CLAY CHEMISTRY AND CLAYS IN DRILLING FLUIDS

Why Are Clays Important ?

The elements that go to make up clay minerals make up 80% of the mass of the earth (Al 8.1%, Si 27.7%, O 46.6%) Clays in Rocks :
In shales / mud rocks / clays causing possible drilling problems In reservoirs giving possible formation damage

Clays in the Fluid :

Bentonite (gel, sodium montmorillonite) for viscosity and fluid loss control in some WBM Organophilic bentonite for viscosity and fluid loss control in OBM Attapulgite for viscosity in salt & very high temperature WBM Drilled solids help with fluid loss control but can give unwanted viscosity

Chemical Composition of Clays

Major Constituents
Silica Aluminum Water

Minor Constituents
Iron Magnesium Sodium Potassium

Physical Properties (structural details)

Fine size Large surface area Chemical reactivity of the surface

Building blocks
There are two basic building units from which all the different clay minerals are constructed : The Octahedral Layer

This consists of two sheets of closely packed oxygen or hydroxides in which aluminum (Gibbsite), iron or magnesium (brucite) ions are embedded.

Building blocks
The tetrahedral Layer

(A)

(B)

In each tetrahedral unit, a silicon atom is located in the center of the tetrahedron, equidistant from the four oxygen atoms. Note that when viewed from above this gives a hexagonal opening.

Building blocks
Tetrahedral and octahedral sheets may combine in different combinations to form over 26 different clay minerals The type of clay mineral will depend on the ratios of the silica to octahedral layer . The nature of ions inbeded in these structures. Other ions associated with the structures.

Clay Structures
KEY:
SILICATE SHEET (T) KAOLINITE:
TO or 1:1

ALUMINA SHEET (O)

MONTMORILLONITE AND MICA (INCLUDE ILLITE) :

TOT or 2:1

CHLORITE:

TOT :0: TOT or 2:1:1

ATTAPULGITE/SEPIOLITE:

TOT or 2:1

Comparison of Structures
Property
Layer type Crystal Structure

Kaolin
1:1 Sheet

Mica
2:1 Sheet

Mont
2:1 Sheet

Attap
2:1 Sheet

Chlorite
2:1:1 Sheet

Particle Shape
Particle Size () Surface Area BET-N2-m2/g BET-H2O-m2/g CEC-meq/100g Viscosity in Water Effects of Salts

Hexagonal Plate
0.5 - 5

Extensive Plates
0.5 - Large Sheets 50 - 110 10 - 40 Low Flocculates

Flakes
0.1 - 2

Needles
0.1 - 1

Plates
0.1 - 5

15 - 20 3 - 15 Low Flocculates

30 - 80 200 - 800 80 - 150 High Flocculates

200 15 - 25 High Little or none

140 10 - 40 Low Flocculates

Charges on Clay Particles

Charges on clays are important as they determine properties such as : Ion Exchange Swelling Behavior Viscosity of Muds

Charges can arise from : Broken edges on clay particles Substitution of Ions in the clay structure

Charges Due to Ion Substitution

All Si All Al All Si

Charges Balanced : Net Charge = Zero

But, commonly (especially in montmorillonite & mica) there are cation

substitutions in both the octahedral and tetrahedral layers

Tetrahedral Layer : Some Si4+ can be replaced by Al3+ or Fe3+ Octahedral Layer : Some Al3+ can be replaced by Mg2+ or Fe2+

These substitutions produce sheets with net negative charge Unlike edge charges, these are permanent and not affected by pH changes Isomorphous substitution is the main reason why clays have ion exchange properties and is the reason why montmorillonite swells in water

Ion Exchange Properties of Clays

The negative charge generated by Isomorphous substitution is balanced by cations held near the clay surface.
+ + + +

Common charge - balancing cations are Na, K, Ca, Mg; these cations are readily exchangeable in montmorillonite
Na+ Na+ Na+ K+ K+ K+ K+

e.g.. KCl solution

+
Na+

Cation exchange capacity of clay can be measured by methylene blue test (MBT) or chemical analysis of displaced cations

Cation exchange
Factors Affecting Replaceability of Exchangeable Cations
Nature of Clay Mineral Montmorillonite Mica / Illite : Easy : Difficult

Chlorite

: Impossible

Nature of original and replacing cations Concentration of exchange solution

Cation exchange
Different cations have different attractions for the exchange sites Assuming all the cation concentrations are the same, the order of increasing replacing power of cations is generally :
Li+ < Na+ < K+ < Mg2+ < Ca2+ < H+ e.g. : At equal concentrations potassium will displace more sodium than sodium will displace potassium.

Increasing the concentration of any given cation will increase the probability that it will displace another cation.
e.g. : It is possible for high concentrations of potassium to displace calcium

Hydration of Cations
The properties of the exchange cations have an important influence on clay properties.

Hydration of cations depends on their charge and size.

High charge & small diameter cations are usually most highly hydrated Low charge & large diameter cations are usually least hydrated

Clay Hydration

The important diameter is the hydrated ionic diameter.

H d H CATION d H d H

Hydrated Ionic Diameter

Atom Na - Sodium K - Potassium Cs - Cesium Mg - Magnesium Ca - Calcium

Dehydrated Ion Diameter A 1.90 2.66 3.34 1.30 1.90

Hydrated Ion Diameter A 11.2 7.6 7.6 21.6 19.0

Broken Edge Charges

When a clay sheet is broken, the exposed edges will have unbalanced charges which can be either positive or negative. In an acidic environment the charges will tend to be positive. In an alkaline environment charges tend to be negative.

One reason for keeping an alkaline pH in the drilling mud is to keep all the clay charges negative. The negative charges will repel each other thus reducing the tendency for flocculation.

Edge charges
Sign of edge charges depends on solution pH
O Si H+ O O OH O Si OHO OH O Si OH

AlOH 2 +

AlOH

Al

O-

OH

OH

OH

Clay Mineral Groups

There are over 400 mineral and rock names to describe clay minerals. Only the following are common and applicable to drilling fluids chemistry Kaolin Composed of single tetrahedral sheet and single octahedral sheet Charges within structure are balanced with few substitutions Strong hydrogen bonding between layers limits swelling Edge charges are sensitive to pH

Clay Mineral Groups

Micas 2:1 lattice with 2 silica sheets sandwiching an octahedral layer Ion replacement occurs in the TETRAHEDRAL layer Charge deficiency is balanced by potassium ions The Potassium fits neatly in the hexagonal holes made by the silica tetrahedral and securely binds the separate layers together.

Clay Mineral Groups

Montmorillonite
A 2:1 lattice structure very similar to mica Ionic substitution occurs in the OCTAHEDRAL layer Cations are unable to approach close enough to completely loose their ionic character The residual ionic character provides attractive forces for adsorbing water.

Sepiolite and Attapulgite

Both consist of long needles. They cannot swell but have a large surface are and can bind water strongly. This means that they are effective viscosifiers

Chlorite

Clay Swelling
The most common swelling clay mineral is montmorillonite. Montmorillonite (bentonite) is used in some drilling fluids to give viscosity and fluid loss control. Montmorillonite is found in many reactive shales. Montmorillonite is found in some sandstone (including reservoir sands). The amount of water taken up by a montmorillonite (& hence the degree of swelling) depends on :
Layer charge of the clay / Ion exchange Nature of the exchangeable cation Nature of the external solution

Clay Swelling : Nature of Exchangeable Cation

Swelling promoted by highly hydrated, low charge exchangeable cations

e.g.. Li+ , Na+

Swelling reduced by high charge, less hydrated cations e.g.. Al3+

K+ reduces swelling because poorly hydrated even though low charge.

Ca2+, Mg2+ reduces swelling because high charge, though highly hydrated.

Clay Swelling
High Salinity Solutions Reduce Clay Swelling
relative distribution of particles with a given spacing, % 100 relative distribution of particles with a given spacing, % 100

K+
78

Ca2+
60

78

K+ Na+ Ca2+

60

25

Na+

25

0 0 10 20 30 40 50

0 0 10 20 30 40 50 space between sheets A space between sheets A

Effect of Low Salt Concentration on space between sheets

Effect of High Salt Concentration on space between sheets

Clay Dispersion / Deflocculation

Clay particles in a fluid can be : Deflocculated Flocculated Aggregated Dispersed Degree of dispersion / deflocculation of clays will affect viscosity, fluid loss control and shale inhibition.

Clay Dispersion / Deflocculation

There are four basic colloidal states of clay particles in a fluid : Deflocculated. There is an overall repulsive force between the particles. This is done by ensuring all the particles have the same charge. (The particles may be aggregates) Flocculated. There are net attractive forces for the particles and they can associate with each other to form a loose structure. Aggregated. The clay sheets are still attached to each other and hydration has not occurred, or the hydration process has been reversed. Dispersed. This is where the aggregates have all been broken down. The dispersed clays may be flocculated or deflocculated.

Colloidal states
Dispersed and deflocculated

Aggregated but deflocculated

Edge to face flocculated but dispersed

Edge to edge flocculated but dispersed

Edge to face flocculated and aggregated

Edge to edge flocculated and aggregated

Clay Dispersion
Mechanical energy causes DISPERSION of aggregates

MECHANICAL ENERGY

Mechanical energy can also break individual mineral grains

MECHANICAL ENERGY

Leads to increased surface area of solids

Clay Deflocculation
1. Change pH
+ +
+ - - - + -

+ + - - - + -+ -

add alkali (OH )

-

add acid (H+)+

< ~ pH 6.5 FLOCCULATED

- > ~ pH 8 DEFLOCCULATED

2. Add chemical deflocculants

+ -

+ +

+ + +

add deflocculant
-

+ - - - +

Clay Deflocculation (cont)

3. Double layers

+ + + +

+ + +

+ +

Add salt

+ + + + + + + + + summation curve energy of repulsion 0 energy of attraction +

+
+ +

Remove salt

+ +

LOW SALINITY DEFLOCCULATED

HIGH SALINITY FLOCCULATED

WITHOUT SALT - NO FLOCCULATION

distance of separation

Clay Deflocculation (Double Layers)

2000 ppm of Na+
200 ppm of Na+ 2% Na+ energy of repulsion 0 energy of attraction energy of repulsion 0 energy of attraction

distance of separation

distance of separation

Intermediate Concentration - Slow Flocculation

High Salt Concentration - Rapid Flocculation

Clay Deflocculation
Chemical energy is used to deflocculate clays

chemical energy

FLOCCULATED

DEFLOCCULATED

The state of deflocculation is determined by surface charges and electrical double layers surrounding particles in suspension

Clay Flocculation
High Salt Concentration Polyvalent Cations Polymeric Flocculants Low pH

Effect of Clay Dispersion/Deflocculation on Suspension Viscosity

To increase viscosity Increase level of solids Add high molecular weight viscosifying polymer Flocculate with calcium or other polyvalent cation Flocculate with salts Flocculate with low pH conditions

To decrease viscosity Dilute with water Disperse with low molecular weight polymers Remove calcium by chemical treatment Disperse with higher pH conditions

Clays in Drilling Fluids

Clays are added to some water based muds to give : Viscosity : Bentonite Sepiolite / Attapulgite Fluid loss control : Bentonite Organophilic bentonite added to oil based muds to give viscosity and fluid loss control. Clays entrained in mud as drilled solids. These give viscosity and fluid loss control.

Bentonite Mud Systems

Instructions for prehydrating bentonite
Treat out any hardness with soda ash. Increase pH to 9 - 10. (1/4 - 1/2 ppb caustic)

Add 30 - 35 ppb API bentonite, or 40 - 50 ppb OCMA bentonite. Always try to keep one pit for prehydrating bentonite. This avoids contamination. Ideally chlorides should be below 2000 mg/l and hardness levels below 100 mg/l. For maximum cost effectiveness the bentonite needs eight hours to fully hydrate. For speed the caustic can be added after the bentonite addition. Bentonite quality may vary greatly so adjust quantities accordingly.

Grades of Bentonite
API Non-Treated bentonite Pure sodium montmorillonite. This is the best grade of bentonite API Treated bentonite Is montmorillonite that reaches certain standards on viscosity and filtration control as set out by API. It may be treated with polymers and/or soda ash to attain the API grade. OCMA Bentonite Treated Calcium montmorillonite, commonly used in Europe

Table of Viscosities Vs Clay Concentration

20

VISCOSITY (cP)

15

10

A B

Dry bentonite in salt solution Dry bentonite in calcium solution

A B

0 SALT CALCIUM 50,000 1500 100,000 3000 150,000 4500 200,000 6000

PPM

Spud Mud
Use bentonite as high viscosity mud for top hole drilling. Can be the whole circulating system or just as sweeps. PROPERTIES - Yield Point should be higher than 30-40 lb/100ft2 MIXING INSTRUCTIONS - Add 70% by volume of the prehydrated gel and 30% by volume of sea water or drill water. Add 1 ppb lime just prior to pumping. (Lime can be added through the hopper or over the pits). Check viscosity; if it is too low add a higher percentage of PHG. If too high increase the water concentration.

Bentonite Muds
1. Fresh water bentonite muds.
2. Sea water bentonite muds. 3. High chloride concentration bentonite muds. PROPERTIES - as required. Normally PV as low as possible. YP 12 - 20. Fluid loss as required. MIXING INSTRUCTIONS - The bentonite concentration will normally be 15 to 20 ppb. For systems 2 and 3 the bentonite will need to be prehydrated in fresh water and then diluted back with sea water to attain the desired concentration. To increase the viscosity, increase the bentonite concentration. To decrease the viscosity :
Decrease the bentonite concentration by dilution or adding new premix. Decrease the solids content.

Fluid Loss Control May be Required

Fresh and sea water systems should use :

CMC (up to 2 ppb) - Deflocculates system PAC (up to 2 ppb) - Deflocculates system Starch (up to 6 ppb) - Will not deflocculate system
or use a combination of the above

At higher chloride levels the CMCs become less effective so only starches and PACs should be used.

Problems Associated with Bentonite Muds

Calcium ions (from anhydrite/gypsum or cement) will flocculate the system. A deflocculant may be needed, also remove the calcium ion with soda ash or bicarbonate. Any increase or decrease in the chloride concentration (whether by formation fluids or from drilling salt deposits) will flocculate the system. (This will increase the viscosity and fluid loss. Increase additions of CMC or PAC to deflocculate.)

Viscosity may be reduced with a thinner prior to casing runs the reduce surge pressures.
High viscosities and gel strengths are usually an indication of excessive solids. Reduce solids conc.. by solids removal eqpt. or dilutions.

Prior to drilling out any cement the system should be pretreated

with 1/2 ppb sodium bicarbonate.

Note : flocculation due to polymers increases the fluid loss control Note : flocculation due to higher chlorides or multivalent cations reduces the fluid loss control