BJ Services

Carbonate Formations
and
Matrix Acidizing

Carbonates

Topics
1.
2.
3.
4.
5.

Types of Formation
Mineralogy
Acid Types
Treatment Design
Summary

Carbonates

1. Types of Formation

Carbonates

Types of Formation
Limestone
Comprised mainly of Calcium Carbonate
but may also contain Calcium Magnesium
Carbonate and Iron Carbonate
3 Types:-

Carbonates

Types of Formation
Organic Limestones
Formed from the Skeletal Residues
of Marine Life
Mainly from Cretaceous and
Tertiary Periods
Relatively high porosity and high
level of Impurities

Carbonates

Types of Formation
Precipitated Limestones
Usually formed as Evapourites
Low Porosity

Carbonates

Types of Formation
Clastic Limestones
Formed as Secondary Sedimentary
Deposits
Wide range of Composition and
Properties

Carbonates

Types of Formation
Chalk
Type of Fine-Grained Limestone
Rocks Tend to be pure White and Soft
Mostly Calcium Carbonate

Carbonates

Types of Formation
Dolomite
Calcium Magnesium Carbonate
Generally Harder and Less Permeable
than Limestones
Often with Natural Fractures

Carbonates

Types of Formation
Marble
Metamorphic Limestone / Dolomite
Very Hard, very Low Permeability
Natural Fractures

Carbonates

2. Mineralogy

Carbonates

Mineralogy
Calcite
Calcium Carbonate (CaCO3)
Easily dissolved by Acid
Main constituent of most Carbonates
Usually organic in Origin

Carbonates

Mineralogy
Calcite
CaCO3 + 2HCl

CaCl2 + CO2 + H2O

Carbon Dioxide stays in Solution Downhole,

But will Cause Foaming as the Acid is
Flowed Back to Surface

Carbonates

Mineralogy
Dolomite
Calcium Magnesium Carbonate
CaMg(CO3)2
Formed by Dolomitization of Limestones
Very soluble in Acid

Carbonates

Mineralogy
Dolomite
CaMg(CO3)2 + 4HCl
CaCl2 + MgCl2 + 2CO2 + 2H2O
Dolomite Requires more Acid per ft3 of
Rock than Limestone or Chalk

Carbonates

Mineralogy
Siderite
Iron Carbonate (FeCO3)
Usually found as minor consituent
of Limestones and Chalks
Easily dissolved by Acid, but can
result in Iron Hydroxide precipitates

Carbonates

Mineralogy
Siderite
FeCO3 + 2HCl

FeCl2 + CO2 + H2O

Ferrous Chloride can cause Ferrous

Hydroxide Precipitates if the Acid
is Neutralised

Carbonates

Mineralogy
Ankerite
Iron-rich Dolomite - Ca(FeMg)(CO3)2
Usually found as minor constituent
of Dolomites
Very soluble in Acid, but can
result in Iron Hydroxide precipitates

Carbonates

Mineralogy
Quartz
Silica - SiO2
Not Soluble in Acid
Can result in Production of Fines

Carbonates

3. Acid Types

Carbonates

Acid Types
Hydrochloric Acid
HCl - also known as Muriatic Acid
Very reactive
Very cheap and readily Available
Main Acid for 80% of Matrix Treatments
in Carbonates

Carbonates

Acid Types
Acetic Acid
CH3COOH - Also called Ethanoic Acid
Mildly reactive
Expensive - used as alternative to HCl
in High Temperatures
Also used to control Iron
Precipitates

Carbonates

Acid Types
Formic Acid
HCOOH - Also called Methanoic Acid
Mildly reactive (stronger than Acetic)
Expensive - used as alternative to HCl
in High Temperatures

Carbonates

Acid Types
Citric Acid
C6H8O7
Will form Calcium Citrate precipitate
if reacted with Calcite
Mainly used in combination with Acetic
Acid for Iron control. Never used
on its own.

Carbonates

4. Treatment Design

Carbonates

Treatment Design
Acid Type
Use HCl Unless you have a
Good Reason to Use another Acid Type
At very High Temperatures, Acetic and/or
Formic Acid is Used because of Slower
Reaction Rate
Choice of Acid Depends on Cost,
Availability, Storage and Function

Carbonates

Treatment Design
Acid Type
On very Water-Sensitive Formations
99% Acetic Acid can be Used, as
this is Essentially Water Free.
Remember that Organic Acids are
Generally Weaker than HCl and will
Require more Tank Volume

Carbonates

Treatment Design
Acid Strength
Strong Acids dissolve more Rock per
Gallon, Require less Storage Volume and
Less Mix Water
Weak Acids Require Less Corrosion
Inhibitor and Get Further from the Wellbore

Carbonates

Treatment Design
Acid Strength
Choice of Acid Strength Depends upon
BH Temperature, Available Storage
Volume and Treatment Objectives
Typical HCl Strengths:7.5%, 15%, 28%

Carbonates

Treatment Design
Corrosion Inhibitors
Corrosion Inhibitors reduce the rate
at which the Acid Attacks the Completion
(and the BJ Equipment)
BJ Standard for Corrosion Protection
is 0.05 lbs/sq ft Metal Loss or Less
BJ Standard for Coiled Tubing Protection
is 0.02 lbs/sq ft Metal Loss or Less

Carbonates

Treatment Design
Corrosion Inhibitors
Inhibitor Intensifiers are used at
Higher Temperatures to Boost the
Effectiveness of the Inhibitors
Corrosion Inhibitors are Expensive
and highly Toxic

Carbonates

Treatment Design
Corrosion Inhibitors
Inhibitor Loading taken from Charts, or
Job-Specific Testing:

BH Temperature
Exposure Time
Completion Material (eg N-80, Cr-13)
CO2 and/or H2S Level
Mutual Solvent Loading
Acid Type and Strength

Carbonates

Treatment Design
Pumping Rate
For Near Wellbore Damage Removal, LCM
Removal or Gravel Pack Cleanouts, pump
at 0.5 to 1.5 bpm.
The Idea is to Keep the Live Acid in the
Near Wellbore Area. Deep Penetration
is Generally Not Required

Carbonates

Treatment Design
Pumping Rate
For Matrix Stimulation, pump at Maximum
Possible Rate, staying below 80% of
the Frac Gradient
It is Possible to Create Wormholes
through the Formation if the Rate
is High Enough

Carbonates

Treatment Design
Pumping Rate
Paccaloni-style Matrix Treatments Involve
Increasing the Rate, as the Acid
Stimulates the Formation
These Treatments can start at 2 or 3 bpm
and Finish at 40 + bpm.
Paccaloni Treatments, combined with Diversion,
Provide the Best Possible Matrix Stimulation

Carbonates

5. Summary

Carbonates

Summary
Matrix Acidizing in Carbonates is Usually
Relatively Easy. If you Pump Acid into
a Carbonate, you should get an
Increase in Production
The Specifics of the Treatment Depend
upon the Temperature, the Formation Type
and Mineralogy, and the Objectives