21 - Carbonate - Fluid Chemistery

Carbonate Acidizing
Chemistry and Physics
Copyright 2007, NExT, All rights reserved

Sandstone Vs. Carbonate
• Sandstone:
• Acid dissolves permeability damaging
minerals that plug the pore space
Damaged
zone Wellbore
• Uniform dissolution
• Carbonate:
• Acid creates new flow paths by
dissolving formation rock
• Wormhole formation
2
A little bit of geology
Depositional
intergranular
matrix
1mm
Diagenetic Processes
1 mm 1 mm
Cementation Dissolution
molds
vugs
3
Stimulation of Carbonates
• The injection of acids into carbonate reservoirs leads to the

formation of highly conductive flow channels.
Matrix Acidizing Fracture Acidizing
Wormholes
Conductive
etch paths
4
Outline
• Carbonate characteristics
• Carbonate dissolution kinetics
• Wormhole formation
• Carbonate acidizing model
• Implications for Fracture Acidizing
• Summary
5
Carbonate Rocks
• Dolomitization creates porosity

• limestone with vugs
• Dissoled limestone (karst)
• Natural fractures
• Usually high effective permeability
• Undamaged formation : skin -1~ - 3
6
Carbonate Rocks
• Limestone
• Rich (>50%) in calcite, CaCO3
• Dolomite
• Rich (>50%) in dolomite, CaMg(CO3)2
• Chalk
• Fine-grained limestone
• Very low primary porosity
7
Limestone
• Oolite
• Structure similar to sandstone
• May have primary porosity
• Good reservoir rock
• Ancient reefs and atolls
• Buried mounds of shells
• May have primary porosity
8
Dolomite
• Forms by the alteration of limestone
• Good reservoir rock
• Generally more k and φ than limestone
• Difficult to physically distinguish from limestone
9
Acids Used in Carbonate Acidizing
(77oF)
Ka = 10
• Hydrochloric Acid, HCl
Ka = 1.77x10-4
• Formic Acid, HCOOH (HFc)
Ka = 1.75x10-
5
• Acetic Acid, CH3COOH (HAc)

[H+ ][A-]
Ka =
HA H+ + A- [HA]
10
HCl-Carbonate Reactions
• Limestone: rich (>50%) in calcite, CaCO3
CaCO3 + 2H+ → Ca2+ + CO2(aq) + H2O
* stoichiometric ratio (ν) = 2
• Dolomite: rich (>50%) in dolomite, CaMg(CO3)2

MgCa(CO3)2 + 4H+ → Mg2+ + Ca2+ + 2CO2(aq) + 2H2O
* ν=4
11
Carbonate Dissolution Mechanisms
• Carbonate dissolution may be influenced by a variety of

processes:
• mass transfer of reactants to surface
• reaction at the surface
• mass transfer of products away from surface
12
Rate Limiting Step
• The slowest step (Rate Limiting Step) controls the overall

rate of dissolution.
• If the surface reaction is the slowest step, then the
dissolution is Reaction Rate Limited.
• If mass transfer (of reactants H+ or products Ca+2, Mg+2) is
the slowest step, then the dissolution is Mass Transfer
Limited.
• The higher the temperature, the more mass transfer limited
the system.
13
Reaction Rate Limited
• Dissolution of calcite is reaction limited at low temperatures

• HCl/limestone at T < 32oF (Lund et al., 1975)
• HCl/dolomite at T < 125oF (Lund et al., 1973)
kr << Kmt , Kmtp Cs ~

~ Cb
RA = ν Rx = ν kr [(Cs)n - (Cps)m /Keq ]
 Ea 
kr = ko exp − 
 RT 
14
Mass Transfer Limited
• Most carbonate acidizing treatments fall into this category

• HCl/limestone at T > 32oF (Lund et al., 1975)
• HCl/dolomite at T > 200oF
Kmt , Kmtp << kr Cs ~~ 0
(If limited by
reactants transport)
RA = Jmt = Kmt (Cb - Cs)
Kmt = f (De, ν, Q, ..)
15
Mixed Kinetics
• More complex
• HCl/dolomite at 125 < T < 200oF
• HAc/limestone (Fredd and Fogler, 1998a)
• HFc/limestone (Takulpakdee, 1998)
• EDTA/limestone (Fredd and Fogler, 1998b)
RA = Kmt (Cb - Cs)
= ν kr [(Cs)n - (Cps)m /Keq ]
= ν Kmtp (Cps - Cpb)
• Must know Kmt, Kmtp, Keq, and kr to determine rate of
dissolution
16
Measuring Kinetic Parameters
• Kinetic parameters can be measured using a rotating disk

apparatus
• Can determine:
• Under surface reaction control
• Surface reaction rate constant (kr)
• Activation energy (E)
• Reaction order (n)
• Under mass transfer control
• Effective diffusivities (Deff)
• Equilibrium constants (Keq)
17
Rotating Disk
• Hydrodynamics are well defined

• Disk surface is uniformly accessible
RA = ν kr [(Cs)n - (Cps)m /Keq ]

Rotating Disk
Reaction Rate
Limited
ite sfer
RA
Lim Tran
d
ss
Ma
RA = Kmt (Cb - Cs)
Acid 1
ω 1+ n'
18
Mass Transfer Coefficient
• Kmt is a function of flow characteristics and diffusion

• Need well characterized flow over reacting surface
• Rotating Disk for Power-Law Fluids k’, n’
(Hansford and Litt, 1968)
−1 1− n' 1
Kmt = Φ ( n' ) D 2/ 3
eff ( k'/ ρ ) 3 ( 1+ n' )
R 3 ( 1+ n' )
ω 1+ n'
19
Diagram Rotating Disk Apparatus
1000 psi N2 Pressure

RPM Control
RESERVOIR
N2 Sparger Magnetic Drive
REACTION VESSEL
Heat Exchanger
Thermocouples
Sample Port
Drain
20
Rotating Disk Apparatus
21
Rotating Disk Operating Ranges
• Temperature: -20oF to 250oF

• Pressure: up to 1500 psi
• Rotation speed: 200 to 1800 rpm
• Acid samples taken every 1 min during the first 7 min of
reaction
• Ca2+ and Mg2+ analyzed using AAS/ICP
V 1  d [Ca +2 ] d [ Mg +2 ] 
RA = ν Jmtp = ν  + 
Ac 2  dt dt 
22
Calcite Dissolution with 15% HCl at T=3oF
4.5
4.0
Rate of dissolution
[mol/cm2/s x 106]
3.5
3.0
2.5
2.0
1.5
1.0
5.0
0.0
5 6 7 8 9 10 11 12 13
ω1/2 [s-1/2]
(Navarrete, 1997)
23
Reaction Rate of HCl/Limestone at T=10oF
1.2E-05
Reaction Rate (gr-mole/cm2/sec)
1.0E-05
19% 23%
8.0E-06 28%
15%
6.0E-06
4.0E-06
3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0
Surface Concentration (gr-mole/L)
(Navarrete, 1997)
24
Kinetic Parameters for HCl
• 15% HCl/Dolomite (Phosphoria) (Li et al., 1993)

• at 80oF < T < 155oF
• E = 7.8 kcal/mole
• n = 0.34-0.55
• 15-28% HCl/Limestone (Navarrete, 1997)
• at -10oF < T < 10oF
• E = 7-9 kcal/mole
• n = 0.63
25
Calcite Dissolution with 3.4% HCl
10
122°F
Rate of dissolution
[mol/cm2/s x 106]
8
6
75°F
4
2 Fredd, 1998
Lund et al., 1975
0
0 2 4 6 8 10 12
ω1/2 [s-1/2]
26
Calcite Dissolution with 3% HAc
0.4 Deff = 1.1x10-5 cm2/s

(Vitagliano and Lyons, 1956)
Rate of dissolution
[mol/cm2/s x 106]
0.3 pH = 2.5
0.2 pH = 3.7
0.1 pH = 4.6
HAc H+ + Ac -
0
0 2 4 6 8 10 12 14
ω1/2 [s-1/2]
(Fredd and Fogler, Chem. Eng. Sci., 1998)
27
Deff for 15% HCl Acid Systems
Acid Type T k’ n’ De
o
F Pa.sn’ cm2/sec
Straight 40 1.59E-3 1.00 1.27E-6
Straight 84 1.09E-3 1.00 2.13E-5
Gelled 84 0.395 0.55 7.92E-6
Gelled 112 0.893 0.42 7.90E-6
Gelled 145 0.749 0.45 9.61E-5
Emulsion 83 0.315 0.67 2.64E-8
Emulsion 109 0.642 0.563 4.29E-8
Emulsion 147 0.109 0.775 4.60E-8
de Rozieres et al., SPE 28552 (1994)

28
Overall Rate of Dissolution
 Co 
R A = κ C −
Q

Cb Bulk fluid Cpb  1 + νKeq 
Kmt Kmtp
1
Cs kr Cps 1+
νKeq
κ =
1 1 1
CaCO3, MgCa(CO3)2 + +
Kmt νk r νKeq Kmtp
29
Factors Affecting Reaction Rates
• Formation composition: chemical or physical

• Area/volume ratio
• Temperature
• Acid concentration
• Pressure
• Flow velocity
• Acid type
30
Formation Composition
• Physical composition
• Pore size
• Pore size distribution
• Size and arrangement of minerals
31
Area - Volume Ratio
• Graph showing the rate of 15% HCl spending for varying

area-volume ratios (80°F, 1,000 psi).
100
Area
80 Volume
% Dissolved
Ratio
60
88:1
40 32:1
20 4:1
0
Time
32
Temperature
• Calcium carbonate (marble) and 15% hydrochloric acid. Test
conditions: 1,000 psi Pressure, 3-5 min Duration, 1:4 Area Volume
Ratio 0.070
0.040
REACTION (g/cm/min)
0.020
0.010
0.007
0.004
0.002
20 40 70 100 200 400
TEMPERATURE (oF)
33
Effect of Temperature
• The optimum injection rate is a strong function of temperature.

• Organic acids and emulsified acids are more effective than HCl when
stimulating high temperature formations.
Penetration depth = 6 inches
Normalized optimum injection
8
rate [dimensionless]
HCl
6 HFc
4 HAc
2
Emulsified HCl
0
50 150 250 350 450
(Fredd, SPE 59537, 2000) Temperature [oF]
34
Acid Concentration
• Reaction rate of hydrochloric acid
11
15% spending
REACTION RATE x 10-4 (lb/ft2/sec)
10
22% spending
9
28% spending
8 34\% spending
37% spending
7
1
0 5 10 16 20 25 30 35
% HCl 35
Pressure Effect on Reaction Rate
• CO2 in solution, no effects

• Pressure > 600 psi
0.10
REACTION RATE(g/cm/min)
0.08
0.06
0.04
0.02
0
0 4 8 12 16 20 24
PRESSURE (psi x 100)
36
Flow Velocity
• Increasing flow increases mass transport

• Increased penetration:
• High mass transfer on flow path
• Slow diffusion
REACTION RATE g/min)
0.16
0.12
0.08
0.04
0 5 10 15 20 25 30
VELOCITY (rpm x 100)

0 37
Dissolution Structures
• Structures change depending on:
• Temperature
• Injection velocity
• Dissolution rate
• Is there any way to rationalize what is happening?
Increasing Injection Rate

38
Wormhole Structure from Radial Flow
Acid
spent
acid
39
Pore Level Carbonate Stimulation
Acid invades porous H+

matrix where it reacts
with the pore walls.
H+
carbonate
40
Pore Collision
Acid attack H+
reduces pore
wall thickness
H+
carbonate
41
Pore Collision
Ever widening H+
pore channels
can collide.
H+
42
Macroscopic Dissolution Channels
Linear Core Example
rock plug
Acid
43
Alternative Dissolution Patterns
Flow
Direction
Face (Compact) Heterogeneous Uniform

Dissolution Dissolution Dissolution
44
Carbonate Dissolution Structures
• Typical transition in dissolution structures observed as the

injection rate is increased from left to right
*Face *Conical *Dominant *Ramified +Uniform
Dissolution Wormhole Wormhole Wormhole Dissolution
*Fredd and Fogler, SPEJ, 1998, 1999; +Hoefner and Fogler, AIChEJ, 1988
45
Effect of Structure on Depth of Penetration
Damaged zone
Face • Face dissolution provides

dissolution insignificant penetration.
Conical • Dominant wormholes

wormhole
represents the most
effective mode of
Dominant
wormhole stimulation.
Ramified • Uniform dissolution does

wormholes not create flow channels.
Uniform
dissolution
46
Description of Wormhole Formation
0.25 M EDTA 0.25 M DTPA 0.25 M EDTA 0.5 M HAc

pH = 13 pH = 4.3 0.5 M HCl 0.5 M HAc pH = 4 pH = 4.6
Q = 0.009 cm3/min Q = 0.01 cm3/min Q = 5.0 cm3/min Q = 1.0 cm3/min Q = 3.0 cm3/min Q = 9.8 cm3/min
Da = 1.1 Da = 1.0 Da = 0.11 Da = 0.12 Da = 0.014 Da = 0.014
PVBT = 20.2 PVBT = 18.8 PVBT = 1.6 PVBT = 2.3 PVBT = 16.2 PVBT = 16.6
Conical Channels Wormholes Ramified Wormholes
(Fredd and Fogler, SPEJ, 1998)

47
Pore Volumes to Breakthrough
0.25 M DTPA, pH=4.3

Pore volumes to breakthrough
100
0.25 M EDTA, pH=13
0.25 M EDTA, pH=4
0.25 M CDTA, pH=4.4
0.5 M HAc
0.5 M HCl
10
1 length = 4 in.
diameter = 1.5 in.
-3 -2 -1 0 1 2
10 10 10 10 10 10
Injection rate [cm3/min]
(Fredd and Fogler, AIChE J., 1998)

48
Damköhler Number
• Transport and reaction in wormhole accounted for by

dependence on the Damköhler number:
Overall rate of dissolution π d lκ

Da = =
Rate of convection Q
κ = overall dissolution rate constant

d = diameter of wormhole
l = length of wormhole
Q = flow rate per wormhole

49
Optimum Damköhler Number
• A wide range of fluid/mineral systems exhibit and optimum
Damköhler number at a value of 0.29
Pore volumes to breakthrough
100 0.25 M DTPA, pH=4.3

0.25 M EDTA, pH=13
Water/Plaster
(Daccord et al., 1989)
0.25 M EDTA, pH=4
0.25 M CDTA, pH=4.4
10 0.5 M HAc
0.5 M HCl
0 1 2
10 10 10
1/Damköhler number
50
Effect of Da on Stimulation Efficiency*
1000
Pore Volumes to Breakthrough
(Inverse of Acid Efficiency)
100
10
1
0.1 1.0 10 100 1000
1/Damköhler Number

51
Optimum Injection Strategy
• Increase the injection rate as the depth of penetration increases to

maintain the optimum Damköhler number of 0.29
60
Typical fluid loss π d lκ
Da =
50
40 Q
30
Low fluid loss
20
10
0
Depth of penetration
(Fredd, SPE 59537, 2000)

52
Optimum Injection Strategies
• Excessive injection rates are required with HCl at 200oF.

• Organic acids and emulsified acids are more effective than
HCl when treatments are limited to low injection rates.
8 HCl HFc HAc

Emulsified HCl
T = 200oF
6
4 Typical
Changing matrix
fluid type at injection
2 constant rates
injection rate
(Fredd, SPE 59537, 2000) Depth of penetration

53
Fluid selection
Surface HIGH HIGH LOW LOW

Reaction Rate plain HCl Org. Acids
high Temp low Temp
Diffusion Rate HIGH LOW HIGH LOW

plain HCl emulsified
Unusual
compact dissolution wormholing Uniform dissolution

M.A. Buijse, and M.S. van Domelen SPE 39583
54
Effect of Structure on Depth of Penetration
• Dominant wormholes were observed to penetrate over 12

inches into the formation.
14
Dominant Wormholes
12
Depth of penetration [in]
10
6 Ramified Wormholes
4
Conical Wormholes
2
Face Dissolution
0 Uniform Dissolution
0 2 4 6 8 10
Volume injected [bbl]
(Fredd, SPE 59537, 2000)

55
Effect of Structure on Skin Evolution
• Skin evolution varies significantly with dissolution structure

because of changes in the depth of penetration.
6
5
Uniform Dissolution
Face Dissolution
Skin [dimensionless]
4
3 Conical Wormholes
2
Ramified Wormholes
1
0
-1 Dominant Wormholes
-2
-3
0 2 4 6 8 10
Volume injected [bbl]
(Fredd, SPE 59537, 2000)
56
Acid Spending in Openhole Wellbores
15 wt% HCl
15.0
13.3
CT-End CT-End
11.7
10.0
HCl conc. 8.3
(wt %)
6.7
5.0
3.3
1.7 Bullhead
through casing
0
0 50 100 150 200 250 300 350
Wellbore Length (m)
57
58
59
Fractured reservoir (Nelson 1999)
Different reservoir management systems:

• Fractures provide the essential storage capacity and
permeability in a reservoir. The matrix has little porosity or
permeability.
• Rock matrix provides the essential storage capacity and
fractures provide the essential permeability in a reservoir.
The rock matrix has low permeability, but may have low,
moderate, or even high porosity.
• Fractures provide a permeability assist in an already
economically producible reservoir that has good matrix
porosity and permeability.
• Fractures do not provide significant additional storage
capacity or permeability in an already producible reservoir,
but instead create anisotropy.
60
Pore Typing and acidizing
Touching vug porosity
• Carbonate rocks are complex

combinations of
• several pore types (e.g., vugs)
• connectivity
• Pore types and amounts control
• Acid distribution
• Leakoff
Separate vug porosity

61
Effect of Heterogeneity in Carbonate Stimulation
• If the rock is
• Vugular
• Naturally fractured
• Acid will follow these natural pathways, etching and enlarging them
• Wormhole assumption will under-predict acid penetration
• Skin factors of -3 in “matrix” treatments require deeper acid stimulation
than is possible with wormholes
62
Carbonate Matrix acidizing conclusions
• Chemistry & physics
• Acid creates new flow path by dissolution of rock
• Two reaction rate regimes
• Mass-Transfer-Limited
• Reaction-Rate-Limited
• Dissolution channel structure is a function of the Damköhler number

• Surface reaction rate
• Mass-transfer to and from the surface
• Acid convection rate
• There is an optimum rate for skin evolution which corresponds to
the formation of dominant wormholes
63
Carbonate Matrix acidizing conclusions
• Wormhole formations occurs because of rapid surface

reaction rates and a highly soluble matrix:
• Enlarged pores can collide (wormholes)
• Deep acid penetration can occur under appropriate conditions
• Skin reduction is critically dependent on acid placement and acid
system properties
• Diversion
• Injection rate
• Acid diffusivity
• Wormhole assumption will under-predict acid penetration
when heterogeneities exists
64

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21 - Carbonate - Fluid Chemistery

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Carbonate Acidizing

Chemistry and Physics

Copyright 2007, NExT, All rights reserved

• The injection of acids into carbonate reservoirs leads to the

• Dolomitization creates porosity

• Forms by the alteration of limestone

• Good reservoir rock

• Generally more k and φ than limestone

• Difficult to physically distinguish from limestone

• Acetic Acid, CH3COOH (HAc)

• Limestone: rich (>50%) in calcite, CaCO3

CaCO3 + 2H+ → Ca2+ + CO2(aq) + H2O

* stoichiometric ratio (ν) = 2

• Dolomite: rich (>50%) in dolomite, CaMg(CO3)2

• Carbonate dissolution may be influenced by a variety of

• The slowest step (Rate Limiting Step) controls the overall

• Dissolution of calcite is reaction limited at low temperatures

kr << Kmt , Kmtp Cs ~

RA = ν Rx = ν kr [(Cs)n - (Cps)m /Keq ]

• Most carbonate acidizing treatments fall into this category

RA = Jmt = Kmt (Cb - Cs)

Kmt = f (De, ν, Q, ..)

• Kinetic parameters can be measured using a rotating disk

• Hydrodynamics are well defined

RA = ν kr [(Cs)n - (Cps)m /Keq ]

• Kmt is a function of flow characteristics and diffusion

1000 psi N2 Pressure

N2 Sparger Magnetic Drive

• Temperature: -20oF to 250oF

Surface Concentration (gr-mole/L)

• 15% HCl/Dolomite (Phosphoria) (Li et al., 1993)

0.4 Deff = 1.1x10-5 cm2/s

de Rozieres et al., SPE 28552 (1994)

• Formation composition: chemical or physical

• Pore size distribution

• Size and arrangement of minerals

• Graph showing the rate of 15% HCl spending for varying

• The optimum injection rate is a strong function of temperature.

• CO2 in solution, no effects

PRESSURE (psi x 100)

• Increasing flow increases mass transport

VELOCITY (rpm x 100)

Increasing Injection Rate

Acid invades porous H+

Linear Core Example

Face (Compact) Heterogeneous Uniform

• Typical transition in dissolution structures observed as the

Face • Face dissolution provides

Conical • Dominant wormholes

Ramified • Uniform dissolution does

0.25 M EDTA 0.25 M DTPA 0.25 M EDTA 0.5 M HAc

Conical Channels Wormholes Ramified Wormholes

(Fredd and Fogler, SPEJ, 1998)

0.25 M DTPA, pH=4.3

Injection rate [cm3/min]

(Fredd and Fogler, AIChE J., 1998)

• Transport and reaction in wormhole accounted for by

Overall rate of dissolution π d lκ

κ = overall dissolution rate constant

(Fredd and Fogler, AIChE J., 1998)

100 0.25 M DTPA, pH=4.3

(Fredd and Fogler, AIChE J., 1998)

• Increase the injection rate as the depth of penetration increases to