Chapter 5: Acidizing

Professor, Dr., S. R. Shadizadeh

1
 Stimulation Techniques
 Mechanical methods
 Hydraulic fracturing
 Explosive fracturing
 Underreaming
 Re- and additional perforating

 Chemical methods
 Acid treatments

 Combined mechanical/chemical methods

 Acid fracturing
 CFA treatments

 Thermal methods
 Wellbore Stimulation: Improving the Productivity Index

 Restoring original state of the formation near the wellbore

• Typical: sandstone acidizing

 Improving near-wellbore permeability even with respect to "non-

damaged" state
• Typical: carbonate acidizing

 Changing streamline structure (eliminating radial convergence of

streamlines)
• Typical: propped fracturing, acid fracturing

S. R. SHADIZADEH, Ph.D., PE.

 Acidizing Methods

 Acid Wash

 Matrix Acidizing

 Acid Fracturing Stimulation

 Acid Wash
Acid wash treatment is a chemical process which dissolves an unwanted
substance in pipe, surface equipment, or flow-lines. It is commonly used
after perforation job.
Matrix Acidizing
 5.1. Introduction
Acidizing is one of the oldest techniques in well stimulation processes
still being used today, though its use only began toward the end of the
last century. Table 1 lists the major events in the early history of
acidizing.

In the case of treating formation damage, acid removes flow restricting

particles, scale deposits, and minerals in the reservoir or in the immediate
wellbore vicinity. The acid mixture holds the dissolved substance in
solution until it is either removed from the well system or over flushed a
safe distance into the formation; then, the well can produce at its natural
potential. Little, if any, increase in productivity will result unless
formation damage actually exists.
 Table 1: Early History of Acidizing
Year Event
1894 Acid was used to stimulate oil production in limestone formations in Lima,
Ohio.
1896 First patent related to acid treatments of wells was issued to Herman Frasch.
1928 Acid was used in Glen Pool, Oklahoma by Gypsy Oil Company, a subsidiary of
Gulf Oil Company.
1929 Subsidiary of Gulf Oil Corporation injected uninhibited hydrochloric acid under
pressure into a well in Lee County, Kentucky.
1930 Acidizing experiments were discontinued.
1932 Dow Chemical Company and Pure Oil Company used an acid treatment of 15%
hydrochloric acid plus arsenic as an inhibitor on a well in the Greendale Pool of
Midland County, Michigan.
Patents were issued to Grebe and Sanford of Dow Chemical Company for
treatments of oil wells with chemicals containing a corrosion inhibitor.
R.H. Carr of the Pure Oil Company was issued a patent on the technique of
chemically treating an oil well by the balanced fluid column method.
Dowel I Chemical Company formed Dowel I Inc. (now Dowell-Schlumberger
from its Well Service Group whose original main responsibility was stimulation
of Dow's brine wells.
Carey K. West formed the Chemical Process Company, a predecessor to Byron
Jackson, Inc. (now BJ-Hughes).
1933 J.R. Wilson with Standard Oil Company filed a patent on a technique for
treating sandstone formations with hydrofluoric acid.
1935 Halliburton Oil Well Cementing Company (now Halliburton Services) began
acidizing oil wells.
1940 Dowel I (now Dowell-Schlumberger) began the first commercial use of
mixtures of hydrochloric and hydrofluoric acid.
Matrix acidizing treatment is designed to remove skin damage that
extends beyond the immediate surface of the perforations or the face of
the producing zone. Acid enters the pore space of the formation below
fracturing pressure and dissolves both the surface of the rock and the
flow restricting contaminants within the matrix (see next Fig.).

A matrix acidizing treatment may be effective penetrating into the

formation only a few inches or up to several feet from the wellbore,
depending on formation permeability. In wells that have suffered from
skin damage, production can increase many fold. However, if a well had
little or no skin damage, an acidizing treatment stimulates natural
production little more than one to two times, depending on its design.
 Matrix Acidizing
(a) A matrix acidizing treatment consists
of slowly injecting acid into the formation
so that it penetrates into the pore spaces of
the rock without fracturing the formation

(b) Matrix acidizing is used primarily in

sandstone formations to dissolve unwanted
materials that have invaded the rock pores
during drilling, cementing and completions
operations.
 5.2. PRINCIPLE & APPLICATION
– ACID INJECTION at P < Pfrac:
• Mainly used to unplug
– BE SURE OF:
• The plugging
• The nature of the plugging
– BEWARE TO SIDE REACTIONS
(particularly in sandstone formations):
• Deconsolidation
• Precipitates
• Emulsions, etc.
 5.3. TYPES OF ACIDS
Whatever their specific formulation, all acids have hydrogen ions that
react with carbonate rock (principally limestone and dolomite) to form
water and carbon dioxide, and with siliceous minerals (sandstone and
clays) to form fluosilicic acid and water.
 5.4. Carbonate Rocks
– HYDROCHLORIC ACID:
• 15 % HCl (or 7.5, 20, 28 %)
– WEAK ACIDS:
• Acetic acid : 10 or 12 % CH3COOH
• Formic acid : 9 % HCOOH
– ACID BASED EMULSION or ACID GEL

Note:
- formation attack and not plugging particles attack
- treatment volume: 0.5 to 2 m3/m (40 to 160 gal/ft)
- hydrofluoric acid forbidden: precipitate of calcium fluoride

- with HCl:
– corrosion inhibition is difficult at high temperature
– the chlorine ions may create sludges with heavy oil
 Main acids used in carbonate rocks
- HYDROCHLORIC ACID "HCl":
CO3Ca + 2 HCl  CaCl2 + CO2 + H2O
(CO3)2CaMg + 4 HCl  CaCl2 + MgCl2 + 2 CO2 + 2H2O

- ACETIC ACID "CH3COOH":

CO3Ca + 2 CH3COOH  Ca(CH3COOH)2 + CO2 + H2O

- FORMIC ACID "HCOOH":

CO3Ca + 2 HCOOH  Ca(HCOOH)2 + CO2 + H2O

- HYDROFLUORIC ACID "HF":

CO3Ca + 2 HF  F2Ca + CO2 + H2O

NOTE: Always add acid to the water, never the water to the acid
 Hydrochloric Acid
Hydrochloric acid (HCl) is the workhorse of the stimulation business,
finding extensive use in both carbonate and sandstone acidizing.
Chemically, hydrochloric acid is hydrogen chloride in aqueous solution.
Composed of hydrogen and chlorine gas, it is gaseous in the chemically
combined state. Hydrogen chloride gas is readily soluble in water.
Concentration is described as percent by weight of HCl gas dissolved in
water. HCl acid is commercially available; its concentration has been
standardized at 20° Be, i.e., 31.45% acid, and it has a specific gravity of
1.160.
Many acidizing treatments employ HCl to some extent. Usually, it is
used as a 15% solution when treating carbonate formations. This
concentration, commonly referred to as regular acid, was originally
chosen because of inadequacies in early inhibitors and difficulty of
preventing corrosion of well tubulars by more concentrated solutions.
Fifteen-percent HCl is used most frequently because it:
 costs less per unit volume than stronger acids and is less costly to
inhibit;
 is less hazardous to handle than stronger acids;
 retains larger quantities of dissolved salts in solution after
spending.

Although acid concentrations higher than 15% may also be used in

carbonate formations, lower strengths are more suitable where acid
dissolving power is not the sole consideration. In sandstone acidizing, for
example, 5 to 7.5% HCl is often used ahead of hydrochloric-hydrofluoric
acid mixtures to prevent precipitation of formation-plugging reaction
products.
The principal disadvantage of HCl is its corrosive action on wellbore tubular goods.
HCl reacts with limestone (CaCO3) to form calcium chloride (CaCl2), water (H2O) and
carbon dioxide (CO2):
As shown, 2 moles of hydrochloric acid reacts with 1 mole of CaCO3 to produce 1 mole
each of calcium chloride, water and carbon dioxide. The molecular weights of these
compounds are as follows:
Compound Molecular Weight
Hcl 36.47
CaCO3 100.09
CaCl2 110.99
H2 O 18.02
CO2 44.01

Thus, to dissolve one pound of limestone, we would need

Necessary volume of acid to saturate the formation
 5.5. Sandstone Rocks

• A-1) SANDSTONES : BASIC PRINCIPLE

– HYDROFLUORIC ACID:
• Main action on clays and feldspars
– BUT:
• Precipitates in presence of carbonate
• Numerous others precipitates
• Deconsolidation
– SO:
• Preliminary laboratory study
• Preflush with hydrochloric acid
• Additives are very important
• Clean-up immediately after the treatment if possible
 Hydrofluoric Acid
Hydrofluoric acid is the primary dissolving chemical used in sandstone acidizing. In
these applications, HF is usually mixed as a dilute solution with HCl, or an organic
acid. Its principal use is to dissolve siliceous minerals.

Within the chemical industry hydrofluoric acid (HF) is available commercially as a

relatively pure material in anhydrous form (where it is fuming and corrosive) or as a
concentrated (40 to 70%) aqueous solution. Anhydrous HF is not used in the field
because its low boiling point of 66.9° F is often exceeded by ambient temperatures. HF
reacts with silica and silicates, such as glass and concrete. It also attacks natural rubber,
leather, cast iron, and many organic materials.

HF is the only acid that reacts either siliceous minerals such as sand and clays. The
reaction of HF on quartz (SiO2), a primary component of sand, is:

4HF + SiO2 = SiF4 + 2H2O

SiF4 + 2HF = H2SiF6

Here, the end reaction product, fluosilicic acid (H2SiF6), is soluble in water, but its
potassium and sodium salts are insoluble. HF contact with formation water containing
CaCl2, MgCl2, NaCl or KCl thus must be avoided near the wellbore. The only salt
solution compatible with HF is ammonium chloride.
The reaction of HF on bentonite clay (Al2(Si4O10)(OH)2) is:

36HF + Al2(Si4O10)(OH)2  4H2SiF6 + 2H3AlF6 + 12 H2O

Hydrofluoric acid also reacts with carbonates; its reaction with limestone is:

2HF + CaCO3  CaF2  + H2O +CO2

HF will react with calcium ions from any source to form the insoluble precipitate
calcium fluoride (CaF2), which can cause sever plugging problems in the formation.
The portion of the reaction that creates calcium fluoride is:
Ca++ + 2F-  CaF2
CaF2 formation can be avoided through the proper use and optimal placement of HCl in
the acid treatment.
- ACTION OF THE HYDROFLUORIC ACID "HF":
• On quartz "Si O2":
4 HF + SiO2  SiF4 + 2 H2O
if HF in exces : SiF4 + 2 HF  SiF6H2
• On clays "SiO2, m Al2O3, n H2O":
6 (1 + m) HF + (SiO2, m Al2O3, n H2O)
 SiF6H2 + m Al2F2 + (2 + 3 m + n) H2O
with intermediate formation of Si F4
• On carbonate "CO3 Ca":
2 HF + CO3Ca  F2Ca + CO2 + H2O

- PREPARATION OF THE HYDROFLUORIC ACID "HF":

HCl + NH4HF2  2 HF + NH4Cl

NOTE: Always add acid to the water, never the water to the acid
A-2) SANDSTONES: IN PRACTICE
– PREFLUSH:
• Hydrochloric acid ( 0.5 V)
– MAIN TREATMENT:
• Mud acid: HCl + HF (V  0.5 to 1.5 m3/m i.e. 40 to 120 gal/ft)
– weak mud acid : 7.5 % HCl – 1.5 % FH
– regular mud acid : 12 % HCl – 3 % FH
– (super mud acid : 12 % HCl – 6 % FH)
– (ultra mud acid : 12 % HCl – 10 % FH)
• Organic mud acid: 9 % HCOOH – 3 % FH
– when chlorine ion may create sludges with heavy oil
– for very hot well
– OVERFLUSH (or afterflush):
• Hydrochloric acid, diesel oil ( 0.5 V to 1 V)
• Injection water (for injection well)
 Hydrochloric-Hydrofluoric Acid Mixtures

Hydrochloric-hydrofluoric acid mixtures are the chief solutions used in

matrix acidizing of sandstone. These acids are very often used as
mixtures because HCl ties up and displaces anions, which in turn
prevents reaction of these anions (e.g., Ca++, Mg ++, etc.) with HF.
Although HF is the only acid effective on siliceous minerals, it is
ineffective as a stimulation agent on carbonates because its reaction
forms insoluble CaF2.

The usual HF solution used in the field contains 3% HF and 12% HCl.
This solution is commonly called regular mud acid. However,
concentrations of HF in HCl solutions range from 0.5 to 9%, and some
operators prefer 1-1/2% HF and 6% HCl.
These mixtures may be formed from the dilution of concentrated
solutions of HF or, more frequently, from the reaction of ammonium
bifluoride (NH4HF2) or ammonium fluoride (NH4F) with HCl. Usually,
15% HCl is used, and enough NH4HF2 or NH4F is added to create a
solution containing 3% HF. Consumption of hydrogen chloride by these
reactions leaves 12% HCl remaining in solution. Similarly, 1.5% HF can
be prepared from 7-1/2% HCl solutions where the final HCl
concentration is 6%.

Corrosion characteristics of HCl-HF mixtures are comparable to those of

HCl alone, and similar corrosion inhibitors are required. Both HCl and
HCl-HF acid mixtures are stronger and more reactive than organic
acids.
 ADDITIVES
• Corrosion inhibitors
• Sequestering or complexing agents (iron retention agents)
• Demulsifiers and antisludge agents
• Wetting agents
• Clay stabilisers
• Solvents:
– mutual solvents:
(EGMBE: ethylene glycol monobutylether)†
– aromatic solvent (xylene, etc.)‡
• Diverting agents

† very often used in the overflush to restore the water wettability, may also be
used in the preflush
‡ used in the preflush in case of heavy oil to avoid the formation of asphaltic
deposits non soluble in acid, dispersing the heavy components
 5.6. IMPLEMENTATION
• A) PRECAUTIONS
• All equipment pressure tested and cleaned
• Fluids prepared beforehand and carefully
• Injection at matrix rate
• Clean-up as soon as possible
• Treatment report

• B) PLACEMENT TECHNIQUES
– BEFORE FINAL EQUIPMENT INSTALLATION WITH A TEMPORARY
STRING:
• Easier setting
but
• Problem to stabilize the well
– AFTER FINAL EQUIPMENT INSTALLATION:
• Squeeze (often difficult to carry out)
• Coiled tubing or snubbing unit
OTHER TREATMENT FLUIDS TO REMOVE PLUGGING

• Slug of diesel oil

• Water
• Solvents
 Fracture Acidizing

Fracture acidizing is a process in which acid is injected at a high enough

rate and pressure to fracture the formation. It usually involves injecting a
viscous pad fluid ahead of the acid to initiate the fracture. Differential
rock removal occurs as the acid reacts chemically with the formation
faces. This results in an uneven etching pattern which increases flow
capacity to the wellbore and provides a higher productivity ratio.

Fracture acidizing has application in carbonate reservoirs, both limestone

and dolomite. There are two main reasons for performing this type of
stimulation treatment. First and foremost is low permeability, where
natural production is not economical; a conductive fracture provides
much more flow area for produced fluid or gas. The second reason is to
overcome damage that extends deeper than matrix acidizing can
effectively reach (see the next Figure).
Fracture Acidizing
END