Chapter

C l a y

S t a b i l i z a t i o n

The problems caused by shales in petroleum activities are not new. At the beginning of the 1950s, many soil mechanics experts were interested in the swelling of clays. It is important to maintain wellbore stability during drilling, especially in water-sensitive shale and clay formations. The rocks within these types of formations absorb the fluid used in drilling; this absorption causes the rock to swell and may lead to a wellbore collapse. The swelling of clays and the problems that may arise from these phenomena are reviewed in the literature [528,529,1788,1900]. Various additives for clay stabilization are shown in Table 3-1.

Properties of Clays
Clay minerals are generally crystalline in nature. The structure of the clay crystals determines its properties. Typically, clays have aflaky,mica-type structure. Clayflakesare made up of a number of crystal platelets stacked face-to-face. Each platelet is called a unit layer, and the surfaces of the unit layer are called basal surfaces. A unit layer is composed of multiple sheets. One sheet is called the octahedral sheet; it is composed of either aluminum or magnesium atoms octahedrally coordinated with the oxygen atoms of hydroxyl groups. Another sheet is called the tetrahedral sheet. The tetrahedral sheet consists of silicon atoms tetrahedrally coordinated with oxygen atoms. Sheets within a unit layer link together by sharing oxygen atoms. When this linking occurs between one octahedral and one tetrahedral sheet, one basal surface consists of exposed oxygen atoms while the other basal surface has exposed hydroxyl groups. It is also quite common for two tetrahedral sheets to bond with one octahedral sheet by sharing oxygen atoms. The resulting structure, known as the Hoffman structure, has an octahedral sheet that is sandwiched between the two tetrahedral sheets. As a result, both basal surfaces in a Hoffman structure are composed of exposed oxygen atoms.

Table 3-1 Clay Stabilizers Additive Polymer latices Partially hydroly zed poly-(vinylacetate)a Polyacrylamideb Copolymer of anionic and cationic monomers Acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropane sulfonic acid Dimethyl diallyl ammonium chloride Nitrogen0 Partially hydrolyzed acrylamide-acrylate copolymer, potassium chloride, and polyanionic celluloseMA Aluminum/guanidine complexes with cationic starches and polyalkylene glycolsMA Hydroxyaldehydes or hydroxyketones Polyols and alkaline salt Tetramethylammonium chloride and methyl chloride quaternary salt of polyethyleneimineSF Pyruvic aldehyde and a triamine Quaternary ammonium compounds In situ crosslinking of epoxide resins Oligomer (methyl quaternary amine containing 3 to 6 moles of epihalohydrin) Quaternary ammoniumcarboxylatesBDLT Quaternized trihy droxy alky 1 amineLT Poly vinyl alcohol, potassium silicate, and potassium carbonate Copolymer of styrene and substituted maleic anhydride Potassium salt of carboxymethylcellulose Water-soluble polymers with sulfosuccinate derivative-based surfactants, zwitterionic surfactantsBDLT
BD, biodegradable; LT, low toxicity; SF, well stimulation fluids. a) 75% hydrolyzed; 50,000 Dalton. b) Shear-degraded; for montmorillonite clay dispersed in sandpacks. c) Injection of unreactive gas.

References [1686] [1014] [ 1878,1880]

[119,1649-1651 ] [1640,1641] [ 100,768] [232] [ 1834] [762] [8-10] [420] [405,406] [832] [829] [ 1401 ] [32] [1643] [ 1390] [42,46]

The unit layers stack together face-to-face and are held in place by weak attractive forces. The distance between corresponding planes in adjacent unit layers is called the c-spacing. A clay crystal structure with a unit layer consisting of three sheets typically has a c-spacing of about 9.5 x 10~7 mm.

In clay mineral crystals, atoms having different valences commonly will be positioned within the sheets of the structure to create a negative potential at the crystal surface. In that case, a cation is adsorbed on the surface. These adsorbed cations are called exchangeable cations because they may chemically trade places with other cations when the clay crystal is suspended in water. In addition, ions may also be adsorbed on the clay crystal edges and exchange with other ions in the water. The type of substitutions occurring within the clay crystal structure and the exchangeable cations adsorbed on the crystal surface greatly affect clay swelling, a property of primary importance in the drilling fluid industry. Clay swelling is a phenomenon in which water molecules surround a clay crystal structure and position themselves to increase the structure's c-spacing thus resulting in an increase in volume.

Swelling of Clays
Two types of swelling may occur. Surface hydration is one type of swelling in which water molecules are adsorbed on crystal surfaces. Hydrogen bonding holds a layer of water molecules to the oxygen atoms exposed on the crystal surfaces. Subsequent layers of water molecules align to form a quasi-crystalline structure between unit layers which results in an increased c-spacing. All types of clays swell in this manner. Osmotic swelling is a second type of swelling. Where the concentration of cations between unit layers in a clay mineral is higher than the cation concentration in the surrounding water, water is osmotically drawn between the unit layers and the c-spacing is increased. Osmotic swelling results in larger overall volume increases than surface hydration. However, only certain clays, like sodium montmorillonite, swell in this manner. Exchangeable cations found in clay minerals are reported to have a significant impact on the amount of swelling that takes place. The exchangeable cations compete with water molecules for the available reactive sites in the clay structure. Generally cations with high valences are more strongly adsorbed than ones with low valences. Thus, clays with low valence exchangeable cations will swell more than clays whose exchangeable cations have high valences. Clay swelling during the drilling of a subterranean well can have a tremendous adverse impact on drilling operations. The overall increase in bulk volume accompanying clay swelling impedes removal of cuttings from beneath the drill bit, increases friction between the drill string and the sides of the borehole, and inhibits formation of the thinfiltercake that seals formations. Clay swelling can also create other drilling problems

such as loss of circulation or stuck pipe that slow drilling and increase drilling costs [1403].

Guidelines
The literature offers several papers that may serve as guidelines for issues such as selecting a proper clay stabilizing system or completing wellbore stability analyses of practical well designs [367,427-429,562,1565].

Mechanisms Causing Instability

Shale stability is an important problem faced during drilling. Stability problems are attributed most often to the swelling of shales. It has been shown that several mechanisms can be involved [680,681]. These can be pore pressure diffusion, plasticity, anisotropy, capillary effects, osmosis, and physicochemical alterations. Three processes contributing to the instability of shales have to be considered [127]: 1. Movement of fluid between the wellbore and shale (limited toflowfrom the wellbore into the shale) 2. Changes in stress (and strain) that occur during shale-filtrate interaction 3. Softening and erosion caused by invasion of mudfiltrateand consequent chemical changes in the shale The major reason for these effects is of a chemical nature, namely the hydration of clays. Borehole instabilities were observed even with the most inhibitivefluids,that is oil-based mud. This demonstrates that the mechanical aspect is also important. In fact, the coupling of both chemical and mechanical mechanisms has to be considered. For this reason, it is still difficult to predict the behavior of rock at medium-to-great depth under certain loading conditions. The stability of shales is governed by a complicated relationship between transport processes in shales (e.g., hydraulic flow, osmosis, diffusion of ions, pressure) and chemical changes (e.g., ion exchange, alteration of water content, swelling pressure). Clays or shales have the ability to absorb water, thus causing the instability of wells either because of the swelling of some mineral species or because the supporting pressure is suppressed by modification of the pore pressure. The response of a shale to a water-based fluid depends on its initial water activity and on the composition of thefluid.The behavior of shales can be classified into either deformation mechanisms or transport mechanisms [1765]. Optimization of mud salinity, density, and filter-cake properties is important in achieving optimal shale stability and drilling efficiency with water-based mud.

Kinetics of Swelling of Clays

Basic studies on the kinetics of swelling have been performed [1699]. Pure clays (montmorillonite, illite, and kaolinite) with polymeric inhibitors were investigated, and phenomenologic kinetic laws were established.

Hydrational Stress
Stresses caused by chemical forces, such as hydration stress, can have a considerable influence on the stability of a wellbore [364]. When the total pressure and the chemical potential of water increase, water is absorbed into the clay platelets, which results either in the platelets moving farther apart (swelling) if they are free to move or in generation of hydrational stress if swelling is constrained [1715]. Hydrational stress results in an increase in pore pressure and a subsequent reduction in effective mud support, which leads to a less stable wellbore condition.

Borehole Stability Model

A borehole stability model has been developed that takes into account both the mechanical and the chemical aspects of interactions between drilling fluid and shale [1231]. Chemically induced stress alteration based on the thermodynamics of differences in water molar free energies of the drilling fluid and shale is combined with mechanically induced stress. Based on this model, it should be possible to obtain the optimal mud weight and salt concentration for drilling fluids. Further stability models based on surface area, equilibrium water-contentpressure relationships, and electric double-layer theory can successfully characterize borehole stability problems [1842]. The application of surface area, swelling pressure, and water requirements of solids can be integrated into swelling models and mud process control approaches to improve the design of water-based mud in active or older shales.

Shale Inhibition with Water-Based Muds

One potential mechanism by which polymers may stabilize shales is by reducing the rate of water invasion into the shale. The control of water invasion is not the only mechanism involved in shale stabilization [133]; there is also an effect of the polymer additive. Osmotic phenomena are responsible for water transport rates through shales.

Inhibiting Reactive Argillaceous Formations

Argillaceous formations are very reactive in the presence of water. Such formations can be stabilized by bringing them in contact with a polymer solution with hydrophilic and hydrophobic links [101-104]. The hydrophilic portion consists of polyoxyethylene, with hydrophobic end groups based on isocyanates. The polymer is capable of inhibiting the swelling or dispersion of the argillaceous rock resulting from its adsorptive and hydrophobic capacities.

Thermal Treatment to Increase the Permeability

To increase the permeability of a certain region of the reservoir, the liquidabsorbed water is evaporated by heating the portion to a temperature above the boiling point of water, taking into account the ambient pressure [897,1487]. The liquid water is evaporated by injecting a water-undersaturated gas, such as heated nitrogen, into the reservoir.

Formation Damage in Gas Production Shut-In

Sometimes it may become necessary to shut-in a gas well when the demand for gas is low. In such instances, the well is shut-in for an indefinite period, after which it is reopened and production is resumed. It often has been found that the production rate of gas from the reopened well is substantially less than it was before the well was shut-in. During production, the inner wall of the production tubing will be coated with a film of condensed freshwater because of the geothermal gradient. This water flows down when production is interrupted and can cause formation damage. This may occur because clays are normally saturated with brine water and not with freshwater. This swelling can be prevented with the injection of some additive, for example, sodium chloride, potassium chloride, calcium chloride, or an alcohol or a similar organic material [1853].

Inhibitors of Swelling
Inhibitors of swelling act in a chemical manner rather than in a mechanical manner. They change the ionic strength and the transport behavior of the fluids into the clays. Both the cations and the anions are important for the efficiency of the inhibition of swelling of clays [503].

Chemicals in Detail Saccharide Derivatives

A drillingfluidadditive, which acts as a clay stabilizer, is the reaction product of methylglucoside and alkylene oxides such as ethylene oxide, propylene oxide, or butylene oxide. Such an additive is soluble in water at ambient conditions, but becomes insoluble at elevated down-hole temperatures [386]. Because of their insolubility at elevated temperatures, these compounds concentrate at important surfaces such as the drill bit cutting surface, the borehole surface, and the surfaces of the drilled cuttings.

Anionic Polymers
Anionic polymers may be active as the long chain with negative ions attaches to the positive sites on the clay particles or to the hydrated clay surface through hydrogen bonding [768]. Surface hydration is reduced as the polymer coats the surface of the clay. The protective coating also seals, or restricts, the surface fractures or pores, thereby reducing or preventing the capillary movement of filtrate into the shale. This stabilizing process is supplemented by polyanionic cellulose. Potassium chloride enhances the rate of polymer absorption onto the clay.

2-Acrylamido-2-methylpropane sulfonic acid

1-Allyloxy-2-hydroxypropyl sulfonic acid Figure 3-1. Monomers for clay stabilizers: 2-acrylamido-2-methylpropane sulfonic acid, 1-allyloxy-2-hydroxypropyl sulfonic acid.