31 - Carbonates Acidizing

Matrix Acidizing Stimulation Techniques
Carbonates acidizing
Chemistry and Physics
Copyright 2009, NExT, All rights reserved

The basic reaction between HCl & limestone
2HCl + CaCO3 CaCl2 + H2O + CO2

10.9ft3 2050lbs 40gal 6620ft3
1000gal
15% 1843lbs
1m3 HCL 15% dissolves 220kg or 81 litres of CaCO3

1m3 HCL 28% dissolves 440kg or 162 litres of CaCO3
With 1m3 HCl 15%

an open hole of 8.5 inches diameter and 1m long
will be increased to 15.2 inches
Thickness 3.3” but damage was 12”,…then?

Carbonate Vs. Sandstone
Carbonate:
• Acid creates new flow paths by
dissolving formation rock
• Wormhole formation
Sandstone:
• Acid dissolves permeability damaging
minerals that plug the pore space
• Uniform dissolution
Damaged
zone Wellbore

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

Mechanism of Dissolution
Surface reaction rates are relatively high, hence mass

transfer limits reaction, leading to highly non-uniform
dissolution patterns
A few large channels called wormholes form
Structure of wormholes depends on many factors including:
• Flow geometry
• Injection rate
• Reaction kinetics
• Mass transfer rates

CARBONATE ACIDIZING
Matrix acidizing of carbonates is all about wormholes: acid-created

channels that are orders of magnitude larger than matrix pores

CARBONATE ACIDIZING
In matrix acidizing, wormholes are our friends

Propagation of wormholes through the damaged zone yields
negative skin
Only a small fraction of the matrix must be dissolved
wormholes
Carbonate Reservoir Acid
Damaged
zone
Wormholing Phenomena
Much larger than pores, hence insignificant pressure drop

through them
If the wormholes propagate through the damaged zone,
 rwh 
s = − ln 
 rw 
Two foot long wormholes propagating from a 6 inch diameter

well yields s = -2.2
Copyright 2009, NExT, All rights reserved 8

Optimal Wormholing Conditions
Wormhole structure depends on rock type, acid type, injection rate,

temperature, …
These effects are captured in a Damköhler number, the ratio of
reaction rate to convection rate
Models guide acid selection more than injection rate (inject at highest
matrix rate)

Outline
Carbonate characteristics
Carbonate dissolution kinetics
Wormhole formation
Carbonate acidizing model
Implications for Fractured reservoir acidizing
Summary

A little bit of geology
Depositional
intergranular
matrix
1mm
Diagenetic Processes
1 mm 1 mm
Cementation Dissolution
molds
vugs
Carbonate Rocks
Dolomitization creates porosity

• Middle East limestone with vugs
Natural fractures
Usually high effective permeability
Undamaged formation : skin -1~ - 3

Carbonate Rocks
Limestone
• Rich (>50%) in calcite, CaCO3
Dolomite
• Rich (>50%) in dolomite, CaMg(CO3)2
Chalk
• Fine-grained limestone
• Very low primary porosity

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

Dolomite
Forms by the alteration of limestone
Good reservoir rock
Generally more k and φ than limestone
Difficult to physically distinguish from limestone

Impure dolomite . Quartz
grains scattered in matrix
Fissured oolitic limestone.

with calcite cement

Anhydrite filling original vugs
in dolomitic matrix
Fractured dolomite with

anhydrite filling fissures

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]

HCl-Carbonate Reactions
Limestone: rich (>50%) in calcite, CaCO3

CaCO3 + 2H+ → Ca2+ + CO2 + H2O
* stoichiometric ratio ν = 2
Dolomite: rich (>50%) in dolomite, CaMg(CO3)2

MgCa(CO3)2 + 4H+ → Mg2+ + Ca2+ + 2CO2 + 2H2O
* stoichiometric ratio ν = 4

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

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.
Reaction Rate Limited
Dissolution of calcite is reaction limited at low temperatures

• HCl/limestone at T < 0°C - 32oF (Lund et al., 1975)
• HCl/dolomite at T < 50°C - 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 

Mass Transfer Limited
Most carbonate acidizing treatments fall into this category

• HCl/limestone at T > 0°C - 32oF (Lund et al., 1975)
• HCl/dolomite at T > 90°C - 200oF
Kmt , Kmtp << kr Cs ~~ 0
(If limited by
reactants transport)
RA = Jmt = Kmt (Cb - Cs)
Kmt = f (De, ν, Q, ..)

Mixed Kinetics
More complex
• HCl/dolomite at 50°C -125°F < T < 90°C - 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

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)
Rotating Disk
Hydrodynamics are well defined

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

Rotating Disk
Reaction Rate
Limited
RA
RA = Kmt (Cb - Cs)
Acid 1
ω 1+ n'

Diagram Rotating Disk Apparatus
1000 psi N2 Pressure

RPM Control
RESERVOIR
N2 Sparger Magnetic Drive
REACTION VESSEL
Heat Exchanger
Thermocouples
Sample Port
Drain

Rotating Disk Apparatus

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)

Factors Affecting Reaction Rates
Formation composition: chemical or physical

Area/volume ratio
Temperature
Acid concentration
Pressure
Flow velocity
Acid type

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
Time

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)
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
(Fredd, SPE 59537, 2000) 50 150 250 350 450
Copyright 2009, NExT, All rights reserved Temperature [oF]
Acid Concentration
Reaction rate of hydrochloric acid

11
10 15% spending
REACTION RATE x 10-4 (lb/ft2/sec)
22% spending
9
28% spending
8 34\% spending
7 37% spending
1
0 5 10 16 20 25 30 35
% HCl
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)

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
0 VELOCITY (rpm x 100)

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

Wormhole Structure from Radial Flow
Acid
spent
acid

Pore Level Carbonate Stimulation
Acid invades porous H+

matrix where it reacts
with the pore walls.
H+
carbonate

Pore Collision
Acid attack H+
reduces pore
wall thickness
H+
carbonate

Pore Collision
Ever widening H+
pore channels
can collide.
H+

Macroscopic Dissolution Channels
Linear Core Example
rock plug
Acid

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
Increasing injection rate

*Fredd and Fogler, SPEJ, 1998, 1999; +Hoefner and Fogler, AIChEJ, 1988
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

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)

Dissolution Pattern Transition in Limestone
HCL – limestone optimal rate
Diffusion-
limited
Fluid loss-
limited

Dolomite Dissolution Pattern With
Temperature

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

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
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)

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

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)

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)
CARBONATE ACIDIZING
Carbonate acidizing design model should predict

• Penetration depth of wormholes
• Wormhole distribution (density)
As a function of
• Acid type and concentration
• Injection conditions (rate schedule)
• Volume injected
• Placement method

Wormhole Models
Optimal wormholing conditions (the optimal rate)

Wormhole penetration
Wormhole density
Global growth rate of the wormhole region

Wormholing Process Modeling
Theoretical models:
• Mechanistic model of single wormhole or collection of
wormholes (Hung et al., 1989; Schechter, 1992)
• Network models (Hoefner & Fogler, 1988; Daccord et al.,
1989)
• Fractal or stochastic models (Daccord et al., 1989; Pichler et
al., 1992)
• Application of these models for design is cumbersome

Mechanistic Model
• If reaction rate is high, all acid transported to end of wormhole

spends in dissolving rock at wormhole tip and extending wormhole
• Mass balance gives wormhole velocity (dL/dt):
dL uend Cend ρ acid β100  uend  Cend 

= =    N Ac
dt (1 − φ )ρ rock  φ  C0 
More acid diffusing to wormhole wall leads to lower acid

concentration at end of wormhole
Greater fluid loss along wormhole leads to lower flux at end of
wormhole
Network Model
• Approximate porous medium as collection of interconnected

capillaries
• Calculates acid concentration in each capillary and increasing
radii of capillaries as dissolution occurs
• Predicts the wormholing patterns observed experimentally
• Difficult to generalize the model for treatment design

Wormholing Process Modeling
Empirical models:
• Simple to apply for design
• Need some supporting laboratory data
Fractal model (Daccord)

Volumetric model (Hill)
Buijse model

Fractal Model (Daccord et al., 1989)
Based on wormhole structure observed when fluid loss-limited

behavior occurs (valid only for rates above the optimum)
• From linear flow experiments with plaster and water
a: experimentally determined constant
aVN Ac − 2 3 −1 3
L= D q V: cumulative volume injected
Aφ
D: molecular diffusion coefficient
dL aN Ac − 2 3 2 3
Since V = qt : = D q
dt Aφ A: cross-sectional area of flow
L: length of wormhole
For fixed volume injected, longer wormhole results at lower

injection rate
Wormhole velocity increases with injection rate to power of 2/3
• From radial flow wormhole patterns with water & plaster:

−1 3 1 d f
bNAcV −2 3 q  
rwh =  D   
 πhφ  h 
−2 3 1 d f 2 3d f
drwh 1  bNAcD   q (1 d f )−1
SinceV = qt: =     t
dt d f  πφ   h
r wh: radius of wormhole penetration
b: constant (1.5x10-5 in SI unit for experiments)
df: fractal dimension (=1.6)
Wormhole velocity increases with injection rate to power 0.4

Wormhole velocity decreases with time
Limitations
Based on diffusion being limiting mechanism for acid
transport
Does not consider role of fluid loss
Based on wormhole network geometry observed in water-
plaster experiments
Likely overestimate distance of wormhole penetration in
carbonate acidizing

Volumetric Model (Hill)
Assumes acid dissolves a constant fraction of rock volume

penetrated
Based on the observation that wormhole velocity is
approximately constant in linear corefloods
Equivalent to assuming a fixed number of pore volumes are
needed to propagate wormholes a given distance

Volumetric Model (Hill)
• For radial flow:

V
rwh = r +
N AcV rwh = rw2 +
(PV )bt πφh
2

ηπφ h
w
where η = N Ac (PV )bt

η : Wormhole efficiency (fraction of rock dissolved in region
penetrated by acid)
(PV)bt: Pore volumes injected at time of wormhole breakthrough
at end of core

Volumetric Model summary
Empirical model
Wormhole efficiency obtained from radial core floods should
accurately predict wormhole propagation in well treatment
with radial flow
If linear core floods uses, actual wormhole propagation in
radial flow will be probably overestimated
Should use a conservative (high end) value of PVbt
More accurate the more “linear” the flow – short wormholes,
large wellbore radius

Buijse Model
Empirical model
Equation derived to fit the PVbt versus injection rate
relationship
Requires PVbt and acid flux at the optimal condition as
parameters

Buijse Model

Buijse Model
Vwh = Weff vi 2/3

(1 − exp(− W v ))
b i
2
Where the interstitial velocity, vi is

q
vi =
2πrhφ
and
v1i −/ opt
3
4
Weff = WB = 2
PVbt −opt vi −opt
Acid Volume Design
Volume of acid needed for a desired penetration of

wormholes can be calculated based on model of wormhole
propagation like Daccord’s model, volumetric model, or Buijse
model
Actual volume can be adjusted based on real-time monitoring

of treatment

Example : Acid Volume Selection
Calculate the volume (gal/ft) of 28 wt% HCl needed to

propagate wormholes 3 ft from a 0.328 ft radius wellbore in a
limestone formation with a porosity of 0.15, using Daccord’s
model, the volumetric model, and Buijse’s model. The injection
rate is 0.1 bpm/ft, the diffusion coefficient is 10-9 m2/sec, and
density of acid solution is 1.14 g/cm3. In linear core floods, the
optimal flux is 0.15 cm/min and the pore volumes to
breakthrough at the optimum is 1.5 pore volumes.

Solutions
Daccord’s model
• Using parameters obtained with water-plaster experiments, predicts
only 8.6 gal/ft of acid needed to propagate wormholes 3 ft from the
wellbore.
Volumetric model
• Acid volume needed is 58 gal/ft. It is the pore space volume in the
region penetrated by wormholes multiplied by number of pore
volumes to propagate wormholes through a given volume of rock.
Buijse’s model
• About 28 minutes of injection are needed to propagate the
wormholes one meter. This is 2.8 bbls, or about 118 gal/ft. The
injection rate is near the optimum. With rates lower the acid
volume needed goes up substantially
Vertical Carbonate: 100oF, HCl, 60gpf
20
15
Short wormholes
Wellbore Skin
10 0.03 BPM
0.5 BPM
4.0 BPM
5 0.03 BPM; Retarded
0
Long wormholes
-5
0 20 40 60
Acid Injected [Bbls]

Horiz. Carbonate: 100oF, HCl, 60gpf
25
20
Wellbore Skin
15
2 BPM
10 30 BPM
90 BPM
5
-5
0 1000 2000 3000 4000 5000

Low Perm. Horizontal Wellbore
25
20
Wellbore Skin
15
10 2 BPM
2 BPM; Retarded
5
-5
0 1000 2000 3000 4000 5000

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)

Acid Type & Concentration
Hydrochloric acid (HCl) most common acid

Weak acids suggested for perforation cleanup and
perforating fluid
Weaker acids can propagate wormholes more
efficiently at higher temperatures
No precipitation reactions to limit acid concentration to
be used
Select acid type and concentration to be near optimal
injection flux

Acid Selection Guidelines
Situation Fluid
Perforating fluid 5% acetic acid
9% formic acid
Damaged perforations 10% acetic acid
15% HCl
15% HCl
Deep wellbore damage 28% HCl
Emulsified acid

Optimal Injection Rate
• For HCl:
m −1  ∆E 1 
E f0 C 0 exp − × 
uopt =  R T
E f 0 : reaction rate constant
Daopt
K d : dissociation constant
• For weak acids: ∆E : activation energy
R : universal gas constant
T : Temperature
( m 2 )−1  ∆E 1  m : reaction order

E f 0 K dm 2Cweakacid exp − × 
uopt =  R T
Daopt

Maximum Injection Rate – Open-hole
For an open-hole completion, maximum flux at wellbore:
k (g fr D − p R )
umax =
 re 
rw µ  ln + s 
 rw 
where: gfr : fracture gradient
D : formation depth

Maximum Injection Rate - Perforated
Maximum acid flux at a perforation:
k (g fr . D − p R )
u max =

n . µ .r p  ln
re 
+ s   r p +
(rI − r p ).l p 

 rw 
 rI ln (rI r p ) 
where: rP : perforation radius

rI: acid leak-off radius
lP : perforation length
n : shot density
Selection of Optimum Acid & Injection Rate
Use k, rmax , acid types and concentrations to generate a

chart of uopt versus 1/T
Calculate maximum acid flux, umax at wellbore according to

fracture gradient and completion type
Select the optimal acid and injection rate according to

formation temperature

Optimum Acid Flux Design Chart for Limestone

Optimum Acid Flux Design Chart for Dolomite

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.

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

Matrix Acidizing of Naturally-Fractured Carbonate
Matrix acidizing of un-fractured carbonates

• Wormhole process occurs
Naturally fractured carbonates
• Smaller fracture widths
- Occur in networks
- Acid enlarges channels
Acid fracturing
• Surface etching of fracture surfaces
• Much deeper acid propagation

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

Simulation of Acidizing Large Single
Fractures
before
acidizing
after
acidizing
experimental
result

10
Channel Length
Channel length (m)
Injection volume (gal/ft)

10
Skin Factor Calculation
Skin
Injection volume (gal/ft)

10
Observations of Acidizing Intersecting Fractures
The main channel or the wormhole always propagates

through one fracture
The preferred fracture usually has a larger width or

rougher surfaces
Only one major pathway is etched in the network

10
Acidizing Fracture Networks
Acid spreads in initially-large width fracture and converges

in initially-small width fracture
Acid penetration distance increases with
• Longer fractures
• Large average fracture width
• Small standard deviation in width distribution
• Low leakoff
The overall acid penetration distance in fracture networks
is much longer than with only matrix flow

11
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 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
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

31 - Carbonates Acidizing

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31 - Carbonates Acidizing

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Matrix Acidizing Stimulation Techniques

Copyright 2009, NExT, All rights reserved

2HCl + CaCO3 CaCl2 + H2O + CO2

1m3 HCL 15% dissolves 220kg or 81 litres of CaCO3

With 1m3 HCl 15%

Thickness 3.3” but damage was 12”,…then?

Copyright 2009, NExT, All rights reserved

Copyright 2009, NExT, All rights reserved

The injection of acids into carbonate reservoirs leads to the

Copyright 2009, NExT, All rights reserved

Surface reaction rates are relatively high, hence mass

Copyright 2009, NExT, All rights reserved

Matrix acidizing of carbonates is all about wormholes: acid-created

Copyright 2009, NExT, All rights reserved

In matrix acidizing, wormholes are our friends

Much larger than pores, hence insignificant pressure drop

Two foot long wormholes propagating from a 6 inch diameter

Copyright 2009, NExT, All rights reserved 8

Wormhole structure depends on rock type, acid type, injection rate,

Copyright 2009, NExT, All rights reserved

Copyright 2009, NExT, All rights reserved

Dolomitization creates porosity

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Forms by the alteration of limestone

Good reservoir rock

Generally more k and φ than limestone

Difficult to physically distinguish from limestone

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Fissured oolitic limestone.

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Fractured dolomite with

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Acetic Acid, CH3COOH (HAc)

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

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

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Carbonate dissolution may be influenced by a variety of

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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 ]

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Most carbonate acidizing treatments fall into this category

RA = Jmt = Kmt (Cb - Cs)

Kmt = f (De, ν, Q, ..)

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Kinetic parameters can be measured using a rotating disk

Hydrodynamics are well defined

RA = ν kr [(Cs)n - (Cps)m /Keq ]

RA = Kmt (Cb - Cs)

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1000 psi N2 Pressure

N2 Sparger Magnetic Drive

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de Rozieres et al., SPE 28552 (1994)

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Formation composition: chemical or physical

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