Chapter 03 Basic Chemistry and Chemical Reaction

BASIC CHEMISTRY AND CHEMICAL
REACTIONS IN DRILLING MUDS
Well Area Operations

Agip KCO Drilling Supervisors Training Course
Drilling Muds RPW2021A 1
INTRODUCTION
This section illustrates the most common chemistry problems which the mud
engineers will have to face. The reactions with the various chemical treatments are
illustrated through practical demonstrations

ANHYDRITES CONTAMINATIONS
The calcium ions which can be derived from gypsum or from the drilling of anhydrites,
are contaminant agents in the majority water-based muds.
It is possible to reduce calcium contamination through caustic soda addition
CaSO4 + Na2CO3 Æ CaCO3 + 2Na+ + SO42–

ANHYDRITES CONTAMINATIONS
Sodium Acid Pyrophosphate SAPP can also be used to treat contamination due to
anhydrites. It should be used with caution because it reduces the pH. If it is used as
a fluidizer, it becomes unstable.
Its reaction with gypsum is as follows:
Na2H2P2O7 + H2O Æ 2NaH2PO4 ;
2NaH2PO4 + 3CaSO4 Æ Ca3(PO4)2 + 2Na+ + 3SO42– + 4H+

CEMENT CONTAMINATION
Ca(OH)2, is a calcium derivative and a flocculant which can be removed with sodium
bicarbonate addition (NaHCO3).
The reaction is as follows:
Ca(OH)2 + NaHCO3 Æ CaCO3 + NaOH + H2O
This reaction forms sodium hydroxide with a consequent increase in the pH also after
the removal of the calcium from the cement.

SEA WATER
Sea water contains calcium and magnesium ions
These ions are bad for water based muds
Due to the fact that the magnesium hydroxide (Mg(OH)2) and calcium hydroxide
(Ca(OH)2) becomes insoluble as the pH increases.
The use of caustic products will allow the removal of calcium and magnesium as
follows:
Mg2+ + 2NaOH Æ Mg(OH)2 + 2Na+ (pH >10)
Ca2+ + 2NaOH Æ Ca(OH)2 + 2Na+ (pH >11)

CARBON DIOXIDE GAS CONTAMINATION
Carbon dioxide (CO2) is an acid gas, a well-known contaminating agent which can be
found in several formations.
Carbon dioxide, in an aqueous solution, will react forming bicarbonates (HCO3–) with
medium pH value, but carbonates (CO32–) at higher pH levels.
Small inflows can be neutralised with caustic soda.
CO2 + H2O Æ H2CO3 (carbonic acid);
2NaOH + H2CO3 Æ 2Na+ + CO32- + 2H2O (pH > 11)

CARBON DIOXIDE GAS CONTAMINATION
pH vs. Caustic Soda in Sea Water

Acqua distillata
Distilled water
Fango ad Acqua dolce

Acqua Marina
Freshwater mud
Sea Water
Rimozione Mg – Inizio conversione

da Ca a Ca(OH)2
Il Magnesio inizia la
precipitazione come Mg (OH)2 Mg2+ Removed – Ca2+ begins
to convert to Ca(OH)2
Magnesium begins to
precipitate as Mg (OH)2
Sea water

SODIUM BICARBONATE AND CARBONATE
CONTAMINATION
Bicarbonate (HCO3–) and carbonate (CO32–) contaminations, can take place because of
the conversion of CO2 gas or the degradation of organic additives, such as lignite and
lignosulphonates, and from the biodegradation of starch or other additives.
However, It is possible to remove the ions with calcium because calcium bicarbonate
Ca(HCO3)2 is soluble.
Therefore, it is possible to transform all bicarbonates to carbonates (over a pH of 11).

SODIUM BICARBONATE AND CARBONATE
CONTAMINATION
Lime (Ca(OH)2) is used to convert HCO³- to CO³ ²- and then for the carbonates
precipitation CaCO³, especially if the pH system won’t be raised at > 11.
2HCO3- + Ca(OH)2 →CACO³ + OH- + H²0
CO³2- + Ca(OH)² → CaCO³ +↓2OH-

↓
When it is necessary to maintain a certain pH value, it is also necessary to use the
right combination of gypsum and lime.
Ca(OH)2 + 2HCO3– Æ CaCO3 ↓ + CO32– + 2H2O

CaSO4 • 2H2 O + CO32– Æ CaCO3↓+ SO42– + 2H2O

H2S CONTAMINATION
H2S is a poisonous and very dangerous gas. The acid can be found in many
formations and fluids.
It can neutralise the olfactory nerves and can be fatal even in small concentrations.
L’H2S smells like rotten eggs.
It must be neutralized immediately with caustic soda or calcium hydroxide so as to

increase the pH to more than 11.5, in order to form a sulphide (S2–), and then
precipitate it with a zinc base.

H2S CONTAMINATION
Neutralisation with caustic soda:
2NaOH + H2S Æ 2Na+ + S2– + 2H2O (at pH >11.5)
Neutralisation with Calcium hydroxide excess maintainance:
H2S + Ca (OH) 2 Æ Ca2+ + S2– + 2H2O (pH >11.5)
Neutralisation by means of precipitation with a zinc based scavenger (ZnO):
H2S + ZnO Æ ZnS + H2O

OXYGEN REMOVAL WITH A SCAVENGER
It is possible to remove the oxygen mixed with mud.
For instance, Solutions of Ammonium Bisulphite, are the most used scavengers for
oxygen and react as follows:
NH4HSO3 + ½ O2 + OH– Æ NH4+ + SO3 + H2O ;
SO3 + ½ O2 Æ SO4

ACID TREATMENTS
The filter cake which contains solids, that are soluble in acid, such as calcium
carbonate used in non-damaging drilling fluids, can be removed from the well by
treatment with hydrochloric acid.
Calcium carbonate dissolution:
CaCO3 + 2HCl Æ CaCl2 + CO2 + H2O

PHOSPHATES
Sodium Acid Pyrophosphates (SAPP) and other phosphates will cause the reaction
and the calcium precipitation:
Na2H2P2O7 + H2O Æ 2NaH2PO4;
2NaH2PO4 + 3Ca(OH)2 Æ Ca3 (PO4)2 + 4H2O +2NaOH

LIGNITE EFFECTS ON CALCIUM
Lignite contains calcium (1.5 to 5%) as part of its chemical composition. The organic
acids in the same way as lignite, must be able to combine as well.
This complex calcium exists in the form of a floc. It is of minute size, and this makes
it difficult to remove with mechanical equipment.
On the contrary, the filter cake allows the majority of the complex acids such as
lignite to pass.


Chapter 03 Basic Chemistry and Chemical Reaction

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Chapter 03 Basic Chemistry and Chemical Reaction

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BASIC CHEMISTRY AND CHEMICAL

REACTIONS IN DRILLING MUDS

Well Area Operations

Well Area Operations

It is possible to reduce calcium contamination through caustic soda addition

CaSO4 + Na2CO3 Æ CaCO3 + 2Na+ + SO42–

Well Area Operations

Na2H2P2O7 + H2O Æ 2NaH2PO4 ;

2NaH2PO4 + 3CaSO4 Æ Ca3(PO4)2 + 2Na+ + 3SO42– + 4H+

Well Area Operations

The reaction is as follows:

Ca(OH)2 + NaHCO3 Æ CaCO3 + NaOH + H2O

Well Area Operations

Sea water contains calcium and magnesium ions

These ions are bad for water based muds

Mg2+ + 2NaOH Æ Mg(OH)2 + 2Na+ (pH >10)

Ca2+ + 2NaOH Æ Ca(OH)2 + 2Na+ (pH >11)

Well Area Operations

Small inflows can be neutralised with caustic soda.

CO2 + H2O Æ H2CO3 (carbonic acid);

2NaOH + H2CO3 Æ 2Na+ + CO32- + 2H2O (pH > 11)

Well Area Operations

pH vs. Caustic Soda in Sea Water

Fango ad Acqua dolce

Rimozione Mg – Inizio conversione

Well Area Operations

Therefore, it is possible to transform all bicarbonates to carbonates (over a pH of 11).

Well Area Operations

precipitation CaCO³, especially if the pH system won’t be raised at > 11.

2HCO3- + Ca(OH)2 →CACO³ + OH- + H²0

CO³2- + Ca(OH)² → CaCO³ +↓2OH-

Ca(OH)2 + 2HCO3– Æ CaCO3 ↓ + CO32– + 2H2O

Well Area Operations

formations and fluids.

L’H2S smells like rotten eggs.

It must be neutralized immediately with caustic soda or calcium hydroxide so as to

Well Area Operations

Neutralisation with caustic soda:

2NaOH + H2S Æ 2Na+ + S2– + 2H2O (at pH >11.5)

Neutralisation with Calcium hydroxide excess maintainance:

H2S + Ca (OH) 2 Æ Ca2+ + S2– + 2H2O (pH >11.5)

Neutralisation by means of precipitation with a zinc based scavenger (ZnO):

H2S + ZnO Æ ZnS + H2O

Well Area Operations

It is possible to remove the oxygen mixed with mud.

NH4HSO3 + ½ O2 + OH– Æ NH4+ + SO3 + H2O ;

Well Area Operations

Calcium carbonate dissolution:

CaCO3 + 2HCl Æ CaCl2 + CO2 + H2O

Well Area Operations

Na2H2P2O7 + H2O Æ 2NaH2PO4;

2NaH2PO4 + 3Ca(OH)2 Æ Ca3 (PO4)2 + 4H2O +2NaOH

Well Area Operations

Well Area Operations

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