Sandstone Reservoirs

Introduction
Treatment uid selection in sandstone formations is highly dependent on the mineralogy of the rock as well as the damage mechanism. Hydrouoric (HF) acid is typically used to dissolve the damaging silicate particles. Nonacid systems are sometimes used to disperse whole mud and allow it to be produced with the treating uid. The criteria for selecting the treating uid are mineralogy, formation damage mechanism, petrophysics and well conditions.

Formation mineralogy
Compatibility and sensitivity
Compatibility of the formation minerals to the various treating uids and their additives is a signicant issue when selecting uids for acidizing. Compatibility implies that permeability does not decrease when the treating uid contacts the formation. This concept of compatibility applies especially to sandstones, where potentially damaging reactions may occur. Compatibility and sensitivity are related concepts. As stated by McLeod (1984), a successful matrix treatment depends on the favorable response of the formation to the treatment uid. The treating uid, therefore, must remove existing damage without creating additional damage through interactions with the formation rock or uids. A formation is sensitive if the reaction between the rock minerals and a given uid induces damage to the formation. The sensitivity of a formation to a given uid includes all the detrimental reactions that can take place when this uid contacts the rock. These detrimental reactions include the deconsolidation and collapse of the matrix, the release of nes or the formation of precipitates. The precipitation of some damaging compounds cannot be avoided. Treating and overush uid stages are sized; so, there is sufcient volume to push potential precipitates deep enough into the reservoir to minimize their effects because of the logarithmic relationships between pressure drop and distance from the wellbore. Sandstones can be sensitive to acid depending on temperature and mineralogy. Ions of silicon, aluminum, potassium, sodium, magnesium and calcium react with acid and can form precipitates at downhole temperatures, once their solubility product is exceeded. If these precipitates occur in the near wellbore area, they can damage the formation. Sensitivity depends on the overall reactivity of the formation minerals with the acid. Reactivity depends on the structure of the rock and the distribution of minerals within the rock, i.e., the probability of the acid reaching the soluble minerals. The sensitivity of sandstone will also depend on the permeability of the formation. Lowpermeability sandstones are more sensitive than high-permeability sandstones for a given mineralogy. Acid formulations should be optimized on the basis of a detailed formation evaluation (Davies et al., 1992, Nitters and Hagelaars, 1990).

Fluid Selection Guide for Matrix Treatments

Sandstone Reservoirs

15

Sandstone petrography
From a mineralogical view, two factors affect the reactivity of a given mineral: chemical composition and surface area. The composition and structure, the petrography, of the rock are important factors used to determine potential sensitivity. Figure 4-1 schematically represents the different constituents of a common sandstone.

Porosity-Filling Minerals Secondary cement (carbonate quartz) Clay (pore lining i.e. illite) Clays (pore filling i.e. kaolinite)

Matrix Minerals Quartz Feldspars Chert Mica

Mud acid soluble/sensitive

Figure 4-1. Constituents of sandstone.

Rock structure
Typically, sandstone reservoirs are made of a framework of silicate grains, such as quartz, feldspars, chert and mica. This framework is the originally deposited sand. Secondary minerals, precipitated in the original pore spaces, are the cementing materials for the grains (most frequently secondary quartz overgrowth or carbonates) and the authigenic clays. The main components of clay minerals are silicon and aluminum; hence, they are called aluminosilicates. The actual solubility of various minerals in a sandstone reservoir depends strongly on their position in the structure of the rock. Only the mineral surfaces that can be contacted by the treating uid will be dissolved. The total specic surface area of the minerals affects their reactivity with HF acids. The larger the surface area is, the more reactive the minerals are. Because of their greater specic area, clays react much faster than feldspars, and feldspars react much faster than quartz, especially in the presence of high proton (H+) concentrations. Table 3-1 in the chapter on formation damage lists the specic area of some common sandstone minerals. Since they are usually the most reactive components, it is important to know the amounts of the various clay minerals in the rock. A petrographic study helps in understanding what response will result from pumping an acid and why. Chapter Six discusses petrographic studies in detail. HCl solubility is commonly used to represent the carbonate content of the sandstone. A petrographic study can verify whether using HCl solubility is an acceptable estimate for carbonate. Other minerals, such as oxides, suldes and chlorite clay, are also partially soluble in HCl. Overestimation of the amount of carbonate will affect uid selection because HF acids are not used in sandstones with calcite content greater than 20%. A limit on carbonate content is needed to avoid the precipitation of calcium uoride from the reaction of HF with calcite. Reservoirs with high calcite content are treated with HCl or organic acids, which are ineffective in dissolving clay and nes particles. If HCl solubility is used for calcite, but is too high because of other HCl soluble minerals, a sub-optimal uid could be selected because of the assumption that an HF uid cannot be used.

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Fluid Selection Guide for Matrix Treatments

Clays
The distinction between clay types depends more on the arrangement of the atoms in their crystalline structure than any major difference in their chemical formula. However, small differences in chemical formula, e.g., the presence of iron, can lead to major problems during treatment. The structures of kaolinite, smectite, illite and chlorite are shown in Fig. 4-2. The structural differences between the clays determine the surface area that is exposed to the reservoir uids. While clay reactivity is a function of this surface area, the location of the clay in the rock matrix is also critical to its reactivity. Simply because the clay is in the rock does not mean that the clay is reactive. Authigenic clays, which grow in the pores from minerals in the connate water (Wilson and Pittman, 1977), can be pore lling or pore lining. Authigenic clays have a large amount of surface area exposed in the pore and can be reactive. Detrital clays, part of the building material in the original matrix, are usually less reactive than authigenic clays, because they have less surface area in contact with the uids in the pore. Clay may also act as cement holding the matrix grains together. As a binder or cement, clay may react with uids such as acid and water to deconsolidate the formation. If the clay cement is shielded by a quartz overgrowth, as is common in many sandstone formations, the clay will not be reactive. Only authigenic clays, unprotected clay cements and the few detrital clays on the pore boundary can potentially cause damage. The common clays that account for most of the real

(a)

(b)

(c)

(d)

Figure 4-2. Photomicrographs of (a) pore-lling smectite sheets, (b) books of kaolinte platelets in a pore space, (c) honeycomb growth of chlorite on a sand grain (d) hairs of illite extending from a sand grain.

Sandstone Reservoirs

17

and perceived clay problems are kaolinite, smectite (montmorillonite), illite and chlorite. Fortunately, these minerals can be dissolved with HF acid; so, the damage can be treated. If formation collapse is a concern when unprotected clay cement is present, the recommended acid strength would need to be adjusted. In recent years, clay compatibility with hydrochloric acid (HCl) has become an issue. All clays have a temperature at which they become unstable in HCl (Table 4-1). Unstable clays decompose quickly and consume all available HCl. Silica gel precipitates, which damage the matrix, are products of the decomposition of these clays. Therefore, the presence of these specic clays can have a large inuence on the ultimate uid recommendation.
Table 4-1. Clay instability in HCl acid (Simon & Anderson, 1990)
Mineral Zeolites Chlorites Illite Mixed layer Smectite Kaolinite Maximum Temperature (F [C]) 75 [24] 150 [65] 190 [87] 200 [93] 200 [93] 250 [121]

Chemistry of sandstone acidizing

The chemical reactions between sandstone minerals and HF acids have been extensively described in the literature. There are three classes of HF reactions: primary, secondary and tertiary.

Primary reactions
Primary reactions describe the action of the unspent acid with the various minerals as follows: HF + mineral Al , Si + H + AlFx + H2 SiF6 + + H2 O +. The presence of calcium (Ca++) will cause calcium uoride (CaF2+) to precipitate. Sodium (Na+) and potassium (K+) can create alkali-uosilicates and alkali-uoaluminates when formation minerals, or sodium or potassium brines, react with the hexauorosilicic acid produced by this reaction. The uosilicate and uoaluminate compounds are more likely to form during the initial phases of the dissolution, since a high concentration of HF relative to the clay enhances the reaction. Precipitation of these compounds will occur when the amount present increases above the solubility limit.

Secondary reactions
Secondary reactions describe the action of the hexauorosilicic acid with remaining acid and the rock as follows: The driving force for this reaction is the greater afnity of uorine for aluminum than for H2 SiF6 + mineral Al , Si + H + AlFx + silica gel.
+

18

Fluid Selection Guide for Matrix Treatments

silicon. Silica gel precipitation is well documented. This precipitation occurs when the initial HF is nearly consumed. An exchange reaction occurs on the surface of the clays and nes to generate uoaluminates and silica gel. The silica is deposited on the surface of the mineral particles, and the uoaluminates remain in solution. This precipitate is more like to occur when fast-reacting aluminosilicates, such as clays, are present. The damaging effect of silica gel precipitates is still a point of debate; however, it does appear that they are more damaging at higher than lower temperatures.

Tertiary reactions
Recently there has been much discussion about whether tertiary reaction products are damaging to the reservoir. Tertiary reactions are the reactions of the aluminum uorides and aluminosilicates. AlFx + mineral Al , Si H + AlF + silica gel ; x > y y This reaction is due to the greater stability of AlFy over AlFx, which leads to continued reduction of the F/Al ratio in spent HF until all remaining HCl is spent. The reaction is insignicant at temperatures below 194F [90C]. At higher temperature, the reaction can be considerable depending on the stability of the formation clays with HCl. As the reaction drives on, and HF is spent, complex aluminouorides may be precipitated out deep in the matrix. Gdanski and Shucharts (1998) recommendations of 9%HCl:1%HF are based on these observations.

Other reactions
Iron is another potential source of precipitation during sandstone acidizing. Precipitation is due to the formation of colloidal ferric hydroxide as the acid spends (pH > 2). Sources of ferric iron (Fe3+) include some minerals (chlorite and glauconite clays) and tubing rust (iron oxide). These reactions begin to precipitate gelatinous ferric hydroxide at a pH of 2.2. The nature of the precipitate (crystalline or amorphous) varies as a function of the anions present (Smith et al., 1969). Precipitation of ferric hydroxide during acid injection is normally not a problem, if an adequate HCl tubing wash was used to remove most of the soluble FeO2 . All acids used for matrix treatments should also contain iron control additives, either sequestering or reducing agents or both. Ferrous iron (Fe2+) is typically not problematic, since ferrous hydroxide precipitates at a pH between 7.7 and 9. The main sources and causes of precipitates formed during sandstone matrix acidizing are summarized in Table 4-2. The formation of these potentially damaging precipitates is affected by the complex mineralogy of many sandstones. The likelihood of damage depends on several factors: ChemicalAre the reaction products soluble either in the overush or the formation uid? CrystallographicAre the precipitates amorphous or crystalline? MorphologicalDo they produce grains that can migrate, or do they cover undissolved particles? ConcentrationIs the concentration high enough to cause plugging in the pore system? PhysicalIs the damage potential also related to rock properties like permeability, pore size, pore conguration or other reservoir characteristics?

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Table 4-2. Possible precipitates in sandstone acidizing

Precipitate Calcium uoride (CaF2) Origin Carbonate-HF reaction CaF2 can be caused by an inadequate HCl preush to remove calcium ions from calcite cementing materials or to ush calcium chloride completion uids away from the near wellbore. Clay and silicate dissolution in HF. Amorphous silica results from both secondary and tertiary HF acidizing reactions. Feldspar and illite clay dissolution in HF produce these primary reaction products. They can also form if seawater or sodium or potassium brines are mixed with spent HF. Silico-aluminate dissolution in HF. Fluoaluminates, like the uosilicates, occur when spent mud acid (H2SiF6) reacts with the formation. They can also form if seawater or sodium or potassium brines are mixed with spent HF. Clay and feldspar dissolution in HF can cause these precipitates. Iron minerals or iron oxides (rust) can react with HCl-HF to produce these compounds.

Amorphous silica Sodium and potassium uosilicates

Sodium and potassium uoaluminates

Aluminum hyroxides and uorides Iron compounds

Reaction front
Sandstone acidizing reactions occur where the uids meet minerals. As uid is injected, the position of the zone where reactions take place moves radially outward from the wellbore. Figure 4-3 represents this moving reaction front. The blue line shows the acid concentration relative to the reaction front. As the acid moves through the near wellbore region where all acid soluble minerals have been dissolved, it retains its full strength. Acid spending takes place in the reaction front. The radial width of this zone depends on the minerals present and the temperature of the reservoir at the point of contact, which is affected by any residual cool down effects due to difference between uid and rock temperature. When the injected uid is totally spent, it moves through the unreacted minerals. The primary reactions occur when fresh acid contacts fresh reservoir. This typically happens in the near wellbore region. As spent acid moves through this same matrix, the secondary and tertiary reactions occur with the reaction products precipitating further away from the wellbore. It is important to keep the injected uid moving to carry reaction products past the critical matrix region of the well.
Minerals dissolved Reaction front Unreacted minerals

Figure 4-3. Moving front reaction.

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Fluid Selection Guide for Matrix Treatments

Sandstone treatment design

Proper treatment design can be very effective in decreasing the negative effects of pumping acids into sandstone through the use of multiple injection stages and correct uid selection. A typical matrix treatment in a sandstone will include a preush, a main uid and an overush. When long intervals are treated, diversion stages are pumped after the overush and before the next stage of preush.

Preush
The sequence of uids used in a sandstone treatment is largely dependent on the damage type(s) being addressed. A preush is a uid stage pumped ahead of the main treating uid. Multiple preush stages are sometimes used to address multiple damage mechanisms and prepare the surface for the main treatment uids. In sandstone reservoirs, the acid preush serves two purposes: To displace the formation brines, usually containing K, Na, or Ca ions, away from the wellbore so there will be no mixing with HF acids. This decreases the probability of forming alkaliuosilicates such as potassium hexauorosilicate. To dissolve as much of the calcareous material as possible, prior to injection of the HF acid to minimize calcium uoride precipitation. Due to reservoir heterogenities, it is unlikely that the acid preush will remove all of the calcite. However, it has been shown that reducing calcite below 6% is sufcient to avoid precipitation (Fig. 4-4). Strength and volume guidelines are based on the criteria set up in the work done by Labrid (1971), Fogler et al. (1976), Kline (1980), Kline and Fogler (1981) and Walsh et al.(1982). This theoretical work was further investigated and conrmed by eldwork done by Gidley (1985), McLeod (1984), Thomas and Crowe (1981) and others.
16 14 12 Max weight percent of HF in acid formation 10 8 6 4 2 0 0 10 20 30 40 Weight percent of HCl in acid formation Figure 4-4 . HCl/HF ratio to avoid precipitation, based on AlF3 and CaF2 precipitation(Walsh et al.,1982). Increasing weight percent of acid consuming minerals left by HCl preflush Ideal case 0% Calcite 3% Calcite 6% Calcite

Using an additional ammonium chloride (NH4Cl) brine preush for sandstone acid treatments is an emerging practice. This preush conditions the formation clays as it moves formation water away from the near wellbore area. The NH4+ ions in the brine exchange with the alkali (Na, K, or Ca) ions on the clay particles; so, they will be displaced from contact with the mud acid. The effectiveness of this procedure appears to be controlled by the brine concentration at a radial distance of 2.5 ft from the wellbore. This preush is pumped at the start of the job to establish injectivity before the regular mud acid treatment is pumped. It is only pumped once and is not a part of the regular treating sequence.
Sandstone Reservoirs 21

Hydrocarbon solvents can be used to remove oil lms and parafn deposits; so, the aqueous acid systems can contact the surfaces of the mineral. These types of preushes affect treatment success because the acid must contact the damage before it can react with it. A solvent preush is typically not a part of the normal uid staging. Like the brine preush, it is pumped before the normal acid treatment. If a diverter is necessary for better coverage, the diverter is pumped between solvent slugs and before the rst acid preush. Mutual solvents can also be added to preush and overush uids. However, they must be thoroughly tested for compatibility with the oil in place. Adding mutual solvents to the preush will help remove oil from the near-wellbore region and leave the rock and damaging materials waterwet. This enhances the rate of acid attack. Mutual solvents can increase inhibitor requirements; so, all formulations must be tested before pumping.

Main uid
The main uid in a sandstone acid treatment is the uid used to remove the damage. It is typically a mixture of hydrouoric (HF) and hydrochloric (HCl) or organic acids. HF acid is used because it is the only common, inexpensive mineral acid able to dissolve siliceous minerals. It is mixed with HCl or organic acid to keep the pH low when it spends to aid in prevention of detrimental precipitates. These mixtures are called mud acids because they were originally developed to treat siliceous drilling mud damage. HF acid should not be used in sandstone formations with high carbonate content. The risk of forming calcium uoride precipitates is too great, since it is unlikely that a sufcient amount of HCl acid preush can be pumped. The accepted cutoff point for the use of hydrouoric acid is 20% calcite + dolomite based on the guidelines developed by McLeod in 1984.

Overush
The overush is an important part of a successful sandstone acid treatment. It performs the following functions:

displacement of the nonreacted mud acid into the formation displacement of the mud acid reaction products away from the wellbore removal of potential oil-wet relative permeability problems caused by some corrosion inhibitors.

The overush uid must be miscible with the acid in order to displace it. Therefore, aqueousbase liquids should be considered as the rst displacing and ushing uid. This may be followed by other uid systems depending on the concerns and well conditions. Studies of displacement fronts indicate that the reactivity and uid character of the overush have a major inuence on the volume required to displace the spent mud acid. Recent experience indicates the advantage of including HCl or acetic acid in the rst part of the overush to maintain a low-pH environment for the displaced spent mud acid stage. The minimum total overush volume should provide at least 3 ft of radial penetration into the formation to move potential problems past the critical matrix where the greatest pressure drop occurs. Damage effects are minimized beyond the critical matrix because of the logarithmic relationship between pressure drop and distance from the wellbore. Volumes that are less than twice the mud acid stage volume should be considered inappropriate. Formation permeability anisotropy may require doubling or even tripling this volume, if the reservoir pressure is sufcient to unload the injected uid. Large overushes help prevent the near wellbore precipitation of amorphous silica. At formation temperatures of 200F [93C] or greater, amorphous silica precipitation occurs while the mud acid is being pumped into the formation. The precipitate is somewhat mobile at rst, but it can set up as a gel after ow stops. If this potentially damaging material is kept moving by the overush uid, it will be diluted and moved beyond the critical matrix.

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Fluid Selection Guide for Matrix Treatments

Sandstone treatment uid selection

Fluid selection rules for each stage of the treatment must consider all of the parameters previously discussed: dissolution of damage, compatibility with rock minerals and reservoir uids and potential damaging reaction products. The rules for the selection of acids are shown below, and they are the same as those in the Fluid Selection Advisor (FSA) of the StimCADE design program. The main selection criteria are the formation mineralogy and permeability. The selection of nonacid uids for treating damages such as organic deposits, wettability changes and water block will be discussed at the end of this chapter. Formation lithology affects the selection of acid strength. Since silts and clays are the component minerals that react with HF acid to cause potentially damaging precipitates, the higher the silt and clay content, the greater risk of precipitation. Increasing the HCl:HF ratio is one way to retard precipitation. HCl increases the dissolving power of the HF and a low-HF content reduces the precipitation of silica. Therefore, as the silt and clay content of the formation increases, the recommended HCl:HF ratio also increases. The presence of HCl sensitive clays will also affect the type of acid chosen. X-ray diffraction (XRD) analysis is the most common test used to determine formation mineralogy. However, this data is not always available. Formation solubility in both HCl and HCl:HF can be used to approximate the total silt and clay content. The difference in these solubilities correlates well to silt and clay content by XRD analysis as seen in Table 4-3. Solubility information, however, does not indicate the type of clay present.
Table 4-3. XRD Versus Solubility Analysis
Formation Muddy sand Brazos sand Miocene A Miocene B Miocene C Silt and Clay from XRD (%) 7.0 13.6 25.0 26.0 34.0 Difference in Solubility between HCl and HCl:HF (%) 5.2 13.0 20.7 22.1 33.6

Permeability affects acid selection by inuencing the amount of damage caused by acid precipitates. A low-permeability formation will be more severely damaged by precipitates than a formation with high permeability. Therefore, weaker acids, which help limit precipitation, are recommended for lower permeability formations.

Brine preush or overush

The NH4Cl brine concentration used in a sandstone acid treatment is based on obtaining a 3% NH4Cl solution at a distance of 2.5 ft from the well when a volume of 50 gal/ft is pumped. The calculation considers the cation exchange capacity of the various silt and clay components in the formation. The recommended brine concentration is calculated automatically in the StimCADE FSA module, or the following equation can be used: Concentration = 3 + % smectite 0.3 + % illite 0.12 + % kaolinite 0.08

) ( ) ( +(% chlorite 0.12) + (% feldspar 0.05)

(Be sure and add the smectite and illite in mixed layer clays to their respective totals.)

Sandstone Reservoirs

23

A minimum concentration of 3% NH4Cl is used if no clays are present. From the equation, it is obvious that the amount of smectite present in the rock has the most effect. If smectite is present, even if the amount isnt known, use a higher concentration of NH4Cl. If the core ow tests exhibit sensitivity to water, smectite should be suspected.

Acid preush or overush

The acid used as a preush or an overush to a main treatment containing hydrouoric acid depends on the silt and clay content of the formation, its permeability and the presence of HCl sensitive minerals, like chlorite, glauconite and zeolites. Table 4-4 lists the acid preush recommendations. For operational simplicity, the same acid is used for both pre- and overush. Organic acids are recommended for use in conjunction with, or instead of, HCl in sensitive formations. Although they will dissolve the carbonate, they work more slowly. When pumping organic acids as stand-alone uids, they should be mixed in ammonium chloride rather than fresh water. Organic acids also act as a low-pH buffer and complexing agent that helps minimize the tendency of iron compounds to precipitate as the acid spends. However, they do not dissolve iron scale or prevent clay swelling.
Table 4-4. Acid Preush and Overush Selection
Lithology Criteria (%) Zeolites >2 2 2 2 02 02 02 02 02 02 0 0 0 0 0 0 Chlorite + Glauconite Any >6 36 36 3 3 3 3 3 3 3 3 3 3 3 3 Silt and Clay Any Any >10% silt or >10% clay <10% silt and <10% clay >10% silt or >10% clay <10% silt and <10% clay >10% silt or >10% clay <10% silt and <10% clay >10% silt or >10% clay <10% silt and <10% clay >10% silt or >10% clay <10% silt and <10% clay >10% silt or >10% clay <10% silt and <10% clay >10% silt or >10% clay <10% silt and <10% clay Any Any Any Any >100 >100 20100 20100 20 20 >100 >100 20100 20100 20 20 10% Acetic 10% Acetic 5% HCl + 5% Acetic 7.5% HCl + 5% Acetic 10% HCl + 5% Acetic 15% HCl + 5% Acetic 7.5% HCl + 5% Acetic 10% HCl + 5% Acetic 5% HCl + 5% Acetic 7.5% HCl + 5% Acetic 10% HCl 15% HCl 7.5% HCl 10% HCl 5% HCl 7.5% HCl Permeability (mD) Acid Concentration

24

Fluid Selection Guide for Matrix Treatments

Main treatment uid

Determining the proper blend of HCl and HF to use in a mud acid mixture, and whether HCl or organic acid is used, is a complex process. The selection depends on the silt and clay content of the formation, its permeability and the presence of HCl sensitive clays. The criteria are similar to those for choosing the acid preush or overush concentration. Table 4-5 lists the recommendations based on these parameters.
Table 4-5. Mud Acid Selection
Lithology Criteria (%) Zeolites >5 >5 >5 >5 >5 >5 25 25 25 25 25 25 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 02 02 02 02 02 02 02 02 02 0 0 0 0 0 0 0 0 0 Chlorite + Glauconite Any Any Any Any Any Any 36 36 36 36 36 36 >9 >9 >9 69 69 69 69 69 69 36 36 36 36 36 36 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Silt and Clay >10% silt and >10% clay >10% silt or >10% clay <10% silt and <10% clay >10% silt and >10% clay >10% silt or > 10% clay <10% silt and <10% clay >10% silt and >10% clay >10% silt or >10% clay <10% silt and <10% clay >10% silt and >10% clay >10% silt or >10% clay <10% silt and <10% clay >10% silt and >10% clay >10% silt or >10% clay <10% silt and < 10% clay >10% silt and >10% clay >10% silt or >10% clay <10% silt and <10% clay >10% silt and >10% clay >10% silt or >10% clay <10% silt and <10% clay >10% silt and >10% clay >10% silt or >10% clay <10% silt and <10% clay >10% silt and >10% clay >10% silt or > 10% clay <10% silt and <10% clay >10% silt and >10% clay >10% silt or >10% clay <10% silt and <10% clay >10% silt and >10% clay >10% silt or >10% clay <10% silt and <10% clay >10% silt and >10% clay >10% silt or >10% clay <10% silt and <10% clay >10% silt and >10% clay >10% silt or >10% clay <10% silt and <10% clay >10% silt and >10% clay >10% silt or >10% clay <10% silt and <10% clay >10% silt and >10% clay >10% silt or >10% clay <10% silt and <10% clay >20 >20 >20 20 20 20 >20 >20 >20 20 20 20 Any Any Any >20 >20 >20 20 20 20 >20 >20 >20 20 20 20 >100 >100 >100 20100 20100 20100 20 20 20 >100 >100 >100 20100 20100 20100 20 20 20 OCA HT OCA HT OCA HT OCA HT OCA HT OCA HT OCA OCA OCA OCA OCA OCA OCA HT OCA HT OCA HT OCA HT OCA HT OCA HT OCA HT OCA HT OCA HT 9 % HCl + 1% HF + 5% Acetic 9 % HCl + 1.5% HF + 5% Acetic 8 % HCl + 2% HF + 5% Acetic 4.5 % HCl + 0.5% HF + 5% Acetic 6% HCl + 1% HF + 5% Acetic 6% HCl + 1.5% HF + 5% Acetic 13.5% HCl + 1.5% HF + 5% Acetic 12% HCl + 2% HF + 5% Acetic 12% HCl + 3% HF + 5% Acetic 9% HCl + 1% HF + 5% Acetic 9% HCl + 1.5% HF + 5% Acetic 8% HCl + 2% HF + 5% Acetic 4.5% HCl + 0.5% HF + 5% Acetic 6% HCl + 1% HF + 5% Acetic 6% HCl + 1.5% HF + 5% Acetic 13.5% HCl + 1.5% HF 12% HCl + 2% HF 12% HCl + 3% HF 9% HCl + 1% HF 9% HCl + 1.5% HF 8% HCl + 2% HF 4.5% HCl + 0.5% HF 6% HCl + 1% HF 6% HCl + 1.5% HF Permeability (MD) Acid Concentration

Sandstone Reservoirs

25

The cleaner the sandstone (lower silt and clay content) and the higher the permeability, the lower the HCl:HF ratio, and the more aggressive the treatment can be. Typically, the HCl:HF ratio is either 4:1, 6:1, or 9:1. A higher volume of weak acid must be pumped to attain the same results as a smaller volume of a stronger acid. This is an important consideration when designing treatments for environmentally sensitive areas where disposing spent acids can create problems. The ratio of HCl:HF should be increased if the formation contains clay rather than calcite cementing materials. Pick the acid concentration recommended in Table 4.5. If the HCl:HF ratio is less than 9:1, change the recommendation to the 9:1 ratio that contains a lower HF content. For example, if a 6:1 HCl:HF uid is normally used, change to a 4.5:0.5 HCl:HF mixture. Mud acids should only be used in formations with less than 20% carbonate (calcite + dolomite) because of the increased risk of forming damaging calcium uoride precipitates at higher carbonate content. HCl or acetic acids are used for these formations. The specic acid used is dependent upon reservoir temperature and the presence of HCl sensitive clays as shown in Table 4.6. Sandstone treatment uid recommendations are automatically determined in the FSA of the StimCADE matrix design program. All rules and special cases discussed in this book are part of this computer program, which will also make diverter recommendations.
Table 4-6. Acid Selection for High Calcite Sandstones
Chlorite + Glauconite >0 >0 0 0 Reservoir Temperature (F [C]) >200 [93] 200 [93] >300 [148] 300 [148] Acid Recommendation 10% Acetic 10% HCl 10% HCl 15% HCl

Specialty acids
ClayACID
ClayACID* treatment is a sandstone acidizing system employing uoboric acid (HBF4). ClayACID treatment not only provides good stimulation but also provides permanent stabilization of clays and other nes as well as eliminating water sensitivity and the mobility of migratory nes (Thomas and Crowe, 1981). The acid slowly releases HF in situ through the hydrolysis of HBF4 according to the following reaction: HBF4 + H 2O HBF3OH + HF At any given time, there is only a limited amount of hydrouoric acid available. The acid is consumed by reaction on clay minerals followed by hydrolysis of uoboric acid to produce more HF. Therefore, ClayACID uid is a retarded acid and can penetrate to a much greater distance from the wellbore before spending than mud acid can. At higher temperatures, >150F [65C], the kinetics of hydrolysis is rapid. Equilibrium conditions dictate that there is only a limited amount of HF present in solution at any given time. For example, at 212F [100C] only 0.15% HF is present. Thus, the reaction rate is similar to a very dilute mud acid solution. The result of having such a limited amount of HF available is a decreased probability of forming precipitates of uosilicates, uoaluminates or silica. A major advantage of the ClayACID system is its ability to inhibit the migration of formation nes. Depending on the mineral attacked, partial dissolution takes place, and boron is included in the lattice of the mineral crystal. As a result of this topochemical reaction, borosilicate reaction products coat the mineral surface. The coating does not plug the pores but desensitizes the minerals and stabilizes nes particles by fusing them to the sand grains.
26 Fluid Selection Guide for Matrix Treatments

ClayACID can be used as an alternative to mud acids in formations that show severe sloughing when treated with mud acid. Clay Acid is also recommended for severe nes migration, which is indicated by rapid declines in production that can be as large as 50percent in 6 months. When used for this application, it is pumped as an overush to a mud acid treatment. There are two ClayACID formulations. Use ClayACID regular for reservoir temperatures up to 300F [148C]. Use ClayACID LT for reservoir temperatures to 130F [54C], but not for temperatures above that. When pumping ClayACID uids, displace the uid just into the formation. Do not overush! To obtain the maximum stabilization effect, the ClayACID feature should react and coat the clays in the critical matrix portion of the reservoir. The well should also be shut in after pumping ClayACID uid due to its longer reaction time. Table 4-7 lists minimum shut-in times by temperature.
Table 4-7. ClayACID Shut-In Time
BHST (F [C]) Min Shut-In Time (hr) Regular ClayACID 100 [37] 110 [43] 120 [48] 130 [54] 140 [60] 150 [65] 160 [71] 170 [76] 180 [82] 190 [87] 225 [107] 250 [121] 300 [148] 96 76 52 35 24 16 11 8 5 3 2 1 0.5 ClayACID LT 48 38 26 18 Not recommended Not recommended Not recommended Not recommended Not recommended Not recommended Not recommended Not recommended Not recommended

Organic clay acid

In cases where high concentrations of acid sensitive clays, such as zeolite, chlorite or glauconite, are present, specialized acids, like OCA* Organic Clay Acid) are available. This acid system can also be used when acidizing sandstone formations with very high-bottomhole temperatures or when the total clay content of the formation is greater than 30%. OCA formulations are mixtures of an organic acid and uoboric acid. When used in matrix acidizing applications, OCA uid

removes formation damage caused by clay and other aluminosilicate minerals minimizes hydrated silica precipitation, which is known as the secondary reaction prevents migration of undissolved nes post acidizing treatments treats high-temperature sandstone wells. OCA uids can be used at temperatures ranging from 80F to 400F [27C to 204C].

There are two formulations recommended for different conditions. The rst formulation, OCA-Regular, is used for temperatures lower than 350F [176C] or in formations containing low concentrations of HCl sensitive minerals. The second formulation, OCA-HT, is intended for sandSandstone Reservoirs 27

stone formations with temperatures 350F [176C] and above or in formations containing more than 5% of zeolite or chlorite. When considering this uid, crude oil compatibility testing is required. If an incompatibility exists, OCA uids may form a thick, rigid emulsion that will inhibit cleanup of the formation. This problem appears to be most commonly associated with highly parafnic crudes.

Mud and silt remover

MSR* mud and silt remover, which dissolves, disperses and suspends damaging particles and nes, can be formulated with HCl/HF mixtures. Naturally fractured sandstone is a very hard, compact, low-porosity and low-permeability formation. The reservoir productivity usually comes from the fracture system. These fractures can be plugged with drilling solids. MSR uids can be used in these types of formations where the plugging particles are located in natural ssures or in hydraulically induced fractures. MSR formulation is determined using the same criteria as a normal sandstone main treating uid. However, if organic acids are required due to extreme high temperature or sensitive clays, consult the regional technical specialist or laboratory. MSR is not normally formulated using organic acids.

Dynamic acid dispersion

DAD* dynamic acid dispersion, is an acid outside-phase emulsion prepared and stabilized with Dispersing Agent U74. The purpose of the dispersion is to simultaneously dissolve acid-soluble minerals and remove oily parafnic deposits. Target areas can be tubulars, perforations or the critical matrix. DAD can be used as a preush ahead of mud acid or ClayACID during matrix treatment procedures. This low-viscosity dispersion allows one-stage cleanup and acidizing of hydrocarbon-coated formations, gravel packs, wellbores and tubulars. Various ratios of acid and hydrocarbon solvent are possible with common dispersions ranging from 90% acid and 10% organic solvent to 50% acid and 50% organic solvent.

NARS uid
NARS* uids are special treating solutions that contain no acid. These uids are used as cleanup and breakdown uids in formations that may be damaged by acid. These solutions are nondamaging to water- or acid-sensitive formations and contain strong chelating and clay suspending agents. They can be used in high-temperature reservoirs (greater than 400F [204C]) but should not be used if downhole temperatures are below 100F [37C]. Two solutions, NARS 200 and NARS201, are currently being used.

28

Fluid Selection Guide for Matrix Treatments

Nonacid treatments
Solvents, bleach and other nonacid fluids are used to treat specific damage mechanisms. The damages and recommended uids are outlined in Table 4-8.
Table 4-8. Recommendations for Nonacid Fluids
Damage Mechanism Asphaltenes or parafn Bacteria Emulsion block or injection carryover of emulsion Injection carryover of oil Mixed organic and inorganic scale deposits Water block Wettability alteration
Consult

Recommendation Xylene Formation Cleaning Solution (M91) followed by acid treatment CLEAN SWEEP* CLEAN SWEEP DAD CLEAN SWEEP CLEAN SWEEP

Matrix Materials Manual for CLEAN SWEEP or DAD recommendation for specic well conditions.

Sandstone Reservoirs

29