Making Mud: Clay Chemistry in Drilling Fluids

Department of Geology & Petroleum Studies
Makerere University
PGP4108: Drilling Fluids
Clay Chemistry and Application
Wycliff Kawule
@2016
PTRL 4024 Drilling Fluids & Cementing Introduction
School of Petroleum Engineering, UNSW
) Drilling Fluid and Its Basic Functions

Drilling fluid (mud) is a fluid used in operations to drill boreholes into the earth.
liquid
gaseous fluids
mixtures of fluids and solids (as solid suspensions, mixtures and emulsions of liquids, gases and solids)
The Basic Functions of Drilling Fluid Includes:
1. Removal of cuttings from the hole.
2. Balancing the hydrostatic pressure, controlling well kicks and blowouts.
3. Cooling and lubricating the bit and drillstring, preventing stuck pipe while drilling.
4. Preventing hole collapsing.
5. Forming an impermeable filter cake on the borehole wall for reducing formation damage and minimizing
lost circulation.
6. Partial aid in supporting drillstring and casing weight by buoyancy.
7. Allowing interpretation of well logs.
8. Transmission of the surface-available hydraulic horsepower to the bit
9. Transmission of signal from downhole to surface ……
5
) Circulating System
SWIVEL
ROTARY
HOSE
STANDPIPE
KELLY
SLUSH PUMP
PUMP DISCHARGE
LINE
MUD RETURN LINE DRILLPIPE
SUCTION BOREHOLE
CHEMICAL TANK ANNULUS
SHALE SHAKER
MIXING HOPPER
SUCTION PIT
SETTLING PIT
TO RESERVE PIT
SHALE SLIDE
6
) Classification of Drilling Fluid

Drilling fluids are commonly classified according to their base fluid:
Water-base drilling fluid.
Fresh water Water is the continuous liquid phase
Chemically treated Solid materials are added to the fluid:
Calcium treated bentonite polymer,
bentonite, polymer barite,
barite chemical additives
Salt water
Oil emulsion
Oil-base drillingg fluid.
Oil-based mud Oil is the continuous liquid phase
Emulsifying agents and barite are added to the fluid
Invert emulsion mud
Air/Gas-base drilling fluid.
Air or natural gas Air/gas is the continuous phase and is compressed
Aerated mud and injected into the hole
Mist Water and other additives are added to improve
Foam carrying properties
Gel foam
7
) Classification of Drilling Fluid

Composition of water based drilling fluid:
Water as continuous liquid phase – to dissolve chemicals for controlling pH and
other ions
Fresh –water fluid (NaCl < 10,000 ppm)
Salt –water
water fluid (NaCl > 10
10,000
000 ppm)
Hard water fluid (large amount of calcium or
megenisium ions)
o It mayy contain oil (emulsion
( mud))
or air (aerated mud) as discontinuous phase.
Inert Fraction– weighting materials
Barite, sand and other inert solids
Little contribution to fluid viscosity
Colloidal Fraction– active and high effect on mud rheology and filtration
properties with a small proportion of the total solids
Clay
Cl particles:
i l bentonite,
b i attapulgite,
l i sepiolite
i li
Polymeric materials: cellulose derivatives, natural and synthetic polymers
Other chemical additives: KCl, NaOH, Na2CO3, etc.
8
PTRL 4024 Drilling Fluids & Cementing Clay Chemistry & Its Application to Drilling Fluid
) Clay
11. What is clay?

¾ Hydration mechanism of clay
Crystalline hydration
Osmotic hydration
Cation exchange capacity (CEC) of clay
Types
T off clay
l
¾ Smectite
¾ Illite
¾ Kaolinite
¾ Chlorite
¾ Attapulgite
A l i and
d sepiolite
i li
¾ Mixed-layer clay
Rheology of clay suspensions with respect to
clay swelling and hydration
Clay particle association
Edge-to-face / edge-to-edge
Face-to-face
The effect of different associations on yield
point and plastic viscosity
Mechanisms of flocculation (gelation)
Yield of clay
¾ Clays applications
¾ Factors affecting yield of clay
¾ Effect of pH
9
) Clay
What is clay?
Clay is defined as naturally occurring material composed primarily of fine-
grained minerals (<0.002 ∼ 0.0039 mm). Clay minerals are chemically
composed of magnesium, aluminium, silicon and oxygen combined in a
mica/flakes-type/sheet-like
mica/flakes type/sheet like structure
structure.
Common examples of clay minerals include chlorite, illite, kaolinite,
montmorillonite and smectite.
Some clays,
clays such as montmorillonite,
montmorillonite have the tendency to swell when
exposed to water, creating a potential drilling hazard when clay-bearing rock
formations are exposed to water-base fluids during drilling, possibly reducing
the permeability of a good reservoir rock.
Some clays are used in drilling fluids to form an impermeable mudcake to
isolate a formation from the invasion of drilling fluid.
The structural difference amongg clays
y ((smectite, kaolinite, chlorite, illite))
determines the surface area exposed to reservoir fluids or stimulating fluids.
Generally, higher surface area indicates higher reactivity.
10
) Clay
Clay is a group of rock-forming minerals
Shale:
o A fine-grained, fissile, detrital sedimentary rock formed by consolidation of
clay- and silt-sized particles into thin, relatively impermeable layers. It is
composed d off clays
l andd other
th minerals,
i l usually ll with
ith a hi
high
h percentage
t off
quartz.
o ISO 14688 grades silts between 0.002 mm and 0.063 mm, with clay
particles being smaller and sands larger
larger.
o Shale typically exhibits varying degrees of fissility breaking into thin layers
because of parallel orientation of clay mineral flakes.
Claystones: Non-fissile
Non fissile rocks of similar composition to shale (<0
(<0.06
06 mm) with
less than 1/3 silt
Mudstones: Non-fissile rocks of similar composition to shale (<0.06 mm) with
1/3 to 2/3 silt particles
particles.
Siltstones: Non-fissile rocks of similar composition to shale (<0.06 mm) with
greater than 2/3 silt (less clay).
Clays can also be found in pore spaces
spaces, as part of the matrix or as grain-cementing
material in sandstone.
11
) Clay
Clay structure
Clays have a mica or flakes-type structure in nature. One Mica or flake is
composed of about ten to twenty tiny crystal platelets which are held together
face-to-face by van der Waals forces.
A single
i l platelet
l t l t iis called
ll d a unit
it layer,
l and
d consists
i t of:
f
o Tetrahedral layer
The basic building blocks of clay minerals
o Octahedral layer
Kaolinite Bentonite
Unit layer
Tetrahedral layer
Octahedral layer
12
) Clay
Tetrahedral layer
The single unit is called tetrahedron: a silicon atom centrally coordinated with
four oxygen atoms;
tetrahedron
The O-atoms
O atoms are very much larger than the Si-atom;
Si atom; the O
O-atoms
atoms can be
imagined as spheres stacked together, touching each other, with the Si-atom
fitting within the hole left in the middle between the much larger O-atoms
13
) Clay
Tetrahedral layer
Infinite number of tetrahedra are grouped together in a hexagonal base network to form a
tetrahedral sheet
The triangular bases of all tetrahedra are joined together. All the tops of the tetrahedra (the
apical oxygen atoms) are at the same side of the sheet (sticking up).
tetrahedron
tetrahedral sheet 14
) Clay
Octahedral layer
The single unit is called octahedron: aluminium or magnesium atoms in an
octahedral coordination with six oxygen or hydroxyl atoms;
An octahedron looks like two pyramids with square bases joined together at the
base;
An octahedron has 6 corners: the four at the square pyramid bases, and the
two at the top of each pyramid;
A positive
i i ion
i (e.g.,
( Mg2+
M 2 or Al3+
3 ) iis present in
i the
h center off the
h octahedron;
h d at
2-
the 6 corner there are oxygen (O ) or hydroxyl groups (OH ); -
octahedron
15
) Clay
Octahedral layer
The octahedra are combined in a layer: the corner of each octahedron (thus
each OH- group or O2- ion) in an octahedral layer is shared by 3 octahedra;
When the central ion is Mg2+, each possible central position is filled by Mg2+ :
t i t h d l such
trioctahedral, h as th
the mineral
i l brucite,
b it Mg(OH)
M (OH)2;
When the central ion is Al3+, only two out of three possible central octahedral
positions are filled, while the remaining 1 out of 3 are vacant: dioctahedral,
such as the mineral gibbsite,
gibbsite Al(OH)3
octahedron octahedral
t h d l sheet
h t
16
) Clay
Structure of Clay Minerals
Clay minerals are formed by combining tetrahedral and octahedral layers.
Different arrangements of these sheets will result in different clays;
The octahedra are tied to the tetrahedra by sharing the oxygen atoms at the
apexes off the
th ttetrahedral
t h d l llayer;
Tetrahedron layers can be attached to each side of one octahedron layer.
17
) Clay
Three-layer clays: tetrahedral layer + octahedral layer + tetrahedral layer. The
tetrahedral layers face inwards and share the oxygen atoms at their apexes with
the octahedral layer and the oxygen network is exposed on both basal surfaces.
This structure is known as the Hoffmann structure (Hamburger).
(Hamburger)
Typical three-layer clays: smectite group
18
) Clay
Two-layer clays: tetrahedral layer + octahedral layer. The oxygen network is
exposed on one basal surface, and hydroxyls are exposed on the other.
Typical two-layer clay: kaolinite group (with dioctahedral layer)
19
) Clay
The sheets in the unit layer
are tied together by covalent
bonds. It is stable.
U
Unitit layers
l are stacked
t k d
together face-to-face to form
the crystal lattice .
The layers in the crystal
lattice are held together only
by van der Waals forces and
secondary valence bond.
C-spacing
¾The distance between a plane in one layer and the corresponding plane in the next
layer is called the c-spacing or the basal spacing.
¾Distance from the centerline of each unit layer to the subsequent layer.
¾9.2 Angstroms for the standard three-layer mineral and 7.2 A for a two-layer mineral.
¾C-spacing is parameter used to quantify hydration of a clay.
20
Note that 1 A = 10-7 mm
) Clay
Electrical charges on clay surfaces
Ideal clays are charge balanced and electrostatically neutral
TETRAHEDRAL
SHEET
OCTAHEDRAL
SHEET
TETRAHEDRAL
SHEET
C-SPACING
G 9.20 A
21
) Clay
Real clays have negative surface charges due to substitution of atoms
o Permanent negative surface charge arises from substitution of cations of
charge +4 and +3 with cations of charge +3 and +2, respectively. For
example,
l if an atom
t off Al+3 iis substituted
b tit t d with
ith M
Mg2+,
2+ th
thatt will
ill produce
d a
charge deficiency of 1.
o This type of atom substitution occurred during the formation of clay
minerals.
minerals
Different type of atoms can exchange in either the octahedral or tetrahedral
sheets. This substitution may lead to a large number of different existing clay
minerals.
22
) Clay
The negative charge on the surface of clay minerals is compensated by the
adsorption of cations.
In the presence of water, since the adsorbed cations can exchange with
cations
ti off another
th species
i iin th
the water,
t ththey are called
ll d exchangeable
h bl cations.
ti
The degree of atom substitution and the different kind of exchangeable cations
have large influence on clay properties such as swelling (hydration),
dispersion and rheological and filtration characteristics.
dispersion, characteristics
23
) Clay
Hydration Mechanism of Clay
Clay hydration or swelling is the adsorption of water that results in an increase
in clay surface volume.
Clay swelling is a function of the following factors:
o Clay structure
o Clay chemical composition
o Amount & type of exchangeable cations available on clay particles.
The most common swelling clays are smectites and smectites mixtures.
Brines, such as potassium Chloride (KCl) are used to avoid clay swelling.
The two main types of clay hydration:
o Crystalline Hydration;
o Osmotic Hydration.
24
) Clay
Crystalline Hydration (surface hydration).
Adsorption of mono-molecular layers of water on
the basal crystal surfaces.
o Electrostatic Double Layer Model
¾ Negative surface charge causes a potential difference

to the surrounding solution;
¾ The surface charge attracts cations and repels anions,
resulting in a potential grading from maximum at the
clay surface to zero in the bulk solution.
¾ The first layer of water is held on the surface by
hydrogen bonding to the hexagonal network of oxygen
atoms (Stern/bound layer), and moves with the
particle and cannot be mechanically removed.
¾ Another layer bonds to the bound layer to satisfy the
remaining potential (diffuse layer). It is independently
mobile if sufficient shear force is available (Shear
plane).
¾ This system of bound layer and diffuse layer is
known as the electrostatic double-layer model. 25
) Clay
Osmotic hydration.
o Water adsorption due to the higher concentration of cations

between layers than in the bulk solution.
¾ Osmotic flow is the movement of water from one aqueous
system to another through a semi-permeable membrane.
¾ Semi-permeable membrane allows water molecules to pass
back and forth, but restricts ions and larger molecules
¾ Osmotic movement is driven by activity differences between
the two systems.
¾ Although no semi-permeable membrane is involved, the
mechanism is essentially osmotic, because it is governed by
a difference in electrolyte concentration.
o Water is drawn between the layers, thereby increasing the c-spacing and permitting the development of
diffuse double layers.
o Osmotic hydration causes much larger increase in bulk volume than does crystalline hydration.
¾ Sodium montmorillonite adsorbs 0.5 g water /g of dry clay, doubling the volume by crystalline
hydration;
¾ It adsorbs about 10 g water / g of dry clay, increasing the volume 20 folds by osmotic hydration.
26
) Clay
Example: C-spacing of mono-ionic montmorillonite flakes in pure water
Cation Maximum c-spacing, Å

Cs+ 13.8
NH4+, K+ 15.0
Ca2+, Ba2+ 18.9
Mg2+ 19.2
Al3+ 19 4
19.4
27
) Clay
Cation Exchange Capacity (CEC) of Clay
What is CEC?
The total amount of cations adsorbed on clay surfaces is called the Base
Exchange Capacity (BEC), or the Cation Exchange Capacity (CEC).
How exchangeable cations affect crystalline hydration?
o Cations bond to the crystal surface in competition with the water molecules, and thus
tend to disrupt the water structure.
o Manyy of the cations are hydrated
y themselves,, i.e. contain shells of water molecules.
How do cation exchange reactions take place?
o Cations and anions are held at basal surface as well as at the edges, both sets of ions
may exchange with ions in the bulk solution.
o Cation exchange between the clay building unit and bulk solution does not alter the
lattice structure of the clay.
o The exchange reaction is governed primarily by the relative concentration of the
different species of ions in each phase;
o In the case of two ions of different valences are present,
present the one with higher valence is
generally adsorbed, the order of preference is as follow:
H+ > Ba++ > Sr++ > Mg++ > Ca++ > Cs+ > Rb+ > K+ > Na+ > Li+
Note that H+ is strongly adsorbed and, therefore, pH has a strong influence on the
28
cation exchange reaction.
) Clay
CEC unit
o The total amount of cations adsorbed in milli-equivalents /100 g of dry clay.
o CEC varies with type of clay; size of clay particle; size and type of cation on the
surfaces.
surfaces
CEC and clay hydration
o High CEC clays have a greater water holding capacity than low CEC clays.
o K+ is more effective than other cations in reducing
g the hydration
y diameter of clay:
y
the hydrated diameter of the K+ ion is very small compared to other cations;
K+ has low hydration energy which allows it to penetrate the clay lattices and become
tightly fixed by the attractive forces on the basal plane.
Clay Minerals CEC Cations Ion Diameter, Å Hydration Energy
meq/100g Dry Clay not hydrated hydrated* kcal/mol
Li+ 1.20 14.6 124.4
Montmorillonite 70 - 130
Na+ 1.90 11.2 97.0
Illite 10 - 40 K+ 2.66 7.6 77.0
Kaolinite 3 - 15 Rb+ 2.96 7.2 71.9
Chlorite 10 - 40 Cs+ 3.34 7.2 66.1

Ca++ 1.98 19.2 377
Attapulgite 5 - 99
Mg++ 1.30 21.6 459.1
Sepiolite 20 - 45 NH4+ 2.16 - 72.5 29
) Clay
The K+ ion is able to

penetrate the clay
interlayer, whereas
other cations cannot
due to their larger sizes
o The type of ion that is exchanged from the clay particle determines the name
given to the clay. For example, Na-montmorillonite or Ca-montmorillonite.
30
) Clay
Types of Clay – Smectite, Illite, Kaolinite, Chlorite, Attapulgite, Sepiolite.
Smectite group
o Smectite minerals have three layers: octahedral aluminum sheet lying between two
tetrahedral silicate sheets by sharing the valences of their oxygen atom.
o Bonding between layers are week and water can enter between layers causing an increase
in the c-spacing – expanding lattice.
31
) Clay
Types of Clay
Smectite group
o Different kind of atom substitutions lead to different
members of smectite group:
Trioctahedral
Principal Substitution Dioctahedral Minerals
Minerals
Prototype (no substitutions) Talc (Mg3Si4) Pyrophyllite (Al2Si4)
Hectorite (Mg3-xLix) Montmorillonite (Al2-
Practically all octahedral
(Si4) xMg
M x) (Si4)
Saponite (Mg3-xAlx) Volchonskoite (Al, Cr)2
Predominantly octahedral
(Si4-yAly) (Si4-yAly)
Vermiculate (Mg3- Nontronite (Al, Fe)2(Si4-
Predominantly tetrahedral
xFex) (Si3Al) yAly)
o Montmorillonite is the best known member of smectite

group and it is the principal constituent of bentonite,
which is widely used in drilling fluid
fluid.
o Atoms substitutions are Al3+ for Si4+ in the tetrahedral
sheet and Mg2+ for Al3+ in octahedral sheet. Therefore
Montmorillonite has negative surface charge.
o Montmorillonite swells greatly because of its expanding
lattice. 32
) Clay
Types of Clay
Illite group
o Illite has a three-layered structure similar to
Montmorillonite.
o The difference is that the substitutions are mainly Al3+ for

Si4+ in the tetrahedral sheets (1/4). Substitutions may also
take place in the octahedral sheet with Mg2+ for Al3+ .
o Illite has higher degree of surface charge than

Montmorillonite. The balancing cation is always K+.
o Illite does not have an expanding

p g lattice,, no water can
penetrate between the layers.
o The strong interlayer bonding is because of higher surface

charge balanced by K+, which just fits into the holes in the
oxygen network. The K+ is fixed and cannot be exchanged.
o Limited ion exchange can take place at the exterior

surfaces of each aggregate.
33
) Clay
Types of Clay
Kaolinite group
o Kaolinite has a two-layered structure, with one
tetrahedral silica sheet bonded to one octahedral
aluminium sheet with very limited atom
substitutions.
o There is strong hydrogen bonding between unit
layers, which prevents lattice expansion.
o Hydration of kaolinite is very low.
o Charges are naturally balanced. There may exist
charges at the broken edges.
o K
Kaolinites
li it are large,
l wellll ordered
d d crystals,
t l which
hi h
do not readily disperse into smaller units in water.
34
) Clay
Types of Clay
Chlorite group
o Chlorites consist of a three-sheet layer (similar to the
smectites) alternating with a brucite (Mg(OH)6 ) layer.
o Th
The positive
iti charge
h iin th
the brucite
b it layer
l (d
(due tto
+3 +2
substitution of Al for Mg ) is balanced by the
negative charge in the three-sheet layer (due to
substitution of Al+3 for Si+4 in the tetrahedral sheet).
o There is no lattice expansion. The bonding between
layers is strong. However, in certain degraded
chlorites, part of the brucite layer has been removed,
allowing some degree of interlayer hydration.
35
) Clay
Types of Clay
Attapulgite and Sepiolite
o Attapulgite clay is completely different in structure
and shape from mica-type minerals. The crystalline
structure is presented in needles shape
shape. Two silica
chains run parallel to the long axis. The chains
form a network of strips which are joined together
along the edges. The upper and lower parts of
each chain are held together by a strip of
aluminium, and/or magnesium, in octahedral
coordination.
o Sepiolite is similar in structure to attapulgite, but
th needles
the dl are wider
id d due th
the ffactt th
thatt each
h strip
ti
is several molecules wider.
36
) Clay
Types of Clay
Attapulgite and Sepiolite
o Attapulgite and sepiolite can be
used in saltwater mud to provide
low-shear
low shear rate viscosity for lifting
cuttings out of the annulus and
for barite suspension.
o Attapulgite and sepiolite are
sometimes
ti called
ll d ""salt
lt gel."
l"
o Attapulgite has no capability to
control the filtration properties of
the mud.
37
) Clay
Clay particle Associations
Surface charge on a clay platelet
o The flat, plate-like particles of clay have two different surfaces:
¾ Planar (basal) surface
¾ Edge surface
o Ions are adsorbed mostly on the basal surfaces, and also on edge surfaces.
o The crystal structure is interrupted at the edge, there may be specific chemical reactions
with
ith b
broken
k valences
l iin addition
dditi tto physical
h i l ((electrostatic)
l t t ti ) adsorption.
d ti
o Electrical charges and exchangeable cations determine particle interactions.
38
) Clay
Surface charge on a clay platelet
o Negative charge on the basal surface due to atom substitutions in the clay lattice structure.
o The charge on the edge surface largely depends on the pH of solution:
¾ positive charge at low pH;
9 example: if kaolinite is treated with HCl, it has positive charge.
The aluminium atoms at the edge react with HCl to form AlCl3, which is a strong
electrolyte
l t l t andd di i t tto Al+3 + 3Cl-.
dissociates
¾ negative charge at high pH.
9 example: if kaolinite is treated with NaOH, it has negative charge
The aluminium atoms at the edge react with NaOH to form Al(OH)3, which is
insoluble.
Note that ion adsorption in kaolinite takes place almost entirely at the edge, so that the
charge on the particle is determined by the charge on the edge.
39
) Clay
Edge-to-face / edge-to-edge association

o Flocculation
o Deflocculation
House of cards
Face-to-face association
o Aggregation
o Dispersion
Stack of cards
40
) Clay
o Flocculation (gelation)
¾ Anything
y g that reduces the repelling
p g forces between the particles,
p or shrinks the
adsorbed water film will bring the particles closer together and promote particle
flocculation.
¾ In the flocculated system, the particles have attractive forces that can lead them to
associate with each other in edge-to-face and edge-to-edge interactions to form a
“loose” or “house of cards” structure in water whenever they are at rest.
41
House of cards
) Clay
o Deflocculation
¾ The opposite of flocculation is termed deflocculation.
¾ In the deflocculated or dispersed system, the particles have repulsive forces that can
lead them to dissociate from each other.
¾ all the particles in the solution must carry the same charge.
42
) Clay
o Aggregation
¾ Clay
ypparticles were lying
y g face-to-face.
¾ If electrostatic layers are compressed enough by cations in the solution due to
dehydration, the particles approach each other close enough to allow the van der
Waals forces to take effect, and bond them together to form an aggregated system
as a Stack of cards
Stack of cards 43
) Clay
o Dispersion
¾ If a breakdown occur in the aggregation
gg g system,
y then the system
y will be in the
dispersion mode.
¾ Both the dispersed and the aggregated systems can be flocculated or deflocculated
44
) Clay
Clay particle association mechanism
o All because of the attractive forces and the repulsive forces between particles
Cross-linking through positive edge to negative surface linkages to form
house of card structure.
the relatively high repulsive potential forces between the basal surfaces which
make the preferred platelet orientation to be the parallel orientation with edge-
to-edge
d association.
i i
45
) Clay
Clay particle associations can be altered by additives and contaminant agents by
altering the surface charge conditions
o Additives for maintaining drilling fluid properties;
Thinner – sodium salt of certain complex anions such as polyphosphates,
tannates, lignosulfonates. Thinners are adsorbed at the edges.
o Drill cuttings and formation fluids acting as contaminant agents.
46
Ca++ from addition of lime or gypsum, or by drilling anhydrite or cement
) Clay
The effect of clay particle associations on drilling fluid properties
o Rheology parameters of drilling fluid:
Yield Point – a measure of the internal resistance of a fluid to initial flow.
¾ The existence of positive and negative charges at the broken edges tends to cause
some re-orientation of particles producing random-structure configurations.
¾ The shear force required to disrupt the clay structure network is the yield point.
Plastic Viscosity – a measure of the internal resistance to fluid flow resulting from
interaction (frictions) of the solids present in a drilling fluid.
¾ It reflects the friction resulting from particles rubbing against each other
other.
¾ Surface charge and hydration of clay particles affects plastic viscosity.
Eff
Effective
ti Viscosity
Vi it – equivalent
i l t viscosity
i it tto Newtonian
N t i fluid,
fl id a ttotal
t l viscosity
i it ddue tto
yield point and plastic viscosity.
47
) Clay
The effect of clay particle
associations on drilling fluid
properties
o Fl
Flocculation
l ti leads
l d to t an
increase in Yield point, but no
effect on plastic viscosity;
o aggregation leads to a decrease
in plastic viscosity due to
reduction in the number of
particles, but no effect on yield
point.
48
) Clay
Yield of Clay
The yield of clay is defined as the number of barrels of 15-centipoise (cp) mud
that can be prepared from one ton of dry clay.
o 15 cp clay suspension can support barite in mud;
o 15 cp is a critical point on the viscosity curve of all clay types.
¾<15 cp, slow increase in viscosity;
¾>15 cp
p sharp
p increase in viscosity.
y
clays are divided into three groups based on their yield:

o High-yield clays (Na-montmorillonite, attapulgite, etc.), yields 45 bbl /ton or higher of 15 cp mud;
o Medium-yield or sub-bentonitic clays (Ca-montmorillonite, etc.), 20-40 bbl /ton;
o Low-yield or native clays (dry lake clays, etc.), less than 20 bbl /ton.
49
) Clay
Example: about 20 lb/bbl of bentonite is required to produce a 15

15-cp
cp viscosity mud:
5.5% solids by weight,
yield 100 barrels per ton,
have 2.5% solids by volume and
weigh about 8.6 lb/gal.
50
) Clay
Factors Affecting Yield of Clay
Concentration of salt:
o Hydration of fresh-water clays
reduced rapidly with increasing
concentration of metallic ions.
ions
o Add Soda Ash to reduce the
metallic ion concentration
through precipitation.
o Use attapulgite clay in salty water.

It develops rheological properties equally well in fresh and salt
waters. The ability to build viscosity does not depend on
hydration, but rather upon the extent to which the bundles of
needles are sheared:
¾ Development of brush
brush-heap
heap structures by the shearing forces.
¾ Strong attractive forces between particles created by the
presence of broken bond charges on the edges.
¾ Limitations: Higher cost, Lack of filtration control, Difficult to
control rheology properties.
51
) Clay
Pre-hydration of clay in fresh water
o First, hydrating the clay in fresh water;
o Then adding the viscous slurry to the salty water with some chemical dispersant .
The initial viscosity increases due to flocculation caused by the addition of the divalent
cation Ca++.
Ca . This, in turn, causes aggregation of the particles and a viscosity decrease
due to dehydration and decreased number of particles.
52
) Clay
Flocculation value
o Clay particles can not flocculate when suspended in fresh water because of
interference between the highly diffuse double layers.
o If an electrolyte is added
added, the double layers are compressed.
compressed
o If enough electrolyte is added, the particles can approach each other so closely
that the attractive forces predominate, and the particles flocculate.
o The critical concentration of electrolyte at which the flocculation occurs is known
as the flocculation value.
53
) Clay
Flocculation value
o The flocculation value depends on:
¾ The species of clay minerals;
¾ The exchange cations;
¾ The kind of salt added. The higher of the valence of the cations, the lower
the flocculation value.
9 Sodium Montmorillonite is flocculated by about 15 meq/l of sodium
chloride.
9 Calcium montmorillonite by about 0.2 meq/l of calcium chlorite.
¾ If the cation of the salt is different from the cation on the clay
clay, it is still true
that whenever polyvalent cations the flocculation value is always lower.
9 The flocculation value of Sodium Montmorillonite by calcium chlorite is
about 5 meq/l.
9 The flocculation value of Calcium montmorillonite by sodium chlorite is
about 1.5 meq/l.
54
) Clay
pH
o The viscosity of a bentonite suspension
is least in the pH range of 7 to 9.5;
o Drilling fluids are rarely operated with a
pH below 7 or in the acidic range.
Application of Clay in Drilling Fluid

Increase viscosity;
Support weighting material;
Reduce water loss;
Protect wellbore by mud-cake.
55

Making Mud: Clay Chemistry in Drilling Fluids

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Department of Geology & Petroleum Studies

PGP4108: Drilling Fluids

Clay Chemistry and Application

) Drilling Fluid and Its Basic Functions

CHEMICAL TANK ANNULUS

) Classification of Drilling Fluid

) Classification of Drilling Fluid

11. What is clay?

o Electrostatic Double Layer Model

¾ Negative surface charge causes a potential difference

o Water adsorption due to the higher concentration of cations

Cation Maximum c-spacing, Å

Chlorite 10 - 40 Cs+ 3.34 7.2 66.1

The K+ ion is able to

o Montmorillonite is the best known member of smectite

o The difference is that the substitutions are mainly Al3+ for

o Illite has higher degree of surface charge than

o Illite does not have an expanding

o The strong interlayer bonding is because of higher surface

o Limited ion exchange can take place at the exterior

 Edge-to-face / edge-to-edge association

 clays are divided into three groups based on their yield:

Example: about 20 lb/bbl of bentonite is required to produce a 15

o Use attapulgite clay in salty water.

 Application of Clay in Drilling Fluid

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Edge-to-face / edge-to-edge association

clays are divided into three groups based on their yield:

Application of Clay in Drilling Fluid