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03/2014 Quang Khnh HoChiMinh City University of Technology 1

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Content & Agenda
Used acidic solutions in matrix acidizing
Basic properties of acid-mineral interactions
Candidate selection
Treatment type selection
Sandstone acidizing design-typical acidizing formulations for sandstone formations
Carbonate acidizing design

Reservoir Stimulation, 3e Economides & Nolte
Petroleum Production Systems - Economides et al., 1994
Production Operations: Well Completions, Workover, and Stimulation -Thomas O. Allen,
Alan P. Roberts,1984
o Matrix stimulation is a technique in which a solvent is injected into the formation to dissolve some of
the materials present and hence recover or increase the permeability in the near-wellbore region.
Such treatments are called matrix treatments because the solvent is injected at pressures below
the parting pressure of the formation so that fractures are not created. The objective is to greatly
enhance or recover the permeability near the wellbore, rather than affect a large portion of the
o The most common matrix stimulation treatment is acidizing, in which an acidic solution is injected to
dissolve minerals in the formation. However, other solvents are also used. The next most common
uids onversare organic solvents aimed at dissolving waxes, parafns, asphaltenes or other organic
damaging materials.
o (Matrix) acidizing is a near-wellbore treatment, with all the acid reacting within
o about 1 ft of the wellbore in sandstone formations and
o a few inches to perhaps as much as 10 ft from the wellbore in carbonates.
o Matrix acidizing can signicantly enhance the productivity of a well when near-wellbore formation
damage is present and, conversely, is of limited benet in an undamaged well.
o The goal of a matrix acidizing treatment is to reduce the non-mechanical skin effect to near zero.
o Main applications for matrix acidizing:
o only when a well has a high skin factor that cannot be attributed to partial penetration, perforation efficiency or other mechanical
aspects of the completion.
o in highly productive wells, the productivity improvement of about 20% that is possible with matrix stimulation of an undamaged
well may be economic.
o in naturally fractured or highly vugular carbonate reservoirs, live acid may penetrate to a sufficient distance to yield a productivity
enhancement greater than that normally expected from a true matrix treatment.
o High permeability formation with damage
o Formations not suitable for fracturing
o Water/Gas Cap near oil zone
o Mechanical treating limitations

o To Supplement Fracturing
o An ideal matrix treatment restores the permeability in the near-wellbore region to a value at least as high
as the original undamaged permeability; it accomplishes this over the entire completed interval and it
leaves the formation in the treated region with high relative permeability to the oil and/or gas phase.

o Designing a treatment should strive to achieve this ideal at the lowest possible cost, which requires
consideration of the many physical and chemical interactions taking place between the injected uids
and the reservoir minerals and uids.
mass transfer of acid molecules to the mineral surface and subsequent reaction at the surface
changing pore structure
precipitation of reaction products
acid uidreservoir uid interactions
variations in reservoir permeability or the distribution of damage

o Hydrochloric Acid (HCl)

o Organic Acids
o Acetic acid (CH3COOH)

o Formic acid (HCOOH)

o Mud Acid (HCl/HF)

Hydrochloric Acid (HCl)
Organic Acids
Mud Acid
Mud Acid
Mud Acid

o The clays, micas, etc. dissolved by mud acid undergo a series of reactions resulting in precipation of
silica gel (Si(OH 4) a hydrated form of silica.

o Acid-mineral reaction stoichiometry

o Acid-mineral reaction kinetics

o Precipitation of reaction products

Acid-mineral reaction stoichiometry


o Minerals present in sandstone pores include

o Montmorillonite (Bentonite) , Kaolinite, Calcite, Dolomite, Siderite, Quartz, Albite (Sodium Feldspar), Orthoclase, and others..

o Mineral origin from invasion of drill, cementing or completion fluids, or host materials occurring naturally

in the rock formation

o Most commonly used acids to dissolve these minerals: hydrochloric acid (HCl) and hydrofluoric acid (HF)

o Silicate materials (such as clays and feldspars) in sandstone pores normally removed using mixtures of
HCl and HF acid

o Carbonate materials usually addressed by HCl alone

Acid-mineral reaction stoichiometry

Primary chemical reactions in acidizing.

Acid-mineral reaction stoichiometry

The stoichiometry of chemical reaction: the number of moles of each species involved in the reation.

Dissolving power of acids: the amount of mineral that can be consumed by a given amount of acid on a
mass or volume basis.
Acid-mineral reaction stoichiometry

Ex: Calculate the Gravimetric and Volumetric dissolving power of 15% Hydrochloric acid with Calcium
carbonate with acid = 0.0654 lb/ft3 , CaCO3= 0.17 lb/ft3

Sol: 15 = 0.15 x 1 x 100.1 / (2 x(36.5)) = 0.206 lb m CaCO 3 / lb m 15 wt% HCl solution

X 15 = 0.206 x 0.0654 / 0.17= 0.08 cuft CaCO 3 / cuft 15 wt% HCl solution
Acid-mineral reaction stoichiometry

Ex: A sandstone formation with a porosity of 0.2 contains 5-vol% albite (sodium feldspar). What is the
minimum volume of 3% HF solution required to dissolve all the albite a distance of 6 in. beyond a 6-in.
diameter wellbore?


Ex: What is the minimum volume of 15% HCl required to dissolve calcite up to 1ft deep in the reservoir

Reservoir porosity 18%

Formation HCl solubility of 10% (Assume all Calcite)

Wellbore radius 0.3 ft

Acid-mineral reaction kinetics

Reaction rate

o The reaction between an acid and a mineral occurs when acid reaches the surface of the mineral by
diffusion or convection from the bulk solution.

o The overall rate of acid consumption or mineral dissolution depends on two distinct phenomena:
o the rate of transport of acid to the mineral surface by diffusion or convection, and

o the actual reaction rate on the mineral surface.

o Usually, one of these processes is much slower than the other. In this case,
o the fast process can be ignored,because it can be thought of as occurring in an insignificant amount of time compared with the
slow process.

Acid reaction occurring in a system

Acid-mineral reaction kinetics

Reaction kinetics

o Kinetics of a reaction is a description of the rate at which the chemical reaction takes place, once the
reacting species have been brought into contact; driven by reactivity of the mineral per unit of surface

o Generally:

- HCl / Carbonate reactions can be considered almost instantaneous, and limited by mass transport

- Most HF-Mineral reactions are slow compared to mass transport rates so overall acid consumption

limited by reaction rate

o Clays will react with HF approx. 2 orders of magnitude faster than silica due to far greater surface area / volume

o Felspars will react with HF approx 1 order of magnitude faster than silica due to greater reactivity
Precipitation of reaction products

o A major concern in acidizing, particularly the acidizing of sandstones, is damage caused by the
precipitation of acid-mineral reaction products. In acidizing sandstones with HF, the formation of some
precipitates is probably unavoidable. However, the amount of damage they cause to the well productivity
depends on the amount and location of the precipitates. These factors can be controlled to some extent
with proper job design.

o The most common damaging precipitates that may occur in sandstone acidizing are :
o calcium uoride (CaF 2 ),

o colloidal silica (Si(OH) 4 ),

o ferric hydroxide (Fe(OH) 3 ), and

o asphaltene sludges.

o The tendency for precipitation reactions to occur in acidizing is predicted with comprehensive
geochemical models of the chemical reactions between aqueous species and the host of minerals
Precipitation of reaction products

o The most common type of geochemical model used to study sandstone acidizing is the local equilibrium
model, such as described by Walsh et al. (1982) and Faber et al. (1994).
o assumes that all reactions are in local equilibrium; i.e., all reaction rates are innitely fast.

o a time-distance diagram for the injection of 11% HCl4% HF into a formation containing calcite, kaolinite and quartz. This plot
shows regions where amorphous silica and aluminum uoride will tend to precipitate.

o A vertical line on the plot represents the mineral species present as a function of distance if all reactions are in local equilibrium.

o By coupling this model with a model of the formation per meability response to both dissolution and precipitation, predictions of
the productivity improvement expected from particular acid formulations may be obtained
Precipitation of reaction products

o Recently, Sevougian et al. (1992) and Quinn (1994) presented a geochemical model that includes
kinetics for both dissolution and precipitation reactions. This model predicts
o less permeability damage than a local equilibrium model because the nite rate of the reactions allows displacing the pre cipitate
farther from the wellbore.
Candidate Selection

Candidate Selection (Recognition) is the process of identifying and selecting wells for
treatment which have the capacity for higher production and better economic return.
Good Wells Make the Best Candidates for Well Stimulation
1. It must have production potential impaired by damage
2. That damage must be treatable through acidizing
3. The NPV of treating with acid should be more attractive than other possible treatments
4. Must be sufficient capacity downstream of the sandface to accommodate expected incr. production

Candidate selection process

o Review numerous wells.
o Review of well logs/records, reservoir characteristics and information on the completion/previous workovers.
o Map the productivity of each well.
o Establish reasonable upper production potential for fracturing and matrix stimulation techniques.
o Evaluate potential mechanical problems.
o Focus on wells with the highest reward and lowest risk.

Typical screening criteria

o Its all about the size of the prize

The chosen chemical treatment fluid should be targeted at the particular type
and location of the formation damage to be removed or treated.
The formation damage/impairment may be related to:
(i) drilling, completion or workover operations,
(ii) produced or (continually) injected fluids,
(iii) injected fluids during specific well operations e.g. well killing.
Chemical treatment types

o In considering the many aspects of the matrix acidizing process, the focus is on the key design
variables; to be useful, any model of the process must aid in optimizing the design.

o The primary design considerations are:

fluid selectionacid type, concentration and volume

injection scheduleplanned rate schedule and sequence of injected uids

acid coverage and diversionspecial steps taken to improve acid contact with the

real-time monitoringmethods to evaluate the acidizing process as it occurs

additivesother chemicals included in the acid solution to enhance the process or to

protect tubular goods.
A Typical Treatment Stages:
Preflush: [usually 50 to 100 gal/ft of perforations is advisable]
A fluid stage, normally hydrochloric acid HCl, pumped ahead of the main treating fluid
in a sandstone matrixstimulation treatment.
One of the purposes of a preflush is to displace formation brines that contain K, Na, Ca ions away from the wellbore,
decreasing the possibility of crystallizing alkalifluosilicates that could plug the pores.
The other purpose of a preflush is to dissolve calcareous materials to minimize calcium fluoride [CaF2 ] precipitation,
and to dissolve iron scale or rust to avoid the precipitation of the gelatinous, highly insoluble ferric hydroxide [Fe(OH)3 ].
Main treating fluid: [usually 50 to 200 gal/ft of perforations is required]
The mixture of hydrofluoric HF and hydrochloric HCl or organic acids formulated to address
formation damage
A specially prepared fluid used to displace matrix acid treatments away from the wellbore at the conclusion
of a stimulation treatment. The overflush is typically formulated from a weak acid (5% HCl) solution or
Ammonium chloride [NH4Cl] brine to maintain a low pH environment in the nearwellbore formation that
prevents the precipitation of reaction products as the treatment fluids are flowed back.
Fluid volume required to push all overflush into the formation. Can be brine/diesel/nitrogen
depending upon cost, expected contamination or reservoir pressure issues.
Typical acidizing formulations for sandstone formations

o Introduction

o Sandstone acidizing models

o Select of acid composition (type & strength (ie. concentration))

o Select of treatment volume

o Select of injection rate

o Select of additives

o Select of treatment type

o Select of diversion technique

Introduction to Sandstone reservoirs
Sandstone acidizing models:
Two-mineral model
Sandstone acidizing models:
Two-acid, three-mineral model
Typical Sandstone Treatment Stages
Select of acid

o The chemistry of a mud acid treatment illustrating how the impairment, formation clays and inter-granular
cements are removed by the mud acid and partially replaced by secondary reaction products. However,
there is an overall increase in porosity and permeability, leading to stimulation of the well.
Select of acid

Acid selection guidelines

Select of treatment volume

Typical mud acid treatment volume guidelines

o Above volumes often adjusted to take into account:

(i) Field experience when treating wells in the same or similar fields. Often between 50% and 100% of the volumes
suggested in are used.
(ii) Practical considerations such as logistics e.g.
(a) how much acid can be delivered to the wellsite? or
(b) how large an acid the volume pumpable during daylight hours?
(iii) Economics (how much acid can we afford based on the expected gain in hydrocarbon production ?)
(iv) Laboratory core flow testing (acid volume required to increase the permeability (by a target amount). The core
may be pre-treated to include damage to the core inlet face by the suspected form of formation damage.
Select of treatment volume

Select of injection rate
Select of injection rate

Determining Fracture Pressure: can be determined a number of ways:

ISIP (Instantaneous Shut In Pressure)

Step Rate Tests

Pre-treatment breakdown (w/brine)

Assumption of 0.7 psi/ft

Injection Pressure
Select of injection rate

Pressure/Rate Limits
Select of injection rate

Paccalonis Max P Max Rate:

Paccaloni's maximum
p maximum rate procedure has two major components:

1.The acid should be injected at the maximum rate and hence, maximum pwf
possible without fracturing the formation; and

2. The treatment should be monitored in real time to ensure that the maximum rate objective is being

met and to determine when sufficient acid has been injected into the formation.
Select of injection rate

Ex of Paccaloni plot for control of treatment injection rate: construct a graph of tubing injection pressure
vs injection rate with S as a parameter
Select of injection rate

Ex: Given the following;

50ft Net oil reservoir to be acidized at 3,150ft depth
Treated through 1.2 ID coiled tubing of length 4,500ft and P max = 2,500 psi
Acid density = 1.07 SG, Acid viscosity = 1.5 cP
75mD sand, B o = 1.8, uo =0.8cP, rw = 0.3ft
Initial skin = +15, estimated final skin = +1.5
Reservoir pressure = 1,250 psi
Frac gradient = 0.7 psi/ft, 250 psi safety margin required

Calculate the following

BHFP limit
Expected rates at start and end of treatment
Expected tubing pressures at start and end of treatment
Minimum HHP (hydraulic horsepower) required
HHP = Pressure (psi) x rate (bbls/min) / 40.8
Select of injection rate

Paccaloni Drawback
A drawback to Paccaloni's method is that it will tend to overestimate the skin effect
because it neglects transient flow effects, as pointed out by Prouvost and Economides
(1988) and confirmed by Paccaloni and Tambini (1990.)
This error can be severe when abrupt rate changes occur; however, in most
treatments, it is not a serious problem because the error will be relatively constant and
the evolution in skin effect is more important than its absolute value.

Prouvost and Economides presented a procedure to calculate more accurately the changing
skin effect during matrix acidizing, but this procedure may require the use of a simulator .
This technique is more applicable to a careful posttreatment analysis, when the injection rate
schedule from the treatment is known.
An alternative realtime monitoring procedure that draws on both Paccaloni's and Prouvost
and Economides approaches is as follows.
Select of injection rate

Alternate approach:
Applying the approximation to the transient flow equation for injection with a skin effect yields

This suggests that the inverse of the injectivity will decrease as the skin effect is reduced by
acidizing. Conversely, when no stimulation is occurring, the inverse injectivity will increase propor
tional to the log of time because of the transient nature of the flow.

To monitor a stimulation treatment, the inverse injectivity can be plotted against the log of time.

As long as the inverse injectivity (P/q) is decreasing, significant stimulation is occurring.

When it levels off or begins to increase, little stimulation is occurring, indicating that injection of
the treatment fluid should be discontinued.
Select of injection rate

Procedure of Alternate approach:

1. Prior to the start of the treatment, develop the relationship between p wf and p inj :
pinj,max = pwf ph + pfric
2. Begin injection at a rate such that pwf =< 0.9 pfrac
3. Plot (p wf p)/q inj vs log(t) during the treatment.
The reservoir pressure (p) to use in the calculation is pi in a new well,
pe in a well with pressure maintenance at the boundary, and p in a confined reservoir.
4. As stimulation proceeds, increase the rate to maintain: pwf =< 0.9 pfrac
5. Stop injection when p/qinj versus log(t) levels off or increases for a significant amount of
injection (2550 gal/ft). When stimulation is no longer proceeding, acid injection
should be stopped.
Select of acid additives

A range of additives to the treatment formulation have been developed to combat one or more
of the forms of formation damage associated with stimulation treatments.
expensive, especially those added to acid treatments.

many of the additives are incompatible with each other and may themselves cause formation damage.

The use of each additive has to be justified separately- it should not be just chosen
because of the claimed advantages in the service company sales catalogue!

The most common, frequently used additives to acid solutions:

corrosion inhibitors,

iron-sequestering agents,

Solvents / Mutual Solvents / Surfactants, etc.

Select of acid additives

A range of additives to the treatment formulation have been developed to combat one or more
of the forms of formation damage associated with stimulation treatments.
expensive, especially those added to acid treatments.

many of the additives are incompatible with each other and may themselves cause formation damage.

The use of each additive has to be justified separately- it should not be just chosen
because of the claimed advantages in the service company sales catalogue!

The most common, frequently used additives to acid solutions:

corrosion inhibitors,

iron-sequestering agents,

Solvents / Mutual Solvents / Surfactants, etc.

Select of acid additives

Corrosion Inhibitors:

almost always required for acid treatments due to the corroding reaction of acid on steel of
tubulars and casing: Fe + 2H + Fe ++ (dissolved) + H2(gas)

The corrosion inhibitor looses its effectiveness as the temperature and treatment time increase
(due to degredation)

The type and concentration of corrosion inhibitor chosen will depend on the acid type, bottom
hole temperature, the type of steel contacted and the expected treatment duration
Select of acid additives

Iron-sequestering agents:
A number of sequestering - or solubilising - agents are available to increase the solubility of iron by forming
soluble complexes. The concentration of sequestrant required to prevent iron hydroxide precipitation depends
on the expected ferric ion (Fe+++) concentration.
Solubility of ferrous and ferric ions as a function of pH
The main source of Fe+++ is the acid reacting with rust in the surface tanks, flowlines and millscale on the tubing. The Fe++ is
mainly (>80%) derived from the formation minerals e.g. chlorite siderite, pyrite etc.
N.B. Fe +++ can catalyse the formation of an asphaltenic sludge when the acid contacts some crude oils.

The cheapest sequestering agent is citric acid but the maximum concentration allowable and the maximum
amount of iron cations that can be sequestered - is limited by the solubility of calcium citrate.
A more expensive alternative, which can be used at higher concentrations, is EDTA (Ethylene Diamine
Tetracetic Acid).
An alternative approach to preventing ferric hydroxide precipitation is to reduce the Fe +++ to Fe ++ by
Erythorbic acid or ascorbic acid (vitamin C).
Select of acid additives

Solvents / Mutual Solvents / Surfactants :

Use of these materials may reduce emulsion formation but can also be the cause of very
stable emulsion formation. Further, they may render the corrosion inhibitor ineffective by
preventing the absorbtion of the inhibitor onto the steel surface. They can be useful in some
circumstances but their employment needs to be properly justified and a full range of
compatibility tests carried out.
A mutual solvent, usually ethylene glycol monobutyl ether (EGMBE) has shown clear benefits
in some sandstone acidizing applications. It often added to the postflush, can improve
productivity apparently by removing corrosion inhibitor that has adsorbed on formation
surfaces and by restoring water-wet conditions
Surfactants are added to acid solutions to prevent the formation of emulsions, to speed
cleanup of spend acid, and to prevent sludge formation.
Select of treatment type

The manner of execution of most matrix treatments falls into one of two classes:

(i) Bullheading: - this term describes a treatment which is pumped down the production tubing.
The treatment, particularly if it employs acids, can displace rust, scale, pipe dope, etc. present on
the tubings inner wall into the formation; leading to formation damage.
Sometimes it is carried out prior to running the tubing since dried mud, cement, etc. present on the
casing wall can now also be dislodged as well as the damaging materials referred to above.
If the formation pressure is sufficiently high, or artificial lift is installed, it is possible to clean the
tubing with a pre-treatment (known as pickling). => injecting into the tubing a volume of acid
(usually equal to 20% of the tubing contents) & displacing it until the leading front of the acid is
a safe distance above the top perforation. The acid, along with the dislodged, potentially impairing
particles, is then produced back to the surface.
Select of treatment type

Bullheading of (cold) fluids from the surface also causes the tubing to contract in length. If this
contraction generates too large tensile stresses in the tubing, the tubing may part or cause
unseating of the packer. Both theses problems may be avoided by pumping through a CT.

(ii) Pumping through a coiled tubing (CT): the end of CT is positioned opposite the perforations.

Prior to the treatment being carried out the inside of the CT often needs to be cleaned e.g. by
pickling with acid. However, this can relatively easily be carried out at the surface, if necessary.

Coiled tubing has a smaller diameter than production tubing - so the maximum pump rate is limited
(due to friction) and the use of ball sealers for diversion is only practical if an unusually large
diameter CT is employed.
Select of diversion technique

A challenge that must be faced in matrix (acid) treatment for a heterogeneous formation is
diversion, in practice the perforated interval will contain a number of formation layers with a
range of permeabilities and, most likely, differing levels of skin damage.
As acid is pumped, it flows preferentially along the most permeable path into the formation.
The acid opens these paths up even more, and less permeable, damaged zones are almost
guaranteed not to receive adequate treatment.
Select of diversion technique

The diversion techniques have been developed to aid the more even fluid distribution
between the various formation layers. The more frequently used diversion techniques:
(i) Mechanical separation using conventional techniques: include control of the point of fluid injection by use
of retrievable bridge plugs placed in packers set between completion zones, dual packers on a work string (equivalent
to the Selective Placement Tool (SPT), sequential perforation etc.
(ii) Coiled Tubing (CT): Conventional CT may be used with the fluid exit ports at right angles to the tubing so that the
perforations are sprayed with a high pressure jet of treating fluid. Alternatively, the CT may be modified with a single
or dual packers to form the SPT. These packers are capable of being expanded and deflated many times so that all
the zones can be treated during one run into the well.
Select of diversion technique

(iii) Ball Sealers:

Ball sealers are nylon covered balls sized so that they can seal off the perforations. Different sized balls are required
depending on the perforation diameter e.g. when big hole or deep penetrating (narrow hole) perforating charges are
The balls are pumped whenever it is desired to change fluid injection from one zone to another. It is found in practice
necessary to pump a 30% - 100% excess of balls above the number of perforations to be sealed.
The density of the ball may be chosen so that it: is buoyant (floats upwards in the treatment fluid due to having a
slightly lower density) or sinks into the rat hole (i.e. denser than the treatment fluid). The ball density relative to the
produced fluid controls whether the ball is produced back to the surface after the treatment is finished.
Select of diversion technique

(iv) Viscous Fluids (gels and foams):

Viscous fluids increase the flow resistance in the layer taking excessive amounts of treatment fluid so that the fluid is
diverted into a new layer. ; break down with time
The diversion process is only effective if the viscous fluid is highly shear thinning i.e. its viscosity increases rapidly
as its flow velocity decreases at greater depths of injection.=> form a viscous plug.
(v) Diverting Agents Techniques: include
-Pack the perforation tunnel with a granular particulate (typically 200 mD)
-Form a low permeability film, on the wall of the perforation. (typically < 1 mD)

The permeability of the diverting agent is mainly dictated by its particle size. Its presence in a perforation will reduce
the injectivity into that perforation, reducing the rate of treatment fluid injection and increasing the flowing wellbore
injection pressure. This will divert the injection stream into a new zone. Further quantities of the diverter material
may be added continuously or intermittently in batches.
Select of diversion technique

The choice of materials used for these two diverting techniques is that they must be capable of:
(a) being prepared in the required range of particle sizes (hence filter cake permeability),
(b) be stable in the treatment fluid,
(c) disappear (dissolve or sublime in the produced fluids) from the perforation so that it becomes fully open to flow once
the well is returned to production and
(d) be non-toxic, cheaply and readily available.

Typical chemicals in the correct particle size ranges used for both particulate and film forming diversion agents are:
(a) Benzoic acid (water / oil / gas),
(b) Sodium Chloride (NaCl or rock salt) crystals (water) and
(c) Oil soluble resin (oil) particles.
In practice, acid and diverting agents are pumped in alternating stages: first acid, then diverter, then acid, then
diverter, and so on.
Select of diversion technique

Choosing of diversion method for matrix acidizing & typical stage sequence for a sandstone acidizing treatment

o Introduction

o Wormholes

o Select of acid

o Select of treatment volume

o Select of injection rate

o Select of treatment type

o Select of diversion technique

Introduction to stimulation of carbonate formations

o Acidizing of carbonate formations is fundamentally different from the acidising of clastic formations due to their differing
physical nature and chemistry:
(i) Carbonates consist of very fine grains exhibiting a vugular or fracture porosity rather than the intergranular porosity
shown by sandstones.
(ii) Carbonates react much more rapidly with hydrochloric acid than sandstones, for the same formation temperature.
Also, the use of mud acid is prohibited due to the limited solubility of calcium fluoride.
o Carbonates are normally found as massive deposits of chalk, limestone or dolomite. Their constituent particles are
much smaller than the typical sand grains found in clastic formations. They will have undergone large porosity and
permeability reductions during burial and diagenesis. Although they are often pure (>95% wt carbonate), they can also
include iron minerals, clays and silicaceous materials giving them a very variable composition.
o The many possible diagenetic processes can lead to formations with similar chemical compositions having a strength
that varies from very strong to behaving similar to toothpaste. Strong and weak layers can be present a small
distance apart. This complicates the planning of well completion - and stimulation - procedures.
Carbonate acidizing is a more difficult process to predict the outcome than sandstone acidizing because, despite the
chemistry of the process being much simpler than that of sandstone acidizing, the physics is more complex.
In carbonates, surface reaction rates are very high, so mass transfer often limits the overall reaction rate, leading to
highly nonuniform dissolution patterns.
A few large channels, called wormholes, are created, such as shown in the figure following, caused by the nonuniform
dissolution of limestone by HCl in a linear core flood (Hoefner and Fogler, 1988.)

o Wormholes,created by dissolution of the rock uniformly (Hoefner and Fogler, 1988.), consist of a main channel from
which many highly branched structures are formed.

o The structure of these wormhole patterns will depend on many factors, including (but not limited to)
flow geometry,
injection rate,
reaction kinetics, and
mass transfer rates.

Since wormholes are much larger than the pores in nonvugular carbonates,
the pressure drop through the region penetrated by wormholes will be insignificant.
Thus, in matrix acidizing, knowledge of the depth of penetration of wormholes
allows a prediction of the effect of acidizing on the skin effect.
Wormholing is also very significant in acid fracturing,
as it will increase fluid loss rates, limiting the penetration of acid down the fracture.

Wormhole Formation and Growth:

o Wormholes form in a dissolution process due to
More acid tends to flow through the larger pores
Since reaction rate is fast almost all acid entering both small & large pores will react causing a dissolution of pore wall
Since larger pores receive more acid they tend enlarge at a rate higher than the rate at which smaller pores
This nonlinear process eventually produce a wormhole.
o This nonlinear process leading to wormhole formation will occur if the reactions are,
transfer limited ( fast reaction rates compared to mass transfer)
mixed kinetics, ( i.e. the mass transfer and surface reaction rate are similar in size.)
The injected acid does not dissolve the rock uniformly, instead it forms wormholes

o The number and extent of the wormholes depend on:

(i) the carbonate formations reactivity (high reaction rates promote few, long wormholes);
(ii) the acid leak-off rate into the matrix (controlled by formation permeability, acid and formation fluid viscosities and the
injection pressure overbalance);
(iii) The presence of higher permeability streaks, fractures, vugs etc will determine the preferred direction of wormhole

At a very low injection rate, the inlet face of the rock will be slowly consumed as acid diffuses to the surface,
This type of dissolution will not occur in a practical acidizing situation in limestone
However, it is of interest as the limiting case as flow rate approaches zero.

With increasing flow rate, a dominant wormhole (or a few) forms and propagates into the porous medium

At relatively low injection rates there will be little branching, and only one or a few large wormholes will be formed,
called diffusionlimited wormholing
Select of acid

o Hydrochloric acid is used to:

(i) bypass drilling or completion damage by dissolving the rock matrix;
(ii) widen natural fractures or secondary porosity so as to improve fluid conductivityto the wellbore
(iii) increase the effective wellbore radius by wormhole formation.
o Dolomite reacts much more slowly with Hydrochloric Acid than chalk or limestone - the optimum reaction rate is
achieved with a concentration of 28% wt HCl acid for all dolomite reservoirs.
o 15% wt HCl is used with the other carbonate formation types.
o The amount of rock dissolved by the acid is determined by:
constant = {volume acid * concentration acid * reaction stochiometry}; depends on the units employed e.g. 1m3 of 4% wt
HCl will dissolve 206kg of limestone with a volume of 0.073m3 assuming a porosity of 5% vol. The corresponding
amounts dissolved when dolomite is treated are some 7.5% smaller.
Choices limited by corrosion realities
Weak acids are suggested for perforation fluid and cleanup, and strong acids are recommended for other treatments.
All theorical models of wormhole propagation predict deeper penetration for higher acid strengths, so a high
concentration of acid is always preferable for wormholes.
Recommended acid type and strength for carbonate acidizing (McLeod, 1984)
Select of acid volume

o The acid volume can be calculated with two methods:

1. Daccords wormhole propagation model and
2. The volumetric model
The former is usually optimistic, whereas the latter is more realistic (Economides et al. 1994) .

The volume injected will directly affect the wormhole length, in turn affecting post treatment skin
Assuming infinite conductivity in wormholes that have penetrated past any damage radius,
post treatment skin can be calculated from: S = ln(rac / rw)

Ex: What would be the resultant skin from a treatment developing 1ft wormhole penetration in a 0.3ft radius wellbore?
Solution: S = ln(1.3/0.3) = 1.4
Note that unlike sandstone stimulation , we are developing negative skin
Select of acid volume

o Daccords Wormhole Progression Model

Select of acid volume

o Volumetric Wormhole Model

Select of acid volume

o Example:
A 28 wt% HCl is needed to propagate wormholes 3 ft from a 0.328ft radius wellbore in a limestone formation (specific gra
vity 2.71) with a porosity of 0.15.
The designed injection rate is 0.1 bbl/minft, the diffusion coefficient is 109 m2 /sec,
and the density of the 28% HCl is 1.14 SG.

In linear core floods, 1.5 pore volume is needed for wormhole breakthrough at the end of the core.
Calculate the acid volume requirement using
(a) Daccords model, and
(b) the volumetric model.

Select of injection rate

o The maximum injection rate and pressure for carbonate acidizing can be calculated the same way as that for
sandstone acidizing. Models of wormhole propagation predict that wormhole velocity increases with injection rate to
the power of 12 to 1. Therefore, the maximum injection rate is preferable.

o However, this approach may require more acid volume. If the acid volume is constrained, a slower injection rate may
be preferable. If a sufficient acid volume is available, the max. injection rate is recommended for limestone formations.

A lower injection rate may be preferable for dolomites. This allows the temperature of the acid entering the formation to
increase, and thus, the reaction rate increases.
At a sufficiently high temperature, the dolomiteHCl reaction may become diffusion limited, leading to much faster
wormhole propagation; that is, at an elevated temperature, dolomite will behave more and more like limestone.

By increasing the reaction rate, acid will penetrate farther into the formation.
Select of injection rate

For a wormhole to form, the initial pore radius must be large enough to allow acid transport beyond the pore inlet

According to Daccord et al. (1989, 1993), the Peclet number P e , which represents the ratio of axial flow to radial
transport in the pores, is the dimensionless variable governing the transition between compact dissolution at low rates
and wormholing at higher rates for a transport-limited reaction (i.e., calcite and high-temperature dolomite)
Select of treatment type

Matrix Treatments:

Wormhole formation during matrix treatments improves the well inflow performance by providing a high conductivity
channel at depth from the wellbore. They are created using either a:

(a) low rate, low volume, low acid concentration treatment.

(Typical values are 0.004m 3 /min/m, 0.3m 3 /m and 14% wt HCl for the injection rate, injection concentration and acid
concentration respectively).
The low rate and long contact time encourages wormhole formation and the bypassing of shallow formation damage.
This type of treatment is most suitable for short intervals (< 12m).

(b) high(er) rate, large volume, high concentration treatment.

(Typical values are 0.025m 3 /min/m, 1.6m 3 /m and 14-28% wt HCl respectively).
The larger acid volume compensates for the reduced wormhole formation caused by the use of the higher pump rate.
Ball sealers are more effective in high rate treatments - making them more suitable for treating longer perforated zones.

Both types of treatments have been applied with success - the preferred method probably depends on the local
situation with regard to formation damage, presence of natural fractures & vugs etc.
Select of treatment type

Acid Wash (or Soak) Type Treatments:

Wormhole formation is undesirable if the treatment objective is to remove near well bore damage (e.g. perforations
plugged with drilling mud, cement etc.) present in a new completion or after a workover. This is because forming the
wormhole will consume a large part of the available acid. Wormhole formation is avoided by keeping the injection rate
very low (<0.0002m 3 /min/m). The treatment is now called an acid wash or soak.

Treatment guidelines are:

(a) use the highest possible HCl acid concentration (max 28%) permitted by corrosion considerations for the planned
treatment time (10 hours or longer);
(b) use a coiled tubing (CT) to place a volume of acid, equal to the casing volume of the perforated interval. If CT is not
available the tubing should be pickled;
(c) The acid should contain an iron sequestrant and, if an oil based mud cake is to be removed, a mutual solvent or
dispersing surfactant.
Select of diversion

Adequate placement of acid into all zones to be stimulated is as important in acidizing carbonates
as it is in sandstones, and the same fluid placement techniques are applicable.

One exception is that in carbonate formations that are vugular or contain large natural fractures larger particle
diverting agents are needed than would be necessary in sandstones.

For a vuggy or fractured carbonate, diverting agents such as Unibeads or benzoic acid flakes are recommended.

In addition to traditional diversion methods, carbonates can also respond well to SDA or Self Diverting Acids
Acids which viscosify as their pH rises reducing the flow potential as the acid spends
and then breaks to low viscosity again as pH approaches 7 (neutral).