ALUMINUM CHEMISTRY INCREASES SHALE STABILITY

BY MIKE JOHNSON, DAVID CLARK - BAKER HUGHES INTEQ

INTRODUCTION

The hydration of clay containing shale has always been a major concern when drilling oil and gas wells.
Upon contact with water, hydrogen bonding occurs at the clay surface, resulting in surface hydration. A
tightly bonded molecular layer of water occurs on the basal crystal surface. Additional molecular water
layers bond to each other, with each layer being less tightly bound.1 Surface hydration is particularly
strong in shales because of high surface area. Additionally, clays may have a lattice-type structure. Such a
structure allows adsorption of water between layers as well as upon the particle surface. Osmotic force
then draws water into the shale panicle, dependent upon the salt concentrations of the shale and the liquid.
This hydration of clay softens and weakens shale formations.

Hole instabilities including hole sloughing, washout, and swelling are attributable to this mechanism.
Additional problems experienced while drilling include shale dispersion, resulting in fine solids build-up
in the drilling fluid, and the adherence of shale to the drill pipe and bit, reducing penetration rates. When
drilling for hydrocarbons, water-based drilling fluids that do not effectively limit the hydration of the
drilled shale may contribute to increased cost or project abandonment. Drilling problems such as stuck
pipe, hole fill, and slow penetration rates will increase drilling difficulty.

Properly designed oil-based drilling fluids eliminate the problem of shale hydration. However, the
expense and environmental concerns increasingly limit their use. Potassium and sodium chloride
applications limit this hydration effect. These systems are effective because the potassium ions exchange
with other ions in the clay structure. The potassium ion limits hydration because of its size, since it is
almost the same diameter as the spacing between the oxygen in the clay's outer silica tetrahedrons. The
tight fit holds the clay platelets together, preventing hydration of inter-layer surfaces.2 The mass action of
high chloride ion concentrations causes a concentration of less hydrated cations on the clay surface,
reducing the clay's negative charge, shrinking the bound water layer, and allowing less swelling.3

ALUMINUM CHEMISTRY

Conventional aluminum salts cannot be effective in the alkaline pH necessary for drilling fluid. For
example, aluminum sulfate or aluminum chloride will form colloidal aluminum hydroxide under alkaline
conditions. Also, free aluminum ions are highly flocculating to clay particles present in drilling fluid. The
high viscosity that results from these salts is unacceptable for drilling operations. Therefore, a complexing
reaction with the aluminum ion is necessary to reduce its tendency to precipitate. The general term for
this structure is a complex. Aluminum salts that have been complexed show stability in alkaline
environments. The degree of stability is a function of the complexing agents, the fluid pH, and time. It
appears that the aluminum complex interacts with oxygen ions on the clay surface.4 The complex
decreases the charge on the clay particle and minimizes the interaction of the clay's surface with water.
The resulting hydration suppression reduces shale problems associated with water-based drilling fluids.

Aluminum chemistry, as successfully applied to drilling fluid, was first described by Chesser and
Perricone5 as an approach to the prevention of balling of gumbo-type shales. A gumbo shale is a
description of physical properties and is not necessarily a mineralogical description. Gumbo shales have a
strong tendency to adsorb water to the point that they become extremely "sticky". The hydrated shale
sticks to itself and subsequently to the drill bit, drill pipe, flow line, and shale shaker screens. Problems
associated with gumbo shales include a decrease in drilling rate, loss of circulation, pipe sticking, and
logging difficulties, all of which increase well drilling cost.

The conception invented by Perricone6 et al. involved the chelation of an aluminum salt with an organic
acid. The chelate requires a pH increase with an alkali, before addition to the alkaline pH drilling fluid.
Field evidence indicated excellent performance with this chemistry, in both lignosulfonate and polymer
drilling fluids. However, cost considerations restricted its use in many areas. The high cost of acid, which
then required neutralization, was cost prohibitive in most applications. Limited solubility of the chelate
and the resulting high premix volumes necessary to maintain concentrations added logistical problems to
its use. These considerations limited this chemistry to only the most severe drilling environments.
Increasing environmental pressure to eliminate the use of oil-based drilling fluids combined with the need
for a fluid with maximum shale hydration inhibition, resulted in a research effort to develop an aluminum
complex with reduced cost. Such a complex was to maintain benefits noted from previous chemistry.

This research resulted in two patents7"8 and a new generation aluminum complex for water-based drilling
fluids. The new generation complex contains higher quantities of aluminum which can be added in a dry
form, with a lower unit cost9.

LABORATORY DEVELOPMENT

Evolution of the new complex included the use of several laboratory methods to monitor its development.
They included particle size distribution analysis, linear measurement tests, aluminum uptake, rheological
measurements, and shale hydration tests.

Particle Size Analysis

As clay hydrates it destabilizes and disperses into smaller fragments. Studies indicate that dispersion
occurs not only on the macro-level of the shale panicle, as demonstrated later in this paper, but also to the
clay particle itself. Traditional drilling fluids reduce dispersion with the addition of high-molecular-
weight polymers and cations from simple salts such as KC1, NaCl, CaCl2, Ca(OH)2, and

Measurements of the dispersion of the clay particles aided the development of the aluminum complex.
Numerous tests using Coulter LS-130 particle size analysis indicated inhibition characteristics of various
aluminum complexes. As clay hydrates and disperses in the liquid phase, the panicle size curve shifts to a
smaller size distribution. Highly reactive clays will hydrate over a short time. Clays containing minimal
amounts of montmorillorute will react more slowly. However, some hydration will occur even with non-
reactive clays, such as illite.10'11

Repeatable results observed from this testing indicated reduced dispersion with the addition of aluminum
complex. Test procedure included the addition of 3.5 g commercial sodium bentonite (montmorillonite)
into 350 cc deionized water. Data shown in Figures 1 and 2 include tests with and without 1,67 g of an
experimental aluminum complex (209). The slurry was then mixed in a blender for 30 minutes. Aging of
samples included static conditions for 16 hours at room temperature and a second set rolled at 150°F for
16 hours. Analysis of particle size distribution indicated a substantial decrease in particle size in the
deionized water sample. The aluminum complex prevented dispersion of the static aged and hot rolled
samples (Figures 1 and 2). Flocculation would also indicate a similar difference in solids distribution.
However, rheological data, as shown later, indicates that no flocculation is occurring from the addition of
the aluminum complex.
Rheological Measurement

One of the most notable benefits of aluminum complex is its resulting decrease in clay hydration. This
decrease in hydration is most obvious as the viscosity attributable to drill solids concentration is reduced.
This feature allows polymer-based systems to be more solids tolerant. Clays that are less hydrated have
lower viscosity and are more tolerant to contaminants. The increased available water decreases the
requirement for deflocculants, especially in polymer systems.

Rheological measurements indicate the inhibition characteristics of a fluid. During the drilling process,
water is adsorbed onto the drilled clays, they hydrate, and the tendency for hole instability increases. The
hydration of commercial and drilled clay also results in an increase in fluid viscosity. This viscosity is the
result of an increase in volume of the clay as it hydrates and an increase in surface area of the clay as it
disperses. Particle flocculation increases viscosity further. When clay concentration is high, flocculation
will result in undesirable continuous gel structure. Such gel structure will increase with time, possibly to a
point that drilling operations become troublesome. The degree of flocculation viscosity of a given water-
clay slurry is the result of the type of clay minerals, their cation exchange type (ability for base
exchange), and the ions present in the solution.

Base exchange in clay occurs when cations in solution replace others adsorbed on the crystalline surface.
Often the adsorbed cations control the swelling and dispersing characteristics of the clay. No alteration of
the crystalline structure occurs in the exchange process. Several factors effect the occurrence of base
exchange in clays. These include the relative replacement power of the available cations in the solution,
the type of clay, the concentration of cations in solution, and the charge deficiency on the clay surface.12
Potassium and calcium ions are most often used to limit the hydration of clays. The ion exchange
occurring from potassium appears to react synergistically with aluminum complex, resulting in an further
decrease in clay hydration. Soluble calcium and magnesium ions interfere with aluminum complex and
must be chemically removed.

The largest draw back to the use of simple salts to control troublesome shales is flocculation that occurs
as the exchange takes place. Previous aluminum complex chemistry demonstrated that no flocculation
occurs to the drilling fluid. Fluid viscosity should decrease as the complex attaches to the clay, reducing
clay hydration. The ability to maintain desirable Theological and filtration control properties was an
important criterion for any improvement in aluminum chemistry for drilling fluids. Aluminum complex
reduces the flocculation effects that occur from the presence of simple salts.
The addition of 17% weight NaCl to seawater also increased the shale hardness to 87% of its original
hardness. The addition of 5 Ib/bbl aluminum complex further increased shale hardness to 95% of its
original hardness, an additional 9% improvement over sodium chloride alone As described in the case
history section, aluminum complex in high salt environments increases hole stability while drilling
extremely reactive shales.
CASE HISTORIES

Freshwater Polymer System

As previously discussed the Venezuelan Misoa Shale is a low hydrateable, reactive shale encountered
while drilling in Lake Maracaibo. Most wells in the area which penetrated this formation have had
problems with drilling rate and hole stability. The majority of the problems result from severe hole
washouts which seem inevitable whenever freshwater drilling fluids are utilized. While oil base muds
offer an obvious solution their use is limited because of their high costs and associated environmental
problems

The original fluids of choice to drill wells in this area were Lignosulfonates While they were successful to
a certain extent they were unable to provide sufficient inhibition to minimize hole enlargement.
Eventually PHPA polymer systems were utilized While these systems provided greater amounts of
lubricity and considerable inhibition the only problems that were alleviated were those associated with
balling and excessive torque and drag Hole enlargement continued to be a problem.

Several attempts have been made to increase the inhibition of PHPA systems by supplementing them with
3 to 4 Ibs/bbl of an aluminum complex. To date there has been little improvement Even though these
wells have experienced very few problems while drilling the end result has been the same. The wells have
continued to suffer considerable hole enlargement and caliper logs indicate little to no improvement over
straight PHPA systems

As was previously mentioned a core of the Misoa formation was tested and verified that minimum
inhibition was being achieved with a fresh water PHPA system supplemented with an aluminum complex.
Based on test results it appears the addition of 10 % by weight of sodium chloride will provide the
necessary inhibition which has been missing to this point in time Preparations are now being made to test
this formulation in the field.
The bars in Figure 9 are proportional to the hole sizes drilled in Green Canyon (Well A) and Garden
Banks (Well B), Gulf of Mexico. They indicate the fluid used to maintain required rheologica! and
filtration properties. The inhibitive characteristic of a drilling fluid minimizes drill solids dispersion, as
welt as decreasing the time to drill the well. These benefits result in an increase in the efficiency of the
solids removal equipment. This improvement in efficiency is reflected as a decrease in mud dilution
volume.

Dilution rate comparisons confirmed approximately 45% reduction in the dilution volumes when drilling
similar hole volumes and maintaining like low gravity solids concentrations This dilution data covers a
total of 13,689 ft of hole drilled by the two wells. The reduction in dilution rate decreased drilling fluid
cost, although the aluminum complex increased the per barrel cost of the fluid.

CONCLUSIONS

Environmental concerns continue to create the need for drilling fluids that will inhibit troublesome shale,
without negative effects to the environment. The use of aluminum chemistry has proven to inhibit the
hydration of clay This chemistry appears to have application in Venezuela

The Misoa shale presented in this paper is not highly hydrateable, but shows strong dispersive tendencies.
It appears that the hydratable smectite clay acts as the bonding agent within the shale structure. As the
smectite hydrates the bonding structure is weakened, creating a condition for the shale to readily disperse
with minimum hydration. Therfore, a drilling fluid containing a high molecular weight polymer, an
aluminum complex, and chloride ions all fulfill essential roles in the stabilization of this shale.

The high molecular weight partially hydrolized polyacrymide (PHPA) polymer attaches to the positive
sites of the shales. This coating reduces shale hydration and dispersion.

The chloride ions create a concentration of less hydrated cations on the clay surface, reducing the clays
negative charge, shrinking the bound water layer, minimizing hydration. The chloride ion also increase
the adsorption of the PHPA and aluminum complex to the shale.

The aluminum complex strongly adsorbs onto the clay surface, much like a low molecular weight
polymer. This adsorption, further reduces shale hydration and dispersion. Complexed aluminum does not
cause flocculation of the reactive clays in the drilling fluid, allowing for better control of filtration and
rheologocal properties.

Shale Test Procedures Using Air Dried, Clean Samples

• Grind and sieve through 100 mesh screen

• Add water to simulate connate water (original salt content has remained in the shale)
• Press wafer maintaining 4 to 5 tons pressure for 10 minutes
• Add to test fluids and hot roll for 16 hours at 150°F (66°C)
• Remove and sieve through 100 mesh screen
• Clean fluid from shale, weigh sample
• Check wafer hardness using penetrometer
• Photograph shale wafer
• Dry shale and re weigh
• Calculate hydration and dispersion that occurred during the test
7. Sheu, J.J. and Bland, R.G.:"Drilling Fluid with Browning Reaction Anionic Carbohydrate, "US Patent
5,110,484 (May 5, 1992).
8. Sheu, J.J. and Bland, R G /'Drilling Fluid with Stabilized Browning Reaction Anionic Carbo-hydrate,"U.S.
Patent 5,106,517 (April 21, 1992).
9. Clark, D.E. and Benaissa, S.:"Aluminum Chemistry Provides Increased Shale Stability with Environmental
Acceptability," paper SPE 25321 presented at SPE Asia Pacific Oil & Gas conference, Singapore,February
8-10, 1993.
10 Chenevert, ME.:"Shale Alteration by Water Adsorption," 7Pr<September 1970) 1141-1148
11. Darley H.C.H.:"A Laboratory Investigation of Borehole Stability," J/T(July 1969) 883-892
12. Jones, Frank O /'Influence of Chemical Composition of Water on Clay Blocking of Permeability," y/T
 (April 1964)441-446.
13. Milpark Drilling Fluids:"Sloughing Shale While Drilling in Western Ecuador,"Tech Brief. (March 1988) vol.2,
no. 1,
14. Trask, David and Wise, W.W.:"Status Report. Deepwater Drilling ?\uids," Petroleum Engineer (September
1991)