Laboratory Studies for

Designing a Matrix Treatment

Objectives of laboratory experiments
Laboratory studies are used to
■ identify damage mechanisms
■ analyze the rock
■ analyze the formation fluids
■ select the optimum treating fluid and design.
Formation cores, samples of formation fluids and sometimes samples of the damaging
material (organic deposit or scale) are the subject of laboratory studies. Various analyses are per-
formed on these samples to obtain the information necessary for designing a matrix treatment.

Core analysis
Core analysis, including flow testing, is an integral part of the laboratory study used to help
design a matrix treatment. Tests performed on cores can be classified as follows:
■ Chemical studies include solubility tests and calculation of iron dissolved in HCl.
■ Petrographic studies include X-ray diffraction (XRD), binocular lens observation, thin section
examination and scanning electron microscopy (SEM).
■ Petrophysic studies determine porosity and permeability.
■ Core flow tests monitor the permeability response of the rock when different fluids are
injected.

Solubility tests
Solubility tests are used to determine the amount of any material that is dissolved by a given sol-
vent. The results are given in weight percent. The solubility of a rock sample in a particular sol-
vent (acid) depends on the mineralogy of the rock. The total solubility is the sum of the solubility
of the mineral components. Table 7-1 shows the solubility of various common minerals in acid.
Carbonate and clay mineral content of the rock are often estimated from solubility test
results. This method is only used if no other information is available. Mineral content is easily
skewed by a variety of factors.
■ Solubility tests are performed under ideal laboratory conditions. The physical rock structure
is destroyed when grinding the sample for the test. Consequently, all the minerals are in con-
tact with a large excess of acid. During acidizing operations in the field, the effective solubil-
ity may be completely different because of the structure of the rock and the position of each
mineral relative to the pore through which the acid flows.
■ Carbonate is assumed to be equal to HCl solubility. However, solubility in 15% HCl includes
not only carbonates but also halite and possibly anhydrites and iron compounds.
■ The solubility of the sample in regular mud acid (RMA), a mixture of 12% HCl and 3% HF
acids, minus the solubility of the sample in HCl is only a rough approximation of the percent
of clays in the formation. Silicates and other HF acid-soluble minerals are also included in the
RMA solubility test. The percentage of micas, feldspars and quartz soluble in RMA can be
many times that of the clays. A large difference between the solubilities in HCl versus RMA
(>30%) normally indicates that there is a large amount of clays, micas and feldspars present.

Fluid Selection Guide for Matrix Treatments ■ Laboratory Studies for Designing a Matrix Treatment 49
 ■ Negligible solubility in either HCl or RMA normally means that the formation is composed
almost entirely of quartz. Acid stimulation may still be viable if the skin damage that is known
to be present is composed of acid-soluble material. However, this fact is not apparent from lab
studies on clean formation samples.

Table 7-1. Solubility of Common Minerals in Acid

Minerals Chemical Composition Solubility
HCl HCl + HF
Quartz SiO2 None Low

Feldspars
Orthoclase K(AlSi3O8) None Moderate

Microcline K(AlSi3O8) None Moderate

Albite Na(AlSi3O8) None Moderate

Plagioclase Na, Ca (Al1 – 2 Si2 – 3 O8) None Moderate

Micas
Biotite K (Mg, Fe)3 (AlSi3O10) (F, OH)2 None Moderate

Muscovite K Al2 (AlSi3O10) (F, OH)2 None Moderate

Clays
Kaolinite Al4Si4O10 (OH)8 None High

Illite (K,H3O)(Al,Mg,Fe)2 (Al4Si4O10) [(OH)2 • H2O] Moderate High

Smectite (Na, Ca)(Al, Mg)6 (Si4O10)3(OH)6 – nH2O None High

Mixed layer Kaolinite, illite or chlorite with smectite None High

Chlorite (Fe, Mg, Al)6 (Si, Al)4 O10 (OH)8 Moderate High

Glauconite (K, Na)(Fe, Al, Mg)2 (Si,Al)4 O10 (OH)2 Moderate High

Zeolites (Ca, Na) AlSiO6 – H2O (general) High High

Carbonates
Calcite CaCO3 High High

Dolomite CaMg(CO3)2 High High

Ankerite CaFe(CO3)2 High High

Scales
Gypsum CaSO4 – 2(H2O) Low Low

Anhydrite CaSO4 Low Low

Halite NaCl High High

Iron oxides Moderate Moderate

50 Fluid Selection Guide for Matrix Treatments

 Petrographic study
Knowledge of the petrography (description and classification) of the formation rock is essential
to understanding the rock’s response to fluid injection. Understanding rock fluid interactions
depends upon
■ what minerals are present
■ where the minerals are located relative to the path of the injected fluid.
The laboratory techniques described in this chapter are used to determine the answers to
these questions and to give insight on how this affects flow through the rocks. Understanding
basic concepts on the formation of sedimentary rocks will help in understanding the laboratory
procedures.

Sedimentary rocks
Most petroleum reservoirs are found in sedimentary rocks such as sandstones, carbonates or
chalks. Sedimentary rocks form at, or near, the earth’s surface at relatively low temperatures and
pressures through the transformation of sediments by diagenesis. Figure 7-1 is a schematic of the
main steps of sedimentary rock formation and their consequence on the flow properties.
Sediments are
■ deposited by water, wind or ice
■ precipitated from solution
■ grown in position by organic processes (e.g., carbonate reefs).

Sandstone Carbonate Rocks

Coarse • Detrial grain
• Detrial minerals
– Fossils

}
Sediment

– Quartz

– Micas }
– Feldspar Framework – Previously
deposited
carbonates
Framework

• Clays • Precipitated mineral

Fine Scattered in – Calcite
the framework – Dolomite
or as laminae – Mud
Diagenesis • Cement • Cement
Grain
– Cementation – Quartz Calcite
– Clays Cement Dolomite
– Compaction – Calcite
– Dolomite
Transformation – Anhydrite Pore
into a rock Etc.

Rock – Transformation of clays Dissolution of shells – Transformation of calcite

– Crystallization of into dolomite
Flow of brines authigenic minerals – Selective dissolution
– Dissolution Changes in porosity Changes in porosity
– Recrystallization Permeability Lining Permeability
Filling

Can be very important

Fracturation Usually minor
for reservoir properties

Figure 7-1. Formation of sandstone and carbonate rock—consequences for their flow properties.

Laboratory Studies for Designing a Matrix Treatment 51

 These three mechanisms coincide with the three main sediment constituents:
■ silicate fragments that are derived from the weathering and erosion of preexisting sedimen-
tary, metamorphic or igneous rocks
■ chemical and biochemical precipitates that are formed at the site of deposition, for example,
evaporite minerals or cement in sandstones or limestones
■ allochems that are skeletal materials, ooliths, faecal pellets, as seen in carbonates.
The coarse particles (0.06 mm–2 mm) form the framework of the sediments. Smaller particles
(clays, lime, mud) are also deposited. The original porosity of the sediment depends on the
■ size of the particles
■ shape (sphericity) of the particles
■ packing of the particles
■ amount of mixing of coarse and fine grains.
During diagenesis, a cementation process transforms the sediment into rock. Cementation
results from the flow of brine through the original sediments. The brines dissolve some compo-
nents and reprecipitate others between the grains of the framework. Cementation reduces the
porosity of the sediments. Dissolution of cementing minerals will increase porosity but cause a
decrease in compressive strength in the rock. Diagenesis stops when a nonreacting fluid, such as
oil, fills the pore system during the formation of the hydrocarbon trap.
Precipitated minerals are called authigenic, meaning formed in place. Most clays found in the
pore network of sandstones are authigenic. In limestones, the transformation of calcite into
dolomite by diagenisis results in new porosity. This transformation, called dolomitization, is
described by the following mechanism:
2CaCO3 + MgCl2 → CaMg CO3 ( )2 + CaCl2 .
Because of this process, dolomites normally have greater porosity than limestones.

Petrographic techniques
Petrographic techniques include thin section examination, X-ray diffraction and scanning
electron microscopy.

Thin section analysis

Thin section analysis is a method used to study rock structure and quantify minerals. The tech-
nique can determine mineralogy, porosity types, grain size, sorting and location of pores, cement-
ing minerals and clay fines.
Rock core samples are impregnated with a colored resin to fill the interconnecting porosity. A
thin slice is then cut off, polished to a thickness of about 30 microns and viewed in transmitted
light with a polarizing microscope. Characteristic shape and size are used to identify the various
minerals. The colored resin identifies interconnected porosity, while the isolated porosity shows
up between the mineral crystals.
The location of minerals is important in acidizing, because the injected solvent will only dis-
solve the minerals that it can contact. Therefore, only minerals available to the interconnected
porosity will contact the acid. This holds true for both the damaging minerals, such as clay par-
ticles, or for cementing minerals, such as secondary quartz overgrowth and carbonates in sand-
stones. The objective is to dissolve as much of the damage as possible to improve flow capacity
while dissolving as little of the cementing material as possible to maintain the integrity of
the rock.

52 Fluid Selection Guide for Matrix Treatments

 X-ray diffraction
X-ray diffraction (XRD) is used to identify rock composition. It is an analytical technique that
looks at the scattering pattern of X-rays through crystalline materials. These patterns are unique
to individual minerals because they are characteristic of their atomic structure. The XRD pat-
terns from unknown materials are compared to known mineral patterns to determine the com-
position of the unknown solid. Crystalline scale deposits can also be identified using XRD.
XRD is a very accurate way of qualitatively determining the mineral composition. However,
quantitative accuracy is relatively poor. This type of testing requires the use of reservoir core
samples. Conventional cores are recommended, because sidewall cores can be contaminated
with drilling fluids and may not be representative of the formation. If sidewall cores are used, the
analysis should be conducted on duplicate cores.

Scanning electron microscopy

Scanning electron microscopy (SEM) is another way of looking at solid particles. It provides two
major advantages over light microscopy: depth of focus and range of magnification. It is designed
for looking directly at the surface of solid objects, and it is particularly useful for the observation
of clays. SEM pictures of clay particles show their distinct shapes. For example, illite is spindly
and kaolinite has a plate-like structure (Fig. 4-2).
With SEM, electrons, instead of light, are used to produce a reflected image of the sample. The
electrons are scanned across the surface and focused with a magnet. They cause the release of
energy in the form of X-rays, light and electrons. Detectors record the energy released from the
sample and convert it into digital or photographic images.
The types of images of interest to geologists and engineers in the petroleum industry are
■ secondary electron images (SEI) generated from the low-energy electrons released from the
sample. This type of image emphasizes the topography of the sample.
■ Back-scattered electron images (BEI) are produced from the high-energy electrons of the
original beam focused on the sample and reflected back from it. This type of image accentu-
ates the compositional differences of the sample.
Like XRD analysis, SEM testing requires the use of reservoir core samples. Conventional cores
are recommended, because sidewall cores can be contaminated with drilling fluids and may not
be representative of the formation. If sidewall cores are used, the analysis should be conducted
on duplicate cores.

Computed tomography
Computed tomography (CT) is a method for obtaining cross-sectional images of the internal
structure of a solid object. Used extensively in the medical field, this technique is also useful for
looking at the internal structure of cores. X-ray images are taken along sequential planes per-
pendicular to the length of the sample. Computers are used to enhance the visualization of the
sample.
The X-rays are focused across an area of the sample and recorded as a pattern of electrical
impulses. The radiation absorption figures are used to assess the relative density of the interior
of the sample. When plotted, the variation in density is shown as variations of brightness, pro-
ducing a detailed cross-sectional image of the internal structure.
An example of this technique in oilfield applications is the study of core samples before and
after acid response tests. In carbonate cores, this can detail the formation of wormhole struc-
tures. In sandstone cores, the dissolution of materials within the pore structure can be visualized.

Laboratory Studies for Designing a Matrix Treatment 53

 Magnetic resonance imaging
Magnetic resonance imaging (MRI) is another diagnostic technique borrowed from the medical
field. It can be used to determine fluid distribution in core samples. The method uses the
response of magnetic fields to short bursts of radio waves to produce the images. Like CT, MRI
images are two-dimensional, cross-sectional, planar views perpendicular to the length of the
sample. The images must be viewed sequentially to visualize the whole core. Additional computer
enhancement can be used to produce a three-dimensional visualization.

Petrophysics
The petrophysic characterization of a rock sample includes measurements of its porosity and
permeability.

Porosity
Porosity is the ratio of the void space volume to the bulk volume of a material. It is a measure-
ment of the amount of space occupied by liquid or gas in the reservoir. Total, effective and resid-
ual porosities are defined as follows:
Pore volume
Total porosity (%) = × 100
Total bulk volume
Volume of interconnected pores
Effective porosity (%) = × 100.
Total bulk volume
Residual porosity = Total porosity – effective porosity
Pore volume = Total bulk volume – grain volume
Effective pore volume = Volume of interconnected pores = Total bulk volume – effective grain volume

The porosity of the sample can be determined by several techniques. Typically, only two of the
three basic parameters, bulk, grain or pore volume, are measured in the laboratory.
Bulk volume can be determined by either volumetric or gravimetric displacement observa-
tions. In either case, fluid penetration into the core sample should be avoided. Direct measure-
ment of fluid displacement is one way of determining bulk volume. Gravimetric techniques
measure either
■ the weight loss of the sample when it is immersed, or
■ the difference in weight of a pycnometer when it is filled with fluid and when it is filled with
fluid and the core sample.
Grain volume is the measure of the volume of the rock grains. This value is estimated by divid-
ing the dry weight of the core sample by the sand grain density. Using the density of quartz,
2.65 g/cm3, for the sand grain density is sufficient for most applications. However, the sample can
also be reduced to grain size, and the actual grain density determined. The Stevens porosimeter
can be used to determine the effective grain volume by using gas expansion.
All methods of determining pore volume measure effective pore volume. The measurement
methods are based on either extraction of fluid from, or injection of fluid into, the rock matrix.
The procedures for determining pore volume by gas expansion are based on Boyle’s law and use
either nitrogen or helium in a constant volume cell. Pore volume can also be determined by
saturating a clean, dry sample with a fluid of known density. The weight gain is used to calculate
pore volume.

54 Fluid Selection Guide for Matrix Treatments

 Porosity obtained from gas expansion methods is consistently higher than porosity obtained
from saturation methods. Errors due to gas adsorption would tend to cause higher calculated
porosities using the gas expansion method. Conversely, errors due to incomplete saturation would
tend to cause lower calculated porosities using the saturation method. However, all methods give
acceptably accurate answers if done carefully. (Bradley, 1987 Ch. 26)

Permeability
Permeability is a measure of the capacity of a porous media to transmit fluids. It can be measured
in situ through pressure transient testing and in the lab using cores. Fluid conductivity mea-
surements using cores are made using gas or nonreactive liquids. Core permeabilities to air
should not be confused with the effective permeability to the reservoir fluid. Air permeabilities
may be an order of magnitude higher than reservoir permeability to fluid.
Absolute permeability is a rock property and should be constant for liquid and gas, since the
core is 100% saturated. However, absolute permeability measured by flowing gas through a core
must be corrected for gas slippage, also called Klingenberg corrections. This is because perme-
ability to gas varies with the pressure used for injection. The correction factor is determined
by plotting gas permeability versus the reciprocal of the mean pressure. Multiple permeability
versus pressure points should fall on a straight line. This line is extrapolated back to infinite
mean pressure (1/p = 0). The point of intersection with the permeability axis is the equivalent
liquid permeability. Klingenberg and others determined that this equivalent liquid permeability
is equal to the liquid permeability through the measured porous media (Bradley, 1987 Ch. 26).

Core flow test

Core flow tests measure the effects of fluids injected into sandstone formations. Permeability is
calculated as a function of time or pore volumes injected. Core flow tests can also determine the
water sensitivity of the rock and examine the reaction of the formation to a proposed treating
fluid or fluid sequence.

Acid response curve test

In acid studies, the permeability change depends on the dissolution and precipitation reactions
that occur. Observations that indicate what dissolves and what precipitates are extremely useful
in selecting the best treatment fluid.
The tests should be run at bottomhole temperature and pressure conditions with backpressure.
For tests with acid, a minimum of 1000-psi backpressure is required to keep the CO2 produced by
the acid dissolution of carbonate components in solution. The flow rates used should ensure that
the fluid movement has minimal effect on the movement of fines contained within the pore struc-
ture. Typically 17 to 30 pore volumes of test fluid are injected. This approximates a treatment of
125 gal/ft.
The formation cores used are typically 1-in. diameter and 12-in. long. They should be cleaned
with aqueous alcohol or ethylene glycol monobutyl ether solutions to remove traces of oil and
ensure that they are water-wet. Using core holders with multiple pressure taps, the test can
examine the effect of each fluid as it penetrates deeper into the core.
Permeability is calculated based on the changes in pressure and plotted as an acid response
curve (ARC). An example of this is shown in Fig. 7-2.
The decrease in permeability seen in Fig. 7-2 indicates probable damage due to mud acid
injection. This may be due to calcium fluoride precipitation or fines release. Removal of calcite
cementing materials by the HCl stage can result in release of fines. This is more detrimental in
low-permeability cores. If large increases in permeability occur during HCl injection, with little
response to mud acid, the mud acid stage may not be required. A smooth increase in permeabil-
ity due to mud or clay acid indicates that the well is a good stimulation candidate.

Laboratory Studies for Designing a Matrix Treatment 55

 2000

Mud acid
1600
3% NH4Cl
1200
Permeability (mD)
800
3% NH4Cl

400

0
0 300 600 900 1200 1500
Volume (mL)

Figure 7-2. Acid response curve of a core treated with HCl and mud acid sequence.

Core flow tests should not be used to estimate treatment fluid volumes. Volumes are based on
the amount and type of damage. Since core flow tests are always run on restored-state, cleaned
cores, there can be damage due to sample preparation. This unknown damage will skew any
attempt to use these tests to estimate treating volumes.
A petrographic study should be done in conjunction with any core flow studies. An accurate
lithological breakdown is very helpful when interpreting acid response curves. SEM studies, both
before and after fluid injection, can also be a valuable tool when determining the effect of the
injected fluid. Sandstone permeability changes, in particular, depend on both dissolution and
precipitation reactions. Observations that indicate what dissolves and what precipitates
are extremely useful in selecting the best treating fluid sequence. Effluent analysis is another
method that can be used to monitor the reactions that occur within the core.

Water sensitivity test

Permeability measurements before and after fluid injection, especially brine, can give insights
into the sensitivity of the formation clays to both fines migration and clay swelling. The typical
procedure calls for sequential injection of the following fluids:
■ n-hexane
■ isopropanol
■ n-hexane
■ isopropanol
■ 3% CaCl2
■ distilled water
■ 3% NaCl
■ distilled water.
The solvent steps are designed to remove oil and water residues from the core. The calcium
chloride followed by distilled water may cause clay swelling or migration. The sodium chloride
followed by distilled water will typically cause clay migration in any sandstone core. Table 7-2
explains the permeability effects of each fluid step.

56 Fluid Selection Guide for Matrix Treatments

Table 7-2. Explanation of Permeability Changes in a Water Sensitivity Test
Fluid Sequence Change Meaning

Hexane to isopropanol Increase Improved cleaning of core, removal of water and/or

alcohol-soluble salts

Decrease May indicate incomplete removal of oil residue.

In very low-permeability cores, adsorption of
alcohol on pore walls may reduce capillary flow.
Wettability factors may contribute

Isopropanol to hexane Increase In low-permeability cores, differences in adsorption

may cause hexane’s permeability to be higher than
those measured with isopropanol.

Decrease May indicate contamination of the hexane or

incomplete removal of water by isopropanol.

Isopropanol to 3% CaCl2 brine Increase Seldom noted

Decrease Common. The decline may be due to strong

adsorptionof water molecules on pore surfaces
and partial expansion of clay aggregates. Some
disintegration may occur in poorly consolidated
cores. Severe permeability loss indicates physical
movement of clay particles. Failure of core to return
to its previous permeability with isopropanol
confirms particle movement.

3% CaCl2 brine to distilled water Increase Seldom noted

Decrease Uncommon, but extremely sensitive cores may

lose some permeability from clay movement

3% NaCl brine to distilled water Increase Seldom noted

Decrease Fines migration

Fluid analyses
Analyses of oil and formation brine provide useful information for fluid selection. Most fluid tests
are used when determining the damage mechanism affecting the well. These tests are discussed
in the “Damage identification” section. Oil compatibility studies should be made with planned
treating fluids and formation oil to investigate the possibility of sludge or emulsion formation
when the treating fluid, either live or spent, contacts the formation oil. The selection of treating
fluid additives is based on the information obtained in compatibility tests.

Acid and oil compatibility

Before pumping into the well, the compatibility between proposed treating fluids and formation
fluids should always be tested. This testing will measure the tendencies to form emulsion or
sludge, which can cause major problems if the treating fluid is incompatible with the formation,
the rate of separation and the phase condition.

Laboratory Studies for Designing a Matrix Treatment 57

 Many types of emulsifying agents occur naturally in crude oils. When formation fluids are
contacted by treating fluids, emulsions of varying degrees of stability may result. For example,
during treatment of an oil well, as the acid is being forced into the formation, an emulsion of the
acid in the crude oil can be formed. These viscous emulsions are slow to return to the wellbore
and, often, are never returned, especially in low-pressure wells. When this occurs, the emulsion
stays in place in the formation and permanently blocks the flow channels. Therefore, it is better
to prevent the emulsion by proper acid plus oil compatibility testing before the treatment.
Although emulsions can be broken if they are already in the formation, this is more difficult.
Surfactants and mutual solvents are generally used to treat emulsions. Cationic, anionic or
nonionic surfactants may be used depending on the nature of the emulsion being treated. Some
mechanically stabilized emulsions may be treated by acidizing the formation to dissolve the
stabilizing fines.
The potential for the formation of acid and produced crude oil emulsions and the optimization
of the de-emulsifier treatment are currently evaluated using API Recommended Procedure RP 42
(1977).
Crude oil sludge is a name given to the black asphalt-like material that precipitates when
certain crude oils come in contact with acid. The precipitate is complex consisting of
asphaltenes, resins, paraffin waxes and other high-molecular-weight components. This material
is present in the crude oil in a colloidal dispersion. Contact with the acid destroys the stability
of the dispersed material and results in its precipitation.
Surfactants are generally used as sludge prevention agents. They stabilize the colloidal mate-
rial to keep the precipitates from forming on contact with the acid. The acid system to be used
in treating a formation should be tested with the crude oil to see if sludge will form. Tests to
determine whether there is a tendency for a sludge to form, at laboratory conditions, is given in
API Bulletin RP 42.

Damage identification
Evaluation of solids or fluids taken out of the well can be useful in determining the damage mech-
anism affecting well performance. Knowing the damage mechanism is particularly important
when treating sandstone reservoirs, since the objective is removal of damage. Testing the forma-
tion brine can help determine scaling tendencies and predict incompatibility during mixing with
foreign brine. Oil samples can be tested for paraffin and asphalt content to estimate the possi-
bility of damage from heavy hydrocarbon precipitation. Analysis of miscellaneous solid particles
from the well can be useful in determining whether the problem is primarily organic or inorganic
in nature. These tests can also help narrow down the type of scale.

Water analysis
Analyses of oilfield waters are used for a variety of reasons. They are helpful when trying to
identify the source of downhole water and when planning waterflood operations. The main uses
of water analysis data in damage assessment includes examining scaling issues and looking at
compatibility with other water that was injected into the reservoir. All water sources associated
with the well, either produced or injected, must be tested.
A typical analysis gives the ionic composition of the water. The standard techniques and pro-
cedures for oil field water analysis are given in API RP 45, Recommended Practice for Analysis
of Oilfield Waters.
The following parameters are typically measured:
■ major cations—positive ions associated with the minerals dissolved in the water
– most common cations—sodium (Na), calcium (Ca), and magnesium (Mg) Concentration
of these ions can vary from <1000 mg/L to >30,000 mg/L.
– fairly typical cations—potassium (K), barium (Ba), strontium (Sr), and lithium (Li) with
concentrations in excess of 10 mg/L
– cations sometimes present—aluminum (Al), ammonium (NH4), iron (Fe), lead (Pb),
managnese (Mn), and zinc (Zn)

58 Fluid Selection Guide for Matrix Treatments

 ■ major anions—negative ions associated with minerals dissolved in the water
– most common anions—chloride (Cl), concentrations can vary from below 10,000 mg/L to
over 200,000 mg/L
– other major anions—bicarbonate (HCO3) and sulfate (SO4) found in concentrations up to
several thousand mg/L Bicarbonate and sulfate concentrations are important in scaling.
– fairly typical anions—bromide and iodide with concentrations ranging from less than 50 to
more than 6000 mg/L for bromide and less than 10 to more than 1400 mg/L for iodide
■ mole fraction of CO2—the amount of this dissolved gas is important in carbonate equilibrium
and can affect carbonate scaling tendencies
■ pH—usually controlled by the CO2/bicarbonate concentrations—it is used in identifying
potential scaling or corrosion tendencies. This measurement should be made in the field at
conditions as close to in situ as possible. The pH changes over time after sampling because of
the formation of carbonate ions due to the decomposition of bicarbonate.
Once the composition is obtained, it can be input into the Scale Prediction module in the
StimCADE design program to estimate potential for scale. The program will handle one or two
water sources and allows the user to specify the amount of mixing. Analysis of wellhead water
samples is sufficient to predict scaling in surface equipment but may not be reliable for estimat-
ing downhole scaling. Pressure decreases as water is produced to the surface causing release of
CO2 and precipitation of scales as the fluid rises. Bottomhole water samples, kept at native pres-
sure and temperature conditions, are necessary for more reliable downhole scaling tendencies.
Proper sampling, transfer and storage procedures are necessary in order to obtain data
representative of the well conditions. A good paper, which includes a discussion on sampling, is
Scale Control, Prediction and Treatment or How Companies Evaluate A Scaling Problem and
What They Do Wrong by Oddo and Tomson, presented at the 1992 NACE (National Association of
Corrosion Engineers) annual conference.

Paraffin and asphaltene content

Paraffins are straight- or branched-chain nonpolar alkanes of relatively high-molecular weight.
Their chains usually consist of 20 to 60 carbon atoms with a melting range of 98° to 215°F [36°
to 101°C]. The solubility of paraffin waxes in crude oil is limited depending on the molecular
weight. Because of the limited solubility, a cooling environment can cause crystallization and
precipitation. One standard test method for paraffin content is UOP 46.
Asphaltenes are colloidal aggregates of condensed, polycylic aromatic hydrocarbons that con-
tain –N, –O, –S, and metal ions. These dispersions are permeated with adsorbed maltene mole-
cules giving the surface a high negative charge. If the negative surface charge comes in contact
with a highly charged positive chemical species, an irreversible neutralization occurs. This neu-
tralization destabilizes the micelle and causes precipitation of the asphaltenes. In addition
to causing plugging, the precipitated asphaltene molecules can also help stabilize emulsions and
sludges. The asphaltene content of a crude oil can be estimated because they are insoluble in
certain solvents. The ASTM standard test method for asphaltene is D3279-90 Standard Test
Method for n-Heptane Insolubles.

Laboratory Studies for Designing a Matrix Treatment 59

 Solids analysis
An analysis of the solids scraped from the tubulars or brought up from the bottom of the well can
be useful in determining what type of damage exists. This type of analysis can determine if there
is scale, an organic deposit or formation fines.
Common laboratory analysis procedures are shown in Table 7-3.

Table 7-3. Solids Analysis Procedure

Procedure Result Indication

Visual inspection Examination of physical characteristics Color

of sample Texture
Friability
Organic/inorganic

Heating of sample Ignition Oil or organic matter

Clean flame Suspect paraffin

Sooty flame Suspect asphaltene

Noisy flame (i.e., pops and sparks) Contains water

Immersion in water Sample dissolves Suspect inorganic salt

(typically NaCl)

Immersion in cold HCl Sample dissolves and gives off odorless gas CO2

Acid doesn’t change color Suspect calcium or

magnesium carbonate

Acid doesn’t change color but sample slowly dissolves Suspect calcium sulfate

Acid turns green or yellow and sample is magnetic Suspect iron carbonate

Sample dissolves and gives off gas that smells Hydrogen sulfide gas
of rotten eggs or lead acetate paper turns brown suspect iron sulfide

If there is no reaction in Sample dissolves and turns green or yellow Suspect iron oxide
cold HCl, immerse the and is magnetic
sample in hot HCl

If there is no reaction in Sample dissolves Suspect silica-based

hot HCl, immerse a compound (e.g., sand or
portion of the sample silt particle)
in mud acid (HCl/HF)

If there is no reaction in Sample dissolves (dissolution will be very slow) Suspect barium or
mud acid, immerse the strontium sulfate
sample in U42 or U104.

60 Fluid Selection Guide for Matrix Treatments

 Using lab data in fluid selection
The previous section shows how laboratory tests can be used to determine damage mechanisms.
This is an important step in selecting the proper fluid to treat the well. Acids would be ineffec-
tive in treating paraffins or emulsions. Organic solvents would be recommended in these cases.
Likewise, the use of mud acids for treating simple HCl soluble scales, such as calcite, in the well-
bore may not be the optimum solution in sandstone formations.
Petrographic and petrophysic studies are particularly important when the reservoir is sand-
stone. It is highly recommended that the mineralogy be defined since there is the potential for
detrimental reaction precipitates when treating with hydrofluoric (HF) acids. The presence of
swelling, migrating or HCl sensitive clays should be know when designing the treatment. These
parameters will influence the type of fluid chosen and the acid strength recommended.
Finally, compatibility testing is necessary to optimize the acid additive package and to verify
that the proposed treating fluid will not cause damage. Proper evaluation before pumping can
save time, money and effort afterwards.

Laboratory Studies for Designing a Matrix Treatment 61