DRILLING FLUID

CONTAMINATION
AND TREATMENT
 RECOGNIZE
THE
CONTAMINANT
DETERMINE
A
TREATMENT
PILOT TEST
TO CONFIRM
TREATMENT
Factors Affecting the
Severity of Contamination

 Type of mud system

 Type of contaminant

 Concentration of contaminant

 Type and concentration of solids

Drilling Fluid
Contaminants
 Solids
 Drilled Solids
 Product contamination

 Liquids
 Water
 Dissolved ions

 Gases
 Hydrogen Sulphide
 Oxygen
 Carbon Dioxide
 Air
Common Chemical
Contaminants

 Cement

 Anhydrite / gyp

 Magnesium

 Salt

 Acid gases (CO2 & H2S)

 CEMENT
CONTAMINATION
Cement Contamination

pH < 11.5

Ca(OH)2 Ca2+ + 2(OH)-

pH > 11.5
Calcium Hydroxide
Solubility vs. pH
% Calcium Solubility
100

80

60

40

20

0
8 9 10 11 12
pH
Cement Contamination
Sources

 Drilling cement

 Contaminated barite
Cement Contamination
Physical Properties of Mud

MW No change
FV Increase
PV No change to slight increase
YP Large increase
Initial Gel Large increase
10-min. Gel Increase
Fluid Loss Increase
Solids No change to slight increase
Cement Contamination
Chemical Properties of Mud

pH Increase
Pm Increase
Pf Increase
Mf Increase
Ca2+ Increase if pH < 11.5
Decrease if pH > 11.5
Cement Contamination
Treatment

 Remove hard cement with solids removal

equipment

 Reduce alkalinities

 Precipitate calcium ion

Cement Contamination
Treatment

Lignite - reduce alkalinities

Ca(OH)2 + 2RCO2H  Ca2+ + 2RCO2- + 2H2O
(Organic Acid)

Bicarb - precipitate calcium

Ca2+ + NaHCO3  Na+ + H+ + CaCO3 
 Cement Contamination
Treatment

SAPP - reduce alkalinities

precipitate calcium

Na2H2P2O7 + 2Ca(OH)2  2Na+ + 2H2O + Ca2P2O7 

 Cement Contamination
PHPA System

CH2 CH2 CH2 CH2 CH2 CH2

CH CH CH CH CH CH +2NH3
-
+ 2OH

C C C C C C

NH NH - O O- O O- O O-
O 2O 2O O
Cement Contamination
PHPA System

CH2 CH2 CH2 CH2 CH2 CH2

CH CH CH CH CH CH
2+
+ Ca

C C C C C C

O O- O O- O O- O O- O OCaOO
 Cement Contamination
PHPA System / Treatment

 Pre-treat with ½ - 1 ppb citric acid to reduce

the pH to 7 .

 Pre-treat with ¼ - ½ ppb sodium bicarbonate

Cement Contamination
PHPA System / Treatment

 Treat the cement contaminated mud at the

flowline with ¼ - ½ ppb citric acid to control
the pH at < 10.0

 Add sodium bicarbonate to treat out the

remaining cement contamination.

 Do not add polymers to the mud until the

cement is treated out and the pH is stabilized
at < 10.0
Cement Contamination
PHPA System / Treatment

Bicarb - precipitate calcium

Ca2+ + NaHCO3  Na+ + H+ + CaCO3 

Cement Contamination
Treatment

 Tolerate:

 Dilute

 Add lignosulfonate

 Add fluid loss control additives if

necessary
ANHYDRITE / GYP
CONTAMINATION
Anhydrite / Gyp
Contamination

Anhydrite
CaSO4  Ca2+ + SO42-

Gypsum
CaSO4 • 2H2O  Ca2+ + SO42- + 2H2O
Anhydrite / Gyp
Contamination: Source

 Formation
Anhydrite / Gyp
Contamination
Physical Properties of Mud

MW No change
FV Increase
PV No change to Slight increase
YP Increase
Initial Gel Increase
10-min. Gel Increase
Fluid Loss Increase
Solids No change
Calcium Hydroxide
Solubility vs. pH
% Calcium Solubility
100

80

60

40

20

0
8 9 10 11 12
pH
Anhydrite / Gyp
Contamination
Chemical Properties of Mud

pH Decrease
Pm Slight decrease
Pf Decrease
Mf Decrease
Ca2+ Increase
Cl- No change
Anhydrite / Gyp
Contamination
Treatment

 Precipitate calcium

 Increase alkalinities
Anhydrite / Gyp
Contamination
Treatment

Soda Ash - treat calcium ion

Ca2+ + SO42- + Na2CO3  2Na+ + SO42- + CaCO3 

Add caustic soda to increase alkalinities

Anhydrite / Gyp
Contamination
Toleration

 Increase pH to 9.5 - 10.5

 Dilution

 Add lignosulfonate for de-flocculation

 CO2 from formation and atmosphere will

eventually precipitate calcium
Anhydrite / Gyp
Contamination
Toleration

If large anhydrite sections are expected,

convert to a gyp mud system

Anhydrite / Gyp
Contamination
System Conversion

 Dilute

 Gyp to excess (8 - 12 ppb)

 Caustic soda (pH 9.5 - 10.5)

 Lignosulfonate for deflocculation

 Ca2+ tolerant Fluid loss control agents (if

necessary)
 MAGNESIUM
CONTAMINATION
Magnesium Contamination
Source

 Seawater

 Formation (carnalite salt)*

*to be discussed in Salt Section

Magnesium Contamination
Treatment

 Precipitate or sequester the

magnesium ion
Magnesium Contamination
Treatment

Add Soda Ash - precipitate

Mg2+ + Na2CO3  2Na+ + MgCO3

MgCO3 is soluble
Magnesium Contamination
Treatment

Add source of hydroxyl to sequester

pH > 10.5

Mg2+ + 2OH- Mg(OH)2

pH < 10.5
Magnesium Contamination
Treatment

LIME
Sequesters magnesium only

CAUSTIC SODA
Sequesters magnesium and calcium

CAUSTIC POTASH
Sequesters magnesium and calcium
Magnesium Contamination
Effect on Mud Performance

 In hard water, clays do not hydrate as

much. Therefore, the filter cake is not as
compressible. This makes fluid loss more
difficult to control.

 Chemicals are not as soluble in hard

water. Therefore, they are not as cost
effective.
 SALT
CONTAMINATION
Salt Contamination
Sources

 Rock salt

 Make-up water

 Formation water
Salt Contamination
Rock Salt

 Halite NaCl

 Sylvite KCl

 Carnalite K MgCl3 • 6H2O

Salt Contamination
Rock Salt (Disassociation)

NaCl + H2O  Na+ + Cl- + H2O

KCl + H2O  K+ + Cl- + H2O

K MgCl3 • 6H2O + H2O 

K+ + Mg2+ + 3Cl- + 7H2O
Salt Contamination
Make - Up Water

Na+

K+

Ca2+

Mg2+

Cl-
Salt Contamination
Physical Properties of Mud

MW Depends on type
FV Increase
PV Increase (if large conc. of salt)

YP Increase
Initial Gel Increase
10-min. Gel Increase
Fluid Loss Increase
Solids Retort indicates increase
Salt Contamination
Chemical Properties of Mud

pH Decrease
Pm Decrease
Pf Decrease
Mf Decrease
Ca2+ Slight to significant increase
depending on the type of salt
Cl- Increase
Salt Contamination
Treatment Options

 Tolerate

 Convert to saturated salt mud

 Displace to oil or synthetic-base mud

Salt Contamination
Toleration

 Dilute

 Sequester divalent cations

 Add lignosulfonate

 Add fluid loss control agent

(if necessary)
Salt Contamination

Convert mud system to a saturated salt

system or displace with an oil or synthetic-

base system to prevent wellbore

enlargement if a large salt section is to be

drilled
Salt Contamination
System Conversion

 Dilute low gravity solids (LGS)

(pilot test prior to conversion if time and
conditions permit)

 Add NaCl to saturation (110 - 120 ppb)

 Add caustic soda to maintain pH at
desired level
 Add lignosulfonate
 Add fluid loss control agents
 CARBONATE /
BICARBONATE
CONTAMINATION
Carbonate/Bicarbonate
Contamination
Sources

 Air (atmosphere) injected by pumps, mixing

hoppers, shale shakers and agitators
 CO2 gas intrusion
 Over-treatment with soda ash or bicarb
 Degradation of certain mud additives
 Most barite
Carbonate/Bicarb Contam.
Physical Properties of Mud

MW No change
FV Slight increase
PV No change
YP Slight increase
Initial Gel Slight increase
10-min. Gel Increase
Fluid Loss Slight increase
Solids No change
Carbonate/Bicarb Contam.
Chemical Properties of Mud

pH Decrease
Pm Decrease
Pf Usually increases
Mf Increase
Ca2+ Decrease
Cl- No change
Carbonate/Bicarb Contam.
Recognition

 Increase in flowline viscosity, progressive gels

and increasing YP
 Little or no response to chemical deflocculants
 A reduction in rheological properties may occur
when caustic soda is added if the pH of the mud
< 10.0 prior to adding caustic soda
Carbonate / Bicarbonate
Equilibrium

r
e
Pn
e
ct
0
0
1
=
C
H
2O3 O
C
3
0
8 -
O
C
H3

0
6

0
4

0
2

0
01
0 2 4 6 8 1 4
21
H
p
r
e
Pn
e
co
tfa
vo
i
ruc
sb
r
an
oe
t
asc
e
pe
isd
t
af
ie
fe
rt
nH
pl
a
ve
us
Yield Point vs. CO32-
and HCO3-

YP (lb/100 ft²)
60
2- -
CO3 HCO3
50

40

30

20

10

0
0 20 40 60 80 100 120 140 160 180 200

Millimoles / Liter
Carbonate/Bicarb
Contamination:Recognition

 Little or no excess calcium

 Decreasing pH with increasing or constant

Pf

 Mf increasing more than Pf

Carbonate / Bicarbonate
Equilibrium
P
e
rc
e
nt
1
0
0
=
H
C
2O3 C
O
3
8
0 -
H
C
O3

6
0
Hydrogen ions
4
0

2
0

0
0 2 4 6 8 1
0121
4
p
H
P
e
rc
e
nt
ofv
ar
i
ous
ca
r
bo
na
t
esp
e
ci
esa
t
di
ff
er
en
tp
Hv
a
lu
es
Methods of Determining
Carbonates

 Pf / Mf Method

 pH / Pf Method

 Garrett Gas Train

Pf / Mf Method

 The Pf/Mf method is not a quantitative

method of determining the
carbonate/bicarbonate ion
concentration in the mud.
 Varying Pf/Mf ratios help establish
trends, which can be used to
determine a probability of carbonate/
bicarbonate contamination.
Pf / Mf Method

 If Mf < 5.0 cc of 0.02N H2SO4, ordinarily

there is no carbonate problem

 If Mf > 5.0 and Mf/Pf ratio is increasing,

a more quantitative method of
determination needs to be employed
(pH/Pf or a Garrett Gas Train)

High concentrations of lignite in muds will show

an elevated Mf. Lignites contain strong organic
acids that buffer the pH between 4.3 - 8.3.
pH / Pf Method

For quantitative analysis of carbonates, an

accurate pH meter is critical.

NOTE:
Small amounts of carbonates will benefit the mud
system, providing a buffering effect which
increases the mud’s stability. All treatments
using the pH/Pf Method allow 20 (mm/l) of
carbonates to remain.
pH / Pf Method

 Measure and record from mud check sheet:

pH, Pf, and water fraction (Wf)

 Determine from calculations the amount of

CO32- and/or HCO3- (mm/l) present in the
mud
Hydroxyl (OH)
Concentration

 The following chart shows that a very

small amount of hydroxyl (OH-) ions are
required to increase the pH of water
(H2O) which has no interfering ions (like
carbonate/bicarbonate ions).
The effect of using caustic soda alone to increase the pH
(with no alkalinity due to carbonates or bicarbonates):

pH NaOH, ppb Pf OH, ppm

9 0.00014 0.0005 0.17
10 0.0014 0.005 1.7
11 0.014 0.05 17.0
12 0.14 0.5 170.0
13 1.4 5.0 1,700.0
14 14.0 50.0 17,000.0
NOTE: Each time the concentration of NaOH goes up
by a factor of 10, the pH goes up one unit.
Hydroxyl (OH)
Concentration

 As an example, only 0.014ppb of caustic

soda (Na+OH-) is required for an 11.0 pH.

 The resulting Pf is only 0.05 ml of

sulfuric acid
Carbonate/bicarbonate
Pf Titration

 In the Pf titration, sulfuric acid (H2SO4-),

is added until the pH is reduced to 8.3.

 Ions that commonly exist in a pH range

above 8.3 are hydroxyl (OH-) ions and
carbonate/bicarbonate (CO32-/HCO32-)
ions
Carbonate/bicarbonate
Pf Titration

 In the Pf titration, the sulfuric acid

(H2SO4-), converts the OH- ion to H20.
The previous two slides show that this
takes very little acid, since very little
caustic is present.
Hydrogen Ion
Concentration

 In the Pf titration, sulfuric acid (H2SO4-),

also converts carbonates (CO32-) to
bicarbonates (HCO3-)

 This requires a hydrogen ion (H) for each

carbonate ion (CO32-) present in the
filtrate. Therefore, the more carbonates
present, the higher the Pf.
Hydrogen Ion
Concentration
P
e
rc
e
nt
1
0
0
=
H
C
2O3 C
O
3
8
0 -
H
C
O3

6
0
Hydrogen ions
4
0

2
0

0
0 2 4 6 8 1
0121
4
p
H
P
e
rc
e
nt
ofv
ar
i
ous
ca
r
bo
na
t
esp
e
ci
esa
t
di
ff
er
en
tp
Hv
a
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es
Carbonate / Bicarbonate
Hydrogen Concentration

 In the Mf titration, sulfuric acid (H2SO4),

is added until the pH is reduced to 4.3,
where all carbonates (CO3) and
bicarbonates (HCO3) are converted to
carbonic acid (H2CO3).
 This requires two hydrogen ions (H2) for
each carbonate ion (CO3) present in the
filtrate. Therefore, the more carbonates
present, the higher the Mf.
Hydrogen Ion
Concentration
P
e
rc
e
nt
1
0
0
=
H
C
2O3 C
O
3
8
0 -
H
C
O3

6
0
Hydrogen ions
4
0

2
0

0
0 2 4 6 8 1
0121
4
p
H
P
e
rc
e
nt
ofv
ar
i
ous
ca
r
bo
na
t
esp
e
ci
esa
t
di
ff
er
en
tp
Hv
a
lu
es
Carbonate / Bicarbonate
Contamination
 Adjust pH to where majority of carbonates
exist and calcium is soluble (pH 10-11)
P
e
rc
e
nt
1
0
0
=
H
C
2O3 C
O
3
8
0 -
H
C
O3

6
0

4
0

2
0

0
0 2 4 6 8 1
0121
4
p
H
P
e
rc
e
nt
ofv
ar
i
ous
ca
r
bo
na
t
esp
e
ci
esa
t
di
ff
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en
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Hv
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es

 Add source of calcium

Calcium Hydroxide
Solubility vs. pH
% Calcium Solubility
100

80

60

40

20

0
8 9 10 11 12
pH
Carbonate/Bicarb Contam.
Treatment

pH < 10 Add lime

pH 10 > < 11 Add lime and gyp

pH > 11 Add gyp

 Chemical Reactions

CO2 Gas Intrusion

pH
CO2 + H2O [ H2CO3 ] (carbonic acid)
4.3
Formation of carbonic acid

[H2CO3] + NaOH NaHCO3 + H2O

4.3-8.3
Formation of bicarbonates as pH increases

NaHCO3 + NaOH Na2CO3 + H2O or

8.3-11.7
[H2CO3] + Ca(OH)2 CaCO3  + 2H2O
(ppt)
Formation of carbonates as pH increases
Garrett Gas Train
Carbonate/Bicarb Contam.
Solids vs. Carbonates

Often a solids problem is perceived as a

carbonate problem. They both increase the
viscosity and gel strengths of the mud,
especially at the flowline.

The following analysis should determine

whether the problem is the result of solids
or carbonate / bicarbonate contamination:
Solids vs. Carbonates

 Analyze the solids of the mud.

Look for trends that have developed

over the past few days.

Pay particular attention to an increase

in low gravity solids, MBT, and PV.
Solids vs. Carbonates

 After complete solids evaluation, look

at the mud chemistry:

If pH  and the Pf is or  , this is the

first sign of a carbonate problem.

If pH  and Pf  also , the problem is

probably solids related.
 HYDROGEN
SULFIDE (H2S)
CONTAMINATION
H2S Contamination
Sources

 Formation

 Anaerobic bacteria (usually insignificant)

 Make-up water (usually insignificant)

H2S Contamination
Recognition

 Increased flowline viscosity, yield

point and gel strengths

 Decrease in pH and alkalinities

 Foul sulfurous odor at the flowline

 Darkening of the mud

 Drillstring turns black

Hydrogen Sulfide Contam.
Physical Properties of Mud

MW No change
FV Increase
PV No change
YP Increase
Initial Gel Slight increase
10-min. Gel Increase
Fluid Loss Slight increase
Solids No change
Hydrogen Sulfide Contam.
Chemical Properties of Mud

pH Decrease
Pm Decrease
Pf Decrease
Mf Decrease
Ca2+ Slight Decrease
Cl- No change
H2S Contamination

H2S H+ + HS- 2H+ + S2-

Approximate Distribution of
H2S, HS-, and S2- as a Function
of pH
P
e
rc
e
nto
fT
ot
alS
u
lf
i
de
1
0
0 -
H
S
2 H
S
1
0

0
.
1

-
2
0
.
01
S
3 6 9 1
2
p
H
H2S Contamination
Treatment

 Add caustic - increase pH

 Add lime - buffer pH

 Add SULF-X

 S2- + ZnO  ZnS  + O2-

H2S Contamination
Treatment

SULF-X

1 ppb removes approximately 1100 mg/l S2-

Chemical Treatment
TABLE 1 CHEMICAL TREATMENT IN U.S. UNITS

Contaminant Contaminating Treatment Treating

Ion Concentration,
lbs/bbl
Carbon Dioxide Carbonate Gyp to reduce pH Mg/l x Fw x
Lime to raise pH 0.00100
Bicarbonate Lime to raise pH Mg/l x Fw x
0.000432
Total Soluble Lime to raise pH Mg/l x Fw x
Carbonate 0.00424

Mg/l x Fw x 1.283
Gypsum and Calcium Soda Ash Mg/l x Fw x
Anhydrite 0.000928
SAPP
Mg/l x Fw x
Sodium 0.000971
Bicarbonate
Mg/l x Fw x
0.000735
Lime or Cement Hydroxyl Sodium PPB excess lime x
Bicarbonate 1.135

SAPP PPB excess lime x

1.150
Citric Acid
PPB excess lime x
1.893
Hard or Seawater Calcium & Caustic Soda Mg/l x Fw x
Magnesium 0.00116
-
Hydrogen Sulfide Sulfide (H2S, HS , SULF-X (zinc Mg/l x Fw x
2-
S ) oxide***) plus 0.00091
sufficient caustic
soda to maintain
the pH above 10.5

*Fw is the fractional % of water from retort

** Excess lime, = .26 (Pm-(Pf x Fw))
*** Other zinc compounds such as chelated zinc or zinc carbonate may also be
used. An excess should always be maintained in the system.
 SOLIDS
CONTAMINATION
Solids Contamination

 Excessive low gravity solids

 Excessive fine solids

Solids Contamination

The effect of solids on a mud is a function of:

 Concentration
 Reactivity
 Size and shape

As bottom-hole temperature increases

the effect of solids also increase
Solids Contamination

Excessive solids increases the

severity of ANY contaminant

Drilling Solids

 Drilled Solids and Drilled Fluids are NOT compatible.

 Drilled Solids affect the following :

Density - Induced fractures, lower ROP

Viscosity - Higher Surge/Swab, Increased pressure losses, difficult mud removal

Fluid Loss - Thicker filter cakes, higher fluid losses, stuck pipe, poor cement bond

Inhibition - Greater washouts, poor zonal isolation

Environment - Dead sea-beds

Drilling Curve - Poor performance

Equipment - High equipment cost / down time

Information - Reduced permeability

Reservoir - Damage due to solids / liquids invading pore spaces

Failure to Control Solids
Effectively

 Slower ROP’s and Drilling problems result in :

 Increased daily charges
 Increased dilution and maintenance charges
 Higher transport, storage and disposal costs
 Open hole interval extended - time related shale problems
more likely
 More bit runs
 Delay in starting production
 Reduced production
Solids Classification

 HGS - S.G. > 3

 All HGS are Inert

 LGS - S.G. < 3

 Reactive - Anionic Polymers, Bentonite, Reactive clays

 Inert - Sandstone, Limestone

 Reactive LGS have an effect because of chemical attractions

and their physical presence (YP)
 They are controlled by maintaining the MBT below

preset levels
 Inert LGS have an effect due to their physical presence (PV)
 They are controlled by the volume allowed in the fluid
Excessive Low Gravity Solids
Physical Properties of Mud

MW Probable slight increase

FV Increase
PV Increase
YP Increase
Initial Gel Increase
10-min. Gel Increase
Fluid Loss Slight decrease
Solids Increase
MBT Increase
Excessive Low Gravity Solids
Chemical Properties of Mud

pH Slight decrease
Pm Slight decrease
Pf Slight decrease
Mf Slight decrease
Pf/Mf Ratio No change
Ca2+ No change to slight increase
Cl- No change to slight increase
Excessive Low Gravity Solids
Treatment

 Displace with new mud

 Perform cost analysis on adding

centrifuge to improve solids control
efficiency
Excessive Fine Solids
Treatment

 Displace with new mud

 Dilute

 Operate centrifuge as barite recovery unit

Particle Size

 The smaller the particle size, the greater the surface area
 3 micron diameter particles have more than 300 times

the surface area of 1000 micron diameter particles for a

given volume.

 Smaller particle sizes cause :

 Greater particle to particle interaction due to particle

collision (PV)
 Greater particle to particle attraction between particles

(YP)
 A reduction in the amount of free water

Particle diameters are always measured in microns

 Size Classification

Common Term API Classification Size (microns) Common Article

Sand Course >2000 Gravel

Sand Intermediate 250 - 2000 Beach Sand

Silt Medium 74 - 250 Human Hair

Silt Fine 44 - 74 Pollen

Clay Ultra Fine 2 - 44 Cement

Clay Colloidal <2 Paint Pigments

Particle Size

 Depends on :
 Size of additives
 Drilling parameters
 Bit Type and Rotary Speed

 Weight on Bit

 Hole Cleaning parameters

 Efficiency

 Flow regime

 Formation Type
 Level of Inhibition
 Residence Time
 Solids Control

 Elimination of Drilled Solids at the first possible

opportunity with a minimum of physical handling
and a minimum of liquid discharge

 Further degradation occurs in :

 The centrifugal pumps

 The mud pumps

 The drill string
 The nozzles
 The hole
Solids Removal Equipment

 Gumbo Buster (optional)

 Shale Shaker

 Sand Traps

 DeSander (optional) Decreasing

Particle sizes
 De Silter Removed

 Mud Cleaner (optional)

 Centrifuge

 FCU (optional)