3: Slide 7 of 76
Example:K sp  [ Ba 2 ][ SO42 ]  1.12 x1010
In pure water with BaSO4 solid present

[ Ba 2 ]  [ SO42 ]
[ Ba 2 ]  [SO42 ]  x Thus x 2  1.12 x1010
BaSO4(s)
hence x  1.12 x1010  1.058x105 M
 [ Ba 2 ]  1.058x105 x 137.33 = 1.45 x103 g / l
 [ Ba 2 ]  1.45 mg / l  1.45 ppm
VERY insoluble
Solubility of other scales cf. - BaSO4
Solubility order:
* CaSO4 >
 § SrSO4 >

 CaCO3 >
§
*  BaSO4
*


codes

The Problem: Carbonate scale (calcite - CaCO3)
• Build up of carbonate scale (CaCO3) due to P
High P + CO2
Low P
Ca2+ P CaCO
Calcite
Precipitate
+ HCO3- 3
Ca2+ + 2 HCO3-  CaCO3 + CO2 + H2O

• Equations for carbonate scale (CaCO3) formation
Physical situation in carbonate scale P&T

gas + CO2(g)
The CO2 in the gas phase (if any) is
CO2(aq) CO32-
in equilibrium with the components Ca2+
in the aqueous phase. HCO3- + H+
HA A-
Overall equation:
Ca2+ + 2 HCO3-  CaCO3 + CO2 + H2O
The set of equilibrium equations are:

P&T
1. CO2(g) = CO2(aq) gas + CO2(g)
2. H2O + CO2(aq) = HCO3- + H+ CO32-

CO2(aq)
Ca2+
3. HCO3- = CO32- + H+ HCO3- + H+
4. Ca + CO3  CaCO3(s)
2+ 2- HA A-
5. H2O = H+ + OH - (water)
6. H.A = H+ + A - (organic acids) Section 3: Slide 13 of 76

Equilibrium equation 1: P&T

P   pi CO32-
CO2(aq)
[CO2(aq) ]= K1(T; pCO2(g) ) P  pgas  pCO2 ( g ) Ca2+
HCO3- + H+
HA A-
Solubility of CO2 ?? (well known)

P   pi
[CO2(aq) ]= K1(T; pCO2(g) ) CO2(aq) CO32-
P  pgas  pCO2 ( g )
10 Ca2+
Solubility
CO2 7. HCO3- + H+
5
18 C
o
mass
100 wts. 5. 100oC
H2O 0
2.
5
Pressure (atm.)
25 50 75 100 125 150 175
(DATA: page 3-101; Perry, Chem. Eng. Handbook, 6th Edn., 1984) Section 3: Slide 15 of 76

Example: 100oC & 2-
[CO2(aq) ]= K1(T; pCO2(g) ) CO3
150 atm.CO ~ 4.4
2(aq) g/100g
~ 44 g/l Ca 2+
10
Solubility HCO3- + H+
[CO2(aq) ] = ~ 1 mol/l
CO2 7. 18oC
5
mass
100 wts. 5. 100oC
H2O 0
2. Pressure (atm.)
5 25 50 75 100 125 150 175
(DATA: page 3-101; Perry, Chem. Eng. Handbook, 6th Edn., 1984) Section 3: Slide 16 of 76
Equilibrium equation 2:
P&T
2. H2O + CO2(aq) = HCO3- + H+ gas + CO2(g)
[ HCO3 ][ H  ]
Where K2   K 2 (T , P) CO2(aq) CO32-
[CO2( aq ) ]
Ca2+
HCO3- + H+
Equilibrium equations 2 & 3:

P&T
2. H2O + CO2(aq) = HCO3- + H+ gas + CO2(g)
[ HCO3 ][ H  ]
Where K2   K 2 (T , pCO2 ) CO2(aq) CO32-
[CO2( aq ) ]
Ca2+
... and HCO3- + H+
3. HCO3- = CO32- + H+
Where [CO32 ][ H  ]
K3  
 K 3 (T , P)
[ HCO3 ]
Equilibrium equations 2 & 3:

P&T
% H2CO3(aq)  HCO3  CO3 - 2-
species in solution
gas + CO2(g)
T=25oC; P = 1 atm.
100
CO2(aq) CO32-
80
*H2CO3(aq) HCO3- Ca2+
% 60 CO32-
distrib-
HCO3- + H+
50%
ution 40
20 * mostly
6.35
10.33 CO2(aq)
4 5 6 7 8 9 10 11 12 13 14
pH -->
(DATA: after Hem, US Geol. Survey Water Supply paper 2254, 1985)
P&T
4. Ca2+ + CO32-  CaCO3(s) gas + CO2(g)
Can define CO2(aq) CO 3

2-
(a) the solubility of CaCO3 (mol/kg) - data ... Ca2+

HCO3- + H+
HA A-
P&T
Solubility data for CaCO3 (mol/kg) vs. T (oC)
CO2(aq) CO32-
0.008
Solubility Ca2+
CaCO3 0.006 p CO2(g) = 0.25 atm. HCO3- + H+
(mol/kg) 0.004
HA A-
0.002
20 40 60 80 100 120 140 T (oC)
(DATA: Plummer & Bussenburg, Geochim. Cosmochim. Acta, 46, 1011-1040, 1982)
P&T
Solubility data - CaCO3 (mol/kg) vs. p CO2(g)
0.012 CO32-
CO2(aq)
0.010 T=100 C o
Ca2+
Solubility
HCO3- + H+
CaCO3 0.008
(mol/kg) 0.006 HA A-
T=150oC
0.004
0.002
partial pressure CO2
20 40 60 (p CO2(g); atm.)
(after - Harberg et al, SPE (PE), 75-84, Feb. 1992)

P&T
Solubility of CaCO3 (mol/kg) - dep. on [NaCl]
0.012 CO32-
CO2(aq)
0.010
1M Ca2+
Solubility 0.2M
NaCl NaCl HCO3- + H+
CaCO3 0.008
(mol/kg) 0.006 HA A-
0.004 pure
H2O
0.002 T (oC)
100 120 140 160
(after - Harberg et al, SPE (PE), 75-84, Feb. 1992)

P&T
Can define CO2(aq) CO 3

2-
(a) the solubility of CaCO3 (mol/kg) - data ... Ca2+

(b) the solubility product or pK4 - data ... HCO 3
-
+ H +
2 2 A-
K 4  [Ca ][CO ]  K 4 (T , P)
3
HA
pK 4   log [Ca 2 ][CO32 ]   log K 4 (T , P)
P&T
pK 4   log [Ca 2 ][CO32 ]   log K 4 (T , P) CO32-

CO2(aq)
Ca2+
pK4 10.8 HCO3- + H+
CaCO3
10.0 HA A-
9.2 CaCO3 less soluble
8.4
20 40 60 80 100 120 140 T (oC)
(DATA: Plummer & Bussenburg, Geochim. Cosmochim. Acta, 46, 1011-1040, 1982) Section 3: Slide 25 of 76
Calculated CaCO3 Solubilities in 1M NaCl
Solubility
(mmolal)
T
P
(from Atkinson, NACE, Corrosion94, Paper 610, 1994) Section 3: Slide 26 of 76

P&T
5. H2O = H + OH (water)
+ -
gas + CO2(g)
The weak dissociation of water is given by
[ H  ][OH  ] CO 2-
K5  CO
but [H2O] virtually constant 2(aq) Ca2+
3
[ H 2O ]
HCO3- + H+
Hence: K w  K5 .[ H 2O]  [ H  ][OH  ]
HA A-
where - Kw = 1.0 x 10 -14 mol/l at 25 oC and 1

atm.
Kw = the ionic product of water
Equilibrium equation 6 (optional):

P&T
6. H.A = H+ + A - (organic acids) gas + CO2(g)
These are weak acids e.g. acetic CO32-

CO2(aq)
  Ca2+
[ H ][ A ]
K5   K5 (T , pCO2 ) HCO3- + H+
[ HA] HA A-
Acetic acid - K5 = 1.74 x 10 -5 (T=25oC; P = 1 atm.)
The set of equilibrium equations are:

1. CO2(g) = CO2(aq)
How do we solve these
2. H2O + CO2(aq) = HCO3- + H+ equations ??
3. HCO3- = CO32- + H+
An example ....
4. Ca2+ + CO32-  CaCO3(s)
5. H2O = H+ + OH - (water)
6. H.A = H+ + A - (organic acids)


• Numerical example calculating CaCO3
precipitation

codes
• Summary and Conclusions Section 3: Slide 30 of 76

• Previous equilibrium equations give a set of (non-

linear)
equations in the unknowns: [Ca2+], [CO32-], [H+] etc.
+
Mass balance and Charge balance to have same no. of
equations as unknowns
• Calculate the equilibrium constants K1, K2 ... at system T

&P
(these appear as coefficients in equns.)
• Solve these equations numerically for unknowns

Simplified EXAMPLE calculation for the carbonate system:

0.1 mole CO2 fully dissolved in 1 kg aqueous
P, T
phase
Excess CaCO3 - solid present in equilibrium;
CO2(aq) CO32- No HA - no gas present; what is [Ca2+] and
Ca2+ pH?
HCO3- + H+
OH-
CaCO3(s)
Simplified EXAMPLE calculation for the carbonate system:

0.1 mole CO2 fully dissolved in 1 kg aqueous
P, T
phase
Excess CaCO3 - solid present in equilibrium;
CO2(aq) CO32- No HA - no gas present; what is [Ca2+] and
Ca2+ pH? NOTATION
HCO3- + H+
mCO2( aq )  [CO2( aq ) ]; mHCO  [ HCO3 ]
3
-
OH
mCO2  [CO32 ]; mCa2  [Ca 2 ]
3
CaCO3(s)
mH   [ H  ]; mOH   [OH  ]
These are the 6 UNKNOWNS
Equations needed for EXAMPLE are: mHCO . mH 

K2  3
mCO
2. H2O + CO2(aq) = HCO3 + H
- + 2( aq )
3. HCO3- = CO32- + H+
4. Ca2+ + CO32-  CaCO3(s)
5. H2O = H+ + OH - (water)
Equations needed for EXAMPLE are: K  mHCO3 . mH 

2
mCO
2( aq )
2. H2O + CO2(aq) = HCO3 + H
- +
mCO 2 . mH 
K  3
3. HCO3- = CO32- + H+ 3
m  HCO3
4. Ca2+ + CO32-  CaCO3(s)
5. H2O = H+ + OH - (water)

2
mCO
2( aq )
2. H2O + CO2(aq) = HCO3 + H
- +
mCO 2 . mH 
K  3
3. HCO3- = CO32- + H+ 3
m  HCO3
4. Ca2+ + CO32-  CaCO3(s) K 4  mCa2 . mCO

3
5. H2O = H+ + OH - (water)

2
mCO
2( aq )
2. H2O + CO2(aq) = HCO3 + H
- +
mCO 2 . mH 
K  3
3. HCO3- = CO32- + H+ 3
m  HCO3

3
5. H2O = H+ + OH - (water)
K 5  mH  . mOH 

2
mCO
2( aq )
2. H2O + CO2(aq) = HCO3 + H
- +
mCO 2 . mH 
K  3
3. HCO3- = CO32- + H+ 3
m  HCO3

3
5. H2O = H+ + OH - (water)
K 5  mH  . mOH 
These are the 4 EQUATIONS
4 Equations - but 6 unknowns mHCO . mH 

K2  3
(Mass Balance + Charge Balance) mCO

2( aq )
mCO 2 . mH 
K3  3
mHCO
3
K 4  mCa2 . mCO
3
K 5  mH  . mOH 
4 Equations - but 6 unknowns

mHCO . mH 
(Mass Balance + Charge K2  3
Balance) mCO
2( aq )
Assume: mCO 2 . mH 
K3  3
CO2 is barely dissociated mHCO

3
(justify) mCO2( aq )  0.1mol / l
Hence K 4  mCa2 . mCO
3
0.1K 2  mHCO . mH 
3
and K 5  mH  . mOH 
4 Equations - but 6 unknowns mHCO . mH 

(Mass Balance + Charge K2  3
Balance) mCO
2( aq )
Assume: mCO 2 . mH 
K3  3
CO2 is barely dissociated mHCO

3
(justify) mCO2( aq )  0.1mol / l

Hence K 4  mCa2 . mCO
0.1K 2  mHCO . mH 
3
and 0.1K 2 K 5  mH  . mOH 

mHCO 
3
mH 
eliminate
4 Equations - but 6 unknowns 0.1K 2

mHCO 
(Mass Balance + Charge 3
mH 
Balance) 0.1K 2
mHCO  mCO 2 . mH2 
3
mH  K3  3
0.1K 2
mCO  0.1mol / l K 4  mCa2 . mCO

Gives 2( aq )
3
0.1K 2  mHCO . mH 
3
K 5  mH  . mOH 
4 Equations - but 5 unknowns
4 Equations - but 6 unknowns 0.1K 2

mHCO 
(Mass Balance + Charge 3
mH 
Balance)
 i .mi 0 ( i  ch arg e on ion i)
i K3 
mCO 2 . mH2 
3
0.1K 2
1.mH   1 mOH   2.mCa 2  2 mCO2  mHCO 3  0
3
K 4  mCa2 . mCO
3
K 5  mH  . mOH 


codes

Thermodynamic Equilibrium Constants at 25°C
DATA
pH vs. CO2 Pressure in NaHCO3 solns.; (22°C & 60 °C)
22oC 60oC
pH pH
[NaHCO3
]
CO2 pressure (bar) CO2 pressure (bar)
NB pH  a.ln  pCO2   b
Solubility of CaSO4 in (a) Pure Water, and (b) NaCl solution
(a) Solubility vs. T - Pure (b) Solubility vs. [NaCl]
water
50oC
Gypsum Solubility
Solubility CaSO4.2H2O (mM/kg)
(mM/kg)
150oC
Anhydride
CaSO4
Temperature (oC) NaCl conc. (molar)
Solubility of Calcite vs. T; A) CO2 pressures in pure water.
B) NaCl solutions at PCO2=12 atm.
Pure Solubility
Solubility water (mM/kg)
(mM/kg) pCO2 = 12
atm.
Temperature (oC) Temperature (oC)
Experimental validation of carbonate scale prediction
Good model validation shown above
Model Comparison ...

But how do commercially available and in-house company
scale prediction models compare on the SAME data ?
Any differences between BaSO4 and CaCO3 ?
Comparison of Different Scale Prediction Programs
First issue in making comparisons is defining the scaling index:
Define [M] = [M++ scaling ion] ; [A] = [-- scaling anion]; Ksp = [M][A]
No scale Satn. Scale Example code
 [ M ][ A] 
Saturation Level, SL    <1 1 >1 DHSAT (French Creek)
K
 sp 
1/ 2
 [ M ][ A]  <1 1 >1 SCALEUP (HWU)
Supersaturation, SP   
K
 sp 
 [ M ][ A] 
Saturation Index, SI  log10   <0 0 >0 Elf Model
K
 sp 
 [ M ][ A]  <0 0 >0 MultiSCALE (PetroTech)

Saturation Ratio, SR  ln  
K
 sp 
(After M D Yuan) Section 3: Slide 51 of 76

The problem: Brine compositions

Conditions
mg/l Formation brine Seawater
Na+ 37370 10890
Temp. Pressure
K+ 940 460
(oC) (bar) Ca++ 12300 428
Mg++ 835 1368
Downhole 125 340 Ba++ 160 0
Wellhead 117 269 Sr++ 785 0
Riser 94 85 Cl- 77000 19766
Ambient 25 1 SO4-- 0 2960
HCO3- 495 130
CO3-- 0 0
OH- 0 0
CO2 (g) 4.5% 0
TDS 129885 35872
pH 4.5 5.5
(After M D Yuan)
The problem: Brine compositions

Conditions
mg/l Formation brine Seawater
Na+ 37370 10890
Temp. Pressure
K+ 940 460
(oC) (bar) Ca++ 12300 428
Mg++ 835 1368
Downhole 125 340 Ba++ 160 0
Wellhead 117 269 Sr++ 785 0
Riser 94 85 Cl- 77000 19766
Ambient 25 1 SO4-- 0 2960
HCO3- 495 130
CO3-- 0 0
cf. BaSO4 OH-
CO2 (g)
0
4.5%
0
0
Ambient
SrSO4 &
TDS
pH
129885
4.5
35872
5.5
CaSO4 Downhole
CaCO3 (After M D Yuan)
300 BaSO4 - Ambient
Mass
Good
ppt. agreement
(mg/l)
Various
codes
(After M D Yuan)
%
Seawater
300 BaSO4 - Ambient 250 BaSO4 - Downhole
Generally
Mass
Good good
ppt. agreement agreement
(mg/l)
Various
codes ?? Some
outliers
% Seawater % Seawater
(After M D Yuan)
700 SrSO4 - Ambient
Good
agreement
Mass
ppt.
(mg/l)
??
(After M D Yuan)
% Seawater
700 SrSO4 - Ambient SrSO4 - Downhole
Good NOT
agreement good
Mass
ppt. agreement
(mg/l)
??

350 CaCO3 - Ambient
Mostly good
agreement
Mass
ppt.
(mg/l)
..but ??
(After M D Yuan)
% Seawater
CaCO3 - Ambient 450

350
Mostly good
agreement
Mass
ppt.
(mg/l)
Considerable
spread
..but ?? ??

Comments on comparisons:
- BaSO4 predictions very good at ambient and downhole
(because it is so insoluble and not very sensitive)
- SrSO4 predictions good at ambient but not good downhole

(this is data tuning issue - Atkinson has some great data)
- CaCO3 predictions good at ambient but not good downhole

(this is partly data tuning and how the various people went
about doing the calculation)


codes

North Sea CaCO3 Scale example
Note:
[Ca2+] = 720 ppm
[HCO3-]
= 650 ppm
(from Schmidt and Bentsen , Adv. in Solving Oilfield Scaling Problems, Aberdeen, 7-8 Oct. 1992)
Field case shown at different temperatures
[HA] = 450 ppm
[HCO3-] = 850 ppm

Precipitate
mg/l 90oC
CO2 = 0.58 mol %
85oC
80oC
Total pressure (bar)
The effect of reduced Pco2
[HA] = 450 ppm
[HCO3-] = 850 ppm

90oC
CO2 = 0.38 mol %
Precipitate 85oC
mg/l
80oC
Total pressure (bar)
North Sea CaCO3 Scale example - summary


codes

Further possible complications in scale prediction
(ia) There may be several coupled scales

e.g. CaCO3, BaSO4, CaSO4, SrSO4, etc...
GAS Must solve CaCO3 equns.

PHASE
P&T
+ ....
gas + CO2(g)
Ba2+ + SO42-  BaSO4(s)
CO2(aq) CO32-
AQUEOUS Ca 2+ Sr2+ + SO42-  SrSO4(s)
PHASE
HCO3- + H+ etc..
HA A- and ..
(ib) There may be several coupled scales + H2S, HA

etc.
e.g. CaCO3, BaSO4, CaSO4, SrSO4, etc...
GAS Must solve CaCO3 equns.
PHASE
P & T H2S(g)
+ ....
gas + CO)2(g)
Ba2+ + SO42-  BaSO4(s)
CO2(aq) CO32-
AQUEOUS Ca 2+ Sr2+ + SO42-  SrSO4(s)
PHASE
HCO3- + H+
HA A- ....................................
+ H2S and HA Section and .. 68 of 76
3: Slide
(ic) There may be several coupled scales + Different

polymorphs
e.g. of CaCO3 and CaSO4 etc...
GAS
PHASE
P&T [Ca2+][CO32- ] = 4.5x10-9 calcite
gas + CO2(g)
[Ca2+][CO32- ] = 6.0x10-9 aragonite
CO2(aq) CO32-
AQUEOUS Ca2+
PHASE
HCO3- + H+ Similar for anhydrite CaSO4 and
- gypsum CaSO4 .2H2O

HA A
(ii) Rather more “exotic” scales may form ...

e.g. FeCO3 ,FeS, CaF2, etc.
GAS Must solve appropriate set of

PHASE
P&T
chemical equations
gas + CO2(g)
Many scale packages now treat

CO2(aq) CO3 2-
AQUEOUS
these scales
Ca2+
PHASE
HCO3- + H+
HA A-
Further possible complications - multiple phases
(iii) We may have to calculate the pCO2 by doing a

coupled PVT calculation
GAS OIL

PHASE
P&T OIL + CH4 PHASE
gas + CO2(g) + CO2(g)
CO2(aq) CO32-
AQUEOUS Ca2+
PHASE ALL 3 PHASE ARE IN EQUILIBRIUM
HCO3- + H+
HA A-
Distribution of CO2 in various phases
DISTRIBUTION OF CO2
P decreasing
Schematic Figure of the 3-Phase Model
The relative CO2 concentrations in each phase


codes

Summary of Talk
We have reviewed:
- Theory of carbonate scale prediction + numerical

example
- Validation and comparison of scale prediction codes
- North Sea field example - carbonate scale
- Additional complications in scale prediction

4 - Thermodynamics of Mineral Scale Prediction: Ken Sorbie

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4 – Thermodynamics of Mineral

Shell, Houston, 10-12 December 2013

• Simple scale prediction models for insoluble salts

• Theory and data for carbonate scale prediction

• Validation and comparison of scale prediction

• North Sea field example - carbonate scale

• Further complications in scale prediction

• Summary and Conclusions

• Simple scale prediction models for insoluble

• Theory and data for carbonate scale prediction

• Validation and comparison of scale prediction

• North Sea field example - carbonate scale

• Further complications in scale prediction

• Summary and Conclusions Section 3: Slide 3 of 76

Basic idea of a scale prediction model

Basic idea of a scale prediction model

G   BaSO4  Ba2  Ba2  SO2  SO2  0

- “mass action” equilibrium const. approach

Basic idea of a scale prediction model

Ksp is the solubility product of BaSO4

Example:K sp  [ Ba 2 ][ SO42 ]  1.12 x1010

In pure water with BaSO4 solid present

• Simple scale prediction models for insoluble salts

• Theory and data for carbonate scale prediction

• Validation and comparison of scale prediction

• North Sea field example - carbonate scale

• Further complications in scale prediction

• Summary and Conclusions

• Build up of carbonate scale (CaCO3) due to P

Ca2+ + 2 HCO3-  CaCO3 + CO2 + H2O

Physical situation in carbonate scale P&T

The set of equilibrium equations are:

2. H2O + CO2(aq) = HCO3- + H+ CO32-

6. H.A = H+ + A - (organic acids) Section 3: Slide 13 of 76

Equilibrium equation 1: P&T

Equilibrium equation 1: P&T

Equilibrium equation 1: P&T

Equilibrium equations 2 & 3:

Equilibrium equations 2 & 3:

Can define CO2(aq) CO 3

(a) the solubility of CaCO3 (mol/kg) - data ... Ca2+

20 40 60 80 100 120 140 T (oC)

(after - Harberg et al, SPE (PE), 75-84, Feb. 1992)

(after - Harberg et al, SPE (PE), 75-84, Feb. 1992)

Can define CO2(aq) CO 3

(a) the solubility of CaCO3 (mol/kg) - data ... Ca2+

pK 4   log [Ca 2 ][CO32 ]   log K 4 (T , P)

pK 4   log [Ca 2 ][CO32 ]   log K 4 (T , P) CO32-

(from Atkinson, NACE, Corrosion94, Paper 610, 1994) Section 3: Slide 26 of 76

where - Kw = 1.0 x 10 -14 mol/l at 25 oC and 1

Equilibrium equation 6 (optional):

These are weak acids e.g. acetic CO32-

The set of equilibrium equations are:

6. H.A = H+ + A - (organic acids)

• Simple scale prediction models for insoluble salts

• Theory and data for carbonate scale prediction

• Validation and comparison of scale prediction

• North Sea field example - carbonate scale

• Further complications in scale prediction

• Summary and Conclusions Section 3: Slide 30 of 76

• Previous equilibrium equations give a set of (non-

• Calculate the equilibrium constants K1, K2 ... at system T

• Solve these equations numerically for unknowns