FLOW ENHANCEMENT

- PART 1: INTRO TO WELL STIMULATION

- PART 2: MATRIX ACIDIZING
- PART 3: HYDRAULIC FRACTURING

by Mohd Fahmi Mustapah

Senior Production Technologist
Majnoon Asset Technical Team (ATT)

30th Jun. 2016

Shell Iraq Petroleum Development B.V.

 PART 2.2: MATRIX ACIDIZING OF
CARBONATES

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 OUTLINE

• Part 2.1
• Introduction
• Candidate Selection
• Matrix Acidizing of Sandstones
• Part 2.2
• Matrix Acidizing of Carbonates
• Part 2.3
• Non-acid Treatments & Additives
• Part 2.4
• Placement/Diversion Techniques
• Lab Experiments
• Part 2.5
• STIM2001 Tool

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 INTRODUCTION

• Whereas the purpose of sandstone acidizing is to dissolve the damage, the primary objective of
matrix acidizing in carbonates is to dissolve the matrix, 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.
• Carbonate acidizing with HCl only (so without HF), is not complicated by a tendency for
precipitates to form, as is the case for sandstone acidizing.
• The reaction products CaCl2, MgCl2 (dolomites) & CO2 are quite water-soluble. Therefore, the
formation of a precipitate or a separate CO2-rich phase is generally not a problem.
• However, despite the simplified chemistry, HCl acidizing of carbonates is a difficult process to
model.
• The reason for this is the high rate at which the reactions take place as compared with that of
HF with the various minerals prevalent in sandstones.

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 PROPERTIES OF CARBONATE ROCK

Composition
• Carbonate rocks have been created by
chemical and biological processes in a
water environment.
• Dissolved carbonates can re-precipitate
when mixed with other waters.
• Marine life often plays an important role
in creating carbonate rocks (shells,
skeletons, etc.).
• Subsequent reactions cause re-
crystallisation. This is instrumental in
the formation of dolomite, for instance.
• The presence of iron may then result in
Classification of carbonates
the formation of siderite (FeCO3).

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 PROPERTIES OF CARBONATE ROCK

Limestones
• 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 color to dolomites,
which may be white, gray, yellowish or blue in color.
Dolomites
• Dolomites are rocks, which contain more than 50% of the minerals dolomite [CaMg(CO 3)2]
and calcite (plus aragonite), with dolomite being more dominant.
• Dolomitisation of carbonate rock, 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.

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 PROPERTIES OF CARBONATE ROCK

Porosity/Permeability
• Porosity of carbonates is of a different nature than the intergranular porosity of sandstones.
• Primary porosity in limestones includes openings between the individual constituent particles
of detrital carbonate rock 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 mineralogical 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
cores, because of the fractured nature of many of these rocks.

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 PROPERTIES OF CARBONATE ROCK

Acids used
• 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 with sandstones.
• The common acids used to stimulate carbonate formations are:
• Hydrochloric acid (HCl)
• Acetic acid (CH3COOH)
• Formic acid (HCOOH)

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 PROPERTIES OF CARBONATE ROCK

Hydrochloric acid (HCl)

• The most commonly used acid in carbonate stimulation, is ordinarily supplied in concentrations
32-36%.
• In well treatments, its normal strength is 15% wt., but the use of a higher concentration of 28%
wt. has also become more popular, in particular for dolomites and shallow, low-temperature
carbonate formations.
Organic Acids (Acetic Acid & Formic Acid)
• Organic acids are weakly ionized, slow-reacting acids, and they do not spend to completion
downhole.
• They are used in high-temperature (> 120 °C) formations, since they are easier to inhibit against
corrosion than HCl.
• For field use they are normally diluted to 10%.
• At concentrations higher than 15% calcium acetate/formate can precipitate.

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 PROPERTIES OF CARBONATE ROCK

• Hydrochloric acid 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.
• Table below shows dissolving capacities of some of these acids:

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 PROPERTIES OF CARBONATE ROCK

Acid/Carbonate Spending Rate

• The rate of HCl-carbonate reactions is usually high, and can be assumed infinite for most
practical purposes.

Factors that affect the overall spending rate include:

• Temperature
• Acid spending rate increases rapidly with temperature.
• A temperature increase of 20-30 °C will about double the spending rate.
• Rock type
• Calcite reacts faster than dolomite.
• This difference is especially important in relatively cool wells.
• However, above a temp. of about 70 °C, the reaction rate with both dolomite & calcite is so high, that the
overall spending rate is determined by mass transport effects.
• So at higher temperatures the difference in reaction rate between calcite and dolomite is of no importance
for the overall spending rate.

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 PROPERTIES OF CARBONATE ROCK

• Acid concentration
• The initial reaction rate of HCl with carbonate rock is nearly proportional with acid concentration up to about
20%.
• Above 20%, the increase is less, reaching a maximum at around 25%, above which the rate actually decreases
due to the large volumes of CaCl2 and CO2 generated in solution.
• Area/volume ratio
• The spending rate of acid is proportional to the surface area that comes in contact with a given volume of acid.
This area/vol. ratio is inversely proportional to the pore channel diameter or fracture width.
• 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).
• It is therefore very difficult to achieve deep penetration of live acid in matrix stimulation treatments.
• In natural fractures, or in a wellbore, acid will have an extended reaction time because of the limited surface
area for reaction.
• Acid type
• HCl acid will react fast, with usually little acid penetration into the formation.
• Weak acids, such as acetic acid and formic acid, react (much) slower and are a good alternative in e.g. high-
temperature wells, where HCl acid spends too rapidly.
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 MATRIX ACIDIZING OF CARBONATES

• The successful matrix stimulation of carbonate reservoirs requires that live

acid penetrate past the formation damage.
• Because of the high reaction rate, HCl tends to etch (carve or cut) preferred
pathways in carbonate rock, apparently following local high-permeability
streaks, rather than progressing through the formation as a uniform front, as
is the case in sandstone acidizing.
• These pathways are soon enlarged by acid reacting at the walls into
sizeable holes that have a diameter much larger than that of naturally
occurring pores.
• This process continues until a few large holes become so dominant that
essentially all the injected acid flows through these pathways, both
enlarging and extending these so-called wormholes.

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 MATRIX ACIDIZING OF CARBONATES

Wormholes
• Wormholing depends mainly on
three processes:
• surface reaction rate, which
determines how fast the acid
reacts with 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.

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 MATRIX ACIDIZING OF CARBONATES

Optimum Injection Rate

• For a carbonate matrix stimulation treatment to be successful, it is important to
acidize under conditions that will lead to the formation of deep penetrating
wormholes, that bypass the formation damage, using minimal acid volumes.
• There are three prevailing theories in the literature that estimate the efficacy of acid
stimulation treatments in carbonate formations.
• These theories predict the conditions at which wormhole formation occurs most
efficiently, and these are based on the existence of:
1. An optimum injection rate at a transition between reaction-rate limited and
fluid-loss limited regimes,
2. An optimum Peclet number (defined as the ratio of transport by convection to
transport by diffusion),
3. An optimum Damköhler (Da) number (defined as the ratio of the overall rate
of dissolution to the rate of transport by convection).

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 MATRIX ACIDIZING OF CARBONATES

• The above models have

been tested in lab
experiments & in field
validations.
• While each of these
models have their merits
and technical limitations,
they also show the
existence of an optimum
injection rate for
carbonate acidizing, i.e.
the formation of deep
penetrating wormholes
using minimal acid
volumes.
Optimum injection rates for the dissolution of limestone by
various stimulation fluids at 22 °C
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 MATRIX ACIDIZING OF CARBONATES

Acid Systems/Treatment Fluids

• The acid system selected should be compatible with the formation matrix,
formation fluids, tubulars and wellbore fluids.
• A significant number of acid formulations has occurred, 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.

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 MATRIX ACIDIZING OF CARBONATES

• Hydrochloric acid
• HCl is the acid of choice in carbonate acidizing.
• The strength of the acid (15-28%) is primarily determined by the bottomhole
temperature.
• At temperatures higher than 150 °C, HCl is usually precluded because of
excessive corrosion, and organic acids are recommended.
• In most matrix treatments of carbonates, the acid is (lightly) gelled to improve
zonal coverage of the acid, to retard the acid reaction rate, and to improve its
fines-suspending properties.
• Organic acids
• Organic acids are used instead of HCl when high bottomhole temperatures
prevent efficient protection against corrosion, or for conditions where prolonged
reaction times are required.

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 MATRIX ACIDIZING OF CARBONATES

• Gelled acids
• Gelled acids were developed primarily for acid fracturing, but they have also
found application in matrix acidizing.
• Acid viscosified with polymers is of particular interest for long horizontal wells,
since an enhanced zonal coverage over the wellbore interval is achieved.
• Gelled acids are also used in fissured or vugular formations with low primary
porosity.
• 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.

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 MATRIX ACIDIZING OF CARBONATES

• Emulsions
• Acid-internal emulsions are obtained by mixing acid with a produced crude or
refined-oil base fluid, in the presence of a surfactant.
• Emulsified HCl, like gelled HCl, is a retarded acid system, since the acid
diffusion rate is decreased, thus retarding the overall acid spending rate.
• Emulsified acids are effective stimulation fluids at low rates, and their main
advantage is a deep penetration, particularly in heterogeneous carbonate
formations with zones of low injectivity.
• The high viscosity improves wellbore coverage, through a self-diverting effect.

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 MATRIX ACIDIZING OF CARBONATES

• In-situ crosslinked acid

• A system that has been successfully used for viscous diversion in carbonates
consists 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 crosslinked gel will effectively stop any further fluid invasion, and divert
subsequent neat acid stages to different parts of the interval.
• The crosslink will break upon further spending, and at a pH value 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 successful treatments have been performed in long horizontal
open hole completions.

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 MATRIX ACIDIZING OF CARBONATES

• Foams
• Foam can be injected as a spacer between treatment stages (multi-stage process)
or, alternatively, part or all (one-stage process) of the acid can be injected as
foam.
• Foamed acids are operationally and logistically more complex to use than
polymer-viscosified acids.
• They require extra equipment and a liquid nitrogen supply.

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 TREATMENT DESIGN CONSIDERATIONS

• Damage is usually limited to the first few inches around

the wellbore.
• In carbonates the radial distribution of such damage may
be affected by the presence of vugs, fractures, etc.
• Impairment removal in carbonates hinges on bypassing,
rather than actual removal of the damage by dissolution.
• Carbonate acidizing design procedures will be discussed
in detail in the session on treatment design with
STIM2001.
• When the damage is very shallow, or is located in the
perforations in new completions or after a workover, an
acid wash or soak can be considered to clean the
perforations.

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 TREATMENT DESIGN CONSIDERATIONS

• Acid wash or soak

• An acid 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 treatment, the rate at which the impairment
is removed is slow.
• Applying some pressure can be used to invoke some fluid movement, but a max
injection rate of some 0.0002 m3/min/m should not be exceeded, to prevent
wormholing.

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 TREATMENT DESIGN CONSIDERATIONS

• The following treatment guidelines apply in perforated completions:

1. Use 28% HCl to maximize 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 used, by circulating two times the tubing content
with 12% 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.

• Lab experiments may help to find the optimum fluid composition & soaking times.
• In some cases it can be considered to use gelling agents during wellbore cleanouts, to
help transport fines out of the wellbore.

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TREATMENT DESIGN CONSIDERATIONS
Carbonate treatment selection chart

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TREATMENT DESIGN CONSIDERATIONS
Acid selection chart for carbonates

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 TREATMENT DESIGN CONSIDERATIONS

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 a process of elimination.
• One of the first parameters to be considered is the bottomhole temperature, in
relation to corrosion concerns and reactivity of the formation.

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 TREATMENT DESIGN CONSIDERATIONS

• If the BHT is very high, i.e. between 150 and 200 °C, 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 °C, HCl acid is precluded, and organic
(acetic) acids must be used.
• Even in cases where HCl can be adequately 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 °C, 15 to 28% HCl can be used.
• If the formation has very low reactivity, as is the case of cold dolomites, the more
aggressive 28% HCl is preferred, provided corrosion of tubulars is not a problem.

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 TREATMENT DESIGN CONSIDERATIONS

• Compatibility testing of the acid system with the reservoir fluids is very important.
• The concern is highest in heavier crudes or any crude that displays sludging or
emulsification problems.
• In that respect, strong acids cause more problems than weaker ones.
• Limiting the HCl concentration to 20% is effective in many cases.
• 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 & rock dissolution.
• If too much rock is dissolved, e.g. in high-porosity 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.

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 TREATMENT DESIGN CONSIDERATIONS

Treatment fluid selection

 Acid Systems

• Apart from small treatments to remove near-wellbore damage, whereby neat HCl
acid (with necessary additives) can be used, in most carbonate matrix treatments
the acid is (lightly) gelled.
• This is done to improve zonal coverage of the acid, to retard the acid reaction rate,
or to improve its fines-suspending properties.

• Some relevant aspects of the various acid systems are discussed below:
• Lightly gelled acids
• Various strengths of HCl with low concentrations of gellant (< 0.5%) for friction
reduction.
• Gelling provides a viscosity of 1-3 cp at ambient temperatures.
• These systems are applicable for high-rate matrix treatments.

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 TREATMENT DESIGN CONSIDERATIONS

• Gelled acid systems

• Various strengths of HCl with higher concentrations of acid gelling agents (2-3%) to
provide higher viscosity.
• These might range from 30 to 40 cp at ambient temperatures, resulting in an enhanced
zonal coverage and reduced fluid loss.
• In-situ crosslinked acid
• Systems that contain HCl, a gelling agent and a pH-sensitive crosslinker.
• These are marketed as Zonal Coverage Acid (ZCA) by Halliburton and Self-Gelling Acid
Diverter (SGAD), by Schlumberger.
• After crosslinking at a pH of 2-3, the gel will break upon further spending of the acid at
pH values above 4.
• 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 treatments in horizontal wells.

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 TREATMENT DESIGN CONSIDERATIONS

• Emulsified acid systems

• Oil outside phase acid systems have been successfully used in situations where a retarded
reaction rate is needed to create deeper acid penetration and wormholes.
• Because of their retarded nature, they can be pumped at low rates, which is beneficial in
heterogeneous formations.
• Also their high viscosities result in better zonal coverage.
• Energized 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.

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TREATMENT DESIGN CONSIDERATIONS
Retardation effectiveness of commercial acid systems

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 TREATMENT DESIGN CONSIDERATIONS

Volume Requirements
• In vertical wells, matrix acidizing treatments can vary in volume from 10-25 gal/ft
(0.12-0.3 m3/m) to as much as 500-750 gal/ft (1.2-1.8 m3/m).
• The treatment volume is generally based on the contact time required for the acid to
dissolve a given amount of rock.
• In low-temperature dolomites, at least 15 minutes of contact time is required.
• In higher-reactivity formations, contact times of 5 minutes may be acceptable.
• The volume of a given treatment stage is simply the product of the contact time and
the pump rate.
• In horizontal wells, the above numbers may lead to excessive amounts of fluid.
• Much lower acid volumes of 0.5 m3/m have been used successfully in the North Sea
and the Middle East, also in conjunction with coiled tubing jetting technology.

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 TREATMENT DESIGN CONSIDERATIONS

Placement/Diversion Techniques
• In carbonate reservoirs, in principle, five main diversion techniques can be used to
improve fluid placement, viz. packers, ballsealers, coiled tubing, chemical diverters
(i.e. benzoic acid, rock salt, polymer systems, wax beads), foam diversion and self-
diverting acid.
• In horizontal wells, the use of mechanical placement techniques, such as packers
and ballsealers, is limited due to the length and nature of the completion (open hole).
• As to the use of chemical diverters, the amounts of material required to treat a very
long section render such diversion method in general uneconomical.
• Moreover, difficulties may arise in transporting the particulate diverters at low
injection rates.
• Therefore, the use of particulates for diversion in horizontal wells in carbonates has
decreased, in favour of foam and temporarily crosslinked acid.

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 EXAMPLES

• SXE Emulsified Acid (Slb)

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 EXAMPLES

• MaxCO3 Acid (Slb)

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 EXAMPLES

• VDA - Viscoelastic Diverting Acid (Slb)

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 EXAMPLES

• StimCarb-HTO Acid System (BHI)

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 EXAMPLES

• Carbonate 20/20 (HIb)

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EXAMPLES

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 SPE PAPERS

Acidizing in the Challenging Environment of the Volga-Urals Region of Russia

Paper Number: 168167, Presentation Date: 2014

• Carbonate stimulation practices in the Orenburg region have continuously improved

over the last 6 years.
• It started with the implementation of degradable balls and polymer-based self-
diverting acid to improve zone coverage.
• Later, viscoelastic, self-diverting acid was introduced to eliminate retained damage
associated with polymers.
• At the same time, viscoelastic selective diverter was used to minimize the risk of
water cut increase after the treatment.
• Finally, foam diversion with and without coiled tubing placement was implemented to
account for reservoir pressure depletion.

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 SPE PAPERS

An Innovative Solution to Optimizing Production in Naturally Fractured Carbonate

Reservoirs in Southern Mexico
Paper Number: 152554, Presentation Date: 2012

• The results of stimulation treatments in southern Mexico’s carbonate reservoirs have

been significantly improved using a new fiber-assisted, self-diverting acid system.
• These reservoirs are thick, deep, and hot.
• Depths are usually greater than 15,000 feet, bottomhole temperatures reach up to
350°F, and permeabilities range from 1 to 1000 mD within the same interval.
• Wells are typically completed with multiple perforated intervals.
• To overcome these challenges, we introduced an innovative degradable diverting acid
system combining the properties of viscoelastic diverting acid (solid-free) and
degradable fibers to southern Mexico.

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