Carbonate Acidizing

Schlumberger - Carbonate Acidizing
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Carbonate Acidizing
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Master Table of Contents
TABLE OF CONTENTS
Table of Contents
1 Objectives
2 Introduction
3 Acid Requirements
4 Acidizing Mechanism
Reference: SWBT, sand contr 4.1 Acidizing Mechanism
Version: 3
Release Date: 30-Aug-2003 4.2 Exercise
EDMS UID: 274758445 5 Carbonate Rocks
Produced: 3-Oct-2003 17:02:48
Owner: WS Training 5.1 Limestone
Author: WS Training
5.1.1 Oolites
5.1.2 Chalks
5.1.3 Ancient Barrier Reefs and Atolls
5.2 Dolomite
5.3 Carbonate Rocks - k and ø
5.4 Exercise
6 Acids Used in Carbonate Acidizing
6.1 Hydrochloric Acid
6.2 Organic Acids
6.3 HCl and Carbonate Rock Reactions
6.3.1 Stoichiometry
6.3.1.1 Stoichiometry Calculation
6.4 Exercise
7 Acidizing Physics
page top
7.1 Reaction Processes
7.1.1 Mass-transfer Limited Kinetics
7.1.2 Surface-reaction Limited Kinetics
7.2 Reactions in Carbonate Rock
7.3 Factors Affecting Reaction Rates
7.3.1 Area/Volume Ratio
7.3.2 Temperature
7.3.3 Acid Concentration
7.3.4 Flow Velocity
7.3.5 Pressure Effect on Reaction Rate
7.3.6 Acid Types
7.3.7 Formation Composition
7.4 Exercise
8 Acid Systems
8.1 Acid Systems
8.2 Emulsions
8.3 Exercise
9 Main Schlumberger Acid Systems
10 Summary
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1
Objectives
TABLE OF CONTENTS
1 Objectives
In this training module, you will learn to do the following:
• Demonstrate a knowledge of factors involved in the matrix acidizing of carbonate rocks.
• Demonstrate an understanding of the geology of carbonate rocks.

Reference: SWBT, sand contr
Version: 3 • Demonstrate an understanding of the physics of the chemical reaction between acid and
Release Date: 30-Aug-2003 carbonate rocks.
EDMS UID: 274758408
Produced: 3-Oct-2003 17:02:48 • Demonstrate a knowledge of the differences between acidizing of carbonate rocks and
Owner: WS Training sandstone reservoirs.
Author: WS Training
• Demonstrate an understanding of stoichiometric calculations involved in the chemical
reactions between acid and carbonate rocks.
• Demonstrate a knowledge of the Schlumberger products and resources available to design

a carbonate rock acidizing job.
page top
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2
Introduction
TABLE OF CONTENTS
2 Introduction
This module is intended to teach the factors involved in the matrix acidizing of carbonate
rocks. To this end, an understanding of the geology of these rocks is necessary. The physics
of the chemical reaction between acid and carbonate rocks is presented, as this is essential to
the complete understanding of carbonate acidizing. Stoichiometric calculations involved in
these chemical reactions are also presented to clarify the process.
Version: 3
Refer to the following documents for useful information both during and after your study of
Release Date: 30-Aug-2003
EDMS UID: 274758401 this module:
Produced: 3-Oct-2003 17:02:48
Owner: WS Training
Author: WS Training • Matrix Engineering Manual (on CD-ROM ITM-1144)
• Matrix Materials Manual (on CD-ROM ITM-1144)
• Reservoir Stimulation by Economides, et al.
• Schlumberger Fluid Selection Guide for Matrix Treatment (TSL-2069)
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3
Acid Requirements
TABLE OF CONTENTS
3 Acid Requirements
The same requirements for selecting an appropriate acid apply for both sandstone and
carbonate rock acidizing.
The acid should:

Version: 3 • react with formation mineral to give soluble products
EDMS UID: 274758402 • react with damage to give soluble or dispersible products
Produced: 3-Oct-2003 17:02:48
Owner: WS Training • be possible to inhibit
Author: WS Training
• be safe to handle
• be low cost and available
page top
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4
Acidizing Mechanism
TABLE OF CONTENTS
4 Acidizing Mechanism

Version: 3
EDMS UID: 274758403 When the productivity from a naturally high-permeability reservoir rock has been reduced as a
Produced: 3-Oct-2003 17:02:48 result of damage, a matrix treatment utilizing the appropriate treating fluids (such as acids,
Owner: WS Training
organic solvents, or NARS) is generally the preferred treatment.
Author: WS Training
Typically, damage is associated with a partial plugging of the formation around the wellbore.
This reduces the original permeability (k) in the damaged area, thus reducing production. This
damage can be removed by dissolution and/or dispersion, or new bypassing channels, such as
wormholes, must be created. Wormholes are channels in the rock formation.
4.1
Acidizing Mechanism
Sandstone reservoir rocks are treated by removing the damaging material either by:
• dissolution (the decomposition into fragments or parts)
• dispersion (the scattering of the fragments or parts)
Carbonate reservoir treatments generally involve the creation of new bypassing channels
(wormholes) and/or the creation of a flow path for damage removal.
page top
4.2
Exercise
Acidizing Mechanism Exercise
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5
Carbonate Rocks
TABLE OF CONTENTS
5 Carbonate Rocks
The ocean is the scene of immensely-varied kinds of carbonate sedimentation, both chemical
and biological. The chemical basis for carbonate sedimentation is the relative abundance of
calcium and bicarbonate ions in sea water.
The rocks generally referred to as carbonate rocks are

Version: 3
Release Date: 30-Aug-2003 • Limestone, CaCO3
EDMS UID: 274758404
Produced: 3-Oct-2003 17:02:48
Owner: WS Training • Dolomite, CaMg(CO3) 2
Author: WS Training
These are referred to as carbonate rocks because they contain the carbonate radical (CO3) in
their molecular composition.
• Limestone
Limestone is the most abundant chemically-precipitated sediment.
Limestone generally refers to rocks that are composed of more than 50% of the mineral
calcite and/or aragonite. Both minerals are forms of calcium carbonate.
Calcite is relatively stable.
Aragonite generally changes over time into calcite.
A small admixture of clay particles or organic matter imparts a gray color to limestone which
page top may be white, gray, dark gray, yellowish, greenish or blue in color; some may even be black.
• Dolomite
Dolomite is formed by the alteration of preexisting limestone. Rocks classified as dolomite

generally contain more than 50% dolomite.
• Tests
Dolomites are quite similar to limestone in appearance. It is difficult to distinguish between

the two with the naked eye. X-ray diffraction and chemical staining are used in the laboratory
to differentiate between limestone and dolomite.Limestone bubbles in cold, dilute acid.
Dolomite bubbles only in hot, concentrated acid.
5.1
Limestone
Hydrocarbon-bearing Limestone Rocks
Oolite
• Structure similar to sandstone
• May have primary porosity
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• Good reservoir rock
Chalk
• Fine-grained limestone
• Very low primary porosity
Ancient reefs and atolls
• Buried mounds of shells
• May have primary porosity
The porosity of a formation can be classified as primary or secondary. Primary porosity is the
porosity as a result of the deposition, and then compaction and cementation of the formation's
material. Secondary porosity is formed within a reservoir after disposition.
5.1.1
Oolites
Oolites are accumulations of sand- and silt-sized, spherical calcium carbonate precipitation
and have a structure similar to sandstone. They normally have excellent original (primary)
porosity and can make good reservoir rock.
Examples of hydrocarbon reservoirs of oolitic origin include
• Reynolds oolite member of the Jurassic age, smackover formation from which the Magnolia
oil field of Arkansas, USA produces
• Mississippian age oolite shoals from which the gas fields of Beaver County, Oklahoma, USA
produce
5.1.2
Chalks
Chalks are extremely fine-grained limestones composed of microfossil shells. These single-
shelled animals are called coccolithophores and grow in shallow, tropical seas. When they die,
their plates or coccoliths, fall to the bottom. If they are not diluted by other sediments, a
chalk can be formed.
During the Cretaceous period, several prominent chalks were deposited.
The Cretaceous chalks include
• Austin Chalk of Texas, USA
• Niobara Chalk of South Dakota, Nebraska and Kansas, USA
• Ekofish Chalk of Danish North Sea
• Sirte Basin of Libya
Because of their fine-grained texture, chalks typically have very low primary porosity.
5.1.3
Ancient Barrier Reefs and Atolls

Reefs are mounds of sea animal shells. The framework is formed by overlapping organic
branches of CaCO3. Ancient barrier reefs and atolls are prolific petroleum reservoirs,
especially in North America.
Ancient reefs which could form hydrocarbon-bearing reservoirs were formed by sponges,
calcareous algae, clam-like animals called rudistids, and other organisms.
Ancient reefs and atolls may have primary porosity.

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5.2
Dolomite
TABLE OF CONTENTS
5 Carbonate Rocks
5.2 Dolomite Dolomite is a sedimentary rock that forms only by the alteration of preexisting limestone.
Magnesium-rich waters, which percolate through limestone, can replace the calcium ions with
magnesium to form dolomite. This occurs in the subsurface after the limestone is deposited.
In impermeable limestone (such as micrite and crystalline limestone) dolomite formation is

Reference: SWBT, sand contr restricted to fractures. Magnesium-rich waters can percolate through these fractures, and
Version: 3 dolomite can form.
EDMS UID: 274758404
Produced: 3-Oct-2003 17:02:48 Dolomite is often a good reservoir rock. The Mg2+ ion is smaller than the Ca2+ ion it replaces.
Owner: WS Training The theoretical volume reduction of the limestone by the formation of dolomite is 12 to 13%.
Author: WS Training The effect of the volume reduction is the formation of pores.
The dolomitized oil field reefs of western Canada have an average 1% more porosity (ø) and a
permeability (k) 10 times greater than the limestone reefs.
The Yates field of West Texas is a giant oil field that produces from the Permian age Grayburg
dolomite reservoir.
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5.3
Carbonate Rocks - k and ø
TABLE OF CONTENTS
5 Carbonate Rocks
5.3 Carbonate Rocks - k and ø The diagenesis of carbonate rocks (including dolomitization) results in formation porosity. In
warm, humid climates, carbonate rocks are susceptible to dissolution near the surface of the
ground. Caves and caverns form as the limestone is dissolved by percolating water.
Fractures often control the movement of water through limestone. As the caves become
larger, the roofs becomes weaker, which may eventually cause them to collapse.
Version: 3 A highly-dissolved limestone (karst) has excellent porosity and permeability. Karst limestone
Release Date: 30-Aug-2003 sometimes contains caves. More often, it has vugs (solution pores up to several inches in
EDMS UID: 274758404
diameter).
Produced: 3-Oct-2003 17:02:48
Owner: WS Training
Author: WS Training The prolific Golden Lane oil field near Tampico, Mexico produces from karst limestone
reservoir rock.
The great Middle East oil fields are mostly in limestone reservoir rocks. Their excellent
porosity and permeability result from the solution pits in the limestone.
The Dollarhide pool west of Odessa, Texas is the largest oil-filled limestone cave discovered to
date. Its height ranges from 3 to 16 ft.
page top
Correlation between porosity and permeability have been found to exist in many carbonate
reservoirs. These correlations are only good on a field by field, rather than a global, basis.
Usually, carbonate rock matrix permeability is small, although production rates are often
considerably higher than one would expect from the permeability of the cores. This is due to
the fractured nature of many of these rocks. The fractures, even those of small width, have
high effective permeability . Consequently, the flow capacity of these rocks is often greater
than that of an average sandstone.
If flow through the critical matrix has been altered by either natural or induced materials that
reduce the permeability, the net result is a damaged zone defined by a number called "skin."
Skin damage is often the result of decreased permeability in the critical matrix and perforation
tunnels. In the undamaged state, many carbonate rocks exhibit negative skin values.
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6
Acids Used in Carbonate Acidizing
TABLE OF CONTENTS
6 Acids Used in Carbonate

Acidizing
The most common treatment for carbonate formations is hydrochloric acid. Formic and acetic
acids are also used, primarily in retarded acid systems or in high-temperature applications.
The chemical formulas for carbonate acidizing fluids are
Reference: SWBT, sand contr 1. HCl (hydrochloric acid)

Version: 3
Release Date: 30-Aug-2003 2. HCOOH (formic acid)
EDMS UID: 274758405
Produced: 3-Oct-2003 17:02:48 3. CH3COOH (acetic acid)
Owner: WS Training
Author: WS Training
For mixing and safety hazards, refer to the Matrix Materials Manual and the MSDS
for each chemical or compound.
6.1
Hydrochloric Acid
HCl is overwhelmingly employed in the acid treatment of carbonaceous formations because of

its moderate cost and soluble reaction products (CaCl2 and CO2 ).
HCl is commonly used at a 15% concentration, originally chosen because of inadequacies in

early inhibitors and the difficulty of preventing corrosion of well tubular goods by more
concentrated solutions. However, with the recent development of improved inhibitors, higher
concentrations have become practical. In some cases, they provide increased effectiveness.
Inhibition becomes more difficult with the addition of other additives such as mutual solvents
and cationic surfactants.
page top
The principal disadvantage of HCl is that it is highly corrosive on wellbore tubular goods. This
corrosion becomes significant and expensive to control at temperatures above 250oF. The
corrosive nature of HCl is critical on tubular goods containing aluminum (Al) or chromium (Cr)
alloys, which are easily damaged by the acid.
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6.2
Organic Acids
TABLE OF CONTENTS

Acidizing
The principal advantages of organic acids are low corrosive action and easier inhibition at high
6.2 Organic Acids temperatures.
The organic acids used in well stimulation are formic acid and acetic acid.
• Acetic Acid
Version: 3 Acetic acid (CH3COOH) was the first of the organic acids to be used in large volumes in well
stimulation.
EDMS UID: 274758405
Produced: 3-Oct-2003 17:02:48
Owner: WS Training Acetic acid is commonly used at 10% concentration. The products of reaction at this
Author: WS Training concentration (calcium and magnesium acetates) are generally soluble in spent acid.
Acetic acid is more expensive than either hydrochloric (HCl) or formic acid (HCOOH).
• Formic Acid
Formic acid (HCOOH) has the lowest cost per volume of rock dissolved.
Formic acid is stronger than acetic acid and weaker than HCl.
Though more corrosive than acetic acid, formic acid corrodes uniformly with less pitting than
HCl. Both formic and acetic acids can be inhibited up to 400oF.
Use the table as a review of the acids used in carbonate acidizing.

page top
Acids Used in Carbonate Acidizing
Name Formula Characteristics Advantages Disadvantages
Hydrochloric HCl • Most commonly • Moderate cost. • Highly corrosive

Acid used acid. on wellbore
• Soluble reaction tubular goods.
• Used at 15% products.
concentration. • Aluminum and
chromium alloys
are easily
damaged by the
acid.
Acetic Acid CH3COOH • Used at 10% • Low corrosive • More expensive

concentration. action. than HCl or
Formic Acid.
• Products of reaction • Easier to inhibit at
are soluble in spent high temperatures.
acid.

Formic Acid HCOOH • Used at 9% • Lowest cost per

concentration. volume of rock
dissolved.
• Stronger than
acetic acid. • Low corrosive
action.
• Weaker than HCl.
• Can be inhibited up
to 400oF.

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6.3
HCl and Carbonate Rock Reactions
TABLE OF CONTENTS

Acidizing
In the matrix stimulation of carbonate rock, the reaction of acid (usually HCl) with the formation
6.3 HCl and Carbonate Rock minerals results in mineral dissolution and the creation of new permeability.
Reactions
In carbonate formations, it is conceivable that near-wellbore permeability can be improved beyond
virgin reservoir value. This can result in a negative skin effect and a substantial increase in well
productivity or injectivity index. (This is in contrast to sandstone reservoirs where matrix stimulation is
used to restore near-wellbore permeability.)

Version: 3
EDMS UID: 274758405
Produced: 3-Oct-2003 17:02:48
Owner: WS Training
Author: WS Training
6.3.1
Stoichiometry
Stoichiometry refers to the proportions of the various reactants participating in a chemical reaction.
Knowing these proportions allows
• calculation of the amount of acid required to dissolve a given quantity of carbonate rock
• determination of the average increase in porosity (ø) resulting from rock dissolution
While the stoichiometry of the reactions between acid and pure limestone or dolomite might be easy
to identify, reactions with naturally-occurring carbonates are often complicated by the presence of
other minerals reactive with acid. The creation of carbonate rocks introduces impurities (mostly
page top siliceous in nature) in the rock matrix.
6.3.1.1
Stoichiometry Calculation
• The Problem
Calculate the weight of limestone dissolved and the volume of CO2 liberated by 1000 gal of 15% HCl.
After you have attempted the calculations, use the Next button to reveal the answers.
Atomic weights
Element Atomic weight
H 1
Cl 35.5
Ca 40
C 12
O 16
• The Solution
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Reaction:
Compound Molecular weight Amount dissolved or liberated Produced (lb)
1000 x 1.075 x 8.33 x 15%
1000 = gal HCl

2 HCl 73 1,343.2 lb
1.075 = specific gravity 15% HCl
8.33 lbm/gal = wt of H2O
CaCO3 100 (1,343.2 x 100) / 73 1,840 lb
CaCl2 111
H 2O 18
809.60 lb or 0.81 lb of CO2 / gal

CO2 44 (1,343.2 x 44) / 73
15% HCl
1 lb of CO2 occupies 8.6 scf (from Schlumberger Field Data Handbook).
Therefore, (0.81 x 8.6 scf) = 6.96 scf CO2 is produced / gal 15% HCl
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7
Acidizing Physics
TABLE OF CONTENTS
7 Acidizing Physics
The acidizing physics of carbonate rocks is affected by
• the kinetics of the reaction (a higher temperature results in a faster reaction)
• the type of mineral (calcite versus dolomite results in a different type of reaction)
Version: 3 • the type of reaction (different types result in different dissolution patterns and, thus, a
Release Date: 30-Aug-2003 different stimulated well performance)
EDMS UID: 274758406
Produced: 3-Oct-2003 17:02:48
Owner: WS Training Other factors involved in acidizing physics include
Author: WS Training
• the flow of a liquid through a porous medium
• instabilities which might result from the natural permeability gradient of the rock
• hydrodynamic and/or capillary forces
• the permeability gradient induced by the dissolution
7.1
Reaction Processes
page top
A chemical reaction between two molecules takes place when they come in contact and have
enough energy to overcome the activation barrier.
Under static conditions, there are two types of acid-solid reactions associated with carbonate
reservoirs:
1. mass-transfer limited kinetics
2. surface-reaction limited kinetics
These reactions occur under extreme conditions. In some cases (for example, dolomite at
intermediate temperatures), transfer and reaction rates are similar, and the reaction is
controlled by both steps.
7.1.1
Mass-transfer Limited Kinetics

In mass-transfer limited kinetics, the activation energy barrier is very low and every collision
successfully results in a reaction.
The global rate of reaction is then limited by the number of contacts and the reaction is said
to be "mass transfer" or "diffusion limited". The limiting process is the transport of acid to the
pore walls by diffusion. In this case, acid reacts immediately when contacting the rock, and
acid concentration at the pore walls is zero.
It is generally agreed that this type of reaction occurs when acid reacts with limestones at all
temperatures and with dolomite at high temperatures. Some recent publications argue that in
matrix flow conditions the reaction is surface- reaction limited.
7.1.2
Surface-reaction Limited Kinetics
Surface-reaction limited kinetics result from a very high activation energy barrier. Only a
small number of molecules in contact react. The kinetics of the reaction is directly limited by
the energy barrier and the reaction is referred to as surface-reaction limited.
Dolomites reacting with acid at lower temperatures follow this kinetic type. The threshold
between the surface- and transport-limited kinetics is generally agreed to be 175oF (80oC).

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7.2
Reactions in Carbonate Rock
TABLE OF CONTENTS
7 Acidizing Physics
7.2 Reactions in Carbonate Dynamic reactions in carbonate rocks are characterized by

Rock
• predominant molecular diffusion (calcite and hot dolomite)
• dissolution affected by acid velocity
• dissolution-produced wormholes
Reference: SWBT, sand contr • changes in skin
Version: 3
EDMS UID: 274758406
Produced: 3-Oct-2003 17:02:48
Owner: WS Training
Author: WS Training
The dissolution of carbonate rocks by acid produces long, empty channels called wormholes.
Experiments have shown that the quantity of rock dissolved (that is, the acid penetration)
depends on acid velocity. A critical velocity needs to be applied to attain the wormholing
regime. Once in this regime, if the injection rate is increased, the acidizing efficiency slowly
decreases.
Because the success of acidizing requires the process to be in the wormholing regime, it is still
recommended to pump as fast as possible 200-500 psi below frac pressure.
Because of the randomness of porous media, it had been shown that during dissolution two
page top
neighboring pores can combine if sufficiently enlarged.
It is difficult to model or predict the development of wormholing in a real rock, as the

mineralogy will never be 100% carbonate.
One advantage of wormholing is that the near-wellbore damage can be bypassed. The
"effective" treated zone becomes much larger than in sandstone acidizing for the same
amount of rock dissolved. It is also larger than in matrix acidizing of carbonates using slow-
reacting acids when the kinetics is limited by surface reactions. In addition, problems of
nonconsolidation in the near-wellbore area are less severe.
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7.3
Factors Affecting Reaction Rates
TABLE OF CONTENTS
7 Acidizing Physics
7.3 Factors Affecting The following factors affect reaction rates:

Reaction Rates
• area to volume ratio
• temperature
• acid concentration
Reference: SWBT, sand contr • flow velocity

Version: 3
Release Date: 30-Aug-2003 • pressure
EDMS UID: 274758406
Produced: 3-Oct-2003 17:02:48 • acid type
Owner: WS Training
Author: WS Training
• formation composition
7.3.1
Area/Volume Ratio
page top The area/volume ratio is defined as the area of rock in contact with a given volume of acid.
Area/volume ratio is an important factor because of the great variations in pore sizes, vugs,
and fracture widths that exist in formation rock.
The graph shows the rate of 15% HCl spending for varying area/volume ratios at 80oF (27oC)
and 1,000 psi. The higher the area/volume ratio, the faster the acid spends.
In matrix acidizing, extremely high area/volume ratios may be encountered. For example, a
10 md (millidarcy), 20% porosity formation may have an area/volume ratio of 28,000 ft2/gal.
A wormhole or natural fracture has a much smaller area/volume ratio of about 32 ft2/gal. The
smaller ratio of the wider wormhole or fracture allows greater penetration of the acid into the
reservoir before its reaction is complete.
It is of interest to note that in a six-inch diameter open hole, the area/volume ratio is only 1
ft2/gal. This indicates that the spending time in the wellbore will be much longer than in the
formation.
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7.3.2
Temperature
TABLE OF CONTENTS
7 Acidizing Physics
7.3 Factors Affecting

Reaction Rates
7.3.2 Temperature
Reference: SWBT, sand contr The graph illustrates the effect of temperature on the reaction rate of calcium carbonate
Version: 3 (marble) and 15% hydrochloric acid. Test conditions were 1,000 psi pressure, 3 to 5 min
duration, and 1:4 area/volume ratio.
EDMS UID: 274758406
Produced: 3-Oct-2003 17:02:48
Owner: WS Training Acid reaction rate increases as temperature increases, because diffusion and surface kinetics
Author: WS Training depend on temperature.
Under flow and no flow conditions, the reaction rate is generally increased as temperature
increases. However under static conditions, the increase in reaction rate with temperature is
much slower.
At 120oF (49oC), the acid reaction rate of HCl on limestone is approximately double that at
70oF (21oC). Other acid formulations have similar increases in reaction rate as temperature
increases.
The increase in reaction rate with organic acid is different from other effects that temperature
can have on limiting the extent or equilibrium conditions of the reaction (for example, the
solubility of CO2.
page top
Temperature also strongly influences the corrosion inhibition of acids. At high temperatures,
greater than 300oF (149oC), protection of tubular goods can hardly be achieved in the
presence of 28% HCl. HCl concentration is reduced to 15% or less, and organic acids, less
corrosive than HCl, are used in partial or total replacement of HCl.
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7.3.3
Acid Concentration
TABLE OF CONTENTS
7 Acidizing Physics

Reaction Rates
7.3.3 Acid Concentration

Version: 3
Release Date: 30-Aug-2003 The graph illustrates the reaction rates of hydrochloric acid at various concentrations.
EDMS UID: 274758406
Produced: 3-Oct-2003 17:02:48
Owner: WS Training The reaction rate of HCl with calcium carbonate is nearly proportional to acid concentration up
Author: WS Training to 20% HCl. From 20% to 24%, the reaction rate increases to a maximum. Above this level
the rate appears to be reduced.
As the acid spends, the reaction rate reduces due to the reduced acid concentration. The
reaction rate also is affected by reaction products such as calcium carbonate and carbon
dioxide.
page top
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7.3.4
Flow Velocity
TABLE OF CONTENTS
7 Acidizing Physics

Reaction Rates
7.3.4 Flow Velocity
Reference: SWBT, sand contr Mass transport is the rate-limiting step for most carbonate rock under flow condition. Reaction
Version: 3
rate increases with velocity because mass transport is highly increased. However, it does not
mean that penetration is shorter because of this faster reaction. The increase in mass transfer
EDMS UID: 274758406
Produced: 3-Oct-2003 17:02:48 by diffusion is slower than the increase in mass transfer occurring along the path by
Owner: WS Training convection.
Author: WS Training
At zero or extremely low velocity (that is, an acid soak), the time for acid to diffuse toward
the surface is much shorter than the time for the acid to move due to convection (flow).
Therefore, the entire rock will be homogeneously and completely dissolved. There will not be
any porous matrix left; the penetration of the acid will be limited for the same initial volume
of acid.
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7.3.5
Pressure Effect on Reaction Rate
TABLE OF CONTENTS
7 Acidizing Physics

Reaction Rates
7.3.5 Pressure Effect on

Reaction Rate
The reaction between HCl and carbonate rock is considered to be independent of pressure at
Version: 3 pressures where CO2 remains in solution (about 600 psi). Below this pressure, gaseous CO2
Release Date: 30-Aug-2003 may be produced during the reaction and little is known of this effect on the reaction rate.
EDMS UID: 274758406
Produced: 3-Oct-2003 17:02:48
Owner: WS Training This kinetic parameter is different from the thermodynamic parameter, where the pressure,
Author: WS Training by increasing the solubility of CO2 in the water phase, limits the extent of the reaction
(equilibrium conditions).
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7.3.6
Acid Types
TABLE OF CONTENTS
7 Acidizing Physics

Reaction Rates
7.3.6 Acid Types

Version: 3
Release Date: 30-Aug-2003 Reaction rate depends on the nature of the acid; for example, formic acid reacts slower than
EDMS UID: 274758406 HCl, and acetic acid reacts slower than formic acid.
Produced: 3-Oct-2003 17:02:48
Owner: WS Training
Author: WS Training The reaction rates depend on
• rate of ionization of the acid
• the diffusion coefficients of the acids
• concentration or activity of the different reacting species in solution
• ionic strength of the solution (that is, the type and concentration of other ions and counter-
ions in solution, mainly calcium and chloride)
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7.3.7
Formation Composition
TABLE OF CONTENTS
7 Acidizing Physics

Reaction Rates
7.3.7 Formation Composition
Important factors in determining the area/volume ratio are

Version: 3 • physical composition of the rock
• pore size
EDMS UID: 274758406
Produced: 3-Oct-2003 17:02:48 • pore-size distribution within the matrix
Owner: WS Training
Author: WS Training
These factors affect the reaction rate and the effective acid penetration.
Formation composition may be more important than the variable chemical composition of a
given type of rock. Two formations having the same acid solubility and permeability (k) may
dissolve at different rates because of their differing physical structure.
Formation composition influences the reaction of acid with carbonates in two ways:
• The size and crystallinity of each calcite crystal affects, to some extent, its dissolution rate;
and
• The pore-size distribution introduces a perturbation effect in the flow. The flow of acid, the
velocity, and the mass transfer are higher in larger pores. This perturbation effect
contributes to minimizing the flow of acid into the small pores. Large conductive channels
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(wormholes) are preferentially formed.
The reservoir heterogeneity (pore-size distribution) strongly influences the number of

wormholes formed.
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8
Acid Systems
TABLE OF CONTENTS
8 Acid Systems
Some of the major Schlumberger acid systems are shown in this table.
Acid Systems
Inhibited HCl Schlumberger X*

Reference: SWBT, sand contr Schlumberger Super X* (>20% HCl)
Version: 3 Primary acid for carbonates
EDMS UID: 274758407 Organic acids Less efficient than HCl
Produced: 3-Oct-2003 17:02:48 Higher temperature applications
Owner: WS Training (Less corrosive, easier to inhibit)
Author: WS Training
Blended acids HCl/organic blends
Less expensive than organic acids
Viscosified acids DGA* series

LCA* acids
Mainly used in acid fracs
8.1
Acid Systems
• Blended Acids
Different blends of HCl with either formic or acetic acids have been used to take advantage of
the cost efficiency of HCl and the reduced corrosion provided by the organic acids.
NOTE: Do not use hydrofluoric acid in carbonates or sandstone containing more than
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20% carbonate. The reaction forms calcium fluoride precipitate.
It should be noted that, in the course of reacting with limestone, HCl reacts as fast and large
amounts of CO2 are produced by the reaction. The quantity of CO2 almost completely stops the
reactivity of the organic acids. The overall result is one of a lower quantity or concentration of
HCl, with the additional expense of the organic acid.
• Inhibited HCl
Inhibited HCl (Schlumberger X or Super X) is the preferred acid for the treatment of carbonate
formations. This is due to its low cost, availability, and its soluble products.
• Organic Acids
Organic acids are preferred for high-temperature applications because of their lower corrosive
nature, ease of inhibition, and seemingly "retarded" reaction characteristics.
• Viscosified Acids
The main use of viscosified acids is in fracturing rather than matrix acidizing. In matrix
acidizing, the macroscopic viscosity would induce a self-diverting effect and limit the injectivity
for a given pressure.
In addition, in matrix treatments, the phenomena of acid diffusion and mass transfer are not
retarded by the apparent viscosity of the fluid. At this scale and area/volume ratio, the diffusion
depends on the viscosity of the solvent (base fluid) and not on the viscosity of the polymer
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solution.
When acidizing at matrix rates, gelled acids are mainly used to clean up formations that contain
very large pores or formations that are fissured. The viscosity of the acid would keep it in the
main flow channel where most of the damage would be located. The retention of some viscosity
after spending helps to maintain the fines (fine particles) in suspension, and gives a better
cleanup in the formation that is not too depleted.
8.2
Emulsions
Emulsions, with acid as the internal phase (that is, completely encapsulated within the oil-
carrying fluid), are one of the best ways to retard the acid reaction rate.
A macroscopic physical barrier (the oil film) prevents direct contact between acid and
formation. Such fluids (such as Super X Emulsion*) had applications as pad fluids in acid
fracturing, where their viscosity was high enough to carry live acid to the fracture tip. The
excessive friction that developed limited the use of these fluids in matrix acidizing.
Microemulsions are stable dispersions of oil-in-water or water-in-oil which are completely

translucent (not turbid) because the size of the droplets is in the range of a few nanometers 10-
9m. Because of their low viscosity, they would be perfect for matrix acidizing except they
require high concentrations of surfactants, which make them expensive.
Stability problems have been found with micro-emulsions in the past, and they are no longer
used.
8.3
Exercise
Acid Systems Exercise
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9
Main Schlumberger Acid Systems
TABLE OF CONTENTS
9 Main Schlumberger Acid

Systems
Tables with information regarding the complete line of Schlumberger products for matrix
acidizing are available from the Schlumberger Business Line Manuals Matrix Materials Manual
(on CD-ROM ITM-1144).
Treating fluids are separated by temperature and range of application. At high temperatures,
organic acids or NARS are used.
Version: 3
Acid Systems for Treating Formations at Low to Moderate Temperatures
EDMS UID: 274758399
Produced: 3-Oct-2003 17:02:48 System Application
Owner: WS Training
Author: WS Training Hydrochloric acid diluted with alcohol • To treat producer wells (prevention of water
blocks) up to 250oF (121oC).
Intensified Acid XX or MSR* (Mud Silt • To dissolve silicates mixed with carbonates up
Remover) system
to 300oF (149oC).
DAD • To dissolve insoluble organic material and

carbonate rock.
Foamed acid • In formations having big pores or vugs.
• When diversion and fast cleanup (in low-

pressure wells) are required.
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Gelled acids • To clean fissured or vuggy formations at
matrix rates.
• Increased viscosity provides better control of

fluid leakoff and facilitates fines suspension
and cleanup.
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10
Summary
TABLE OF CONTENTS
10 Summary
This module covered the factors involved in the matrix acidizing of carbonate rocks, including
the geology of carbonate rocks. The physics of the chemical reaction between acid and
carbonate rocks was studied, as this knowledge is essential to the complete understanding of
carbonate acidizing. Stoichiometric calculations involved in these chemical reactions were also
presented to clarify the process.
Version: 3
EDMS UID: 274758400
Produced: 3-Oct-2003 17:02:48
Owner: WS Training Copyright © 2007 Schlumberger, Unpublished Work | All Rights Reserved | Legal Information
Author: WS Training
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Schlumberger - Carbonate Acidizing

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In this training module, you will learn to do the following:

• Demonstrate a knowledge of factors involved in the matrix acidizing of carbonate rocks.

• Demonstrate an understanding of the geology of carbonate rocks.

• Demonstrate a knowledge of the Schlumberger products and resources available to design

• Matrix Materials Manual (on CD-ROM ITM-1144)

• Reservoir Stimulation by Economides, et al.

• Schlumberger Fluid Selection Guide for Matrix Treatment (TSL-2069)

The acid should:

• be low cost and available

Reference: SWBT, sand contr

• dissolution (the decomposition into fragments or parts)

• dispersion (the scattering of the fragments or parts)

Acidizing Mechanism Exercise

The rocks generally referred to as carbonate rocks are

Limestone is the most abundant chemically-precipitated sediment.

Calcite is relatively stable.

Aragonite generally changes over time into calcite.

Dolomite is formed by the alteration of preexisting limestone. Rocks classified as dolomite

Dolomites are quite similar to limestone in appearance. It is difficult to distinguish between

Dolomite bubbles only in hot, concentrated acid.

Hydrocarbon-bearing Limestone Rocks

• Structure similar to sandstone

• May have primary porosity

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• Good reservoir rock

• Very low primary porosity

Ancient reefs and atolls

• Buried mounds of shells

• May have primary porosity

Examples of hydrocarbon reservoirs of oolitic origin include

During the Cretaceous period, several prominent chalks were deposited.

The Cretaceous chalks include

• Austin Chalk of Texas, USA

• Niobara Chalk of South Dakota, Nebraska and Kansas, USA

• Ekofish Chalk of Danish North Sea

• Sirte Basin of Libya

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Ancient reefs and atolls may have primary porosity.

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In impermeable limestone (such as micrite and crystalline limestone) dolomite formation is

6 Acids Used in Carbonate

The chemical formulas for carbonate acidizing fluids are

Reference: SWBT, sand contr 1. HCl (hydrochloric acid)

HCl is overwhelmingly employed in the acid treatment of carbonaceous formations because of

HCl is commonly used at a 15% concentration, originally chosen because of inadequacies in

6 Acids Used in Carbonate

Use the table as a review of the acids used in carbonate acidizing.

Name Formula Characteristics Advantages Disadvantages

Hydrochloric HCl • Most commonly • Moderate cost. • Highly corrosive

Acetic Acid CH3COOH • Used at 10% • Low corrosive • More expensive

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Formic Acid HCOOH • Used at 9% • Lowest cost per

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6 Acids Used in Carbonate

Reference: SWBT, sand contr

Knowing these proportions allows

Element Atomic weight

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Compound Molecular weight Amount dissolved or liberated Produced (lb)

1000 x 1.075 x 8.33 x 15%

1000 = gal HCl