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Additives for Matrix Treatments

Introduction
Although the 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 main treating fluid is designed to effec-
tively remove, or bypass, the damage. Additives are used to prevent excessive corrosion, sludging
or emulsions; they provide uniform fluid distribution, improve cleanup and prevent the precipi-
tation of reaction products. Additives are also used in preflushes and overflushes to stabilize
clays, disperse paraffin or asphaltenes and inhibit scale or organic deposition.
Certain additives are used in almost all acid formulations. Corrosion inhibitors, surfactants,
mutual solvents and iron control agents address problems caused by corrosion, emulsions and
sludging. Other types of additives deal with clay control, friction reduction and scale inhibition.
There are also specialty additives available for less frequently occurring problems.

Major additives
Acid corrosion inhibitors
Acid corrosion inhibitors reduce the corrosion of well tubulars by acids. They adsorb on the sur-
face of the pipes to form a protective film, thus reducing the reaction rate of acid with steel. Acid
corrosion rates increase with temperature, and the ability of the inhibitor to adsorb on steel
decreases with temperature. Inhibitor aids are used synergistically with inhibitors to decrease
corrosion. The main factors affecting corrosion are metallurgy, acid type and concentration, agi-
tation, temperature, pressure, inhibitor solubility and concentrationthe ratio of metal area to
acid volumecontact time, presence of inhibitor aids and the influence of other additives.
Table 6-1 shows the inhibitor selection guidelines for the currently available inhibitors and
inhibitor aids.

Surfactants
Surfactants are chemicals containing both oil- and water-soluble groups with the ability to alter
liquid to liquid and gas to liquid interfacial properties. They are used in acidizing to reduce sur-
face or interfacial tension, reduce capillary forces, control wettability, prevent or break emul-
sions, prevent or break water blocks and disperse or suspend fines. They are also used as foaming
agents. The quantity of surfactant used is a function of the application. Surfactants that lower
surface or interfacial tension or provide water-wetting are normally used at 0.2% to 0.5%. Other
applications require higher concentrations.
Surfactants are classified by the ionic nature of their hydrophilic groups. There are four
categories:
anionicnegatively charged
cationicpositively charged
nonionicnot charged
amphotericpositive or negative or not charged depending on pH.
Anionic surfactants are balanced with positively charged ions (i.e., Na+). Cationic surfactants
are balanced with negatively charged ions (i.e., Cl). Anionic and cationic surfactants should not
be used together because they may produce insoluble precipitates or neutralize their respective
activities. Most surfactants used in well treatments are a combination of anionic and nonionic
surfactants. The Schlumberger Matrix Materials Manual should be consulted to determine the
correct surfactant to use for a specific application.

Fluid Selection Guide for Matrix Treatments Additives for Matrix Treatments 43
Table 6-1. Corrosion Inhibitor Selection Options
Acid Metal Temperature Inhibitors Inhibitor
Category Composition Range (F) Aid
HCl systems
HCl Carbon steels (J55, N80, Up to 300 A261 or A262, A201 or
(5%28% HCl) P110 and coiled tubing) A259 or A262, A264 A153
MSR acid Chrome steels (9% and 13% Cr)
300400 A270 A201
Mud acid
(6% HCl/1.5% HF, Corrosion rersistant alloys Up to 350 A282 A281
12% HCl/3% HF) (2205 DUPLEX, 25 Cr, 25 CrW)
MSR acid, ClayACID 13% Cr steels
Titanium alloys Any Cannot be inhibited

Emulsified acid systems


DAD Carbon steels (J55, N80, Up to 300 A261, A264 or A259 A201
SXE P110 and coiled tubing) Up to 200 A262 A201
Chrome steels (9% and 13% Cr)
SXE-HT 200325 A262 A201

Gelled acid systems


DGA 100 Carbon steels (J55, N80, Up to 350 A261, A264 A201
DGA 200 P110 and coiled tubing) Up to 200 A262,A264 A201
Chrome steels (9% and 13 Cr)
DGA 300 Up to 200 A262 A201
DGA 400,SDA, LCA Up to 400 A262 A201

Alcoholic acids
Up to 30% Isopropanol Carbon steels (J55, N80, Up to 250 A262 A153
(F3) or Methanol (K46) P110 and coiled tubing) Up to 225 A259, A261 A153
Chrome steels (9% and 13 Cr)

Gas well acids


Gas well acid Carbon steels (J55, N80, Up to 250 A261, A262 A179
Gas well mud acids P110 and coiled tubing)
Chrome steels (9% and 13 Cr)

Organic acid systems


Acetic acid (10% L400), Carbon steels (J55, N80, Up to 500 A186, A272
Formic acid (9% L36), P110 and coiled tubing) Up to 00 A262,A264
Organic mud acids, Chrome steels (9% and 13 Cr) Up to 200 A262
Citric acid, OCA Corrosion resistant alloys Up to 500 A186 or A272
(2205 Duplex, 25 Cr, 25 CrW)
13% Cr steels
Titanium alloys Any Cannot be inhibited
Chelating agent systems (CAS)
U105, U106 Carbon steels (J55, N80 Up to 500 A186 or A272
P110, coiled tubing)
Chrome steels (9% and 13% Cr)
Corrosion resistant alloys Up to 500 A186 or A272
(2205 Duplex, 25 Cr, 25 CrW)
13% Cr steels
Titanium alloys Any Cannot be inhibited

44 Fluid Selection Guide for Matrix Treatments


Mutual solvents
Mutual solvents are multifunctional, nonionic agents that are soluble in oil, acid, freshwater and
brines. They penetrate deeper than surfactants and increase miscibility by decreasing surface or
interfacial tension. Mutual solvents are more effective than most surface-active agents in water-
wetting, preventing emulsions and minimizing particle plugging. Additionally, they dissolve oil on
the formation pore surfaces and fines, leaving them water-wet. Formation fines that are water-
wet have a lower tendency to stabilize emulsions. The net result is that mutual solvents improve
the cleanup of spent acid following the treatment. The recommended concentration is a function
of the mutual solvent used and the well conditions, but it varies from 0.5% to 35%. Additive incom-
patibility becomes an issue when mixing different surfactants or mutual solvents.

Iron control
Iron control is required in acid treatments to control the precipitation of iron compounds from
the spent acid. The injected acid dissolves iron from rust, millscale- or iron-containing minerals
in the formation. As the acid spends, ferric iron (Fe3+) precipitates as ferric hydroxide resulting
in particulate damage. In sour wells, precipitation of elemental sulfur and iron sulfide can also
be a problem. Injection of HCI may also cause flocculation and precipitation of asphaltene sludge
due to interactions between dissolved ferric iron and asphaltenes present in the crude.
Iron dissolved during an acid treatment can exist in either the Fe3+ or Fe2+ oxidation state.
Upon spending of the acid, the Fe3+ will start to precipitate at a pH of approximately 2.2. By the
time the spent acid reaches a pH of 3.2, essentially all of the dissolved Fe3+ will be precipitated
as the hydroxide. Fe2+ hydroxide will not precipitate below a pH of 7.7. Since spent acid usually
reaches a maximum pH around 5.2, precipitation of Fe2+ is rarely a problem.
Previous studies show that most Fe, dissolved by the treating acid, is present in the Fe2+
oxidation state. An estimate of the average Fe2+ to Fe3+ ratio in spent acid is about 5:1 (Smith et
al., 1969). However, this varies greatly depending on the well conditions and the type of forma-
tion being treated.
Controlling iron during well treatments involves operational practices as well as chemical
additives.
Iron in the tubing should be removed prior to the stimulation by pickling the tubing or using
a protected work string.
The acid must not contain high levels of Fe3+. Using clean or lined surface equipment can avoid
contamination.
The use of appropriate chemical additives can control the iron.
The use of effective corrosion inhibitors will prevent iron from the treating equipment from
being added to the well.
There are two types of chemicals used for iron stabilization: chelating agents and reducing
agents. Chelating agents associate with iron Fe3+ or Fe2+ to form soluble species. Some commonly
used chelating agents include citric acid, acetic acid, EDTA and NTA. Schlumberger has a chelat-
ing agent, U106, that is very soluble in acid systems and, therefore, has a higher iron control
capacity. It can control >10,000 ppm Fe3+ in acidizing applications up to 300F [148C].
Reducing agents change, or reduce, the Fe3+ to Fe2+ to avoid precipitation. Erythorbic acid
(L058) is the main reducing agent used within Schlumberger.
The choice of the iron control agent used for a specific application is a function of the amount
of iron, the downhole temperature, the presence of H2S and cost. In particular, the presence of
H2S changes the iron precipitation problem. The reaction of H2S and Fe3+ results in the precipi-
tation of free sulfur and the reduction of Fe3+ to Fe2+. If this occurs at a pH around 2, the Fe2+
will further react with the sulfide to form ferrous sulfide (FeS), an insoluble precipitate. A com-
bination of chelating and reducing agents can control iron in sour environments. The chelating
agent is necessary to prevent the FeS precipitation, while the reducing agent is needed to reduce
any Fe3+ present in the acid and prevent the sulfur precipitation problem. In treating sour wells,
iron contained in the treating acid is the only concern. The Fe3+ must be eliminated to prevent
the precipitation of sulfur.

Additives for Matrix Treaments 45


A sulfide-scavenging chemical, M295, is available from Schlumberger. This additive will con-
trol precipitation in sour environments with a single chemical that works by reacting with the
H2S to form soluble byproducts. The main advantage of this system is that less chemical is needed
to control the same problem. The M295 additive also enhances the performance of common
corrosion inhibitors, and, unlike other commercially available sulfide scavengers, the chemical
used in this product does not interfere with the acid dissolution of existing iron sulfide scale.

Minor additives
Clay control agents
Formation damage can result from the dispersion, migration or swelling of clay particles. The two
main methods of clay control are ionic neutralization and particle fusion.
In order to cause ionic neutralization, the additive is adsorbed on the clay surfaces by either
electrostatic attraction or ion exchange. Charge neutralization reduces the ion-exchange capac-
ity of the clays, reducing susceptibility to clay swelling. Brines, such as potassium or ammonium
chloride as well as quaternary amine polymers and quaternary surfactants, are used in this clay
control method. Typically, brines are used because of their low cost and ready availability.
Polyquaternary amines are organic polymers that are adsorbed on the clay surfaces by ion
exchange. Because of the multiple amine units, the molecules adsorb strongly with many points
of attachment. These chemicals are relatively expensive, and the treatment will degrade when
contacted by brines. Quaternary surfactants are used as clay stabilizers in dry gas wells.
Adsorption occurs due to electrostatic attraction. These materials also tend to oil wet the clay
particles, which also minimizes their adsorption of water.
Particle fusion can be chemically caused by the use of ClayACID fluid or organosilanes.
ClayACID is an acid system in which fluoboric acid reacts to generate hydrofluoric acid in situ.
A topochemical reaction occurs with boron being incorporated into the crystal lattice of the min-
eral. These reaction byproducts (borosilicates) appear as a coating on the initial rock surfaces.
The coating desensitizes the mineral and fuses them to the sand grains. However, ClayACID
fluid is not considered an additive, but rather a separate acid system.
Organosilanes are organic compounds containing silica. When added to acid, they hydrolyze
to form silanols, compounds with multiple Si-OH sites. These Si-OH sites react with similar sites
present on the siliceous mineral surfaces to form siloxane (Si-O-Si) bonds. A nonoil-wetting
polysiloxane coating forms on the siliceous mineral surface due to these reactions. The coating
stabilizes the fines and clays by blocking ion-exchange sites and increasing interparticle
attractive forces.

Organic dispersants
A relatively new method of removing organic deposits is the use of dispersant surfactants in
combination with organic solvents. The surfactants penetrate and loosen organic deposits; so, the
solvents can effectively dissolve or remove them. Concentrations of 1% to 10% volume to volume
are used depending on the deposit type, the hardness and adhesion of the deposit and the bot-
tomhole temperature. For matrix, wellbore and tubing cleanup treatments, a soaking period of
several hours is recommended.

Friction reducers
Friction reducing additives are used to suppress fluid turbulence when pumping acid treatments
through coiled tubing. Some polyacrylamides are excellent friction reducers for acid and can
greatly reduce the friction pressure drop in tubulars at concentrations of 1 to 4 lbm to 1000 gal
of acid. For example, at 10 bbl/min, a concentration of 4 lbm of J120 to 1000 gal of 28% hydrochlo-
ric acid (HCl) gives approximately a three-fold reduction in pressure drop. However, the effec-
tiveness of most polymers is limited because they degrade rapidly in acid, particularly at elevated
temperatures. Viscoelastic surfactants also have friction-reducing effects.

46 Fluid Selection Guide for Matrix Treatments


Scale inhibitors
Scale prevention involves the use of chemical inhibitors that affect the nucleation growth or
adherence of scale crystals. The inhibitor can either be continuously added to production or
injection fluids or displaced into the formation as an overflush to an acid treatment. When either
overflushed or squeezed into the formation, the chemical is adsorbed onto the rock, or precipi-
tates as widely dispersed, low-solubility particles in the pore spaces. The inhibitor is solubilized
into the produced or injected fluid at concentrations of a few parts per million. This small con-
centration is sufficient to inhibit scale development.

Specialty additives
Alcohols
Alcohols, such as isopropanol and methanol, are used in acid or other aqueous fluids to lower
surface and interfacial tension, increase vapor pressure and improve cleanup. These attributes
make them effective in treating water blocks, enhancing fluid recovery, retarding acid reactivity
and decreasing water content. They are commonly used in gas wells to reduce water damage and
to decrease surface tension.
There are major disadvantages that decrease the use of this additive. They include the high-
concentration requirements, high-cost, low-flash point, increased corrosiveness, as well as
incompatibility and acid reaction issues. Concentrations of 20% or higher are needed to provide
beneficial effects. The large volume requirements make the treatment more expensive and
depress the flash point of the acid-alcohol mixtures. More corrosion inhibitor is required for acid-
alcohol mixtures, which also increases the treatment cost. Some crudes are incompatible with
these alcohols, and some formation rocks may also be extremely sensitive to aqueous solutions
containing high concentrations of alcohols.

Antifoamer
Antifoamer prevents excess foam from being formed in surface equipment during mixing of
fluids containing specific surfactants. Concentrations of 0.05% to 0.1% volume to volume are
typically used to avoid operational problems

Formation cleaner
Formation cleaner M91, a strong oxidizer solution, is used to kill and remove bacteria and polymer
residues from the matrix of a productive formation. It is more efficient than bactericides that
simply kill the bacteria.

Emulsifiers
Emulsified treating fluids are mixtures of aqueous and organic phases. Surfactants are the main
emulsifying agents. Emulsions can be used to either isolate the internal phase of the emulsion,
so it is not as reactive, or to create a fluid with higher viscosity than the base fluids. An example
of an emulsified fluid is DAD, a combination of an organic solvent and an acid, which is used to
treat mixed organic and scale deposits.

Diverting agents
Successful matrix treatments depend on the proper placement of the treating fluids. In general,
this means uniformly distributing the fluids into the entire producing or injecting interval.
In some cases, this may also mean limiting fluid entry into certain parts or the formation, for
example, a watered-out zone. Proper fluid placement can be a difficult in any well, but it becomes
a real challenge in treating horizontal wells. When acid is pumped into a well, it naturally tends

Additives for Matrix Treaments 47


to flow into the highest permeability, or less damaged, zone and through open perforations. The
proper placement of acid between regions of different injectivities can be accomplished using
mechanical or chemical diversion techniques.

Mechanical
Mechanical diversion methods, such as straddle packers, require good isolation between zones
and special equipment. Ball sealers, another mechanical method, are not effective in openholes,
gravel packs or in wells with a large number of perforations. Additionally, the slow pump rates
frequently used in matrix acidizing are often insufficient to achieve good ball seating.

Chemical
There are several categories of chemical diverters, including particulates, foam and viscosity
forming agents. Particulate diverters form a cake of solid particles in front of high-permeability
layers thus directing the flow to less permeable zones. Since the entry of the treating fluid in each
zone is limited by the resistance of the cake (Doerler and Prouvost, 1987), diverting agents
enable the flow to equalize between zones of different permeabilities. Particulate diverters can
be used in sandstone or primary porosity dolomites. Both water- and oil-soluble materials are
available for use in either injection or production wells. Coarser materials (flakes), possibly fol-
lowed by smaller particle-sized diverting agents, are sometimes used as bridging agents in vuggy
or fractured formations.
Foams have been used for acid diversion since at least the 1960s. Surfactant foamers are
added to fluids that are injected with nitrogen gas during the treatment to create the diversion
effect. The acid itself can be foamed with the addition of gas and surfactant, or more commonly,
foam can be injected in alternating slugs with acid.
Foam properties that cause diversion are fundamentally different than the properties that are
important for foams used in drilling, fracturing or well cleanout. Within the tiny pores of the oil
or gas reservoir, foam bubbles, larger than the individual pores, are squeezed down into elongated
shapes and span several pores with a liquid film or lamella. Each bubble forms a separate film or
lamella; multiple bubbles result in multiple lamellae (Ettinger and Radke, 1992; Falls et al.,
1989). The capillary forces on the lamellae dominate the behavior of the foam; viscous forces in
the conventional sense are relatively unimportant. It is the viscous forces that are important in
other foam applications. Therefore, analogies to these other foams can be misleading.
The key to the success of foam as a diverter is low-gas (and consequently liquid) mobility dur-
ing foam injection and gas trapping during subsequent injection of liquid. The fraction of the pore
space completely blocked by the foam declines as the pressure gradient increases.
Pumping chemicals that cause a temporary increase in viscosity in the matrix can also cause
diversion. SDA* Self-Diverting Acid and other similar materials block the growth of wormholes in
carbonate acidizing by temporarily forming a barrier in the wormhole that halts channel growth
and loss of fluid from the wormhole. SDA is a temporary, cross-linked fluid that will lose its
viscosity as the acid spends.
Viscosity diversion is also possible using viscoelastic surfactant (VES) technology (Chang, et
al., 1998). This is the basis of the OilSEEKER* Acid Diverter, which preferentially channels the
treatment into the oil zones and away from the water zones. When this viscous material is
pumped into the formation, it is broken by residual hydrocarbons. It is more stable in water zones
with very little residual hydrocarbon; so, it retains its higher viscosity and diverts the subsequent
fluid stage into a different part of the reservoir. A pumping sequence of VES diverter, HCl, VES
diverter, HCl, and so on has been shown to effectively divert acid into and stimulate multiple
zones of varying permeability in a single wellbore.
Foams, SDA, and OilSEEKER contain no solids. SDA and OilSEEKER have the additional
advantage of being a single-phase fluid, so no nitrogen is required. SDA is used specifically in
carbonate formations. Foam and OilSEEKER can be used in either sandstones or carbonates.

48 Fluid Selection Guide for Matrix Treatments