Stimulation

SIEP 99-5638
December 1999
Stimulation
Field
Guidelines
Part III
Carbonate Stimulation
SIEP 99-5638
December 1999
Stimulation
Field
Guidelines
Part III
Carbonate Stimulation
SEPTAR Stimulation Team
This document is restricted. The copyright of this document is vested in Shell International Exploration and
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© SIEP B.V. 1999
SHELL INTERNATIONAL EXPLORATION AND PRODUCTION B.V.

EPT-AWW
Further copies can be obtained from the STEP Library.

Acknowledgment
These guidelines have been formulated with the use of internal Shell documentation
and publications in the open literature. This document is a confidential document,
for use by Shell personnel only.
The use of Halliburton and Schlumberger Dowell documentation is gratefully

acknowledged, as well as the very useful discussions with Halliburton (M. Buijse,
K.A.W. van Gijtenbeek) and BJ Services International (B. Ritchie) staff.
Stimulation Field Guidelines - Carbonate Stimulation Acknowledgment • i

Contents
Introduction 1
Properties of carbonate rock 3

Composition 3
Porosity/Permeability 4
Types of acid 5
Acid/carbonate dissolving power 5
Acid/rock reaction rate 6
Pressure 7
Temperature 7
Acid concentration 7
Area/volume ratio 8
Formation composition 8
Stimulation selection considerations 9

Problem well identification 9
Analysis of the skin factor 9
Damage classification 11
Candidate selection 11
Selection of treatment 12
Matrix treatments 13
Acid fracturing treatments 14
Treatment design 16
Matrix treatments 17
Introduction 17
Acid wash or soak 17
Matrix acidising 18
Wormholing 19
Increasing wormhole length 22
Applicability of emulsified acid 24
Diversion 25
Treatment fluids 25
Stimulation Field Guidelines - Carbonate Stimulation Contents • iii
RESTRICTED SIEP 99-5638
Acid fracturing 27
Introduction 27
Controlling factors 28
Length of etched fracture 28
Fracture conductivity 29
Propped acid fracturing 30
Closed fracture acidising (CFA) 30
WISPER technique 31
AcidFrac software application 32
Diversion techniques 35
Introduction 35
Mechanical techniques 36
Packer and bridge plug arrangements 36
Selective Placement Tool 36
Coiled tubing (CT) 37
Ballsealers 37
Particulate diverting agents 39
Viscosified fluids 41
Emulsified acids 42
Foamed fluids 43
MAPDIR technique 43
Laboratory testing 45
Introduction 45
Rock composition and strength tests 46
Fluid compatibility tests 46
Acid reaction tests 47
Static reaction tests 48
Rotating disk tests 48
Annular flow tests 49
Hollow-core tests 49
Parallel plate tests 50
Acid-etched conductivity tests 51
Special applications 53
Horizontal wells 53
Naturally fractured carbonates 54
Exploration wells 56
High pressure wells 58
High temperature wells 59
Low temperature wells 60
iv • Contents Stimulation Field Guidelines - Carbonate Stimulation

Matrix treatment design guidelines 61
Introduction 61
Damage characterisation 62
Formation characteristics 62
Treatment fluid selection 63
Base acids 63
Acid systems 64
Selection of additives 65
Non-acid matrix treatments 66
Maximum allowable injection rate/pressure 67
Volume requirements 68
Placement strategy 68
Acid fracturing design guidelines 71

Introduction 71
Well condition and parameters 72
Reservoir and rock parameters 72
Treatment type 73
Frac-fluid and acid type 75
Acid reaction rate parameters 77
Fracturing fluid additives 78
Placement technique and pump rate 78
Measure in-situ stress profile (if feasible) 80
Determine the optimum fracture length and conductivity 81
Calculate a detailed design using ShellFrac and AcidFrac 81
Appendix I Commercially available matrix acidising systems 83
Appendix II Maximum injection rate for matrix treatments 87
Appendix III Acid reaction rates of carbonate rock 89
Index 93
Stimulation Field Guidelines - Carbonate Stimulation Contents • v

Introduction
Long before acidising of sandstones with mud acid became widely accepted,
acidising of carbonates with hydrochloric acid had been applied in many parts of
the world. The first carbonate well treatment with acid was actually carried out in
1895 with some success, but this did not have direct follow-up because of serious
corrosion problems. Not until the discovery of arsenic inhibitors in 1932, which
were applied in treatments with very good results, stimulation of carbonates with
acid has become a generally accepted practice.
In general, well stimulation techniques mostly relate to chemical and mechanical

techniques, or a combination thereof. Chemical well stimulation usually refers to
matrix acidising, both in sandstones and in carbonates. Mechanical well stimulation
mostly refers to hydraulic fracturing, primarily in sandstones, and combined
mechanical/chemical stimulation (acid fracturing) occurs in carbonates.
Matrix acidising aims at the removal of impairing material near the wellbore by
injection of acid – at a pressure below fracturing pressure – into the porous matrix
of the reservoir. It can be applied in both sandstone and carbonate reservoirs, but
the methods, objectives and mechanism for each type of rock are completely
different. The objective of conventional sandstone acidising is to restore
permeability of the sandstone to its undamaged condition by removal (dissolution)
of formation fines, clays, etc. from the near-wellbore area. Damage removal is
accomplished by injection of acid, mostly mixtures of HCl and HF, called mud
acid.
In carbonates, matrix acidising not only provides opportunity to remove damage
from the vicinity of the wellbore, but it also tends to increase near-wellbore
permeability by acid dissolution and enlargement of pore throats and the creation
of flow channels (wormholes), which can often result in a negative skin value (i.e.
stimulation). Matrix acidisation in carbonates is usually carried out with HCl only,
and it is a much more straightforward process than acidising in sandstones. This is
because most of the reactant products in carbonates are soluble in the spent acid.
The use of mud acid in carbonates is precluded in view of the precipitation of
calcium fluoride (CaF2) when HF reacts with calcium carbonate.
As to mechanical well stimulation, hydraulic fracturing in sandstones involves the

pumping of a viscous fluid at a pressure above fracturing pressure into the formation
Stimulation Field Guidelines - Carbonate Stimulation Introduction • 1
to rupture the formation. A propping material, transported by the frac fluid, is placed
in the fracture to prevent it from closing completely after the treatment. The
proppant-filled fracture thus creates a (highly) conductive flowpath towards the
wellbore.
Acid fracturing in carbonates is a stimulation technique in which acid is injected at

pressures above the fracturing pressure of the formation, so that a hydraulic fracture
is created. Usually a viscous pad is injected ahead of the acid to initiate the fracture,
then plain acid, gelled acid, foamed acid or emulsified acid is injected. Fracture
conductivity is created by the acid differentially etching the walls of the fracture,
i.e. the acid reacts nonuniformly with the fracture walls to provide channels that
will remain open to flow after the fracture has closed upon release of the fracturing
pressure. Acid fracturing can only be applied when the reaction rate between acid
and the rock is fast and complete, i.e. currently only in carbonate reservoirs using
HCl, possibly in combination with organic acids.
Many improvements have been made in carbonate acid stimulation since the first
commercial acid job in 1932. One of the most important advances has been the
recognition that fracturing was actually occurring in a majority of matrix acidising
treatments. Injection rates of most early acidising treatments were high enough to
cause fracturing, but this was called "breaking down" the formation. It was
recognised that a "breakdown" had to occur if the job was going to be a success.
Since such acidising is now recognised as a fracturing process, fracturing principles

(fracture mechanics and dynamics during stimulation, closure and production) are
being used to increase live acid penetration into the formation. On the other hand,
unlike failures with hydraulic fracturing with proppants, which can yield
catastrophic results and a wellbore full of sand, in acid fracturing it is impossible to
"screen out " an acid treatment. This lack of "feedback" has allowed the Industry to
ignore the consequences of inadequate acid fluid loss control. Part of the reason for
this is that even if an acid fracturing job turns into a large matrix acidising
treatment, the production from the well usually increases dramatically.
The choice of what acid (type, strength) to use in matrix acidising and what acid
fracturing technique to use, or even the choice of whether to carry out a matrix
treatment or acid fracturing treatment, is not always clear. In this manual,
guidelines will be presented to help deciding on when a carbonate stimulation
treatment is required, and on what will be the most successful type of treatment.
2 • Introduction Stimulation Field Guidelines - Carbonate Stimulation

Properties of carbonate rock
Composition
Carbonate rocks have been created by chemical and biological processes in a water
environment. Dissolved carbonates can reprecipitate when mixed with other
waters. Marine animal life often plays an important role in creating carbonate rocks
(shells, skeletons, etc.). Subsequent reactions can cause recrystallisation. This is
instrumental in the formation of dolomite, for instance. The presence of iron may
then result in the formation of siderite (FeCO3).
Limestones are composed of more than 50% carbonate minerals; of these, 50% or
more consist of calcite and/or aragonite which are both CaCO3. A small admixture
of clay particles or organic matter imparts a gray colour to limestones, which may
be white, gray, yellowish or blue in colour.
Dolomites are rocks which contain more than 50% of the minerals dolomite
[CaMg(CO3)2] and calcite (plus aragonite), with dolomite being more dominant.
Dolomitisation of carbonate rocks, i.e. the replacement of calcite by dolomite,
involves a contraction (an increase in porosity) of about 10-12%, if the reaction
proceeds as follows:
2 CaCO3 + Mg++ → CaMg(CO3) 2 + Ca++
However, subsequent precipitation of carbonates in pores may also destroy (part of)
the porosity formed as a result of dolomitisation. Figure 1 shows a schematic
classification of carbonates as a function of their composition.
Stimulation Field Guidelines - Carbonate Stimulation Properties of carbonate rock • 3

Impurities (Clay, silt, etc.)
Non-carbonates
50% 50%
Impure dolomite Impure Impure Impure limestone

calcareous dolomitic
dolomite limestone
10% 10%
Calcareous dolomite Dolomitic limestone
100% Dolomite 50% 100% Limestone
Carbonate rocks
Figure 1 - Classification of carbonates
Porosity/Permeability
Porosity of carbonates is of a different nature than the intergranular porosity of
sandstones. Primary porosity in limestones includes a.o. openings between the
individual constituent particles of detrital carbonate rocks and openings within the
skeletal and protective structures of invertebrates and within the tissue of algae.
Secondary porosity in carbonate rocks includes fractures due to contraction of
sediment during consolidation or because of mineralogic changes, or resulting from
crustal movements, from leaching in general, or intercrystalline pores produced by
dolomitisation.
Well-defined porosity/permeability relationships generally do not exist for

carbonate reservoirs. This is mostly due to the different nature of porosity and
permeability in carbonates (e.g. vuggy, fractured porosity vs. intergranular porosity
in sandstones). Moreover, although the permeability of many limestone and
dolomite reservoirs is very low, their productivity is often considerably higher than
one would expect from the permeability of the cores, because of the fractured
nature of many of these rocks. On the other hand, particularly in chalky limestones,
e.g. as found in the North Sea, the formation consists abundantly of coccospheres
and coccoliths, which may result in a very high porosity up to over 40%, with
permeabilities of less than 1 mD.
4 • Properties of carbonate rock Stimulation Field Guidelines - Carbonate Stimulation
Types of acid
Although a wide variety of carbonates is found in nature, their reaction with HCl -
and other, organic acids - is governed by a simple ionic reaction:
CO3-- + 2 H + ↔ CO2 + H2O
Apart from the possible formation of ferric hydroxide (due to the pick-up of iron
from the tubing) there are no complicating precipitation reactions, as is the case in
sandstones.
Hydrochloric acid, the most commonly used acid in carbonate stimulation, is

ordinarily supplied in concentrations of 32 – 36%. In well treatments, its normal
strength is 15% by weight, but the use of a higher concentration of 28% by weight
has also become more popular, in particular for dolomites, and shallow, low
temperature carbonate formations.
Organic acids, viz. acetic acid (CH3OOH), and formic acid (HCOOH) are weakly
ionised, slow-reacting acids and they are used in acidising carbonates primarily in
wells with high bottom hole temperatures (above 120 ºC), thus causing
significantly lower corrosion rates, or for conditions where prolongued reaction
times are required. For field use acetic acid solutions are normally diluted to 15%
or less. At concentrations greater than 15%, one of the reaction products, calcium
acetate, can precipitate. Similarly, the concentration of formic acid is normally
limited to 15% because of limited solubility of calcium formate.
Hydrochloric acid solutions can be blended with either formic or acetic acid. Such
mixtures are used to obtain more dissolving power per gallon of acid solution.
Formic and acetic acids can also be blended together.
Acid/carbonate dissolving power

The dissolving power of an acid is the volume of rock dissolved per unit volume of
acid. One litre of 15% w HCl will dissolve 222.5 g of CaCO3 which, with a density
of 2710 g/l amounts to a volume of 0.082 l. Hence, the dissolving power of 15% w
HCl for CaCO3 is 0.082.
Figure 2 lists values for the dissolving power of different acids and concentrations
for limestone (simple carbonate) and dolomite (mixed carbonate). It is useful when
comparing the maximum dissolution of rock of the different acids and it may be
used to estimate the total amount of acid required. However, in practice, for organic
acids it may take long before the total dissolving power is reached, i.e. their
reaction rate with carbonates may be relatively low. The dissolution of carbonate is
suppressed if CO2 is held in solution due to the pressure downhole. Also the
presence of oil can reduce the reaction rate.

Acid/carbonate dissolving power
Acid/rock combination Acid concentration
5% 10% 15% 30%
HCI/Limestone 0.026 0.053 0.082 0.175

Formic acid/Limestone 0.012 0.020 0.024 0.043
Acetic acid/Limestone 0.014 0.027 0.042 0.084
HCI/Dolomite 0.023 0.046 0.071 0.152
Formic acid/Dolomite 0.012 0.019 0.022 0.035
Acetic acid/Dolomite 0.012 0.024 0.036 0.072
* Data for organic acids have been adjusted for simulated downhole conditions (90 ºC, 140 bar)
Figure 2 - Dissolving power of various acids
Acid/rock reaction rate

The combination of chemical equilibrium and stoichiometry (i.e. the number of
molecules required for the dissolution of a given amount of solid) of a reaction
determines the thermodynamic end point of the reaction, without considering the
time involved to reach equilibrium. The progress in time of a reaction is reflected
in the reaction rate. This reaction rate determines the distance acid can travel away
from the wellbore (at a given pumprate) before it is completely spent, i.e. reached
equilibrium. The time required for the acid to spend, is called spending time, not to
be confused with acid reaction rate, which defines the rate at which acid spends.
The reaction rate is the combined effect of three processes (see Figure 3):
1. The diffusion of acid from the bulk of the solution to the rock surface.
2. The actual acid/rock reaction rate at the rock surface.
3. The diffusion of reaction products from the rock surface to the bulk of
the solution.
The slowest of these processes determines the actual overall acid spending time.
The diffusion processes involved are to a large extent controlled by the shear rate
of the fluid flowing in the porous medium. At high shear rates (high pump rates)
the reaction is truly chemical reaction rate controlled; at low pump rates the
diffusion process is more important. The actual behaviour of the acid/rock reaction
further depends on pressure, temperature, acid concentration, area/volume ratio of
the rock, and formation composition (chemical and physical). These aspects are
briefly discussed below.

Element of acid
1. Transport of acid to rock

surface
3. Transport of reaction
products to the bulk of
the acid phase
2. Chemical reaction at rock surface
Figure 3 - Pictorial view of acid/carbonate rock reaction
Pressure
The reaction rate between the acid and carbonate rock decreases with increasing
pressure, with the most noticeable effect at the low pressure range (< 28 bar) where
evolution of the CO2 in gaseous form is only partially suppressed. At higher
pressures (over 70 bar) the effect of pressure changes is negligible.
Temperature
Acid reaction rate increases directly with temperature, and a reaction rate at 60 –
70 ºC is effectively double that at 30 – 35 ºC.
Acid concentration
The initial reaction rate of hydrochloric acid with carbonate rock is nearly
proportional to its concentration up to 15-20%. Above 20% however, the increase
is less, reaching a maximum at around 25%, above which the rate actually
decreases.

Area/volume ratio
Area/volume ratio, that is the reactive surface area of rock in contact with a given
volume of acid, is inversely proportional to the pore channel diameter or fracture
width. The importance of this factor is illustrated by the following wide ranges of
ratios that may be encountered:
Ratio (sqft/gal)
Rock matrix : 10% porosity, 10 mD permeability 28,000 : 1

Fracture : 0.001 inch width 3,200 : 1
0.1 inch width 32 : 1
Wellbore : 4.0 inch diameter 1.6 : 1
With an extremely large surface area of rock matrix having small diameter channels
and narrow-width fractures, the reaction time of acid is very short (matter of
seconds). With wider fractures, or in a wellbore, acid will have an extended reaction
time because of the limited surface area for reaction.
Formation composition
The most important factor that governs the effectiveness of an acidising treatment
is the rock or formation composition. The reaction time and, therefore, the possible
penetration distance of live acid are the key factors in the acidising process.
Pore size distribution and pore shapes contribute to wide differences in acid
responses from one well treatment to the next, often within a given producing
interval. Thus it is this reaction factor (rock composition, texture and structure) that
renders it impractical to make carbonate acidising a pure science in application.

Stimulation selection considerations
Problem well identification

Sooner or later during the lifetime of almost any well, production problems will
occur. Production may decline, due to natural (e.g. produced fines), or induced (e.g.
mud remnants) near wellbore damage. Also the natural productivity may be low,
due to disappointing reservoir properties, such as low matrix permeability, or the
absence of a natural fracture system.
Generally, good candidates for stimulation are wells that will not flow at all due to
near wellbore damage or low permeability. In order to assess the cause and extent
of the problem, as a first step, well and production data should be collected and
analysed for aspects such as:
• Well completion (type and size of tubulars, perforations, downhole

chokes, etc.)
• Reservoir potential (what is the matrix permeability?)
• Existence and (potential) causes of damage
• If damage is present, what is the skin factor?
Depending on the outcome of such initial screening of above aspects, it can

generally be decided whether a matrix acidising treatment would be required (high
skin factor), or whether an acid fracturing treatment would be more effective (low
formation permeability).
Analysis of the skin factor

The skin factor (S) is a measure of the ease with which fluids flow from the
undisturbed reservoir to the wellbore. It represents the pressure drop due to
additional resistance to flow of reservoir fluid in the near-wellbore region.
Stimulation Field Guidelines - Carbonate Stimulation Stimulation selection considerations • 9

Note that a negative value of S will result in a pressure drop less than may be
expected on the basis of the reservoir permeability, i.e. this means that the well has
been stimulated, or that natural fractures exist, as is the case in many carbonate
formations.
The skin factor is frequently determined by means of the so-called Horner plot of
the pressure data from a pressure build-up test. It is a dimensionless mathematical
concept, and it represents the combined effect of a number of factors of which
formation damage is only one. For a proper interpretation of the skin (and hence for
the determination of the appropriate remedial action), the contribution of each
factor needs to be analysed. These factors comprise the following:
Stot : Total skin factor (Horner skin)

Sdam : Skin due to formation damage, positive. This is what we are trying to
remove by a matrix treatment.
Sperf : Skin due to limited perforation height, positive. This results from the well
not being perforated over the complete reservoir height, e.g. to minimise
gas or water coning.
Sturb : Skin due to turbulent (non-Darcy) flow, mainly applicable to gas flow,
positive. This is often caused by flow convergence due to an inadequate
number, and dimensions of perforations.
Sdev : Skin due to wellbore deviation, negative. At high deviation angles the
increased effective length of the reservoir section open to flow, increases
the "natural" well productivity.
Sgravel : Skin due to gravelpacking, usually positive. However, in principle
underreamed, open hole gravel packed wells might have a negative skin
due to the increased wellbore radius.
Sstim : Skin due to stimulation, negative. This is in particular true for
hydraulically/acid fractured wells.
Stemp : Skin due to temperature transition in water injectors, usually positive, due
to lower mobility of the cold injection water, compared to the hotter
formation water.
Sfiss : Skin due to the near-wellbore presence of natural fissures, negative. This
can greatly enhance well productivity.
The real skin due to damage (that portion of the total skin that can be removed by
matrix treatments) can thus be isolated from the total skin, using the following
formula:
Sdam = Stot – ( Sperf + Sturb + Sdev + Sgravel + Sstim + Stemp + Sfiss )
For each of these components, formulae have been derived by various authors.
Details may be found e.g. in the Production Handbook. The programme HORVIP
can also be used to roughly estimate Sdam. The skin components between brackets
in the above expression are also called pseudo-skin, and they cannot be removed
by acid.
10 • Stimulation selection considerations Stimulation Field Guidelines - Carbonate Stimulation

Damage classification
If the well appears to suffer from near-wellbore damage (i.e. removable by matrix
treatments), it should be attempted to classify the nature and extent of the damage.
In principle, formation damage is classified according to the process or operation
which caused the damage to develop:
• Impairment related to drilling, completion and workover operations.
• Impairment induced by the produced fluids (or in case of injection wells,

by the continuously injected fluids).
• Impairment as a result of injected fluids during specific operations, such

as (re)perforation, stimulation, etc.
The history of the well is essential for proper diagnosis of the nature and extent of
formation damage. It should be noted, that when attempting to remove damage in
matrix treatments, acid will only dissolve acid soluble materials. Many other forms
of formation damage, such as emulsion blocks, precipitation of organic material,
scale, etc. will not respond to treatment with acid. In fact, the problems may be
exacerbated. In carbonates such damage can still be bypassed with acid, if this is
not too deep. A large number of different treatments have been proposed to solve
these problems. Unfortunately, this group of damage removal treatments is not
supported by a great deal of science. Successful treatment design in these cases is
usually found by trial and error.
Candidate selection
In order to get maximum benefit from the stimulation expenditure, a proper
candidate and treatment selection is of paramount importance. The well and
reservoir requirements for successful stimulation are dictated by economical
constraints, which may be translated into the following rules of thumb:
• The reservoir must contain adequate volumes of moveable hydrocarbons,

i.e. the hydrocarbon saturation should be 30% or more.
• The well should produce with a (expected) watercut of 50% or less. If the
interval to be treated is close to the water table, the dissolution of e.g.
calcitic material contained in natural fractures may bring on early water
production, if removed from these fractures.
• The gross reservoir height for an acid fracturing treatment should be at

least 10 m, while for a matrix treatment, there is no minimum
requirement. In horizontal wells, which typically have long intervals, no
such limits exist.

• Permeability for a successful matrix treatment should be for gas reservoirs

> 1 mD, and for oil reservoirs > 20 mD. For an acid fracturing treatment
this ranges for gas reservoirs from 0.01 – 10 mD, and for oil reservoirs
from 1 – 50 mD.
• The reservoir pressure should be high enough to initiate and maintain

hydrocarbon flow towards the wellbore. Roughly speaking this means for
gas reservoirs: twice the abandonment pressure, and for oil reservoirs: not
more than 80% depletion.
• The production system (tubing, flowline, separators, etc.) should be able

to accommodate the extra production.
It is stressed that the above values are not rigid criteria, but merely guidelines for a
first selection of stimulation candidate wells. In general, there should be a clear
indication of substantial production gains, provided the treatment is planned and
executed in an optimum manner.
Selection of treatment
The selection of the stimulation technique is dependent on the type of reservoir, the
production objectives and the economics. Matrix acidising treatments are normally
less expensive than fracturing treatments, and they are applicable also in a
significant percentage of horizontal wells today. In fact, matrix acidising of vertical
and horizontal wells, completed in long sections, with adequate kh, should be
considered the preferred stimulation technique, followed by the more aggressive
acid fracturing technique.
Formation damage in sandstones is usually limited to the first few inches around
the wellbore. In carbonates, the radial distribution of such damage may be
significantly affected by the presence of vugs or fractures. As indicated in the
introduction, matrix stimulation in carbonates hinges on bypassing, rather than
actual removal of the damage by dissolution. The above considerations lead to a
number of different treatment procedures, depending on the extent of the damage
and the type of formation. Figure 4 indicates the preferred type of treatment for
different situations.
This selection chart is valid for both calcite and dolomite. However, if the
treatment temperature in dolomites is less than 60 ºC, typical values for "low
volume" and "high volume" will shift to higher values, or the use of heated acid
could be considered.

Type of Acid Matrix treatment **) *) Wormholes
rock/damage wash/soak low volume high volume CFA Acid frac (MHF) required
Plugged * * No
perforations
Shallow damage,
no vugs or fracs * (*) No
Shallow damage,
vugs or fracs * (*) (Yes)
Deep damage,
no vugs or fracs * Yes
Deep damage,
vugs or fracs * * (*) Yes
Deep or shallow damage,

low permeability with natural fracs * * (*) No/(n.a.)
Deep or shallow damage,

low permeability, no natural fracs * * n.a.
* CFA (Closed Fracture acidising) MHF (Massive Hydraulic Fracturing)

** Low volume: 0.2 - 0.4 m3/m, 15% HCl. High volume 1.2 - 2.0 m3/m, 15 - 28% HCl.
Figure 4 - Carbonate treatment selection chart
Matrix treatments
Matrix acidising is the most commonly used remedial stimulation treatment, also in
carbonates. Matrix stimulation is designed to remove (or in carbonates, also to
bypass) the skin due to damage, and it will not alter other components of the total
skin, such as partial reservoir penetration, collapsed tubulars and other mechanical
problems.
In Figure 5 some guidelines are given with regard to the choice of acid for matrix
acidising, depending on the type of carbonate rock.

Type of acid: Mud Acid 28% HCl 15% HCI Organic acid Retarded
Main (SFMA) HCI
Mineral composition
< 10% carbonate *) ++ + + + -
10 - 50% carbonate - + ++ + -
Impure dolomite - ++ ++ - -
Impure calcareous dolomite - + ++ + -
Impure dolomitic limestone - + ++ + -
Impure limestone - + ++ + -
Pure dolomite - ++ + - -
Calcareous dolomite - ++ + + -
Dolomitic limestone - + ++ + -
Pure limestone - + ++ + +
* Essentially sandstone acidising
Legend: + + Preferred + Reasonable - Poor
Figure 5 - Acid selection chart for carbonates
Acid fracturing treatments

Acid fracturing, also called fracture acidising, is a stimulation process whereby the
formation is treated with acid, usually hydrochloric acid, at an injection pressure
sufficient to fracture the formation or to open existing fractures. Acid fracturing is
generally limited to the cleaner, higher solubility, limestone or dolomite formations.
Dirty carbonate rocks are not candidates for acid fracturing, for the following
reasons:
• The creation of acid-etched flow channels will be impaired because of low

solubility of the rock.
• The release of insoluble materials will tend to plug any conductive etch
patterns created by the acid.
Acid fracturing is never used in the treatment of sandstones because acid, even
hydrofluoric acid (HF), will not adequately etch sandstone fracture faces. Even if
the sandstone is cemented with a carbonate cement, materials released through the
dissolution of the carbonate cement will plug the fracture.
The best application for acid fracturing may be in low-permeability carbonate

reservoirs, having a limited number of natural fissures. After the selection of a
candidate well for an acid fracturing treatment, a decision has to be made as to
which type of acid fracturing treatment to apply. In Figure 6, a simplified selection
scheme is shown.
Non- Soft Hard Fractured

carbonate carbonate carbonate carbonate
Propped frac* ++ ++ + -
Acid frac - - ++ +
WISPER - ++ ++ +
Propped acid frac - + - -
CFA - ++ ++ ++
* Including Skinfrac
Legend: + + Preferred + Reasonable - Poor
Figure 6 - Fracturing treatment selection chart for carbonates
Chalk formations can be a problem in acid fracturing because of soft formation

characteristics (the acid-etched fracture may collapse). Proppant fracturing may be
best in deep carbonate reservoirs, because the depth, high temperatures, and high
closure pressures are detrimental to the length and conductivity of an acid-etched
fracture. In addition, corrosion inhibition costs are usually high in these situations.

Treatment design
Having selected the acid stimulation well candidate, and the type of treatment, the
next step is to formulate a design. Stimulation treatment design of carbonate
formations is influenced by many factors, which are different for matrix treatments
and acid fracturing. For both types of treatment, software computer applications
have been developed, which can often also be used on-site to make final
adjustments to the treatment design, based on information obtained on-site (e.g. the
results of a minifrac, while preparing for an acid fracturing treatment). For matrix
treatments the programme STIM2001 is available since July 1999, while for acid
fracturing treatments AcidFrac can be used, which is contained in ShellFrac.
Guidelines for treatment design for both types of stimulation, are discussed/
presented later in this document.

Matrix treatments
Introduction
Formation damage in sandstones is usually limited to the first few inches around
the wellbore. In carbonates the radial distribution of such damage may be
significantly affected by the presence of vugs or natural fractures. Depending on the
extent of the damage, an acid wash or soak can be carried out, or a matrix
stimulation, which, depending on the results of a careful evaluation of the well’s
history and reservoir parameters, can be a treatment for relatively shallow damage
(2 to 3 ft around the wellbore), or a treatment for deep damage (> 5 ft around the
wellbore).
A treatment for shallow damage typically involves using 0.2 – 0.4 m3/m of 15% w
HCl at a pump rate of 0.004 m3/min/m (possibly somewhat higher in dolomites).
The low pump rate provides a long near-wellbore contact time, and may thus be
particularly suitable for removal of shallow damage in homogeneous carbonates. In
this process, most of the acid is spent near the wellbore, and wormholes will not
penetrate deeply into the formation.
A treatment for deep damage requires the formation of deeply penetrating

wormholes, and typically 1.2 – 2.0 m3/m of 15 – 28% w HCl is injected, usually at
the highest rate possible, not exceeding fracturing conditions, when using neat or
lightly gelled acids. When using emulsified acids, which are highly retarded, lower
pump rates can be used to obtain deeply penetrating wormholes.The formation of
long wormholes is discussed later in this chapter.
Acid wash or soak

The primary objective of an acid wash or soak is to break down perforations in new
completions or after workovers. A soak should allow enough time for the acid to
penetrate the perforations and to disperse (or in some cases dissolve) plugs caused
by mud, filtercakes, cement, etc. Wormholing should be avoided, in order not to
create highly conductive channels in which the acid spends rapidly, thereby leaving
the remainder of the wellbore untreated. Due to the stationary character of the
Stimulation Field Guidelines - Carbonate Stimulation Matrix treatments • 17
treatment, the rate at which the impairment is removed is very slow. Applying some
pressure can be used to invoke some fluid movement, but a maximum injection rate
of some 0.0002 m3/min/m should not be exceeded, to prevent wormholing. The
following treatment guidelines apply in perforated completions:
1. Use 28% w HCl to maximise the dissolving power, if corrosion aspects

permit.
2. Volume of acid approximately equal to the casing volume across the

perforated zone.
3. Acid preferably spotted across the perforated zone using coiled tubing.
4. Pre-clean tubing, if no coiled tubing can be applied, by circulating two

times the tubing content with 12% w HCl.
5. Add an iron sequestering agent to the acid.
6. If the presence of oil-based mud cake is suspected, an alcohol (e.g.

isopropyl alcohol), a mutual solvent or a dispersing surfactant should be
used.
7. Soaking time should be 12 hrs or longer.
Laboratory experiments may help to find optimum fluid composition and soaking
times. The corrosion inhibition schedule should be adapted to these long exposure
times. In some cases it can also be considered to use gelling agents during wellbore
cleanouts, to help transport fines out of the wellbore.
Matrix acidising
Matrix acidising is the most commonly used remedial stimulation treatment, also in
carbonate formations. Matrix acidising should only be considered when the native
permeability of the formation can provide hydrocarbon flow at economical rates
after the damage has been removed. It is not a solution to poor reservoir quality.
Typically, the lower permeability limit for matrix acidising is about 20 mD for an
oil well, and about 1 mD for a gas well, although this may very much depend on
the presence of a natural fracture system, particularly in horizontal wells.
The primary objective of matrix acidising in carbonates is to remove, but most of

all, to bypass damage, by creating wormholes and thus to increase the effective
wellbore radius and its average effective permeability. The formation is therefore
actually stimulated (unlike in sandstone reservoirs), and the skin value is
decreased, often to negative values of up to –5. In matrix acidising the intention
should be to inject acid below fracturing pressure. However, in practice, in many
cases the formation will be fractured, as said earlier, or natural fractures will be
18 • Matrix treatments Stimulation Field Guidelines - Carbonate Stimulation
opened, albeit not on purpose. Such treatments are still considered as - high rate -
matrix treatments, to differentiate them from purposely designed acid fracture
treatments.
Numerous studies reported in the literature regarding carbonate acidising have

shown that the dissolution pattern resulting from the acid - carbonate reaction can
be characterised as being one of three types, i.e.:
1) compact dissolution, in which most of the acid is spent near the formation
face,
2) the wormholing pattern, in which live acid is transported deeper into the
formation, and long wormholes will be the result,
3) uniform dissolution, in which many pores are enlarged, as typically occurs

in sandstone acidising.
The pattern created depends on acid flux, with the compact pattern created at
relatively low acid injection rates, the wormhole pattern developing at intermediate
injection rates, and the uniform dissolution pattern at high injection rates. It has also
been shown, that the acidising process is most efficient (defined as the process that
will enhance near-wellbore permeability to the greatest depth, with the smallest
amount of acid), when the wormholing pattern develops.
Both 15% and 28% HCl are frequently used in matrix acidising applications in
carbonates. The higher concentration of acid can dissolve more carbonate, but will
require more corrosion inhibitor, may cause wellbore stability problems, and may
have a greater tendency to create sludges and emulsions. Matrix acidising has been
successfully performed in carbonate wells with reservoir temperatures approaching
205 ºC, using organic acids or blends of formic and acetic acid. Recently the use of
chelating agents, such as ethylenediaminetetraacetic acid (EDTA) has been found
to provide the properties necessary for a matrix stimulation fluid in carbonate
formations (wormholes formed at low injection rates, of particular interest in
heterogeneous formations with zones of low injectivity), while not requiring
additives to control corrosion or asphaltic sludge precipitation.
Wormholing
Due to the fast reaction of HCl with carbonate rock, when pumping acid into the
formation, branched channels or wormholes are created. A picture of a wormhole
formed by acid reaction in carbonate rock is shown in Figure 7. Unless an acid soak
or wash is required, or a near-wellbore stimulation, wormholing is the preferred
dissolution process in matrix acidising of carbonates.

Figure 7 - Epoxy casting of wormhole structure
Wormholing depends mainly on three parameters:
• surface reaction rate, which determines how fast the acid reacts with the
rock surface,
• acid diffusion rate, which determines the rate at which acid travels from
the bulk of the fluid to the rock surface,
• acid injection rate into the matrix.
Wormholes will only form if the diffusion rate determines the overall acid spending
rate, which happens when the acid/rock reaction rate is high. In limestones,
wormholing with HCl occurs at temperatures above 0 ºC, as determined in
laboratory testing. Since in dolomite the reaction with HCl is slower, wormholing
will only occur at temperatures above 50 ºC.
The wormhole growth rate depends on acid diffusion and injection rate. If the
diffusion rate is high (when using plain HCl) the acid will spend quickly after
entering the formation. The wormhole growth rate will not be high and relatively
short and wide channels will be the result. This also happens when the acid
injection rate is low. A combination of high diffusion rate and low injection rate can
lead to a situation where wormholes will not form at all, and this can lead to face
dissolution or compact dissolution, which does not result in a reduction of the skin.
As described extensively in the literature, the occurrence of wormholes is likely if

convection (related to flow rate) equals the acid diffusion rate, and thus if the so-
called dimensionless Peclet number, representing the ratio of convection over
diffusion, equals unity. To prevent the formation of wormholes altogether, the
Peclet number should be less than unity, which corresponds to a maximum
injection rate of some 2 x 10-4 m3/min/m of perforated interval, assuming 13 shots
per meter (4 shots/ft). Except perhaps during "pressure soaking", this is an
impractically low value, and implies that under most circumstances the formation
of wormholes cannot be avoided. These wormholes are, however, relatively short
and wide, and therefore not suited for bypassing formation damage into the
reservoir.
A number of investigators found that, after reaching a maximum, the wormhole

growth rate, and hence the effective length of the wormholes, decreases with the
one third power of the Peclet number and hence the injection rate. This is shown in
Figure 8, which has been compiled with data from various authors. For HCl and
acids with a comparable reactivity with carbonates, a practical optimum rate is
obtained with a Peclet number of around 10. While Figure 8 is based on core flow
tests, and translation to field conditions is uncertain, with certain assumptions an
optimum pump rate for wormhole development can be calculated as a function of
the completion of the well, i.e. open hole or perforated. Figure 9 shows the
optimum pump rate (i.e. creating maximum wormhole length) as a function of the
perforation density. Also indicated is the value for open hole completion. This
graph is valid for calcite reacting with HCl and mixtures of HCl and acetic or
formic acid, and also for dolomite reacting with HCl above 60 ºC. At lower
temperatures, higher rates are required to reach optimum wormhole length.
1000
Rate of increase in wormhole length
(Core flow tests)

core length
100
1/3 slope
10
1
0.01 0.1 1 10 100
Injection rate (cc/min)
Figure 8 - Effect of injection rate on wormhole development

Injection rate (m3/min/m perforated)

0.007
0.006
0.005
0.004
0.003
0.002
0.002
0.001
0 10 20 30 40 50
Shot density (shots/m)
Legend: Perforated Open hole
Figure 9 - Injection rate for maximum wormhole length
While the wormholing efficiency decreases at injection rates above the optimum
rate, this is only a marginal effect, since the effective length of the wormholes
decreases only with the third power root of the Peclet number. In order to let live
acid to be transported as deeply as possible into the formation, it is frequently
recommended to pump acid at the highest rate possible, staying below fracturing
conditions, also to promote even distribution of acid over the entire interval to be
treated (in line with Paccaloni’s maximum-rate technique, which will be discussed
later in this document). In practice this means that the injection rate during the
treatment is adjusted (increased) continuously to keep the bottomhole pressure at a
high value, or just below fracturing pressure.
Increasing wormhole length

Another way of increasing wormhole length (instead of increasing the pump rate),
is to decrease the acid diffusion rate, not the acid reaction rate with the rock
surface. Acid systems with this property are called "retarded" systems. Gelled HCl
and emulsified HCl are the two diffusion retarded systems commonly used in
carbonate acidising. Traditionally, they have been in use as acid fracturing fluids,
but they have also found application in matrix acidising. Their higher viscosity
improves wellbore coverage, through a self-diverting effect.
Gelled acids are typically used to clean up formations that contain very large pores
or vugs, or fissured formations. The viscosity of the acid will keep it in the main
flow channel, where most of the damage is located. However, a potential problem
with polymer gelling agents is filtercake formation, which retards the surface
reaction rate and inhibits wormhole growth.
The use of emulsified acids is one of the best ways to retard the acid spending rate,
and their use for matrix treatments has recently received renewed attention in the
literature, with several applications in practice. Emulsified acids are effective
stimulation fluids at low flow rates, and their main advantage is a deep penetration,
particularly in heterogeneous carbonate formations, with zones of low injectivity.
In acid-internal emulsions, the acid (typically HCl of varying strengths) is present

as the internal phase, while the external phase is a produced crude or a refined
hydrocarbon. The volume fraction of the internal phase can range between 50 and
80%. A surfactant is necessary to generate an acid-in-oil emulsion.The acid droplet
size distribution of recently proposed emulsified acids is between 1 and 77 µm. The
size of these droplets is large compared to those in microemulsions. Economically,
coarse emulsions are more attractive than microemulsions because only a small
amount of emulsifier is required (< 3%), while the volume of the acid internal phase
can be high (up to 80%). In microemulsions, the volume of the acid phase is limited
(< 30 %) while the amount of emulsifying agent is often high (> 20 %).
In emulsified acid, with the acid as the internal phase, the retardation is caused by
the relatively low mobility of the acid droplets. As a result emulsified HCl will react
relatively slowly and can penetrate deeper into the formation, even at low injection
rates, before it is spent. Retardation results in deeper wormholes because the length
of the wormholes depends on the concentration of acid that reaches the tip of the
wormhole. The more retarded the acid system, the less acid is spent on the
wormhole surface area as it flows to the tip and the higher the concentration of acid
that reaches the tip. As a result these wormholes are longer, but also much narrower.
This will still result, however, in an increased effective permeability of the
stimulated (damaged) zone in which these wormholes develop around the wellbore,
by at least a factor of 10.
From the simple expression for skin factor:
S = ( k / ka – 1 ) ln ( ra / rw )
where k is the formation permeability and ka is the altered, effective permeability

of the area with wormholes, extending from the wellbore radius rw to a radius ra,
and with k/ka << 1, it can thus be observed that the skin value practically only
depends on the wormhole penetration depth. Therefore deeply penetrating
wormholes are to be preferred above short wormholes.This can be achieved by
using retarded acids, such as emulsified acid, which are particularly useful for tight
carbonate rock (low k) or deeply damaged rock.

Emulsions with acid as the outer phase have also been successfully applied in the
Middle East. Such systems also show retarding properties, despite the fact that acid
is in direct contact with the formation. Retardation is caused by the oil droplets
acting as physical barriers that reduce the rate rate of diffusion by increasing the
mean travel path of acid. The degree of retardation of these systems is significantly
less than that of acid-internal emulsions, however.
Applicability of emulsified acid

Emulsified acid systems may have a high viscosity. Therefore, the high pumping
pressure when pumping emulsified acid, may limit their use, and extensive
laboratory testing is required to determine the most optimum surfactant system
required for emulsification. Emulsified acid systems can be formulated in such a
way that the emulsion breaks when the acid spends. In this way, excessively high
treating pressures, caused by the flow of high viscosity emulsion in the formation,
can be avoided. The stability of the emulsified acid is a major concern, however,
and if the acid separates from the emulsion before reaching the zone to be treated,
it will not be retarded. Once prepared on the fly, they should be pumped
immediately (within one hour). However, if the emulsion breaks prematurely in the
wellbore due to operational problems, corrosion inhibitor effectiveness is
significantly reduced. The high viscosity of emulsified acid is useful in matrix
applications to improve the distribution of acid on different permeability zones
(heterogeneous carbonates).
In summary, emulsified acids are effective stimulation fluids at low flow rates.
Their main advantage is a deep penetration in conditions where plain HCl gives
compact dissolution patterns, i.e. in zones of low injectivity.
One major drawback of the application of in particular acid-in-oil emulsions may

be that they will not be allowed for environmental considerations in some areas,
such as in the North Sea.
Furthermore, it is to be noted that a reduction in the acid reaction rate already

occurs in oil-bearing formations, hence the applicability of emulsified acids may be
limited in oil-bearing formations.

Diversion
Effective diversion of reactive acid to achieve uniform treatment of the entire
interval, is necessary for the successful matrix acidising in carbonates. When
injected, the acid naturally tends to follow the path of least resistance, that is to the
higher permeability zone and/or least damaged zone. Since damage must be removed
from the entire producing interval, effective diversion techniques must be employed.
Diversion is necessary when treating perforated or open hole sections greater than 30
ft. The problem of correct placement of the acid is therefore compounded in
horizontal wells, due to the often significant lengths of the section to be treated.
Diversion in carbonates is generally more difficult than in sandstones because of

the ability of the highly reactive HCl to drastically increase permeability in
carbonate rock as it reacts in the pore spaces and flow channels of the matrix. For
example, most oil soluble resins are not useful for diversion in acidising of
carbonates since the resin particles are not able to bridge the large flow spaces
created by the acid reaction. Other solids such as benzoic acid flakes and rock salt
also have limited application.
Apart from particulate diverters, a number of methods and techniques which are
commonly used for acid diversion in matrix treatments include mechanical tools
(packers, bridge plugs), ball sealers, coiled tubing, gelled acids (also with pH
sensitive crosslinkers), emulsified acids and foams. These placement techniques are
discussed in more detail later in this document.
Treatment fluids
A lot of different acid formulations have emerged, and disappeared again, over the
years. The principal acid has always been (and still is) hydrochloric acid. Most
novel acid formulations were aimed at retardation of the acid spending rate by
viscosifying or emulsifying the acid which slows down the acid diffusion rate. The
retarded nature of these acids, especially emulsified acids, results in deeper
wormholes since more live acid can thus reach the tip of the wormholes.
Service companies have marketed a number of alternatives for retarding HCl.

These acids can be divided into two main groups:
• Chemically retarded acids, which, by adding retarders such as alkyl

sulfonates, alkyl phosphonates or alkyl amines to acid, reduce the reaction
rate by forming hydrophobic films on carbonate surfaces with a protective
film which acts as a barrier to slow down acid attack.
• Emulsified acids, which, by slowing down the mobility of acid (droplets),

result in an overall reduction in acid spending rate.

An overview of some commercially available retarded acids is given in Figure 10.

It should be noted, that the retardation factor for plain HCl at any concentration, is
one. Therefore, a retarded acid has a retardation factor greater than one. Acid-
external emulsions have a retardation factor of around 2, while acid-internal
emulsions have a retardation factor of around 10, depending on the temperature of
the formation.
The acids are usually formulated with a number of additives aimed at combating
various problems. A wide range of additives is commercially available. Although
the usefulness of some of these additives can be questioned, the acid should at least
contain a corrosion inhibitor. Otherwise the strong acid will attack the tubular
goods, wellhead, etc. Furthermore, pure HCl flushes should almost always contain
a sequestering agent. This will prevent precipitation of iron hydroxide (from iron
dissolved from the tubing and certain iron containing minerals) as the acid is
spending inside the pores of the formation rock.
Acid system Acid type Retardation

15% 28%
HCI plain n.a. <1-2
SGA-HT linear gel <2 unstable
DSGA linear gel 2-5 2-5
XL 1580 X-linked gel 2-5 unstable
Super Sol Organic/HCI <2 n.a.
Super X Oil external emulsion >5 2-5
Poly emulsion acid Acid external emulsion 2-5 2-5
CRA-78 Chemically retarded <1-2 <2
DGA-200 Surfactant viscosifier <2 <2
Retardation factor = reaction rate of plain 15% HCI / reaction rate of retarded acid
Figure 10 - Retardation effectiveness of commercial acid systems

Acid fracturing
Introduction
Acid fracturing is a well stimulation process in which either acid alone (usually
HCl), or a viscous nonreactive fluid (the pad fluid) consisting of linear or cross-
linked guar based fluid preceding the acid, is injected into a carbonate formation at
a pressure sufficient to fracture the formation. As the acid flows along the fracture,
portions of the fracture face are dissolved. Since flowing acid tends to etch the
fracture walls in a nonuniform manner, conductive channels are created which
usually remain open when the fracture closes. When straight acid is used without a
pad fluid, the fracture will generally be short and narrow, since the rate of fluid loss
for acid is very high, due to its high reactivity with the carbonate rock. If a viscous
pad is used, a relatively long and wide fracture will be formed, which will begin to
close as the acid is injected, thereby etching the fracture walls to create conductive
channels.
The basic principles and objectives of acid fracturing are the same as for propped
fracturing treatments in sandstones. In both cases the goal is to produce a
conductive fracture with sufficient length to allow more effective drainage of the
reservoir. The major difference is how fracture conductivity is achieved. In propped
fracturing treatments, sand or other propping agent is placed in the fracture to
prevent closure when pressure is released. Acid fracturing basically relies on non-
uniform etching of fracture faces to provide the required conductivities. Acid
fracturing can only be applied when the reaction rate between acid and the rock is
fast and complete, i.e. currently only in carbonate reservoirs using HCl, possibly
combined with organic acids. However, occasionally treatments have been
successful in some sandstone formations, containing carbonate-filled natural
fractures.
Acid fracturing is not generally recommended for formations that are less than 80%
soluble in acid, the preferred solubility is greater than 90%. However, if acid
solubilities are between 75 and 85%, and cores are available, special laboratory
tests can be used to determine whether to apply acid fracturing or propped fracture
treatments, by analysing the differential etching patterns and flow capacity values
generated in these tests. Fracture conductivity tests are discussed later in this
document.
Stimulation Field Guidelines - Carbonate Stimulation Acid fracturing • 27
Controlling factors
The success of an acid fracturing treatment is determined by two characteristics of
the fracture formed by the acid reaction, viz.:
• length of the conductive fracture,
• conductivity of the fracture.
These characteristics are briefly discussed below.
Length of etched fracture

The effective fracture length is controlled by the acid fluid-loss characteristics and
the acid spending during its travel down the fracture.
Excessive fluid loss can severely limit fracture growth. Wormholes formed by the
preferential reaction of acid through large pores of the rock are the main
mechanism by which excessive fluid loss occurs. In general acid fluid-loss
additives are not being used extensively because of lack of performance and cost
limitations. Most common techniques for fluid loss control involve the use of a
viscous pad preceding the acid. Often multiple stages of nonreactive viscous pad
are being used, which are designed to enter and seal wormholes created by the acid
stages. The nonacidic pad can be a crosslinked, gelled water, that has some
tolerance to a low-pH environment. By using alternating acid and gel stages, leak
off into wormholes is controlled.
Fine particulate material can also be added to the pad stages in aid of fluid-loss
control. Such material fills/bridges the wormholes and natural fractures. The most
commonly used material is 100-mesh sand, usually added at a concentration of
120-360 kg/m3. Oil soluble resins and rock salt can also be considered for this
purpose.
Acid fluid loss can also be reduced by gelling or emulsifying the acid itself. This
method of control has become widely used since the development of more acid-
stable thickening agents, such as xanthan biopolymers and certain surfactants.
Gelled or emulsified acid systems have viscosities several times higher than
straight acid, thus making it unnecessary to use viscous pads in some cases.
The use of foamed acids can be one of the most effective methods for controlling
acid fluid loss. Fluid-loss control is further enhanced by the use of a viscous pad
preceding the foamed acid. However, foaming the acid does reduce the effective
amount of acid available for etching, since there is less acid present per unit volume
injected. As a result, 28% HCl should be used in preparing the foamed acid to
maximise the amount of acid available for fracture etching.
28 • Acid fracturing Stimulation Field Guidelines - Carbonate Stimulation

As to the acid spending in the fracture, the acid spending rate usually depends on
the rate of acid transfer to the wall of the fracture, and not on the acid reaction
kinetics. As a result, the flow rate of the acid in the fracture and the fracture width
are major factors in controlling acid spending. As an illustration of the importance
of fracture width, an increase of fracture width from 0.1 to 0.2 inch results in an
increase in acid penetration distance from 120 to 177 ft. Further factors of
importance to acid spending are volume of acid used, acid concentration, the
formation temperature and the composition of the formation.
Various materials and treating techniques have been developed for controlling the
acid spending rate. These are quite similar to those used for fluid-loss control, but
their action is quite different. One of the most common methods involves the
injection of a viscous nonreactive pad preceding the acid. The pad reduces the acid
spending rate by increasing the fracture width and cooling of the fracture surfaces.
Emulsification is also a commonly used means of retarding the acid spending rate,
like in matrix acidising. Oil-outside emulsions are the most common, because the
external oil phase physically separates the acid from the reactive carbonate surface.
Gelled acids can also be used in acid fracturing treatments, and they are usually
considered to be retarded. However, some controversy exists in the literature,
where it is stated that in reality the amount of retardation provided by the increased
acid viscosity is probably small, and gelling the acid may actually accelerate the
acid reaction rate under flowing conditions, thought to be due to improved transport
of reaction products from the carbonate surface by the more viscous acid. On the
other hand, comparable tests performed under conditions simulating leak off into
the fracture face, showed that the acid reaction rate was reduced as a result of the
gelling agent depositing a filter cake on the surface of the fracture.
Fracture conductivity
Acid must react with the walls of the fracture to form a channel that remains open
after acid fracturing treatment. Flow channels can be formed as a result of an
uneven reaction with the rock surface or preferential reaction with minerals
heterogeneously distributed in the formation. The conductivity of the fracture is
determined by the volume of rock dissolved, the roughness of the etched rock
surface, rock strength and closure stress. If the reaction rate is too high, then the
acid will tend to spend excessively at or near the wellbore, resulting in poor
conductivity closer to the tip of the fracture. High reaction rates can also result in
too much rock volume being dissolved, which may not necessarily lead to higher
conductivities once the fracture closes, especially in soft carbonates. On the other
hand, if the reaction rate is too slow, then the amount of rock dissolved may be
insufficient to prevent fracture closure.
Various techniques and materials have been developed, aimed at maximising

fracture conductivity. The technique most commonly used involves the injection of
a viscous pad ahead of the acid. The presence of this higher viscosity fluid in the
fracture promotes viscous fingering of the thinner acid which follows. This
selective acid flow also increases penetration distance and tends to create deep
channels with good conductivity. Propping agents have also been used in acid
fracturing treatments to obtain higher conductivities. This is discussed in the next
section.
Propped acid fracturing

In very soft carbonates, the walls of the etched channel may be too weak to
withstand the closing pressure of the fracture under producing conditions. The
channel may lose its conductivity, which will render the stimulation totally
ineffective. To prevent this, proppant may be used to keep the channels open. Such
a treatment then comprises an acid fracturing treatment followed by a proppant
stage. The advantage of this approach over conventional propped fracturing, is that
a relatively high fracture conductivity can be obtained with relatively low proppant
concentrations. However, practical results (offshore Denmark and Norway) show a
rapid decline of production after the initial increase in production. With the
introduction of more sophisticated fluids and equipment for conventional
fracturing, allowing more aggressive designs with higher sand concentrations, the
application of propped acid fracturing has virtually been abandoned, being replaced
by "conventional" propped hydraulic fracturing in such soft carbonates.
Closed fracture acidising (CFA)

On a number of occasions, e.g. in fractured carbonates, or soft chalks after an (acid)
fracture treatment, the resulting fracture conductivity may be too low for a
sustained higher productivity. This can be due to the etched fracture face being too
smooth, or it softens with acid, or the formation strength is insufficient to prevent
closure due to the overburden pressure.
The CFA procedure has been developed as an alternative solution to the problem of
fracture closure which sometimes results from standard acid fracturing. This
procedure consists of the injection of a low viscosity acid at a pressure just below
the fracture closure pressure. Acid flows out into the closed fracture, which still
forms a preferential flow path for the acid, thereby rapidly dissolving much more
of the formation than if it were flowing in an open fracture. This is due to the very
high surface over volume ratio of the closed fracture, as was discussed earlier in
this document. This causes a wormhole type penetration of the acid along the
original fracture plane. Since only a small portion of the overall fracture face will
be dissolved into relatively deep channels or grooves, the remaining unetched
fracture face can hold these channels open under very severe formation closure
conditions, without completely collapsing the etched channels. This is especially
beneficial in chalk formations.
The CFA technique is also applicable in previously fractured formations, as re-
treatment, possibly even after several years, and in naturally fractured formations,
in which case wormholes will then be formed along the natural fracture plane.
WISPER technique
For an acid fracturing treatment to be successful, the pattern of flow channels
formed must be irregular: if the acid merely dissolves a thin layer of the entire
surface of the fracture, the fracture surface will close up when the pressure is
removed, and productivity will not be improved.
fracture
cement
casing
low-viscosity prepad
high-viscosity pad
acid etched channel
perforations
Figure 11 - Artist’s impression of the WISPER process
This is really a problem only in homogeneous carbonate rock. In heterogeneous

carbonates the nonuniform structure of the rock ensures that the etching pattern is
irregular enough. The right etching pattern in homogeneous carbonates, such as
chalks, can be achieved with the WISPER technique, an acronym for WIdely
SPaced Etched Ridges, an acid fracturing process which was developed, and has
been patented by Shell. In this process, the well is perforated at widely spaced
intervals, e.g. 2 ft of high-density perforations (4 spf or more) every 5 ft. A fracture,
designed to penetrate deeply into the rock, is created by injecting a highly viscous
pad. The low-viscosity acid is then pumped into the viscous preflush. Because of
the difference in viscosity between the pad and the acid, the latter fingers its way
through the viscous pad in a dendritic pattern. A schematic of the WISPER process
is shown in Figure 11. By careful control of the perforation spacing and the
viscosity difference, it is possible to create long fingers of acid that do not merge
with each other. Consequently, the etched pattern dissolved in the rock reaches deep
into the reservoir. This method of stimulation has been used with great success in
fields that were otherwise uneconomic to produce in the North Sea and the Middle
East.
The Shell Group of Companies has done extensive laboratory work in order to
optimise the fingering of acid through a viscous pad. This work showed that one of
the controlling parameters is to maintain the viscosity ratio between the pad and
acid to around a value of 300 in order not to have the fingers merge together.
Furthermore, a distinction must be made between linear and radial fingering. The
former is produced by flow in a fracture that is coplanar with the well, and the latter
by flow in a fracture that lies in a plane perpendicular to the well. Since hydraulic
fracturing occurs preferentially perpendicular to the direction of minimum in-situ
stress, the linear case may be assumed to apply to (near) vertical wells, and the
radial case to horizontal or deviated wells. The difference between linear and radial
fingering is illustrated in Figure 12.
Vertical well Horizontal well
Figure 12 - Influence of wellbore orientation on viscous fingering pattern
Of all the viscous gels investigated as to the development of viscous fingers that do
not merge, but remain distinct, biopolymers have clear advantages over other gels,
such as HPG gel, for WISPER applications. However, their application may be
limited, due to their high cost.
AcidFrac software application

Several acid fracturing models have been developed since 1970. The purpose of
such calculations is to obtain the acid-etched width, length and conductivity of the
created fracture. To calculate the amount of rock dissolved, an acid reaction model
must be used to calculate the amount of acid spent.
ShellFrac 4.0 (SIEP 98-5525, March 1998) is a system that conforms to Windows
standard commands, and that can be used to perform the complete process of on-
site optimisation of a fracture treatment schedule; from optimising the minifrac
volumes, analysing minifrac/microfrac shut-in pressure decline tests to the
subsequent optimisation of the fracture treatment schedule.
AcidFrac, which is part of ShellFrac, can evaluate the fracture dimensions created
by a given pad and acid volume, given the values of overpressure at shut-in, overall
leakoff coefficient and fracture closure pressure determined using FracTest (used to
analyse the minifrac data and provide the parameters for fracture treatment design,
e.g. leak-off coefficient and overpressure). For further details, the reader is referred
to the above referenced document.

Diversion techniques
Introduction
In any stimulation treatment, proper placement of the acid is a critical factor to the
success of the treatment. If the acid is not directed to the intended interval, the
treatment objective, production improvement, may be missed altogether. The
problem of proper placement is compounded in horizontal wells, often containing
a potentially producing interval covering several hundred feet. Moreover, diversion
in carbonates is generally more difficult than in sandstones, because of the ability
of the highly reactive HCl to drastically increase permeability in carbonate rock as
it reacts in the pore spaces and flow channels of the matrix.
There are various diversion techniques available for both matrix acidising and acid
fracturing of carbonates, viz.:
• mechanical techniques,
• use of particulate material,
• use of viscosified fluids, and emulsified acids,
• use of foams.
The latter two are less applicable as diversion techniques in acid fracturing
treatments.
For matrix acidising treatments, in recent years, injection at the highest possible
matrix treating rate, not exceeding fracturing conditions (the MAPDIR technique),
has been promoted as the best means of assuring sufficient acid placement in all zones.
Computer models have been developed for the simulation of various placement
techniques. These are included in STIM2001, a joint Halliburton/Shell computer
programme for the design of matrix treatments, available since July 1999.
The above placement and diversion techniques will be briefly discussed in the
following sections.
Stimulation Field Guidelines - Carbonate Stimulation Diversion techniques • 35
Mechanical techniques
These techniques use mechanical means to isolate a particular zone for injection, or
selective placement of stimulation fluids. Except for ballsealers (see below),
mechanical diversion methods are usually more reliable than other diversion
techniques. However, they are not effective in wells where zonal isolation has not
been achieved through effective cementation of the production casing.
Packer and bridge plug arrangements

Complete zonal isolation is obtained by packing-off a section of the completion
interval, for instance by a combination of a retrievable packer and a retrievable
bridge plug. This effective method is very expensive, however, and requires a rig.
Also the perforation intervals should include blank sections to allow setting of the
packers. In most cases, this is therefore not an economically viable system.
For horizontal wells, which frequently have been completed as open hole
completions, or with slotted/pre-drilled uncemented liner, this mechanical method
is not suitable. External casing packers (ECPs) may help to improve wellbore fluid
management by compartmentalising the annulus, although the optimum ECP
position for remedial treatments already should be known when the completion is
designed. Whilst in principle many ECPs could be used to deal with the uncertainty
in the optimum position, their number is usually restricted to avoid deployment
problems and to reduce initial well costs.
Selective Placement Tool

A straddle-packer selective placement tool has been developed that is run on coiled
tubing, can pass through production tubing and can be repeatedly set in casing. It
is fitted with high-expansion straddle-packers. Nowsco UK Ltd. was the first
company to bring such a tool on the market; several other companies (Halliburton,
DS, Baker) followed.
The current tool has the following limitations that need to be borne in mind.
• It has a maximum operating temperature of 110 ºC.
• The rubbers applied in the tool are sensitive to most solvents, particularly
those with a high aromatic hydrocarbon content.
A number of applications for the SPT have been identified. In the context of this
manual the most relevant applications are:
36 • Diversion techniques Stimulation Field Guidelines - Carbonate Stimulation

• Acid stimulation of specific intervals with optimum volumes of fluid.
• Treatment of highly inhomogeneous carbonate formations.
In most cases of chemical treatment, the SPT is the most economical means of
ensuring 100% selectivity.
The SPT, when run on coiled tubing, can also be used for matrix acidising in cased
horizontal holes for zones to be selectively treated, but this requires a good
casing/formation seal, which is not always available.
The SPT cannot be used in acid fracturing treatments, since the coiled tubing on
which it is run, precludes pressures and flowrates required for fracturing.
Coiled tubing (CT)

The use of coiled tubing can be considered for the placement of matrix treating
fluids, both in cased and open hole situations, especially when long intervals in
horizontal wells are to be treated. The combination of employing coiled tubing and
a (temporarily cross-linked) gelled acid system, or foam as a diverting agent, has
proved effective as a diversion process in carbonate formations in horizontal wells.
Acid can be spotted through the CT, possibly while it is being withdrawn from the
toe towards the heel of the horizontal section. Other CT-based methods in matrix
acidising of horizontal wells, involve either circulating up the CT/tubing annulus,
or bullheading acid or inert fluid along this annulus. Moreover, the use of CT with
a jetting tool, provides an excellent means of establishing direct communication of
the acid with the formation face in long open hole sections (vertical or horizontal).
Ballsealers
Ballsealers are small rubber coated nylon balls. They are available in a density
range of 0.9 – 1.4 g/cm3. They have been often used to divert fluids, both in matrix
acidising treatments and in acid fracturing treatments over long or multiple
intervals. This diversion method has been successfully applied both in vertical and
horizontal perforated wells. The absence of perforations in open hole completions
means that ballsealers cannot be applied in this situation.
The action of ballsealers is based on the idea that the balls are carried along with
the stimulation fluid towards a perforation, which they will subsequently shut off.
In order for the balls to seat, the fluid velocity needs to be sufficiently high. As a
guideline, the following values have been used: 3 bpm in a 4.5" casing, 4 bpm in
5.5" casing, and 7 bpm in 7" casing. The perforations should be of a consistent size,
round and free from burrs. Ballsealers require a pressure differential of 100 – 200
psi to seat efficiently. This should be kept in mind when planning the number of
perforations to be balled, and the treament pump rate. In order to compensate for
non-seating balls, the number of balls that is being used is usually 10-20% higher
than the number of perforations believed to be taking the fluid.
A computer programme (BALLSEAL) has been developed, which simulates the

behaviour of balls under various circumstances. BALLSEAL is available under
STIM2001.
Buoyant balls have a higher seating efficiency than non-buoyant balls. However,
buoyant balls have the disadvantage that they will be produced back to surface. As
a compromise, the density of the balls can be chosen such that they will be buoyant
in the treatment fluid, but have a density that is greater than the produced fluids.
The balls will then sink to the sump, and can be left at the bottom of the well.
However, during a workover they can still pose problems. In deviated or horizontal
wells, buoyant ballsealers tend to travel along the topside of the wellbore, thus
reducing the chance of seating on perforations with other orientations than wellbore
topside. Buoyant ballsealers may therefore be less applicable in deviated or
horizontal wells, particularly with zero degree phased perforations.
As to the quality control on density of commercial ballsealers, it has been observed

that on average 20 – 30% of the ballsealers deviate more than the 5% scatter,
specified by the manufacturers. Especially for the 0.9 – 1.0 g/cm3 density
ballsealers, such deviations cannot be tolerated. It is therefore suggested for field
treatments, to check the densities of the balls on-site by immersing them in fluids
with the desired densities (upper and lower specification limit, e.g. methanol/water
mixtures). Only ballsealers that float in the high-density fluid and that sink in the
low-density fluid should be accepted.
Recently water soluble balls, constructed from collagen, have been developed.
This eliminates a range of potential difficulties, such as the possibility that the
balls will remain downhole where they can make drilling out bridge plugs
difficult, failure to unplug during flow back in low pressure reservoirs. Balls,
which are belatedly produced at surface, can block chokes. The collagen balls vary
more in diameter and show more imperfections on their surface than do balls made
from rubber. The balls are stable in hydrocarbons and have a specific gravity of
1.2 g/cm3. The solubility rate increases with increasing temperature and
decreasing pH. Tests show that the balls can hold a pressure differential of 19.2
MPa at 50 ºC for 2 hours before failure. They have been used up to 120 ºC, for a
short duration (20 minutes). This limits their use to relatively short stimulation
jobs, and so their usefulness in treating long wells with multiple zones will be
limited.

Particulate diverting agents
This technique uses chemical diverters, e.g. benzoic acid and its derivatives, to
create a diverter cake, either at the perforation or at the formation face.
The buildup of a diverter cake in perforations can be simulated with the computer
programme PLACE, which is part of STIM2001.
Chemical diverters fall into two types:
1. Those forming a thin, but very low-permeability film on the formation face.
They can effectively plug off a high injectivity or thief zone. However, there
is the risk of almost total injectivity loss if too much diverter is used.
Examples are fine grained oil soluble resins (particle size < 10 micron) and
"liquid diverters", e.g. Halliburton’s Matriseal O or J363 of DS.
2. Those creating a relatively high-permeability diverter cake, usually by

filling up the perforation. Once the diverter cake is formed, distribution of
the treatment fluids is controlled by the resistance of the cake rather than
by the varying resistance of the formation. All zones will receive similar
volumes of treatment fluids. Examples are commercial grades of benzoic
acid (e.g. TLC-80, Halliburton), salts of benzoic acids (J 363, DS or Divert
III, BJ, both sodium benzoate; see remarks below) and coarse grades of oil
soluble resins (> 50 micron).
Neither types of chemical diverters require zonal isolation to work. However, the
main disadvantage is that, if they are not removed by the produced fluids, they can
cause impairment too. In most cases clean-up is rather slow. Many cases of slow
clean-up after diverted acid stimulation treatments may be attributed to the diverter
not (completely) dissolving in the back-produced fluids.
Nevertheless, chemical diverting agents, in particular benzoic acid, can be used

successfully, provided a number of design rules are observed:
1. In general we suggest to use straight benzoic acid (rather than salts of

benzoic acid), since it is soluble in formation water and oil, and it
sublimates in gas.
2. The effective downhole particle size of benzoic acid is influenced by the

type and order of addition of surfactants and inhibitors. The preferred
order of mixing is surfactant, inhibitor and finally the diverter. Acidic
slurries prepared in this way show reasonably stable particles for 1 – 2
hours.
3. In order to maintain the permeability of the diverter cake, continuous

addition of benzoic acid throughout the treatment is preferred. Figure 13
shows the minimum concentration to be applied for effective diversion.
4. During acid fracturing treatments of uncased horizontal wells, the

simplest method to isolate one created fracture from the next, is to pump
blocking material (rock salt, benzoic acid or mothballs) in batches
between the stages of a continuous large fracture treatment. Unfortunately
this method does not provide much control over spacing of the fracture
initiation points along the wellbore.
5. Cake build-up is a function of concentration, inflow profile, length of

perforated interval, shot density, injection rate, etc. Note that benzoic acid
is slightly soluble in acid: at concentrations of less than 1 kg/m3 no cake
will be formed. This solubility increases with temperature. At
temperatures above 90 ºC, the solubility of benzoic acid is so high, that its
use becomes impractical.
600
Av. particle size (µm)
500
No cake build up
400
300
200
Stable diverter cake
100
0
2 4 6 8 10 12
Concentration (kg/m3)
Figure 13 - Stability of benzoic acid diverter cake in hydrochloric acid
The use of particulate diversion material for matrix acidising treatments in

horizontal wells, which can be so long that cementing and perforating options are
discarded due to their cost, would require so many diverter stages, that such
treatment would be prohibitively expensive. As a rough estimate, the diverting
agent on its own would cost about $ 5000,= for every 100 ft of open hole section.
In such a case the preferred diverting technique consists of pumping viscous banks
into sections of high fluid intake. This is further discussed in the next section.

Viscosified fluids
Viscosified fluids, or acids viscosified by polymer (or by foam), are probably
applicable to all completion types. They are of particular benefit in horizontal, open
hole wells, where many other diversion and selective-placement techniques cannot
be applied. The diversion behaviour of viscosified fluids can be simulated with the
computer programme PLACE.
In the use of viscosified fluids, viscous pills (e.g. polymer solution) are injected in
between acid flushes. In order to work, a number of prerequisites should be
fulfilled:
• An adequate volume of polymer must be placed in the unimpaired zone.
• The subsequent acid must have direct access to the impairment.
• The polymer must not cause impairment, and must be easily removed by
the produced fluids.
In practice, these requirements, especially the latter, are difficult to meet. Currently
available products, (Temblok systems (Halliburton), Protectozone (D/S), Clean
plug (BJ)), have been used with limited success.
A better alternative is to gel the acid itself, to be injected. The requirements for
successful application of gelled acids are:
• The acid gel should have sufficiently high viscosity at the treatment
temperature for a sufficient length of time.
• The acid gel should lose its viscosity after treatment to promote rapid
clean-up.
With viscosified acid, the mechanism of diversion is viscous diversion, through the
increase in flow resistance in higher-permeability regions, which have been taking
the treatment fluid first. Since gelled acid is a shear-thinning (non-Newtonian)
fluid, its viscosity also increases further away from the wellbore, thereby blocking
the following acid, and diverting it to other, less permeable zones. In such a way
the gelled acid acts as a self-diverting system. Biopolymer acid gels satisfy both the
above criteria and act as self-diverting acid systems. Moreover, such shear-thinning
behaviour also has the advantage of enabling the operator to pump the viscous acid
at relatively high rates.
For Shellflo-S (a biopolymer in use in the late eighties), the transition temperature at
which the gel loses its viscosity, is 65 ºC, but this can be adjusted over a fairly wide
range of temperature with various chemicals, including some acids. For instance,
addition of 5% formic acid increases the transition temperature to around 74 ºC.
Gelation of acid with Shellflo-S is sensitive to iron (III) ions. Therefore a reducing
agent (e.g. erythorbic acid or vitamin C) has to be added. N.B. an ordinary
sequestering agent, such as citric acid, is not effective here. Contrary to the non-
acid Shellflo-S gels, the acid gel loses its viscosity permanently, due to rapid
chemical degradation of the polymer, which takes place above the transition
temperature. These properties make a system with such biopolymers particularly
useful for the removal of shallow damage, e.g. caused by mud remnants. Shellflo-S
is no longer available as a commercial product, but other similar products are
available from several oil-field manufacturers (e.g. Servo, Kelco).
The following procedure when using gelled acids, has been applied successfully:
1. Run coiled tubing to below the perforated interval; if a large sump is

present, a bridge plug may be placed to reduce the dead volume.
2. Inject the required volume of gelled acid by pumping through both the
coiled tubing and the coiled tubing/tubing annulus, maintaining the same
rate through both conduits.
3. Displace the acid with a suitable brine.
4. Close the well in for 12-24 hours to allow for sufficient reaction time
(depending on the type of acid and damage) and proper breakdown of the
viscosity.
Other systems that have been proposed and used for viscous acid diversion consist
of acid mixed with a gelling agent and a pH sensitive crosslinker. Initial spending of
the acid during leakoff and wormholing will produce a rise in pH to a value of 2-3,
which initiates a significant increase in viscosity due to crosslinking. The cross-
linked gel will effectively stop any further fluid invasion, and divert subsequent
neat acid stages to different parts of the zone. The crosslink will break upon further
spending, and at a pH value of above 4, the viscosity of the fluid will return to its
original value. Such a pH sensitive crosslinked gel is ideally suited for acid
diversion in long intervals, and a number of treatments have been successfully
performed in long horizontal open hole completions in the North Sea and the
Middle East. Utilisation of coiled tubing enhances fluid placement in treatment of
such long intervals.
Emulsified acids
With emulsified acid, whereby the acid is present as the internal phase, the fluid
system, which is a non-Newtonian fluid (shear-thinning behaviour), has a
significantly higher viscosity than the reservoir fluid. This will result in improved
wellbore coverage, diverting more fluid to the low permeability and/or damaged
zones. The fluid velocity may still be low in these zones, but the retarded nature of
the emulsified system still provides efficient wormholing, even at low rates.

Foamed fluids
Foam can be injected as a spacer between treatment stages (multi-stage process) or,
alternatively part or all (one-stage process) of the treating acid can be injected as
foam. Foam diversion has probably the potential for wider application than any of
the diversion methods, discussed above.
The diversion of foam is based on the phenomenon that the liquid films that separate
the bubbles in a foam, enormously reduce gas mobility in the formation; the low-
mobility gas in turn drives down liquid saturation and thereby reduces liquid relative
permeability. As a result, the foam as a whole has low mobility in rock, and like
viscosified fluids, foam increases the resistance to flow into a given interval.
Foamed acids are operationally and logistically more complex to use than polymer-
viscosified acids. They require extra equipment and a liquid nitrogen supply. With
tubing head limitations, it is not always possible to use foam due to high friction in
the wellbore, combined with low hydrostatic head. Furthermore, they have less
dissolving power (per unit volume of acid). The high gas content of foam, whilst
improving clean-up, also in the presence of fines, makes its application more
difficult to control. Since foam is compressible, pressure variations alter the foam
properties that govern the flow division across the interval. Hence, variations in the
surface pressure do not directly reflect downhole performance; there is presently no
experimentally validated engineering model of foam flow in porous media that can
be used for design or control purposes.
Finally, a problem with the use of foams in horizontal wells is posed by the
horizontal nature of the flow: foam, being a two-phase system, may tend to
seggregate while flowing along the (long) horizontal section. This can lead to
diverter hold-up at the heel of the well, or to preferential treatment of the lower or
upper part of the wellbore.
MAPDIR technique
The MAPDIR (MAximised Pressure Differential and Injection Rates) diversion
technique, developed by Paccaloni, has been promoted as the best means of
assuring sufficient acid placement in all zones during matrix stimulation
treatments. MAPDIR applies wherever Darcy’s law holds. In practice, the method
consists of injecting acid at the highest possible matrix treating rate, at a constant
bottom hole pressure, slightly below the fracturing pressure. This requires continual
increases in the injection rate as the acid removes damage and thereby increases the
well injectivity. A high success rate has been reported with this technique, with
success quantified as a large reduction in skin factor.
In terms of its effect on acid coverage, the MAPDIR technique is not a diversion
method in the same sense as the other methods discussed in this chapter; it does not
reduce relative flow to high-injectivity intervals, nor increase relative flow to low-
injectivity intervals. However, the MAPDIR technique does clearly result in the
highest possible injection rate into low-injectivity intervals, while any of the other
diversion techniques may reduce injectivity into low-injectivity intervals. So, in
this sense, MAPDIR achieves the goal of any diversion method – to ensure
complete acid coverage of all zones.
The MAPDIR technique is especially suited for diversion in matrix treatments of

unfractured carbonates. Here, the acid reaction rate is usually high and mass
transport limits the overall acid spending rate. The result of the acid/rock
dissolution process therefore strongly depends on the acid flow rate. When acid is
pumped into a carbonate formation that contains zones with different degrees of
damage, the zones with the least damage will accept the largest amount of acid, and
these can be stimulated effectively. A lower amount of acid flows into the more
severely damaged zones. An increase in the total injection rate will result in higher
flow rates into all zones. In particular, the zones with severe damage can benefit;
the increased flow rate may cause a transition from a compact dissolution regime
without much stimulation, to a wormholing regime, with effective stimulation.
A number of methods to monitor the decrease in skin factor during this matrix
stimulation treatment from recorded wellhead pressure (or derived bottomhole
pressure) and injection rate, are available. The one presented by Paccaloni uses
instantaneous pressure and rates, from which the skin factor is derived during the
treatment. For this purpose the concept of damage ratio (DR) was introduced,
which simply represents the ratio of productivity index with real skin (S ≠ 0) and
with zero skin. An example of the measured wellhead pressure superimposed
(dashed line) on a graph of wellhead pressure versus injection rate, shows the
progress of matrix treatment, i.e. decreasing DR, in Figure 14.
A drawback of the method is that it results in more acid than is necessary being
injected into high-injectivity intervals. In addition, the benefits of this method are
being reduced when the attainable bottom hole pressure is less than the desired
value, because of limitations in surface pressure or pumping capacity.
Wellhead Pressure, Pti (psi)
Injection Rate, qi (BPM)

Figure 14 - Job control graph during MAPDIR treatment
Laboratory testing
Introduction
Various laboratory test procedures are available to support the design of carbonate
acidising treatments. They range from simple beaker tests (for instance to check the
compatibility of different fluids) to complicated core flow tests. In general, laboratory
tests are aimed at:
• Identification and (if possible) quantification of damage,
• Determination of the most suitable stimulation treatment, in a

semiquantitative sense,
• Determination of the key parameters required to formulate a practical

design,
• Checking the necessity for, and the effectiveness of additives for fluid
optimisation.
The following laboratory testing methods can be carried out when designing a
stimulation treatment in carbonate formations, although they are not always
required:
• Rock compostion and strength tests,
• Fluid compatibility tests,
• Acid reaction tests.
Stimulation Field Guidelines - Carbonate Stimulation Laboratory testing • 45

Rock composition and strength tests

As to formation characterisation, the following analyses can be performed:
1) Composition, i.e. the percentage calcite, dolomite, clay.
2) Acid solubility – if the core has a low solubility, the acid insoluble
materials should be analysed.
3) Porosity and permeability measurements.
4) SEM and/or petrographic analyses, to determine the structure of the

carbonate matrix, the pore structure and the cementing material. SEM
analysis can indicate whether acid-insoluble minerals are uniformly
distributed throughout the core, or if they are isolated in clasts or
microfractures.
5) Rock strength tests give information on the hardness of the formation to

be treated, which can indicate the likelyhood of etched fractures to
collapse after an acid fracturing treatment. The most commonly used
hardness test is the Brinell Hardness (BHN) test. More cumbersome tests
are unconfined compressive strength (UCS) tests, thick walled cylinder
(TWC) tests, and triaxial compressive strength tests. Such tests yield
information on Young’s modulus and Poisson’s ratio, useful for the design
of an acid fracturing treatment.
Fluid compatibility tests

Impairment is often caused by incompatibility between different fluids, either
chemically (precipitates) or physically (emulsions). These effects can be studied
qualitatively by mixing various fluids, to which the well has been exposed during
drilling, completion, etc. in test tubes, and examining the effects.
In general, the following fluids should be tested:
• Mud filtrate
• Cement filtrate
• Completion brines
• Reservoir fluids (formation water, crude oil, condensate)
Fluids 1-3 should only be tested for newly completed or worked over wells. They
can be made up according to information from drilling reports, etc., or from
samples of actually used fluids. Reservoir fluids can also influence the selection of
46 • Laboratory testing Stimulation Field Guidelines - Carbonate Stimulation
acid to be used. Generally, most problems may arise with heavy crudes, or crudes
having emulsification properties. Moreover, strong acids (20 to 28% HCl) may
cause more problems than weaker acids, and limiting the HCl concentration to 20%
or less is effective in many cases. Alternatively, the use of organic acids or an
appropriate additive package may be required to prevent acid sludge or
emulsification. Reservoir fluids to be used in testing should preferably be actual
samples from the field, although formation water may also be reconstituted.
In fluid compatibility testing, in principle no precipitates, (stable) emulsions or

other incompatibilities should be observed. The fluids should either form a single
phase or unstable emulsions that quickly separate into two phases. The tests may be
carried out at ambient temperature and pressure.
In case a (black) precipitate is observed when mixing crude oil and acid, an
additional test to verify the occurrence of sludge should be carried out. In this test
acid and crude oil are thoroughly mixed (e.g. using a high speed mixer) and
subsequently aged for 24 hours. Then the mixture is poured out through a 100 mesh
stainless steel wire screen. If no solids remain on the screen, no sludge was formed.
If there are solids, these may either be stiff emulsions, paraffins or sludge. To
separate out sludge, the screen should be washed alternately with warm water and
a suitable solvent (e.g. Shellsol T). This will remove the emulsions and paraffins,
but not the sludge. If sludge is observed, the test may be repeated with acids
containing anti-sludge agents.
Acid reaction tests

Acid reaction tests are used for the design of acid fracturing treatments. The
effectiveness of an acid fracturing treatment depends on fracture length and fracture
conductivity. In turn, the conductivity depends on the fluid loss and the amount of
rock dissolved as acid flows through the fracture. Therefore, to predict the
stimulation result from an acid fracturing treatment, one must first estimate the
acid-reaction kinetics. These kinetics depend on the rate of transport of the acid to
the surface of the fracture, the rate of acid reaction at the surface, and the transport
away from the surface of reaction products.
Laboratory tests for determination of acid reaction rates and for etched fracture
conductivity are the following:
• Static reaction tests
• Rotating-disk tests
• Annular flow tests
• Hollow-core tests

• Parallel plate tests
• Acid-etched conductivity tests
Static reaction tests

In a static reaction test, a piece of rock is dissolved in acid. Such solubility tests are
performed under ideal laboratory conditions. They indicate the maximum solubility
of the formation.The interpretation of the results of this test is difficult, because the
transport of the acid to the surface of the rock is controlled by unknown free
convection, and the effective solubilities during acidising may be completely
different.
Rotating disk tests

The overall rate of the heterogeneous reaction of hydrochloric acid with the
carbonate fracture wall is a function of the mass transfer towards the surface and of
the reaction at the surface. Either, or both of these factors may control the
penetration distance of live acid into the fractured formation. It has been
demonstrated that this combined process can be accurately modelled in a rotating
disk measuring device.
Charging tunnel Pressure
Acid reservoir
Automatic sampler
Reaction
vessel Fraction collector
Chalk disk
Figure 15 - Carbonate/acid reaction rate cell

The rotating disk test is a dynamic test, whereby polished disks of core (normally
5 cm in diameter) are rotated through an acid solution, and partially dissolved by
the acid. In these experiments, the fluid velocity distribution is well defined and the
mass transfer coefficient can be calculated, viz. it is a function of the square root of
rotational speed. The advantage of this method is that the well defined mass
transport allows surface reaction kinetics to be accurately measured. In Figure 15,
the instrument set-up is shown schematically.
The system is pressurised with nitrogen to about 200 bar to ensure that carbon
dioxide produced in the acid/carbonate reaction, remains in solution. Maximum
operating temperature is 200 ºF (93 ºC). During an experiment, small liquid
samples (1-2 ml) are withdrawn from the reactor at regular intervals by an
automatic sampling device. The calcium and magnesium concentration in the
samples is then determined by automatic titration or by an atomic absorption
spectrometer, and the acid concentration in the samples is calculated. The reaction
rate can be derived by plotting the acid concentration as a function of time.
The overall rate of the heterogeneous reaction of the acid with the carbonate rock,
(as indicated before, a combined mass transfer and surface reaction process) is a
function of the acid concentration, the shear rate (i.e. average fluid velocity in the
fracture) and temperature. Concentration dependence is normally determined by
measuring reaction rates at various acid concentrations.
Gelled and emulsified acids cannot be run on the system, because they will not be
completely stirred by the rotation of the core.
Annular flow tests

In an annular flow reactor, acid flows in the annulus between the reactive carbonate
core and the inert reactor body. Annular flow tests can be conducted at temperatures
comparable to the field conditions. They can be used for routine as well as
screening type experiments. As a good approximation, the annular space can be
considered as a thin slot. However, leakoff cannot be simulated during the test.
Hollow-core tests
The hollow-core test method was developed to evaluate the acid reactivity both
with and without fluid leakoff. It can be used to measure the acid reaction of non-
Newtonian fluid, i.e. gelled acids, under dynamic conditions. Figure 16 shows the
setup of a hollow-core test cell.
In a hollow-core test, a hole is drilled through the center of the core. Acid can flow
axially through the center, to measure the acid reaction rate. The acid can also flow
radially through the wall, to measure leakoff. Hollow-core equipment can be
operated at a system pressure of 1000 psi (7 MPa), with radial pressure drops across
the core ranging up to 30 psi, to achieve radial fluid leakoff. However, as mentioned
in literature, the geometry is incorrect and accurate measurement requires fully
developed velocity profiles.
Radial Fluid Flow
Axial Fluid Flow
O-Rings
Hollow Limestone Core
Epoxied Ends
Figure 16 - Hollow-core test cell
Parallel plate tests

Parallel plate tests, in which acid flows past parallel carbonate plates, have the
correct geometry, and allow examination of the effect of leakoff during an acid
reaction test. They can also be used to measure the acid reaction of non-Newtonian
fluids; therefore, the actual acidising fluids can be tested. The conductivity of acid-
etched rocks can also be measured. However, this method does not easily separate
the mass transfer from the surface reaction kinetics. These experiments are also
difficult to repeat on a large number of samples. A schematic setup is shown in
Figure 17.

Core samples From pump
Artificial
Cover ring Core holder Inlet fracture Cell body
Sealing
Spacer Outlet Viton Gasket O-ring
Fluid loss line
To fluid loss collection To acid collection
Figure 17 - Acid fracture conductivity cell
Acid-etched conductivity tests

Acid-etched conductivity tests are performed to measure the conductivity of a
created and acid-etched fracture. Test samples are circular disks, 2.25 to 4 in. (5.72
to 10.2 cm) in diameter, and 0.5 in. (1.27 cm) thick. Samples are cut from the core
such that the surface exposed to acid, is in the same plane as a vertical fracture.
Core disks are mounted in lead, and the face of the sample is turned flat with a
lathe, whereafter a hole is drilled through the axis of the sample and the lead
mounting. The sample is then placed in the etching test cell with the turned face of
the sample touching a Hastelloy plate, which acts as the opposite fracture face.
Figure 18 shows a schematic view of the etching test cell.
Acid flows upward through the center of the test sample and radially across the
simulated fracture face, at 1000 psi (6.89 MPa) backpressure, and at test
temperature. After the etching time has elapsed (usually 15 minutes), closure stress
may be applied, and the etched fracture conductivity can be measured. The
etching/conductivity measurement sequence can be repeated several times.
Etching equipment construction allows all strengths of acid to be tested. Acids may
be non-viscous, gelled, foamed, emulsified or chemically retarded. The samples are
mounted in lead, that tends to lose form around 8000 psi (55.1 MPa) closure stress.
Testing may be conducted at temperatures up to 375 ºF (190 ºC).
Hastelloy plate
Closure stress
Core
Lead mold
Hastelloy base
Inlet for acid, Other side of

manometer, and flow meter manometer
Figure 18 - Etching test cell
The acid etching test is of particular importance when optimising treatment designs
for low temperature formations (cold dolomites), chalk formations (closed fracture
acidising) and low-solubility carbonates.

Special applications
Horizontal wells
Formation damage removal, or bypassing, in horizontal wells in carbonate
formations is not principally different from that of vertical wells as far as selection
of candidates and treatment fluids is concerned. Apart from the (usually) larger
fluid volumes involved, the design procedures follow the guidelines given in the
relevant sections of this manual. The major difference, however, lies in the
placement of the treatment.
Effective matrix treatments in long horizontal sections require optimum placement

techniques. Many horizontal wells have open hole completions, possibly with
slotted liner or prepacked screen. These completions restrict the application of
mechanical techniques, such as packers and selective placement tools, and also the
use of ballsealers. In case of a horizontal well completed with perforated, cemented
liner, the use of ballsealers may not be efficient, since depending on their densities,
they tend to shut-off either the top part or the bottom part of the horizontal section.
Also the use of particulate diverters is often not feasible, since the treatment would
become too costly due to the many diverter stages required in long horizontal
sections.
The above considerations make diversion procedures based on the use of

viscosified, or temporarily activated cross-linked gelled, or foamed acids
particularly attractive. Also the use of viscous banks, to be pumped into sections of
high fluid intake, has become more applicable nowadays. Coiled tubing should be
employed for the placement of matrix treating fluids, in both cased and open hole
situations. Bullheading matrix treatments in carbonate reservoirs tends to result in
non-uniform treatments.
As far as acid fracturing treatments in horizontal holes are concerned, since the
geometry of the fractures will be determined by the in-situ stresses, the well
trajectory could be planned (if possible) to ensure that either a longitudinal or a
transversal fracture is created during fracturing. Unlike vertical wells, horizontal
well fractures do not always initiate perpendicular to the minimum in-situ stress.
This occurs because a shear failure mechanism, which is not present during
fracturing of vertical wells, also operates during the initiation of a fracture from a
Stimulation Field Guidelines - Carbonate Stimulation Special applications • 53
horizontal well. Fractures in open hole, regardless of the azimuth of the well, will
generally initiate along the wellbore and later realign to be perpendicular to the
minimum stress. This will increase near-wellbore tortuosity and can increase the
treatment pressure.
In acid fracturing treatments of cased, cemented horizontal wells, the use of

ballsealers has been successful. Individual zones in such completions can also be
isolated by a physical barrier such as bridge plugs, packers or by large plugs of
proppant. If bridge plugs and packers are used to isolate different zones, then the
well is normally killed before another packer is set and the next area is stimulated.
This continues until all zones are treated, after which the well is killed and all plugs
and packers are removed. Although this method achieves effective isolation of
zones, it is expensive, time consuming and the process of killing the well can lead
to formation damage.
Fewer techniques are available for diversion during acid fracturing of uncased
horizontal wells, and far fewer reports are contained in the literature. The
simplest method to isolate one fracture from the next is to pump blocking
material such as rock salt, benzoic acid or moth balls between stages of a
continuous large acid fracturing treatment. Unfortunately this method does not
provide much control over the spacing of the fracture initiation points along the
wellbore. In summary it can be stated, that more study is required for reliable
methods for controlling and placing acidised fractures in open hole or slotted
liner completed horizontal wells.
Naturally fractured carbonates

Many carbonate reservoirs around the world contain natural fractures. These
fractures are frequently rather permeable and form the main flow path for the
hydrocarbons from the reservoir into the wellbore. On the other hand, wells drilled
through such fissured reservoirs can suffer from very severe formation damage due
to the invasion of the natural fractures by large amounts of drilling mud and loss
circulation materials.
Stimulation of such wells should be aimed at:
• Removal of the damage induced by the high fluid losses and the measures
taken to cure those losses, and
• Further increase of the conductivity of the natural fractures by dissolution

of the (natural) minerals present in the fractures. If the interval to be
treated is close to the water table, this may bring on early water
production, however.
For a proper selection of a stimulation fluid for naturally fractured carbonate

reservoirs, the following guidelines can be given:
54 • Special applications Stimulation Field Guidelines - Carbonate Stimulation
1) Determine the most likely source of damage, by studying the drilling and
completion reports.
2) Get a clear description of the type of fractures and their possible contents.
This involves core studies (mineralogy) and geological advice.
3) Apply the selection chart given in Figure 19, to determine the most
appropriate type of acid.
4) If core samples are available, perform core flushing tests to confirm the
applicability of acids selected on the basis of Figure 19.
Formation Fractures
Open or filled with Filled with Filled with mud

calcitic material siliceous fines remnants, etc.
Calcite HCI (10 - 15%) HCI (10 - 15%) + HCI (10 - 15%)
silt suspending agent silt suspending
agent, small volume
Dolomite HCI (10 - 15%) HCI (28%) + HCI (28%) +

silt suspending agent silt suspending
agent, small volume
Figure 19 - Acid selection chart for naturally fractured carbonates
Also with regard to injection rates, treatments of fractured carbonate rocks involves
a compromise between two options. Removal of a mudcake from inside the
fractures near the wellbore, is enhanced by a low pump rate (longer contact time,
no by-passing). On the other hand, effective removal of fracture filling
materials/minerals as deeply as possible, is promoted by pumping fast, possibly
even exceeding the fracturing limit. It depends very much on the local situation,
whether to use a low or high pump rate, or possibly a combination of both, i.e.
initially pumping at a low rate to effectively dissolve a mud cake, followed by
continued injection at a high rate.
Other examples from the literature, referring to the removal of deep damage due to
significant mud losses, mention the application of a large overpressure into the well
in order to move the mud bank and make it accessible by the treating fluids. The
operation then becomes an acid fracturing type treatment, with the following
objectives:
- open the natural fissures and displace the mud,

- strip the mud from the fracture walls,
- restore reservoir rock and particles of damaging materials to a water-wet
state (if necessary), therefore allowing the acid to react with, and its
suspending agent to adsorb onto the minerals surfaces,
- disperse, suspend and produce back all non-dissolved damaging particles,
- etch the natural fractures for better conductivity near the wellbore.
The damage removal fluid package usually consists of three successive fluids.
A titanate-crosslinked, low pH, high viscosity gel compatible with acid is pumped
first to open and widen the natural fractures. The mud cake is dislodged and the
mud filtrate is displaced (with a favourable mobility ratio) into the pattern of
fissures. A mud dilution effect is obtained with the reservoir oil through a
considerable increase in the investigation radius.
A "Mud and Silt Remover" acid system based on 28% hydrochloric acid is pumped
after the crosslinked gel. It incorporates the usual corrosion inhibition schedule, an
iron control agent and a friction reducer. A water wetting surfactant, a silt suspending
agent and an emulsion/sludge preventer are usually added. Their concentrations are
designed from the results of compatibility studies between the drilling mud, the
reservoir oil and the acid. The acid system must be as fluid as possible in order to
promote turbulence in the fissures and complete the mud removal at the fracture wall.
A linear gel displaces the acid, and is followed by a short diverter stage of
crosslinked gel, carrying ballsealers. For this purpose the well must be completed
accordingly, i.e. with a cemented liner across the payzone. Wellhead and tubulars
must be selected in advance to withstand fracturing pressures, downhole as well as
at surface. Pre and post job well performances demonstrate huge increases in
productivity index, due to the clean-up of the natural fissures around the wellbore
as a result of above treatments.
Exploration wells
Often production technologists or stimulation engineers are asked whether
stimulation of a particular exploration well is useful.
The main objective for a stimulation treatment in an exploration well is, from a
petroleum engineering point of view, to establish that producible hydrocarbons are
present and, if possible, produce at a rate sufficient to obtain a good well test. It is
not the intention to optimise the treatment, so as to maximise the productivity.
With this in mind, the following guidelines have been compiled in discussions with
engineers from various operating companies:
1) For a successful stimulation, a minimum hydrocarbon saturation of 25%

is required. Stimulation cannot create oil or gas.
2) Selection of type of stimulation:

for gas wells: acid fracturing if the matrix permeability is less than 1 mD,
for oil wells: acid fracturing if the matrix permeability is less than 50 mD,
but to some extent dependent on the viscosity of the reservoir fluids.
However, in wells with a significant natural fracture system, whereby the
secondary porosity (from the fractures) can be (much) greater than the
matrix permeability, an (extensive) acid treatment should be considered,
not necessarily exceeding fracturing pressure, when pumping the
treatment.
3) Perforation policies in exploration wells should be such that only a limited

length of the zone of interest is perforated. This minimises the risk of
water or gas influx after stimulation. This is particularly important in case
a well is likely to be fractured. Additional perforating can always be done
after stimulation, if required.
4) Every effort should be taken to gather data relevant to the design of a

(possible) treatment. Whenever possible, time should be taken to perform
leak-off tests, to take side-wall samples for mineralogical analysis
(Mineralog, SEM study), etc.
5) Prior to drilling of the exploration well, a scheme of action should be

made (and agreed on by all parties involved) with respect to the likelihood
of a successful stimulation. Approval for the additional costs and time
involved should be obtained to ensure management commitment.
Such a plan could, for instance, be as follows:
1) Confirm hydrocarbon shows during the drilling phase.
2) If information from other sources, e.g. other wells in the area indicates
that fracturing might be required, perform microfrac to obtain important
data for possible fracture treatment.
3) Take oriented core of the microfrac.
4) Repeat these steps as appropriate.
5) Run logs over target interval and determine reservoir quality, hydrocarbon
saturation, etc.
6) Take side-wall samples, if step 3 was omitted, and determine some basic
properties, such as formation composition, porosity, strength, etc.
7) Run casing and perforate a limited interval over the first zone of interest.
8) Carry out initial production test, to obtain preliminary data on

permeability, skin, etc.
9) Decide on the basis of the log interpretation and initial production test
results, whether or not stimulation is feasible (apply above guideline No. 2).
10) If yes, perform acid or other damage removal treatment.
11) Carry out a production test.
12) In case of low productivity, run AcidFrac, using data from e.g. microfrac
tests, to assess the prospects for acid fracturing.
13) Design and perform acid fracturing treatment, if warranted.
14) Carry out production test.
15) If necessary, shoot additional perforations.
16) Repeat production test.
Following a plan like the above, ensures that every possible and necessary step is
taken to prove the existence of producible hydrocarbons or otherwise.
Practical circumstances may demand the omission of several of the above steps,
however.
High pressure wells

Most wells are drilled up to depths of 3000 – 4000 m (9000 – 12000 ft) in
hydrostatic reservoirs. Pressures and temperatures encountered in those wells fall
in the range covered by the specifications of the equipment and products provided
by the major stimulation contractors. Surface equipment, like pumps and lines,
usually has a pressure rating up to some 1300 bar (20000 psi), while most products
have been designed for use up to 120 ºC (250 ºF).
High pressure wells require a surface treating pressure of, say, a thousand bar or
more. Usually this is not a problem because the tubulars, etc., are designed for high
pressure service. However, occasionally the injection pressure during acid
stimulation may considerably exceed the static wellhead pressure. From an
operational point of view, this presents the following potential problems:
1) The wellhead may not be rated up to such high pressures. This problem
may be overcome by the use of a wellhead isolation tool. These tools are
offered by all major stimulation contractors. They have the added
advantage that high quality steel components of the Christmas tree are
protected from contact with corrosive acids.
2) The tubing string may not be suitable for such high pressures. This can be
overcome (to some extent) by pressurising the tubing/casing annulus.
3) The high pressure may prohibit the use of coiled tubing.

4) In many cases, the pump rate has to be limited to ensure that the maximum
allowable pressure is not exceeded. The span between reservoir pressure
and fracturing pressure tends to be small in high pressure areas. Therefore,
in many cases the treatments will have to be carried out at a maximum
pressure, with a variable injection rate, depending on the effect of the
treatment.
5) The reduction in injectivity, inherent to the use of diverting agents,

ballsealers, etc., may result in extremely low pump rates, and eventually in
premature termination of the job. Hence, diversion should be considered
carefully, and only applied if it is vital for the success of the treatment.
High temperature wells

The influence of high temperatures on the design, execution and performance of
acid stimulation treatments in carbonates is perhaps more drastic than the effect of
high pressures.
1) Reaction rates are faster, resulting in a limited penetration depth of live

acid. To combat this, retarded acids may have to be applied, such as:
• Emulsified (acid-in-oil) acid, with a recently developed high-

temperature emulsifier surfactant mixture, which is stable to
temperatures up to 180 ºC.
• A combination of organic acids (acetic and formic acid), which have

extended reaction times, possibly in combination with a high-
temperature, high molecular-weight polymer gelling agent.
Alternatively, cool-down preflushes could be applied. A drawback of this procedure

is that substantial amounts of water may have to be injected, which can adversely
affect clean-up after the treatment.
2) Corrosion of tubulars at high temperatures is much more severe than at

low temperatures for two reasons:
• being a chemical reaction, its rate doubles every 10 ºC temperature

increase, and
• most current commercial inhibitors start to decompose at temperatures

above 100 – 120 ºC. However, corrosion inhibition systems are
available that protect tubulars up to 180 ºC.
The current way to combat this higher corrosion is to add high (excessive?)
concentrations of corrosion inhibitors and intensifiers. Also here cool-down flushes
will help to reduce the corrosion problems. However, it should be borne in mind
that return acid, although spent, is hot and still very corrosive, and it should
therefore contain sufficient corrosion inhibitor. Unfortunately, corrosion inhibitors
tend to stay behind in the formation. Therefore, an overdose might be required to
compensate for loss of inhibitor through adsorption in the formation.
Overdisplacement of the acid (in case of a matrix treatment) will alleviate the
problems. In any case, it is strongly recommended to include corrosion tests with
(simulated) spent acid in the corrosion testing program.
The use of organic acids can also be considered to minimise corrosion problems in
high-temperature applications. The blends can be designed so that the dissolving
power is equivalent to HCl, with significantly reduced corrosion rates. Although the
base acid cost for a formic/acetic acid is normally about twice that of HCl,
inhibition costs are generally less.
Low temperature wells

It may be necessary to enhance the reactivity of HCl on carbonate rock, especially
dolomites, at low temperatures (i.e. < 50 ºC for limestones, and < 90 ºC for
dolomite), because of the relatively short contact time of the acid with the carbonate
rock. This can be accomplished in matrix acidising by injection rate design,
chemical approaches and with temperature. With low temperature acidising, larger
volumes, lower injection rates with strong (28% HCl) acid or heated acid may be
required to obtain a sufficient reaction rate.
Two techniques were developed years ago to enhance the reactivity of HCl and are
still in use today in limited applications. The first technique involves adding a very
low concentration of HF (about 0.25% by weight). This low concentration
enhances the reactivity of the mixture and ensures that minimum damage from HF
reaction products are introduced. However, this technique is not recommended
Shell practice. The second process involves adding several gallons of ammonium
hydroxide to HCl just prior to pumping. Temperatures as high as 60 ºC can be
obtained using this method and it has proven beneficial for treating shallow, low
temperature dolomites. Also a mechanical means (hot oiler or steamer) can be used
to heat up the acid.
To obtain maximum acid penetration in acid fracturing treatments, the first step in
the treatment design is to select fluids that have the lowest leakoff coefficient.
Increasing the conductivity of an acid-etched fracture is simply a matter of
pumping more acid, since the more acid pumped, the wider the etched width of a
fracture. In low temperature acid fracture treaments also a low injection rate
(though above fracturing rate) should be used. Finally, depending on the particular
conditions and requirements, the choice exists to apply a propped fracturing
treatment.

Matrix treatment design guidelines
Introduction
The high degree of reservoir uncertainty, caused by the heterogeneous nature of
carbonate formations, sometimes makes candidate selection for matrix treatments
difficult. The goal of the candidate selection process is to select wells with
relatively low risk and high reward potential. High-skin wells are obvious choices
for matrix stimulation. It should be noted, as was said earlier, that matrix
stimulation is designed to remove the skin due to damage, and it will not alter other
components of the total skin, termed "pseudoskin". Pseudoskin can be caused by
partial reservoir penetration, poor perforations, collapsed tubulars, and other
mechanical problems.
Once a well has been recognised as a candidate for matrix stimulation, a typical
design should address the following aspects, and involve the following steps:
• Damage characterisation (cause, severity, location).
• Formation characteristics.
• Treatment fluid selection.
• Selection of additives.
• Maximum allowable injection rate/pressure within matrix flow regime.
• Placement strategy.
For the above steps in treatment design, computer models have been developed.
STIM2001, which recently (July 1999) has become available as a joint Shell/
Halliburton project, is a software application for the comprehensive design,
execution, and evaluation methodology of matrix stimulation treatments of
sandstones and carbonates, and which brings a structured engineering approach to
the problem of well stimulation. Another computer programme available is
StimCADE of Schlumberger.
Stimulation Field Guidelines - Carbonate Stimulation Matrix treatment design guidelines • 61

Last, but not least, as in any stimulation design, the experiences with earlier
stimulation treatments in wells in the same field or formation, or in comparable,
neighbouring fields, should be fully taken into account in the design.
Damage characterisation
The type and location of the damage should be determined in order to select the
proper treating fluids. To properly characterise the formation damage, a complete
history of the well is necessary. Every phase from drilling to production/injection
must be evaluated. Sources of damage may include drilling, cementing, completion
and workover, production, stimulation and injection operations. The damage itself
can be due to emulsions, wettability changes, water blocks, scale, organic deposits
(paraffin/asphaltenes), mix deposits (a mixture of scale and organics), silt and clay,
and bacterial deposits. Although the type(s) of damage may not always be precisely
identified, quite often the most probable type can be determined. Thus, most matrix
treatments incorporate treating fluids that can remove more than one type of
damage. This is particularly the case in sandstone acidising, and less in carbonates,
where the damage can very efficiently be bypassed with long wormholes.
Drilling damage in horizontal wells can be very high due to the long exposure time
during drilling (mud damage and the mechanical action of the drill pipe on the
formation face).
Formation characteristics
The mineralogical composition of the carbonate formation, i.e. the percentage of
calcite, dolomite, clays etc., is an important parameter for treatment design. So is
the average HCl solubility of each interval to be treated, and the minerals that could
cause problems, i.e. the insoluble minerals such as clays and fines, which upon
dissolution of the rock matrix, will result in the release of insoluble material, which
could cause plugging of the created flow paths. An adjusted treatment design, e.g.
the use of foamed acid, with its higher fines carrying capacity, would have to be
considered in such cases.
Dolomite is frequently associated with anhydrite (anhydrous calcium sulfate). In

dolomite formations containing anhydrite, when treated with HCl, the anhydrite
will first be dissolved, but gypsum (hydrated calcium sulfate) will quickly
reprecipitate because of its low solubility. These properties may have a significant
impact on treatment design.
The type and distribution of porosity in carbonates can have a strong influence on
the extent of the damage and on the acid penetration. Reservoirs with a high matrix
permeability, or with an extensive fracture system, can be severely (deeply)
damaged by invasion of solid particles. If high permeability is due to large,
62 • Matrix treatment design guidelines Stimulation Field Guidelines - Carbonate Stimulation
interconnected pores, short and very wide wormholes may form. These properties
can vary dramatically within the same reservoir. A carbonate with basically the
same constitution, may have a very different porosity and permeability and, as said
earlier, a reasonable relationship between porosity and permeability does often not
exist in carbonate formations. On the other hand, there are massive carbonate
formations, which, due to their very compact and hard nature have usually very low
matrix porosity and permeability.
However, such formations are usually fractured and most of the reservoir porosity
is formed by these fissures. This will then also significantly impact the treatment
design.
Treatment fluid selection

Base acids
After having reviewed the formation characteristics, such as rock composition,
structure, permeability, porosity and strength, as well as the type of damage, the
properties of the reservoir fluids in relation to the selection of the treatment fluids,
must be considered. Furthermore, bottomhole temperature and pressure must
always be taken into consideration, as these parameters are of major importance for
the choice of a base acid and/or additive package.
Selection of a base acid is usually done by process of elimination. One of the first
parameters to be considered is the bottomhole temperature (BHT), in relation to
corrosion concerns and reactivity of the formation. If the BHT is very high, i.e.
between 150 and 200 ºC, corrosion concerns are the primary design parameters,
and due to the inability to provide long-term corrosion protection, a 15% HCl or
9% formic acid is recommended. If the BHT is extremely high, i.e. > 200 ºC, HCl
acid is precluded, and organic (acetic) acids are to be preferred. Even in cases
where HCl can adequately be inhibited, the high cost of inhibitors may lead to the
selection of a weaker acid blend. Moreover, high corrosion inhibitor loadings can
actually be damaging to the formation. Below 150 ºC, 15 to 28% HCl can be used.
If the formation has very low reactivity, as in the case of cold dolomites, the more
aggressive 28% HCl is to be preferred, provided corrosion of tubulars is not a
problem.
Compatibility testing of the acid system with the reservoir fluids is very important.
Generally, the concern is highest in heavier crudes or any crude that displays
sludging or severe emulsification problems. Generally, strong acids cause more
problems than weaker ones. Limiting the HCl concentration to 20% is effective in
many cases. Other times, the use of organic acids, an appropriate additive package,
or a solvent preflush may be required to prevent acid sludge or emulsification.
Compatibility with the formation rock addresses the acid reaction rate and rock
dissolution. If too much rock is dissolved, e.g. in high-porosity soft chalks, which
could cause rock failure, a weaker acid solution (10 – 15% HCl) is preferred. Hard,
dense, low-porosity dolomites would require a stronger acid solution (20 – 28%
HCl). In fissured reservoirs, damaged by silt and clay, a silt/mud remover
treatment, consisting of a blend of 7.5 to 15% inhibited HCl and special clay
dispersing, suspending and chelating agents, is recommended.
Acid systems
Apart from small treatments to remove near-wellbore damage, whereby neat HCl
acid (with necessary additives) can be used, in most matrix treatments the acid is
(lightly) gelled or emulsified. This is done to improve zonal coverage of the acid,
to retard the acid reaction rate, or to improve its fines-suspending properties. A
summary of commercially available acid systems is given in Appendix I. Some
relevant aspects of these are discussed below.
Lightly gelled acid, - various strengths of HCl acid with low concentrations of
gellant (e.g. DSGA at 4 l/m3) for friction reduction. Gelling provides a viscosity of
1 – 3 cp at ambient temperatures. These systems are applicable for high rate matrix
treatments, for near-wellbore damage, so viscosity is not meant to provide
enhanced zonal coverage.
Gelled acid systems – various strengths of HCl acid with higher concentrations of
acid gelling agents (e.g. DSGA at 20 l/m3 to 30 l/m3) to provide higher viscosities.
Viscosities might range from 30 to 40 cp at ambient temperature, and the viscosity
provides a higher pressure drop in near-wellbore damage, matrix treatments. This
results in an enhanced zonal coverage and minimises fluid loss.
Viscosity building systems – systems that contain HCl, a gelling agent and a
crosslinker.The system crosslinks when the acid spends in the formation, and the
pH increases to a value of about 2. The crosslinked gel builds viscosity in the range
of 100 to 200 cp, and it effectively stops any further invasion and diverts a
subsequent acid stage to the next zone to be treated. The crosslinked gel will break
upon further spending at a pH value of about 3 to 4, and the viscosity of the fluid
will return to its original value. The systems can be built to work in HCl acid at
strengths from 5 – 28% acid. The self-gelling acid system is particularly suited for
diversion of matrix treatments in horizontal wells, by pumping alternatively stages
of crosslinked gelled acid and of neat acid.
Emulsified acid systems – oil outside phase acid systems have been successfully
used in situations where a retarded reaction rate is useful to create long wormholes
that deeply penetrate into the formation, thus bypassing the damage. Because of
their retarded nature, they can be pumped at low rates, which is beneficial in
heterogeneous formations. Also their high viscosities result in a better zonal
coverage. In some cases it may be necessary to pump neat acid in front of the
emulsified acid to create flow paths into the formation.

Energised and foamed acid systems – in reservoirs where the reservoir energy is
low, some form of additional energy may assist in the unloading of the fluids
introduced into the formation. These energised fluids are usually prepared with
either CO2 or nitrogen, at percentages (or qualities) of 50 to 65% gas phase.
Foamed fluids have been used to improve both diversion and leakoff control in
matrix and acid fracturing treatments. Again, the foams can be prepared with either
CO2 or nitrogen and are typically at 65 to 75% gas phase (at downhole conditions).
The expected benefits of the use of foam with the required additional equipment
should be carefully evaluated against the conditions one is trying to treat.
Selection of additives
Although proper fluid selection is critical to the success of a matrix treatment, the
treatment may be a failure if the proper additives are not used. The major treating
fluid is designed to effectively remove or bypass the damage. Additives are used to
prevent excessive corrosion, sludging and/or emulsions, provide a uniform fluid
distribution, improve cleanup and prevent precipitation of reaction products.
Additive selection is primarily dependent on the treating fluid, the type of well,
bottomhole conditions, the type of tubulars and the placement technique.
Since there is a large number of additives available, which may be different for
various contractors, the choice of additives to use can be rather difficult. However,
as stated before, two additives should be included in carbonate stimulation, viz. a
corrosion inhibitor (always), and (almost always) a sequestering agent, for
prevention of iron hydroxide precipitation.The use of a sequestering agent should
be justified on the basis of tests or calculations.
There are many sources of iron, which can cause problems during an acid
treatment. Iron can be dissolved in acid from surface tanks, pumping equipment,
tubings, casings and minerals in the formation. However, the most contributing
source of iron has been identified to be from tubular goods. Iron scales, mill scales
and rust are present in many new and old wells. In this connection it is
recommended to always carry out an acid pickling job of tubings/casings prior to
carrying out the acid stimulation job. This can be done by simply spotting 20 bbls.
of 15 – 20% HCl down the (coiled) tubing and up the annulus.
The different service companies offer a large suite of acid additives. If the decision
to use additives is left to them, one might end up with an expensive mix of,
sometimes superfluous, chemicals and in the worst case, incompatible materials.
Often the mutual compatibility of the various additives is overlooked. So, although
the know-how on the chemicals is very much the domain of the stimulation
contractors, their recommendations should always be checked critically. Apart from
the inclusion of a corrosion inhibitor and (possibly) a sequestering agent, all other
additives are optional and should only be used if specific well conditions require
their use and only after thorough testing for compatibility.

Additive Effect of overdose
Corrosion inhibitor Sludge, emulsions, facilities upsets

Oil wetting formation rock reducing effective permeability
De-mulsifier Formation of stable emulsion in facilities,

well and near well bore region
Silt suspending agent Emulsions and foaming problems
Clay stabilisers Loss of effective permeability
Figure 20 - Harmful effects of additive overdose
One of the most common mishaps in acidising is additive overdose. Figure 20 lists
some of the problems that can occur in the well and surface equipment during and
after an acid job.
If the need for a particular additive cannot be clearly demonstrated, its use is not
justified. Also, if the stimulation contractor or manufacturer of an additive does not
wish to disclose basic information about its chemical nature, it should not be used.
Non-acid matrix treatments

Some forms of damage cannot be removed by acid, or they might even be
intensified by the use of acid. Wax and/or asphaltene problems need treatment with
hydrocarbon solvents rather than acids, for instance. In this document non-acid
matrix treatments are not further discussed, but reference is made to Report EP 94-
1901, October 1994, Stimulation Field Guidelines Part I, Matrix Treatments, where
the following treatments are discussed:
• Wax and asphaltene removal treatments
• Hot oil treatments
• Solvent treatments
• Dispersant treatments
• Chemical and electrical heat treatments
• Removal of emulsions, pipe dope, etc.
• Scale removal
• Enzyme treatments
• Hypochlorite treatments
Maximum allowable injection rate/pressure

A major step in matrix treatment design is to determine the conditions for matrix
flow regime. To avoid fracturing the formation, the bottomhole pressure must not
exceed the fracturing pressure. Pressures exceeding the fracturing pressure in a
matrix stimulation treatment are undesirable, since the treatment fluid may then not
dissolve or disperse near-wellbore damage. Moreover, fractures can also propagate
beyond boundaries and lead to an increase in water or gas production.
The maximum allowable injection rate into a vertical well that does not fracture the
formation, is derived from Darcy’s radial flow equation. This equation (Equation I)
is given in Appendix II. It is a simplified inflow performance relationship, which
does not account for transient effects, multiphase flow or reservoir heterogeneities.
Moreover, the value of maximum injection rate obtained with the initial skin value,
can only be used as a guideline for determining the initial rate.
The maximum injection rate into a horizontal well under matrix conditions, is given
in Equation III of Appendix II. The equation indicates that qi,max is directly
proportional to the length of the horizontal reach of the well, for a given set of
conditions. Normally, therefore, qi,max is significantly higher in a horizontal well
than in a vertical well, completed in the same formation.
The maximum allowable surface pressure to avoid fracturing the formation, is

given by the following equation:
P s = P fg x d – P h + P f
where
P s = maximum surface pressure (psi)
P fg = fracture gradient (psi/ft)
d = TVD to mid-perforations (ft)
P h = hydrostatic pressure (psi)
P f = pipe friction pressure (psi)
Normally, as a safety factor, the actual maximum allowable pressure is 80 to 90%

of this value. It should be noted that P f , the tubular friction pressure, can be very
high in coiled tubing. Due to this, maximum injection rates are limited through
coiled tubing in most treatments in horizontal wells. For example, qi,max is normally
1 1
less than 1.5 BPM and 2.5 BPM down 1 / inch and 1 / inch coiled tubing
4 2
respectively, even with friction reducer.
Volume requirements
As to the volume requirements of treatment fluids in matrix acidising, the following
guidelines are given:
• for intervals of more than 150 m net formation : 0.6 m3/m
• for intervals of between 100 and 150 m net formation : 0.9 m3/m
• for intervals of less than 100 m net formation : 1.2 m3/m
The above numbers should be used as indicative only, and depending on the type
and depth of the damage to be treated, significant deviations from these numbers
may be required, also taking local experience from earlier treatments into account.
In horizontal wells, with sometimes very long openhole sections, the above
numbers may lead to excessive amounts of treatment fluids. In for instance, North
Sea operations, much lower volumes of 0.5 m3/m have been used with success. This
can be achieved by using coiled tubing jetting technology, such as the Rotojet (BJ),
which is the best means of establishing direct communication to the near wellbore
area. Moreover, with this technique also an efficient placement over the interval to
be treated, is achieved. Coiled tubing jetting technology has also been applied
successfully in horizontal wells completed with predrilled or slotted liner.
Placement strategy
The placement strategy is an important step in the design of a matrix treatment.
Successful matrix treatments depend on the uniform distribution of the treating
fluid over the entire vertical or horizontal interval, or into each natural fracture
system encountered in the well. If complete zonal coverage is not achieved,
production will remain impaired. Its importance is magnified in a horizontal well
due to the long interval.
Matrix stimulation treatments are often performed in multilayered reservoirs,

containing zones with widely different injectivities. This difference in injectivity
may be caused by either different permeabilities, or uneven severity of the damage.
Diversion techniques are designed to achieve uniform treatment of the entire
interval. Without diversion, there is no assurance of complete zonal coverage.
Diversion is recommended on all matrix treatments of intervals of 10 m or more.

Acid placement or diversion can be accomplished by mechanical means or
chemical means. The means chosen depends, as previously discussed, on a number
of factors including wellbore geometry and available equipment. Mechanical
diversion, which includes straddle packers, ballsealers, etc. are only applicable in
cased and perforated completions. This is mostly not the case in horizontal wells,
and if available, this method of diversion is very expensive, if a rig is required.
Chemical diversion techniques include viscosifying acids, gel slugs, particulates
(i.e. benzoic acid flakes, wax beads, rock salt, etc.), emulsified acids and foams. All
techniques can work under more than one situation, but should be optimised for the
given reservoir and wellbore. In horizontal wells, the use of particulates for
diversion is not feasible due to the high cost involved in the amounts of material
required to treat the (very) long horizontal sections. Here, the preferred diverting
technique may consist of pumping viscous banks in the sections of high fluid
intake. These banks are made of either non-Newtonian gels or foams, having
downhole qualities in the 60 to 85% range. In particular, the use of coiled tubing
for fluid deployment and diversion, when using a temporarily activated cross-
linked gelled acid system, has been promoted recently in literature for matrix
acidising in horizontal wells in carbonate reservoirs. As mentioned before, the use
of coiled tubing with a jetting tool, e.g. having jets in a spiral shape for 360 degree
coverage, has also been successfully applied recently.

Acid fracturing design guidelines
Introduction
When designing an acid fracturing treatment, all factors affecting the success of the
treatment must be considered. In low-to moderate temperature wells, acid fluid loss
control may be the most important consideration. In high temperature wells,
effective acid penetration distance often is limited by rapid spending, and retarded
acids should be considered. In some soft formations the treatment should be
designed specifically to maximise fracture conductivity.
Once a candidate well for an acid fracturing treatment has been identified, an acid
fracturing design will be formulated, normally using a computer simulator such as
FracCADE (Schlumberger), ADP (Halliburton), or Fracpro and MFrac 2.0 (BJ).
Shell has developed the AcidFrac programme, contained in ShellFrac, used to
determine the etched fracture dimensions created by a certain pad/acid volume.
Before designing an acid fracturing procedure, a number of steps have to be taken
by the designer, which in summary, are the following:
1. Determine the well condition and parameters.
2. Determine the reservoir and rock parameters.
3. Select the treatment type.
4. Select frac-fluid (incl. fluid loss coefficient) and acid type.
5. Determine acid reaction rate parameters.
6. Select fracturing fluid additives.
7. Select placement technique and pump rate.
8. Measure in-situ stress profile, if feasible.
9. Determine the optimum fracture length and conductivity.
10. Calculate a detailed fracture treatment design using ShellFrac and AcidFrac.
Stimulation Field Guidelines - Carbonate Stimulation Acid fracturing design guidelines • 71
Further steps will include planning for the treatment, the execution of the treatment
and the post-job reporting and evaluation, whereby the results of earlier fracjobs in
the same formation or in neighbouring fields, should be fully taken into account.
Well condition and parameters

During fracturing the well will be exposed to much higher pressures than during
production. Also, cooling down by cold fracturing fluids will cause forces in the
completion that can lead to ballooning, unseating of packers, etc. Therefore, the
well condition needs to be checked, by using e.g. the programme WSTUBE, which
is part of WELLCAT. In critical cases, the use of a tree-saver, and pressuring the
casing-tubing annulus can alleviate the problems to some extent.
The quality of the cement bond is another important factor, as a poor cement bond
may complicate the execution of a fracturing treatment.
As to the well parameters, the following data are required as input to ShellFrac and
AcidFrac:
- tubing inside diameter,

- length of tubing string (ah bthf), (default = depth to mid perforations)
- depth to mid perforations (tvd bthf),
- wellbore radius,
- perforated interval (net), (default = formation height)
- perforation diameter, (default = 6.26 mm = 0.246 inch)
- perforation density, (default = 4 shots/ft).
Reservoir and rock parameters

The following data on reservoir rock are required:
- Brinell Hardness or Elasticity Modulus,

- Poisson’s ratio, (default = 0.25)
- compressibility ratio, (default = 0.4)
- tensile strength, (default = 1.379 MPa = 200 psi)
- overburden gradient, (default = 0.02262 MPa/m = 1 psi/ft)
- minimum horizontal stress (downhole),
- Instantaneous Shut-In Pressure, to be measured during minifrac test,
- overpressure at shut-in, to be measured during minifrac test,
- fluid-loss coefficient.
Apart from the above data required for input into the fracture simulator,
mineralogical evaluations of formation material are also of importance in the
design of an acid fracturing treatment. Mineralogy can be determined by X-ray
72 • Acid fracturing design guidelines Stimulation Field Guidelines - Carbonate Stimulation
diffraction analysis and SEM examinations. While for this purpose cuttings can be
used as a sample, the use of whole cores is preferred, which are also required for
determination of the acid reaction rate parameters (see later).
On reservoir flow, the following data are required:
- drainage radius,
- formation height,
- porosity,
- permeability,
- reservoir temperature,
- reservoir pressure,
- pressure drawdown / overbalance.
On reservoir fluid, the following data are required:
- specific gravity,
- gas-oil ratio (only for oil), (default = 90 m3/m3 = 500 scf/bbl)
- average water saturation, (default = 0.5)
- reservoir fluid viscosity, (default = calculated by ShellFrac)
- reservoir fluid compressibility, (default = calculated by ShellFrac).
Not all of the above data are essential to arrive at a properly calculated design, and
in case of lacking data, default values are used in the calculations.
Treatment type
There are various treatment types from which the designer can choose the one most
applicable to the existing conditions.
In a conventional, standard acid fracturing treatment, at most three stages are

pumped: preflush, acid and overflush. The preflush, which can be a waterbase
filtercake building pad or a pad of a linear gel that does not build a polymer cake,
is used to initiate a fracture and lower the temperature around the fracture. When
plain acid is used, acid reaction is very fast, dissolving large amounts of rock near
the wellbore, but creating little penetration distance. Reaction retarding additives
can be added to slow down the acid spending rate, or the acid can be gelled. An
optimum design must compromise between acid penetration distance and rock
dissolving efficiency. The function of the overflush is to push the acid volume
forward, thereby increasing the penetration distance and dissolving rock further
from the wellbore. For plain acid, a large overflush is not needed, because it cannot
efficiently increase penetration distance. However, if the acid reaction is retarded,
an overflush can be very effective in increasing penetration distance.
A viscous fingering treatment consists of pumping a viscous preflush prior to the

acid, with a viscosity difference of at least 50 cp, by which considerable viscous
fingering can occur. Since the acid is less viscous and goes forward through a
narrow channel created inside the viscous preflush region, it moves forward much
faster than the viscous preflush. Once the channels overtake the viscous preflush,
they are assumed to widen to cover the complete gross height.
Acid fingering has three positive effects:
1. The overall velocity of the acid in the fracture is increased slightly by

the fingering behaviour.
2. The acid-etched length is increased.
3. The acid leakoff area is decreased.
The WISPER process has been developed for homogeneous carbonates, whereby
the viscous fingers are created through widely spaced groups of perforations, and
with a viscosity difference between the pad and the acid of around 300, to avoid
merging of the fingers. The acid will contact only a fraction of the total fracture
surface, resulting in a limited relative etched height. In AcidFrac the default value
for relative etched height is 0.4.
In the alternating stages type treatment, the fracture is created by a gelled water
pad, after which alternating stages of acid and additional pad are pumped. The
additional pad stages are designed to enter and seal wormholes created by the
preceding stage of acid. Acid leakoff into wormholes is thus slowed down, and
treatment efficiency is improved.
A fine particulate solid is often added to the pad stages to aid in fluid-loss control.
Examples are 100 mesh sand, oil-soluble resins, and fine salt. These particulates
help bridge wormholes and natural fractures.
Acid leakoff can also be reduced by gelling the acid. This method of control has
become widely used with the development of more acid-stable thickening agents.
Some viscous acid systems make use of an in-situ crosslinker (Zonal Coverage
Acid, ZCA, of Halliburton and Leakoff Control Acids, LCA, of Schlumberger,
Enhanced Acid System, EAS, of BJ Services). As the acid leaks off through
wormholes, the fluid crosslinks to plug the wormhole, stopping fluid loss. By
maintaining more live acid in the fracture, a longer fracture of higher conductivity
is achieved. As the reaction continues, the crosslink breaks, allowing easy cleanup.
There are also truly crosslinked acid systems, like XL Acid III of BJ, which have a
viscosity in excess of 500 cp, and thus provide excellent fracture propagation and
leakoff control characteristics. However, the very high viscosity may limit their
application, depending on the wellbore configuration.
As a special case, the closed-fracture acidising (CFA) technique can be used in

situations where it is desired to reopen previously created fractures by pumping a
prepad fluid at high rates. The fractures are then allowed to close naturally, or part
of the prepad is flowed back to force the fractures to close. Next, acid and any
necessary additives and diverters are pumped below fracturing pressure. This
technique can also be used immediately after an acid fracturing treatment, for
enhanced etched fracture conductivity.
Frac-fluid and acid type

After choosing a treating technique, treatment designers must select the fluid
system(s) best suited for that technique. The selection of fracturing fluid and acid
type depends mostly on reservoir mineralogy and bottomhole temperature. When
using a gelled pad to create a hydraulic fracture, the fluid must remain in the
induced fracture to propagate the fracture to the desired length. Accurate fluid-loss
and rheological data are essential to a good hydraulic fracture design. Fracturing
fluid is lost initially through spurt loss, which is the fluid lost instantaneously on
initial exposure to newly created fracture walls, before the overall fluid-loss
coefficient starts controlling leakoff. Fluid leakoff can be reduced by adding fluid-
loss material to the fluid system.
The most common acid used has always been (and still is) hydrochloric acid. As the
objective of most acid fracturing treatments will be to maximise the acid
penetration, acid leakoff control will be the most important aspect to consider. As
discussed above, this can be achieved by using acid fluid-loss additives, or by
gelling the acid system, or a combination thereof. However, in particular oil-soluble
resins have as a limitation for their use, the high concentration of additive required
for fluid-loss control, of some 200 lbm resin mixture/1000 gal acid.
Guidelines for the selection of acid type as a function of bottomhole temperature

and for soft chalks, calcite and dolomite, for both gas and oil reservoirs, are
summarised in Figure 21. In particular for chalks and limestones, at temperatures
above 100 ºC, the use of retarded acids, such as acid-in-oil emulsions can be
considered, or the application of cooldown procedures. For dolomites the
temperature for these possibilities to be considered, should be some 50 ºC higher.
For acid fracturing treatments in high temperature formations (> 150 ºC), the use of
(gelled) organic acids, if economically justified, should also be considered.
The use of foamed acids can be considered when the reservoir has a low
bottomhole pressure, and load water recovery would require extensive swabbing
time. Moreover foamed acids have good fines recovery capabilities. Deep
penetration of live acid is not as likely because of rapid spending, and the wellhead
pressure will be higher because of increased friction pressure and lower hydrostatic
pressure.

Selection of acid type
Gas Treatment size
Small Medium Large

(< 1m3/m) (1 - 5 m3/m) (> 5m3/m)
Soft chalk
Temperature < 50 ºC + - *
Temperature 50 - 100 ºC - * *
Temperature > 100 ºC * * *
Calcite
Temperature < 50 ºC + + -
Temperature 50 - 100 ºC - - *
Temperature > 100 ºC - * *
Dolomite
Temperature < 50 ºC + + +
Temperature 50 - 100 ºC + + -
Temperature > 100 ºC + - *
Oil
Soft chalk
Temperature < 50 ºC + + -
Temperature 50 - 100 ºC + - *
Temperature > 100 ºC - * *
Calcite
Temperature 50 - 100 ºC + - -
Temperature > 100 ºC - - *
Dolomite
Temperature 50 - 100 ºC + + -
Temperature > 100 ºC + + -
Legend: * Retarded HCI - 15% HCI + 28% HCI
Figure 21 - Acid fracturing selection chart

Acid reaction rate parameters
Acid reaction rate parameters relate to acid solubility tests, rotating disk tests and
acid etched fracture conductivity tests.
From acid solubility tests it can be decided, whether to use acid fracturing or a
proppant fracture treatment. Moreover, these tests indicate the amount of fines that
may be released. Because of the potential amount of fines produced from a low-
solubility formation, treatment designers must determine a minimum acid solubility
at which the acid fracturing treatment should be performed.
Acid reaction rates, are an essential input parameter for AcidFrac. The designer has
three different options to specify the reaction rate:
1) If the reaction rate constant and the order of the reaction are known, they
can be directly input.
2) If this information is not available, acid reaction rates are preferably

measured in rotating disk equipment. The results of at least two,
preferably three, rotating disk experiments at different acid
concentrations are required. The following parameters need to be input
in AcidFrac:
• The overall reaction rate as determined in the rotating disk

experiment,
• The acid concentration (as wt. %),
• The rotational speed of disk.
3) If the reaction rate is not known, and (results from) a rotating disk is not
available, the reaction rate can also be determined from hollow core
experiments. Again, the parameters of two experiments have to be
specified. For further details, reference is made to the ShellFrac Users
Manual (SIEP 98-5225).
In Appendix III a brief summary is given on acid reation rates of carbonate rock,
and on relationships for the reaction of limestones and dolomites with hydrochloric
acid.
Acid etching tests are performed to measure the conductivity of the created and
acid-etched fracture, as a function of acid strength, gelling agents and closure
stress. One of the results may be that although good rock dissolution can be
achieved, the fracture faces are etched uniformly, such that poor differential etching
was achieved. This would therefore indicate the need for a fingering-type
treatment.

Fracturing fluid additives

The most critical aspect for achieving a good acid fracturing treatment relates to
fluid-loss control, and therefore additives and/or gelling agents can be mixed with
the fracturing fluids, to control fluid loss through wormhole growth into the
fracture walls, or into natural fissures and fractures, intersecting the hydraulic
fracture. Various treating techniques and additives have been developed as means
of controlling acid fluid loss. These include:
• acid-gelling agents, or emulsified acid,
• addition of solid particulates, like oil-soluble resins, or 100-mesh sand,
• injection of gelled water pads, alternately spaced with stages of (gelled)

acid.
Many methods of thickening the acid exist. Filter cake-building polymers have
been widely used, but tests have indicated that the filter cake is quickly eroded and
penetrated by the acid. Once this occurs, acid fluid loss is identical to that observed
if no gelled pad were used. The use of viscosity building systems, which rely on the
acid generating viscosity over a narrow pH window, as the acid spends, has been
discussed in the literature as being excellent acid fracturing fluids.
A fine particulate solid is often added to the pad stages to aid in fluid-loss control.
For this purpose, the solid particles should be relatively large, since they need to
block the relatively large wormholes when they develop when acid leaks away
through the pore throats. Research has indicated, that the use of 100-mesh sand is
particularly suited for this purpose. It should be used at a starting concentration of
0.25 lb/gal and possibly reaching a concentration of 1 lb/gal.
When using alternating stages, the gelled pad stages are designed to enter and seal
wormholes created by the preceding acid stages. Acid leakoff into wormholes is
slowed, and the acid remains in the fracture longer and increases the amount of
rock removal along the induced fracture face, thus creating fracture-face
conductivity.
Placement technique and pump rate

In an acid fracturing treatment, sometimes the potential producing interval covers
several hundred feet in vertical and deviated wells, but almost certainly in
horizontal wells. For such a condition, the designer has to consider some form of
diversion otherwise the entire treatment may be placed in the section that first
breaks down at the lowest fracture initiation pressure. Diversion techniques that can
be considered in acid fracturing are packers and bridge plugs, ball sealers and
particulate diversion.

Packers and bridge plugs provide complete isolation by packing-off a section of
the completion interval, but the method is expensive since it requires the presence
of a rig. For horizontal wells, which frequently have been completed open hole or
with a slotted liner, this mechanical method is not suitable.
Ballsealers can be a very effective diversion means in acid fracturing of cased and
perforated completions, and they have also been successfully used in horizontal
wells. As said earlier, perforation orientation in deviated and horizontal wells is
critical for the efficient seating of the balls and the sealing off of perforations. In a
treatment pumped in stages, the balls should be added to the viscous carrying fluid
following the overflush sub-stages.
Particulate diversion can be used in acid fracturing treatments, when ball sealers
cannot be used for effective diversion. As the treating fluid is pumped into the first
initiated fracture, the particles can bridge on the perforations (or the wellbore in an
openhole completion). When sufficient particles accumulate, they cause a fracture to
be initiated in other sections of the formation. Granular diversion in horizontal wells
may not be a feasible option, because so many diverter stages would be required, that
the treatment would become prohibitively expensive. Diversion in horizontal open
holes may be achievable by placing large plugs of proppant, which has been used
succesfully in Shell hydraulic fracturing operations in sandstone formations.
An important design criterion of acid fracturing treatments is the pump rate, which
determines the created fracture dimensions and treating pressures. In most acid
fracturing treatments the fluids will be pumped at the highest achievable pump rate,
to achieve deeper penetration of the acid into the hydraulic fracture. The maximum
achievable pump rate depends on the horse power of the available equipment and
the maximum allowable bottom hole pressure, tubing friction and wellhead/
completion limitations.
The maximum allowable wellhead pressure, which can be taken as some

percentage of the maximum pressure rating of the surface equipment, can be
calculated by:
P w = σ min + P e – P h + P f
where
P w = maximum allowable wellhead pressure,
σ min = minimum in-situ effective stress
P e = fracture net pressure
P h = hydrostatic pressure
P f = total friction pressure

The fracture net pressure in acid fracturing is never larger than 250 psi. The
maximum injection rate can be calculated for any acidising fluid. Acid emulsions,
ungelled acids and foamed ungelled acids exhibit high friction pressure in the
tubulars, which may limit the maximum injection rate, thereby limiting acid
penetration into the fracture. Foams have another limiting factor, low hydrostatic
pressure, which can also limit injection rates.
Measure in-situ stress profile (if feasible)

In order to determine the most likely fracture geometry, ideally, detailed
information (in-situ stress and mechanical properties measurements at top and
bottom for relevant zones) is required for each layer. This information can be
obtained by carrying out several microfrac measurements, by injecting e.g. mud or
completion fluid into a small section (1 m, perforated or open hole), while
measuring (preferably downhole) the injection and fall-off pressure.
In practice, however, this method may be too expensive, and therefore logs are
being used to obtain a complete stress profile. Obtaining and processing sonic data
is the basis for logging systems that provide stress information. Basically, two
waveforms are analysed to provide the data. These waveforms are the P waves
(compressional) and the S waves (shear). Computer analysis processes the data and
produces the log presentation. The major logging companies offer special acoustic
logging services, such as the dipole shear sonic imaging, and the long-spaced sonic
and sonic digital tools (Schlumberger), for estimating the in-situ stress profile and
the mechanical properties of the formation. It must be emphasised, that these logs
need to be calibrated against actual in-situ stress measurements, and therefore at
least one microfrac measurement may still need to be carried out. Also, (extended)
casing leak-off tests may provide information on in-situ stress levels.
Schlumberger have recently developed an "in-situ stress logging" tool, which

allows stress measurements by isolating a small zone, pumping a small liquid
volume into it, and measuring the detailed pressure development during fracture
initiation, extension and flow-back.
To fully benefit from in-situ stress measurements, appropriate fracture models have
to be applied, with the assistence of SEPTAR. However, also without these
simulators a reasonable estimate of the extent of the fracture can be made, using
simpler models incorporated in ShellFrac.

Determine the optimum fracture length and
conductivity
The optimum fracture length and conductivity can be established through an
economic evaluation balancing the greater costs and risks of a large scale acid
fracturing treatment against the expected increase in well productivity. The
preferred tool for this is FraPS (Fracture Performance Simulator), a PC based
single well simulator for fractured wells. FraPS calculates the expected production
performance of both non-fractured as well as fractured wells and thus allows a
comparison of productivity improvements for various fracture sizes. It also
includes a cost/revenu evaluation (for gas only).
Calculate a detailed design using ShellFrac

and AcidFrac
ShellFrac is Shell’s computer program for the complete process of on-site
optimisation of a fracture treatment schedule. AcidFrac can be run together with
FracDesign, a module under ShellFrac, which is used to optimise the pumping
schedule, given certain fracture dimensions, or to determine the fracture
dimensions created by a certain pumping schedule.
For planning purposes with the contractor, the most likely pumping schedule, based
on, for instance, information from other wells, should be selected. Alternatively,
compare designs provided by the stimulation contractor, with designs obtained
through AcidFrac. Screen the treatment with the service company – acid fracturing
is a complex operation, that requires good coordination of all parties involved.
Carry out a minifrac (just) prior to the main acid fracturing treatment, to confirm:
• estimates of in – situ stress,
• leak – off coefficient,
• fracture overpressure.
Revise the treatment design on – site, if necessary, with ShellFrac/AcidFrac.

Basically, the question should be addressed, whether the fracture geometry as
determined with FraPS, can still be achieved. If not, the volumes involved should
be adjusted. Alternatively, the pad volume could be adjusted, according to a
"contingency design chart".

Appendix I
Commercially available matrix acidising systems
Halliburton – Carbonate 20/20 Matrix Acidising Systems
Acid Composition Advantages
Carbonate Completion Acid 10 to 28% HCl This totally soluble acid blend is
+ FDP-S562A inhibitor universally applicable to most well
+ FDP-S562B anti-sludge conditions. Designed to minimise
Optional: emulsion and sludge problems even
FDP-S562C H2S scavenger in sour wells.
FDP-S562D iron reducer
FDP-S562E dispersant
Carbonate Stimulation Acid 15% HCl Gelled acid improves stimulation

+ 2% SGA-HT results. Moderate viscosity enhances
Optional: zonal coverage and minimises fluid
1 to 4% gelling agent loss.
SGA-HT, SGA-II, SGA-III
Fines Recovery Acid 70 v/o nitrogen The system of choice for low-
30 v/o 20% HCl solubility formations. Gelling agent
(2.5% SGA-1 in the HCl) also functions as a foaming agent
and fines suspender. Foam enhances
fines carrying capacity and aids in
fluid recovery.
Carbonate Emulsion Acid 70 v/o 22% HCl Ultra-retarded acid system enhances
30 v/o diesel zonal coverage and efficiently
(2.5% AF-61 in the diesel) generates wormholes under nearly
all conditions.
Zonal Coverage Acid 15% HCl + 2% SGA-II The ultimate in-situ diversion for
+ 4.5% gal/Mgal XL-1 matrix acidising and fluid-loss
+ 2 gal/Mgal BF-1 control in fracture acidising.
+ 4 lb/Mgal Ferchek
Hot Rock Acid 9% Formic – 13% Acetic The system of choice when
+ 0.5% MSA-II corrosion concerns or formation
+ 0.5% LoSurf-259 compatibility problems preclude the
+ 1.5% SGA-HT use of HCl.
Note: Corrosion inhibitor packages will vary based on BHT, required contact time and tubular metallurgy. Job designers should always
conduct emulsion tests with a representative crude sample to ensure that the appropriate surfactant loadings are used.
Stimulation Field Guidelines - Carbonate Stimulation Appendix I • 83

Main Dowell Acid Formulations For Carbonate Matrix Acidising

Acid/Description Treatment / Reservoir Recommended Advantages
Conditions Applications
Dowell X Production restricted due to Matrix Acidising and Acid Economical and versatile
Inhibited HCl 5 to 15% damage or low formation Fracturing; Carbonate and
permeability (27 to 204 °C) Iron Scale Solvent
Super X Production restricted due Matrix Acidising or Acid Greater dissolving power
Inhibited concentrated to damage or low Fracturing; removal of than equal volume of
HCl formation permeability (27 formation damage or scale Dowell X
20 to 28% to 177 °C) deposits
XX Intensified Acid Low or damaged Matrix Acidising or Acid Accelerated reaction rate
Inhibited HCl with HF permeability in dolomite Fracturing with dolomite and
intensifier or siliceous limestone siliceous limestone
reservoirs (27 to 204 °C)
Super X EmulsionSXE 27 to 150 °C All applications Highly retarded with oil

Emulsified HCl i.e. 70/30 outside phase
HCl/oil
MSR 100, MSR 150 Drilling muds lost to the Matrix Acidising; Acid Brings back large amounts
Blend of 7.5 to 15% formation; or reservoir has Fracturing; Formation of muds and clays;
inhibited HCl and special a high percentage of silts Cleaning; Wellbore minimises reprecipitation
clay dispersing, suspen- and clays (27 to 121 °C) Cleanup and Gravel-Pack of dissolved iron
ding and chelating agents Cleanup Fluid
DGA100 Carbonate reservoirs Acid Fracturing; reactive Exceptional fluid-loss

Thickened inhibited 15% (especially older wells) stages in DUOFRAC II control and improved etch
HCl where wider and deeper treatments patterns; suspends and
penetrating fractures are removes silts and solids
needed (27 to 121 °C) with spent acid returns
DGA200 Low-temperature Acid Fracturing; Forma- Retarded reaction rate;

HCl thickened up to a carbonate reservoirs tion Cleaning of Fissured reduced leakoff, low vis-
maximum of 28% Reservoirs, DUOFRAC II cosity when spent for
treatments for low- good cleanup; liquid
temperature wells (66 °C) additive gels up to 28%
HCl
Continued on next page
84 • Appendix I Stimulation Field Guidelines - Carbonate Stimulation

Acid/Description Treatment / Reservoir Recommended Advantages
Conditions Applications
DGA300 High-temperature Acid Fracturing; Retarded reaction rate;

HCl thickened up to a carbonate reservoirs Formation Cleaning of reduced leakoff,
maximum of 28% Fissured Reservoirs, continuous- or batch-mix
DUOFRAC II treatments applications; stable at high
for high-temperature wells temperatures. Gels up to
(149 °C) 28% HCl
DGA400 Carbonate reservoirs less Acid Fracturing; Reduced leakoff; batch-

HCl thickened up to a than 149 °C Formation Cleaning of or continuous-mix
maximum of 28% Fissured Reservoirs; operations; stable at high
DUOFRAC II treatments temperatures
Foamed X Low-pressure, low- Acid Fracturing and Improved leakoff control

Stable inhibited HCl and permeability carbonate Formation Cleaning of and well cleanup with
foam; 55 to 85% foam reservoirs (27 to 121 °C) Fissured Reservoirs more efficient return of
quality treating fluids
SDA (Self Diverting Acid) Carbonate reservoirs less Formation Stimulation, Self diversion mechanism,
HCl thickened up to a than 149 °C Cleaning of Fissured deep acid penetration
maximum of 28% Reservoirs
Stimulation Field Guidelines - Carbonate Stimulation Appendix I • 85

BJ Services International Matrix Acidising Systems

Type/Name Purpose/Advantages
Lightly gelled acid High-rate, near-wellbore treatments. Excellent friction

Various strengths of HCl acid with low concentrations reduction.
of gellant (e.g. DSGA or AG-57L at 4 l/m3)
Gelled Acid 100, Gelled Acid 200, Gelled Weak Acid Enhanced zonal coverage, fines suspending and
Various strengths of HCl with various concentrations of reaction rate retardation
gellant
In-situ crosslinked acid, (Enhanced Acid System) Effective diversion for treatment of long intervals,
Various strengths of HCl, 5 to 28% horizontal wells
XL Acid III (various strengths of crosslinked HCl acid) Suitable for high viscosity diversion stages in matrix
acid treatments
Emulsified acid systems (oil outside phase) Improved zonal coverage, deeper acid penetration, long
wormholes
Foamed acid Improved diversion, leak off control and fines recovery
Organic acid High-temperature treatments
Specialty acid systems, e.g. One Shot Acid "Plus" Treatment of asphaltenes and sludges.
Blend of aromatic solvents and acid
86 • Appendix I Stimulation Field Guidelines - Carbonate Stimulation

Appendix II
Maximum injection rate for matrix treatments

The maximum injection rate, q imax , into a vertical well under matrix conditions,
is given in Equation I. This equation is a simplified inflow performance
relationship: it does not account for transient effects, multiphase flow, or reservoir
heterogeneities. The injected fluid is assumed to be incompressible. The effective
permeability is the permeability to the injected fluid. The value of maximum
injection rate is obtained with the initial skin value, and can therefore be used only
as a guideline for determining the initial rate.
_
4.917 x 10 - 6 kh ( P fg x d - ∆ps - p r )
q i max = (I)
µβ ( ln rs / rw + S )
If the fracture gradient, P fg , is not known, it can be estimated by adding 0.25 psi/ft
to the bottomhole static pressure gradient (a good estimate for areas not tectonically
active).
The fracture gradient can also be estimated from the following relationship:
ν
P fg = ( σ V – p) + p ( II)
(1-ν)
The maximum injection rate into a horizontal well under matrix conditions, is
calculated by using equation III:
4.92 x 10 – 6 L √ k H k V
q i max = ( P fg x d - ∆ps - p_ r ) ( III ) , where
µBF
8 hB π LW ( h – LW )
F = 1/2 ln { ___________ cot [ _____ ] } + 1/2 { S - ________ β} ( IV )
π rw( 1 + β ) 2h L
Stimulation Field Guidelines - Carbonate Stimulation Appendix II • 87

Equation III indicates that the maximum injection rate is directly proportional to the
length of the horizontal reach of the well, and normally the maximum injection rate
in a horizontal well is significantly higher than in a vertical well, completed in the
same formation.
Nomenclature
B = formation volume factor (res bbl/stb)
P fg = fracture gradient ( psi/ft)
h = net height of the formation (ft)
d = true vertical depth (ft)
k = undamaged permeability (mD)
kH = horizontal permeability (mD)
kV = vertical permeability (mD)
∆
_ ps = safety margin, 200 to 500 psi
pr = average reservoir pressure (psi)
qi = injection rate, bpm
rs = drainage radius (ft)
rw = wellbore radius (ft)
S = skin factor, dimensionless
β = √ kH kV
L = length of horizontal reach of well (ft)
LW = distance from reservoir bottom to horizontal well (ft)
µ = viscosity of injection fluid (cp)
ν = Poisson’s ratio (dimensionless)
σv = overburden pressure (psi)
p = pore pressure (psi)
88 • Appendix II Stimulation Field Guidelines - Carbonate Stimulation

Appendix III
Acid reaction rates of carbonate rock

The kinetics of a reaction between hydrochloric acid and carbonate rock (limestone
or dolomite) may be described by a power law relationship:
R = k Con (I)
where
R = reaction rate, (kg m -2 s -1)
k = reaction rate constant, (kg 1 – n m 3n – 2 s -1)
Co = original acid concentration, (kg m -3)
n = order of reaction
The term "reaction rate constant", (k), is actually a misnomer, since k will vary
with temperature. For dolomites, where the reaction of HCl with the rock is almost
entirely controlled by the reaction at the surface, the temperature dependency of
the reaction rate constant can be described by the following Arrhenius Law
expression:
k = A o exp ( – E a / RT ) (II)
where
E a = activation energy, (kJ/mol)
R = gas constant, (8.3143 J/mol K)
T = temperature, (K)
A o = pre-exponential factor, (kg 1– n m 3n – 2 s -1)
For calcites, where the surface reaction rate can be considered to be almost
instantaneous (compared with the diffusion process, see also Fig. 3), the effect of
the temperature on the reaction rate constant is determined almost completely by
that of the temperature on the effective diffusion coefficient of the mass-transfer
process, which is a function of the temperature itself and the temperature dependent
viscosity.
Stimulation Field Guidelines - Carbonate Stimulation Appendix III • 89

Acid reaction rates are preferably measured in rotating disk equipment, but they
can also be determined from hollow-core experiments, and less often from parallel
plate tests. These latter tests are mostly used for studying acid-etched
conductivities. If carefully conducted, reactivity data from these various tests will
be consistent with each other.
Acid reaction tests in rotating disk equipment are commonly performed at standard
conditions, which at SEPTAR (Shell Exploration and Production Technology
Applications and Research) are 65 ºC and 100 rpm (318 s – 1). These reaction rate
parameters are then used as input for the AcidFrac programme, which will make the
necessary corrections, through experimental correlation functions, for temperature
and shear rate effects, expected to exist during the acid fracturing treatment.
In Table I a summary is given of some reactivity data for various carbonates, with
HCl at 65 ºC, at 100 rpm.
Reaction rate Reaction rate constant

order, n k
10 – 5 kg1 – n m3n – 2 s –1
Limestones
Carrara marble 1.0 7.0

Maastrichtian chalk 1.71 0.18
Abu Dhabi chalk 0.72 12.0
Gorm chalk (North Sea) 1.28 2.3
Qatar chalk 0.90 5.4
Yibal chalk (Oman) 1.23 1.8
Indiana limestone (US) 1.24 3.2
US formations (average, 38 ºC) 0.24 2.9
(range 0.13 – 0.31) (range 1.1 – 5.17)
Dolomites
Belgian outcrop 0.7 11.0

Stassfurt carbonate (Germany) 0.7 5.5
Canadian dolomites 0.7 5.0
US formations (average, 38 ºC) 0.37 7.6
(range 0.22 – 0.55) (range 2.0 – 9.5)
Table I - Reaction rate parameters for various carbonates
90 • Appendix III Stimulation Field Guidelines - Carbonate Stimulation

The numerous rotating disk experiments carried out at SEPTAR, have led to
generalised equations for the dissolution rate of carbonate rock in HCl. For
limestones and chalk, the dissolution in HCl at 65 ºC and a shear rate of 318 s – 1
(100 rpm) can be described with sufficient accuracy by the following equation:
R = 3.0 x 10 – 5 C o1.20 (III)
For the dissolution of dolomites with HCl, the reaction rate has been determined as
follows:
R = 33 e – 33000/ RT Co 0.5 (IV)
The relationship for dolomites was validated with rotating disk measurements for
temperatures ranging between 25 ºC and 95 ºC. The activation energy was
determined to be 33 ± 2 kJ/mol.
The above relationships have been incorporated in the AcidFrac programme as a

default, and they can be used if no measured reaction data of the formation to be
stimulated, are available. Alternatively, the design engineer can select appropriate
parameters from Table I. In general, however, it can be stated that it is best practice
to determine reactivity data in the laboratory as a function of temperature for each
carbonate considered for an acid fracturing treatment.
When acid fracturing of high-temperature carbonate formations is being planned,

the use of retarded acids can be considered, since retarded acid penetrates more
deeply into the hydraulic fracture, thereby increasing acid-etched length. The acid
retardation factor, RF, is defined as the reaction rate of plain, non-retarded, acid
over the reaction rate of retarded acid. Plain acid can be 15% or 28% HCl, and both
reaction rates are measured at the same shear rate and temperature. Table II
provides approximate retardation factors for various acid systems, used in acid
fracturing, at different temperatures.
95 ºC 65 ºC 25 ºC
Acid 15% 28% 15% 28% 15% 28%
Type
Plain 1.0 1.0 1.0 1.0 1.0 1.0

Linear gelled 2.6 2.7 2.5 2.1 1.3 1.1
(DSGA)
Oil-external 6.5 3.4 11.0 2.7 34.0 2.8
emulsion
Acid-external - 3.0 - 4.7 - 1.1
emulsion
Organic/HCl 1.5 - 1.6 - 1.3 -
Table II - RFs of different retarded acids
Stimulation Field Guidelines - Carbonate Stimulation Appendix III • 91

Index
A
Inhomogeneous, 19, 23
Acetic acid, 5, 63 Naturally fractured, 54
AcidFrac, 16, 32 Soft, 30
Acid fracturing, 2, 14, 27, 71 Chalk formation, 30
Acid placement, 35 Chelating agents, 19
Acid reaction rate, 6, 77, 89 Chemical diversion, 39
Acid reaction test, 47 Closed fracture acidising, 30, 74
Acid solubility, 27, 46 Coiled tubing, 37
Acid spending, 6, 29 Compact dissolution, 19, 20
Acid systems, 64, 83 Corrosion
Acid wash/soak, 17 Inhibition, 26, 59, 65
Additives, 65, 66 Laboratory testing, 60
Alternating stages, 28, 64, 74, 78 Crosslinked acid, 42, 64, 74
Anhydrite, 62
D
B
Damage classification, 11, 62
BALLSEAL, 38 Damage ratio, 44
Ballsealers, 37 Deep damage, 17, 55
Benzoic acid, 39 Differential etching, 27
BHN, 46, 72 Dissolving power, 5
Biopolymer, 41 Diversion, 25, 35
Bottomhole temperature, 63 Dolomites, 3
Bridge plugs, 36 Dolomitisation, 3
C E
Calcite, 3 EDTA, 19
Candidate selection, 11 Emulsified acid, 23, 24, 42, 64
Carbonates Environmental considerations, 24
Composition, 3, 46 Exploration wells, 56
Homogeneous, 31 External casing packer, 36
Stimulation Field Guidelines - Carbonate Stimulation Index • 93
F L
Fines, 18, 43, 77 Limestones, 3
Fluid compatibility, 46, 63 Low permeability reservoirs,15
Fluid loss control, 28 Low temperature wells, 60
Foamed acid, 28, 43, 65, 75
Formic acid, 5
Frac fluid, 75 M
Fracture conductivity, 29
Fracture etching, 29 MAPDIR technique, 43
Fracture gradient, 87 Matrix treatment, 13, 17, 61
Fracture width, 29 Maximum allowable rate, 67, 87
Fracturing pressure, 79 Mechanical diversion, 36
FraPS, 81 Microemulsions, 23
Mud and silt remover, 56, 64
Mud losses, 54, 55
G
Gelled acid, 23, 29, 41, 64 N
Gypsum, 62
Natural fractures, 54
Non-acid matrix treatments, 66
H Non-Newtonian fluids, 41
Heterogeneous carbonates, 23
High pressure wells, 58 O
High temperature wells, 59
Hollow-core test. 49 Oil soluble resins, 28, 39
Homogeneous carbonates, 31 Optimum pump rate, 21
Horizontal wells, 53 Organic acid, 5
Hydroxy Propyl Guar (HPG), 32
P
I
Paccaloni, 43
Impairment Packers, 36
Drilling, completion, 11 Parallel plate test, 50
Injected fluids, 11 Particulate diversion agents, 39
Produced fluids, 11 Peclet number, 20, 21
Inhomogeneous carbonates, 23, 27 Petrographic analysis, 46
In-situ stress, 80 Pickling, 65
Insoluble minerals, 62 PLACE, 39
Placement strategy, 68
Poisson’s ratio, 46, 72
J Porosity
Primary, 4
Jetting-tool, 37, 68, 69 Secondary, 4
94 • Index Stimulation Field Guidelines - Carbonate Stimulation
Propped acid fracturing, 30 V
Pseudoskin, 10, 61
Viscosified acid, 41
Viscous diversion, 41
R Viscous fingering, 31, 73
Viscous pad, 30
Radial fingering, 32
Reaction rate, 6, 89
Reducing agent, 41 W
Retardation, 23, 25
Retardation factor, 26, 91 Wellbore geometry, 69
Retarded acid, 23, 25, 26, 59, 91 WISPER technique, 31, 74
Rock strength, 46 Wormholes, 1, 19, 20
Rotating disk test, 48
S
Selective placement tool, 36
Self diversion, 24, 41
Sequestering agent, 26, 65
Shallow damage, 17
Shear-thinning fluid, 41
ShellFlo-S, 41
ShellFrac, 16, 33
Sludge, 47
Skin factor, 9
Soft carbonates, 30
Static reaction test, 48
STIM2001, 16, 35
Stress profile, 80
T
Thick walled cylinder testing, 46
Treatment design, 16
U
Uniform dissolution, 19
Stimulation Field Guidelines - Carbonate Stimulation Index • 95

SHELL INTERNATIONAL EXPLORATION AND PRODUCTION B.V.

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SIEP 99-5638

© SIEP B.V. 1999

SHELL INTERNATIONAL EXPLORATION AND PRODUCTION B.V.

Further copies can be obtained from the STEP Library.

The use of Halliburton and Schlumberger Dowell documentation is gratefully

Stimulation Field Guidelines - Carbonate Stimulation Acknowledgment • i

Properties of carbonate rock 3

Stimulation selection considerations 9

iv • Contents Stimulation Field Guidelines - Carbonate Stimulation

Acid fracturing design guidelines 71

Appendix I Commercially available matrix acidising systems 83

Appendix II Maximum injection rate for matrix treatments 87

Appendix III Acid reaction rates of carbonate rock 89

Stimulation Field Guidelines - Carbonate Stimulation Contents • v

In general, well stimulation techniques mostly relate to chemical and mechanical

As to mechanical well stimulation, hydraulic fracturing in sandstones involves the

Acid fracturing in carbonates is a stimulation technique in which acid is injected at

Since such acidising is now recognised as a fracturing process, fracturing principles

2 • Introduction Stimulation Field Guidelines - Carbonate Stimulation

2 CaCO3 + Mg++ → CaMg(CO3) 2 + Ca++

Stimulation Field Guidelines - Carbonate Stimulation Properties of carbonate rock • 3

Impurities (Clay, silt, etc.)

Impure dolomite Impure Impure Impure limestone

100% Dolomite 50% 100% Limestone

Figure 1 - Classification of carbonates

Well-defined porosity/permeability relationships generally do not exist for

CO3-- + 2 H + ↔ CO2 + H2O

Hydrochloric acid, the most commonly used acid in carbonate stimulation, is

Acid/carbonate dissolving power

Stimulation Field Guidelines - Carbonate Stimulation Properties of carbonate rock • 5

Acid/carbonate dissolving power

Acid/rock combination Acid concentration

5% 10% 15% 30%

HCI/Limestone 0.026 0.053 0.082 0.175

Figure 2 - Dissolving power of various acids

Acid/rock reaction rate

2. The actual acid/rock reaction rate at the rock surface.

6 • Properties of carbonate rock Stimulation Field Guidelines - Carbonate Stimulation

1. Transport of acid to rock

Figure 3 - Pictorial view of acid/carbonate rock reaction

Stimulation Field Guidelines - Carbonate Stimulation Properties of carbonate rock • 7

Rock matrix : 10% porosity, 10 mD permeability 28,000 : 1

8 • Properties of carbonate rock Stimulation Field Guidelines - Carbonate Stimulation

Problem well identification

• Well completion (type and size of tubulars, perforations, downhole

• Reservoir potential (what is the matrix permeability?)

• Existence and (potential) causes of damage

• If damage is present, what is the skin factor?

Depending on the outcome of such initial screening of above aspects, it can

Analysis of the skin factor

Stimulation Field Guidelines - Carbonate Stimulation Stimulation selection considerations • 9

Stot : Total skin factor (Horner skin)

Sdam = Stot – ( Sperf + Sturb + Sdev + Sgravel + Sstim + Stemp + Sfiss )

10 • Stimulation selection considerations Stimulation Field Guidelines - Carbonate Stimulation

• Impairment related to drilling, completion and workover operations.

• Impairment induced by the produced fluids (or in case of injection wells,

• Impairment as a result of injected fluids during specific operations, such

• The reservoir must contain adequate volumes of moveable hydrocarbons,

• The gross reservoir height for an acid fracturing treatment should be at

Stimulation Field Guidelines - Carbonate Stimulation Stimulation selection considerations • 11