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 uids select the optimum treating uid and design.

Formation cores, samples of formation uids and sometimes samples of the damaging material (organic deposit or scale) are the subject of laboratory studies. Various analyses are performed on these samples to obtain the information necessary for designing a matrix treatment.

Core analysis
Core analysis, including ow testing, is an integral part of the laboratory study used to help design a matrix treatment. Tests performed on cores can be classied 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 ow tests monitor the permeability response of the rock when different uids are injected.

Solubility tests
Solubility tests are used to determine the amount of any material that is dissolved by a given solvent. The results are given in weight percent. The solubility of a rock sample in a particular solvent (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 contact with a large excess of acid. During acidizing operations in the eld, the effective solubility 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 ows. 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.

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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 HCl Quartz Feldspars Orthoclase Microcline Albite Plagioclase Micas Biotite Muscovite Clays Kaolinite Illite Smectite Mixed layer Chlorite Glauconite Zeolites Carbonates Calcite Dolomite Ankerite Scales Gypsum Anhydrite Halite Iron oxides SiO2 K(AlSi3O8) K(AlSi3O8) Na(AlSi3O8) Na, Ca (Al1 2 Si2 3 O8) K (Mg, Fe)3 (AlSi3O10) (F, OH)2 K Al2 (AlSi3O10) (F, OH)2 Al4Si4O10 (OH)8 (K,H3O)(Al,Mg,Fe)2 (Al4Si4O10) [(OH)2 H2O] (Na, Ca)(Al, Mg)6 (Si4O10)3(OH)6 nH2O Kaolinite, illite or chlorite with smectite (Fe, Mg, Al)6 (Si, Al)4 O10 (OH)8 (K, Na)(Fe, Al, Mg)2 (Si,Al)4 O10 (OH)2 (Ca, Na) AlSiO6 H2O (general) CaCO3 CaMg(CO3)2 CaFe(CO3)2 CaSO4 2(H2O) CaSO4 NaCl None Solubility HCl + HF Low

None None None None

Moderate Moderate Moderate Moderate

None None

Moderate Moderate

None Moderate None None Moderate Moderate High

High High High High High High High

High High High

High High High

Low Low High Moderate

Low Low High Moderate

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Petrographic study
Knowledge of the petrography (description and classication) of the formation rock is essential to understanding the rocks response to uid injection. Understanding rock uid interactions depends upon

what minerals are present where the minerals are located relative to the path of the injected uid.

The laboratory techniques described in this chapter are used to determine the answers to these questions and to give insight on how this affects ow 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 earths 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 ow properties. Sediments are

deposited by water, wind or ice precipitated from solution grown in position by organic processes (e.g., carbonate reefs).

Sandstone Coarse Sediment Detrial minerals Quartz Feldspar Framework Micas

Carbonate Rocks Detrial grain Fossils Previously Framework deposited carbonates Precipitated mineral Calcite Dolomite Mud

Fine

Clays Scattered in the framework or as laminae Cement Quartz Clays Calcite Dolomite Anhydrite Etc. Transformation of clays Crystallization of authigenic minerals Changes in porosity Permeability Grain Cement Pore

Diagenesis Cementation Compaction Transformation into a rock Rock Flow of brines Dissolution Recrystallization

Cement Calcite Dolomite

Dissolution of shells

Transformation of calcite into dolomite Selective dissolution Changes in porosity Permeability

Lining Filling

Fracturation

Usually minor

Can be very important for reservoir properties

Figure 7-1. Formation of sandstone and carbonate rockconsequences for their ow properties.

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These three mechanisms coincide with the three main sediment constituents:

silicate fragments that are derived from the weathering and erosion of preexisting sedimentary, 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 mm2 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 ne grains.

During diagenesis, a cementation process transforms the sediment into rock. Cementation results from the ow of brine through the original sediments. The brines dissolve some components 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 uid, such as oil, lls 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 technique can determine mineralogy, porosity types, grain size, sorting and location of pores, cementing minerals and clay nes. Rock core samples are impregnated with a colored resin to ll 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 identies 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 dissolve 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 particles, or for cementing minerals, such as secondary quartz overgrowth and carbonates in sandstones. The objective is to dissolve as much of the damage as possible to improve ow capacity while dissolving as little of the cementing material as possible to maintain the integrity of the rock.

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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 patterns from unknown materials are compared to known mineral patterns to determine the composition of the unknown solid. Crystalline scale deposits can also be identied 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 uids 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 magnication. 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 reected 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 reected back from it. This type of image accentuates 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 uids 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 eld, this technique is also useful for looking at the internal structure of cores. X-ray images are taken along sequential planes perpendicular 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 gures 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, producing a detailed cross-sectional image of the internal structure. An example of this technique in oileld applications is the study of core samples before and after acid response tests. In carbonate cores, this can detail the formation of wormhole structures. In sandstone cores, the dissolution of materials within the pore structure can be visualized.

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Magnetic resonance imaging

Magnetic resonance imaging (MRI) is another diagnostic technique borrowed from the medical eld. It can be used to determine uid distribution in core samples. The method uses the response of magnetic elds 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 measurement of the amount of space occupied by liquid or gas in the reservoir. Total, effective and residual porosities are dened as follows: Total porosity (%) = Pore volume 100 Total bulk volume Volume of interconnected pores 100 . Total bulk volume

Effective porosity (%) =

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 observations. In either case, uid penetration into the core sample should be avoided. Direct measurement of uid 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 lled with uid and when it is lled with uid and the core sample.

Grain volume is the measure of the volume of the rock grains. This value is estimated by dividing 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 sufcient 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 uid from, or injection of uid into, the rock matrix. The procedures for determining pore volume by gas expansion are based on Boyles 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 uid of known density. The weight gain is used to calculate pore volume.

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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 uids. It can be measured in situ through pressure transient testing and in the lab using cores. Fluid conductivity measurements using cores are made using gas or nonreactive liquids. Core permeabilities to air should not be confused with the effective permeability to the reservoir uid. Air permeabilities may be an order of magnitude higher than reservoir permeability to uid. 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 owing gas through a core must be corrected for gas slippage, also called Klingenberg corrections. This is because permeability 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 innite 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 ow test

Core ow tests measure the effects of uids injected into sandstone formations. Permeability is calculated as a function of time or pore volumes injected. Core ow tests can also determine the water sensitivity of the rock and examine the reaction of the formation to a proposed treating uid or uid 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 uid. 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 ow rates used should ensure that the uid movement has minimal effect on the movement of nes contained within the pore structure. Typically 17 to 30 pore volumes of test uid 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 uid 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 uoride precipitation or nes release. Removal of calcite cementing materials by the HCl stage can result in release of nes. 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 permeability due to mud or clay acid indicates that the well is a good stimulation candidate.

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2000 Mud acid 1600 3% NH4Cl 1200 Permeability (mD) 800 3% NH4Cl 400 0 0 300 600 900 Volume (mL) Figure 7-2. Acid response curve of a core treated with HCl and mud acid sequence. 1200 1500

Core ow tests should not be used to estimate treatment uid volumes. Volumes are based on the amount and type of damage. Since core ow 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 ow studies. An accurate lithological breakdown is very helpful when interpreting acid response curves. SEM studies, both before and after uid injection, can also be a valuable tool when determining the effect of the injected uid. 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 uid sequence. Efuent 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 uid injection, especially brine, can give insights into the sensitivity of the formation clays to both nes migration and clay swelling. The typical procedure calls for sequential injection of the following uids:

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 uid step.

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Table 7-2. Explanation of Permeability Changes in a Water Sensitivity Test

Fluid Sequence Hexane to isopropanol Change Increase Decrease Meaning Improved cleaning of core, removal of water and/or alcohol-soluble salts May indicate incomplete removal of oil residue. In very low-permeability cores, adsorption of alcohol on pore walls may reduce capillary ow. Wettability factors may contribute In low-permeability cores, differences in adsorption may cause hexanes permeability to be higher than those measured with isopropanol. May indicate contamination of the hexane or incomplete removal of water by isopropanol. Seldom noted 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 conrms particle movement. Seldom noted Uncommon, but extremely sensitive cores may lose some permeability from clay movement Seldom noted Fines migration

Isopropanol to hexane

Increase

Decrease Isopropanol to 3% CaCl2 brine Increase Decrease

3% CaCl2 brine to distilled water

Increase Decrease

3% NaCl brine to distilled water

Increase Decrease

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

Acid and oil compatibility

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

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Many types of emulsifying agents occur naturally in crude oils. When formation uids are contacted by treating uids, 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 ow 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 difcult. 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 nes. The potential for the formation of acid and produced crude oil emulsions and the optimization of the de-emulsier 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, parafn 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 material 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 identication
Evaluation of solids or uids taken out of the well can be useful in determining the damage mechanism affecting well performance. Knowing the damage mechanism is particularly important when treating sandstone reservoirs, since the objective is removal of damage. Testing the formation brine can help determine scaling tendencies and predict incompatibility during mixing with foreign brine. Oil samples can be tested for parafn and asphalt content to estimate the possibility 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 oileld waters are used for a variety of reasons. They are helpful when trying to identify the source of downhole water and when planning waterood 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 procedures for oil eld water analysis are given in API RP 45, Recommended Practice for Analysis of Oileld Waters. The following parameters are typically measured:

major cationspositive ions associated with the minerals dissolved in the water most common cationssodium (Na), calcium (Ca), and magnesium (Mg) Concentration of these ions can vary from <1000 mg/L to >30,000 mg/L. fairly typical cationspotassium (K), barium (Ba), strontium (Sr), and lithium (Li) with concentrations in excess of 10 mg/L cations sometimes presentaluminum (Al), ammonium (NH4), iron (Fe), lead (Pb), managnese (Mn), and zinc (Zn)
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major anionsnegative ions associated with minerals dissolved in the water most common anionschloride (Cl), concentrations can vary from below 10,000 mg/L to over 200,000 mg/L other major anionsbicarbonate (HCO3) and sulfate (SO4) found in concentrations up to several thousand mg/L Bicarbonate and sulfate concentrations are important in scaling. fairly typical anionsbromide 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 CO2the amount of this dissolved gas is important in carbonate equilibrium and can affect carbonate scaling tendencies pHusually controlled by the CO2/bicarbonate concentrationsit is used in identifying potential scaling or corrosion tendencies. This measurement should be made in the eld 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 sufcient to predict scaling in surface equipment but may not be reliable for estimating downhole scaling. Pressure decreases as water is produced to the surface causing release of CO2 and precipitation of scales as the uid rises. Bottomhole water samples, kept at native pressure 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.

Parafn and asphaltene content

Parafns 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 215F [36 to 101C]. The solubility of parafn 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 parafn content is UOP 46. Asphaltenes are colloidal aggregates of condensed, polycylic aromatic hydrocarbons that contain N, O, S, and metal ions. These dispersions are permeated with adsorbed maltene molecules 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 neutralization 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.

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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 nes. Common laboratory analysis procedures are shown in Table 7-3.
Table 7-3. Solids Analysis Procedure
Procedure Visual inspection of sample Result Examination of physical characteristics Indication Color Texture Friability Organic/inorganic Oil or organic matter Suspect parafn Suspect asphaltene Contains water Suspect inorganic salt (typically NaCl) CO2 Suspect calcium or magnesium carbonate Suspect calcium sulfate Suspect iron carbonate Hydrogen sulde gas suspect iron sulde Suspect iron oxide

Heating of sample

Ignition Clean ame Sooty ame Noisy ame (i.e., pops and sparks)

Immersion in water Immersion in cold HCl

Sample dissolves Sample dissolves and gives off odorless gas Acid doesnt change color Acid doesnt change color but sample slowly dissolves Acid turns green or yellow and sample is magnetic Sample dissolves and gives off gas that smells of rotten eggs or lead acetate paper turns brown

If there is no reaction in cold HCl, immerse the sample in hot HCl If there is no reaction in hot HCl, immerse a portion of the sample in mud acid (HCl/HF) If there is no reaction in mud acid, immerse the sample in U42 or U104.

Sample dissolves and turns green or yellow and is magnetic Sample dissolves

Suspect silica-based compound (e.g., sand or silt particle) Suspect barium or strontium sulfate

Sample dissolves (dissolution will be very slow)

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Using lab data in uid selection

The previous section shows how laboratory tests can be used to determine damage mechanisms. This is an important step in selecting the proper uid to treat the well. Acids would be ineffective in treating parafns 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 wellbore may not be the optimum solution in sandstone formations. Petrographic and petrophysic studies are particularly important when the reservoir is sandstone. It is highly recommended that the mineralogy be dened since there is the potential for detrimental reaction precipitates when treating with hydrouoric (HF) acids. The presence of swelling, migrating or HCl sensitive clays should be know when designing the treatment. These parameters will inuence the type of uid chosen and the acid strength recommended. Finally, compatibility testing is necessary to optimize the acid additive package and to verify that the proposed treating uid will not cause damage. Proper evaluation before pumping can save time, money and effort afterwards.

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