DRILLING

DRILLING FLUID
FLUID
CONTAMINATION
CONTAMINATION
AND
AND TREATMENT
TREATMENT
 IDENTIFY
THE
CONTAMINANT
DETERMINE
A
TREATMENT
PILOT TEST
TO CONFIRM
TREATMENT
 T RE AT

TH E
M I N AN T
CO NT A
 Factors Affecting the
Severity of Contamination

 Type of mud system

 Type of contaminant

 Concentration of contaminant

 Type and concentration of solids

 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 pH and alkalinities

 Precipitate calcium ion

 Cement Contamination
Treatment

Lignite - reduce alkalinities

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

Bicarb - precipitate calcium

Ca2+ + 2NaHCO3  2Na+ + 2H+ +  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

O NH2 O NH2O O- O O- O O- O 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

OH OH OH

2 C CH2 C CH2 C + 3Ca(OH)2

O C O
O OH

O- OH O-
2 C CH2 C CH2 C + 6H2O + 3Ca2+
O C O
- Citric Acid - reduce pH
O O
 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
Source

 Formation
 Anhydrite / Gyp
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
 Anhydrite / Gyp
Chemical Properties of Mud

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

 Precipitate calcium

 Increase alkalinities
 Anhydrite / Gyp
Treatment

Soda Ash - treat calcium ion

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

Add caustic soda to increase alkalinities

 Anhydrite / Gyp
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
Toleration

If large anhydrite sections are expected,

convert to a gyp mud system

 Anhydrite / Gyp
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
Source

 Seawater

 Formation (carnalite salt)*

*to be discussed in Salt Section

 Magnesium
Treatment

 Precipitate?

 or Sequester?
 Magnesium
Treatment

To Precipitate:

Add Soda Ash

Mg2+ + Na2CO3  2Na+ + MgCO3

MgCO3 is insoluble
 Magnesium
Treatment

To Sequester:

Add a source of hydroxyl

pH > 10.5

Mg2+ + 2OH- Mg(OH)2

pH < 10.5
 Magnesium
Treatment

LIME Ca2+(OH-)
Sequesters magnesium only

CAUSTIC SODA Na+ OH-

Sequesters magnesium and calcium

CAUSTIC POTASH K+OH-

Sequesters magnesium and calcium
 Magnesium
Effect on Mud Performance


Clays do not hydrate as much in hard water


Fluid Loss is more difficult to reduce


Products are not as soluble
 SALT
CONTAMINATION
 Salt Contamination
Sources

 Rock salt

 Make-up water

 Formation water
 Types of Rock Salt

 Halite NaCl

 Sylvite KCl

 Carnalite K MgCl3 • 6H2O

 Salt
(Disassociation)

NaCl + H2O  Na+ + Cl- + H2O

KCl + H2O  K+ + Cl- + H2O

K MgCl3 • 6H2O + H2O 

K+ + Mg2+ + 3Cl- + 7H2O

 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

 Add Caustic Soda to control pH

 Add lignosulfonate to control the YP

 Add fluid loss control agent

(if necessary)
 Salt Contamination
Conversion/Displacement

Convert the mud system to a saturated

salt system or displace with an oil or

synthetic-base system
 Conversion to a Saturated
Sodium Chloride System

 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
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/Bicarbonate
Physical Properties of the Mud

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

pH Fluctuate
Pm Depends
Pf Usually increases
Mf Increase
Ca2+ Decrease
Cl- No change
Carbonate / Bicarbonate
Equilibrium

Percent
100
=
H2CO3 CO3
80 -
HCO3
60

40

20

0
0 2 4 6 8 10 12 14
pH
Percent of various carbonate species at different pH values
 Yield Point vs. CO32-
and HCO3-

YP (lb/100 ft²)
-
2-
60
CO 3 HCO 3
50

40

30

20

10
0
20 40 60 80 100 120 140 160 180 200

Millimoles / Liter
Carbonate/Bicarbonate
Treatment

pH < 10 Add lime

pH 10 > < 11 Add lime and gyp

pH > 11 Add gyp

Garrett Gas Train
 HYDROGEN
SULFIDE (H2S)
CONTAMINATION
 H2S Contamination
Sources

 Formation

 Anaerobic bacteria (usually major source)

 Make-up water
 H2S Contamination
Indicators

 Increased flowline viscosity, yield

point and gel strengths
 Decrease in pH and alkalinities
 Darkening of the mud
 Barite lumps
 Drill string turns black
 Hydrogen Sulfide
Physical Properties of the 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
Chemical Properties of the Mud

pH Decrease
Pm Decrease
Pf Decrease
Mf Decrease
Ca2+ Slight Increase
Cl- No change
 Hydrogen Sulfide
Chemical Reaction

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

 Approximate Distribution
of H2S, HS-, and S2-
as a Function of pH
Percent of Total Sulfide
100

H2S HS -
10

0.1

2-
0.01 S
3 6 9 12

pH
 Hydrogen Sulfide
Treatment

 Increase the pH to > 11.0

 Buffer the pH > 11.0
 Precipitate out the Sulfides
 S2- + ZnO  ZnS  + O2-
 Hydrogen Sulfide
Treatment

SULF-X (ZnO)

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
S2-) oxide***) plus 0.00091
sufficient caustic
soda to maintain
the pH above 10.5

*Fw is the fractional % of water f rom 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 the bottom-hole temperature increases,

the effect of solids also increase
Excessive Low Gravity Solids
Physical Properties of the 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 the 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 Fine Solids
Physical Properties of the Mud

MW Slight or No change
FV Slight increase
PV Increase
YP Slight increase
Initial Gel Slight increase
10-min. Gel Increase
Fluid Loss Slight or No change
Solids Increase
MBT Slight increase if solids are reactive,
no change if barite
 Excessive Fine Solids
Chemical Properties of the Mud

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

 Perform a cost analysis to determine

whether to add a centrifuge to improve
solids control efficiency

 Add a centrifuge based on the cost

analysis and operate as a barite
recovery unit
Excessive Low Gravity Solids
Treatment

 Dilute with fresh (newly mixed) mud or

water where applicable.

 Maximize your solids control

equipment performance,

 Add deflocculants (dispersants).

Solids Contamination
Effect

Excessive solids increases the

severity of ALL contaminants