Acid Stimulation

Acid Stimulation

Review

Acid Stimulation removes near wellbore damage. This topic will discuss the
practical implications in sandstone acidising and the solid-liquid reactions.

Content
Introduction

Matrix acidising is a stimulation treatment that is particularly effective in removing near

wellbore damage. A reactive fluid (normally acid) is injected in to the matrix at a
pressure below the fracturing pressure. The reactive fluid results in the dissolution of
some of the matrix resulting in an increase in permeability. The acid enters the rock, and
flows through the natural pores and flow channels, reacting with the walls of the pores
and enlarging them. It will also react with the clay particles attached to the walls of the
pores and with invading fines and clay particles in the pore throats. The reaction
between the acid and the rock slows down as the acid is spent until finally the reaction is
completed, and additional radial penetration of the spent acid produces no additional
reaction.
The design of an acidising stimulation treatment requires and understanding of:
• chemical reactions between the fluid and the solids that make up the formation
matrix;
• the flow of liquid through porous media;
• possible instabilities such as viscous fingering and wormholeing.

Solid Liquid Reactions

A chemical reaction between two molecules takes place when they come into contact
with one another, and they have enough energy to overcome the activation barrier. It is
possible to identify two extreme cases. In the first the activation barrier is very low and
every molecular collision results in a reaction, and the global rate of the reaction is
therefore limited only by the number of contacts. The other case exists where very high
activation energy is required and only a small number of molecules in contact will react.
The energy barrier therefore limits the kinetics of the reaction. The first case outlined
above is referred to as diffusion or mass limited, whereas the second is said to be
reaction limited. Reactions between a solid and a liquid do not display any particular
differences except that only one of the two reacting molecules can move. Therefore,
since the reaction can only take place at the interface between the solid and the liquid,
the reaction is often referred to as surface reaction limited.

Kinetics of Reaction

The rate of reaction, which is expressed as the number of moles of reacting molecules
per unit time, ie, moles per second. The rate can be determined from Equation 1 below
for surface reaction limited scenarios:
Equation 1 qs = k j ⋅ A ⋅ Cm

© IIT Madras 2011 1

 Acid Stimulation

Where:
qs reaction rate (mole/sec)
kj reaction rate constant (mole-m litm cm-2 sec-1)
A area of the solid (cm2)
C concentration of the reactant (mole/litre)
m order of the reaction (dimensionless)
The simplest reactions have m equal to 1, ie. the rate is simply proportional to the
concentration. For mass transfer limited reactions, the number of moles reacting per unit
time is described by Nernst (1904):
D⋅ A⋅C
Equation 2 qd = ⋅ 10 − 3
δ
Where:
qd reaction rate (mole/sec)
D diffusion constant (cm2 sec-1)
A area of the solid (cm2)
C concentration of the reactant (mole/litre)
δ characteristic length constant (cm)
Nernst’s law assumes implicitly that the concentration at the interface is zero. The
characteristic length constant represents the thickness of the zone surrounding the solid
where the concentration varies from C (in the bulk of the reactant) to zero (at the
interface). In a more general case, the concentration is not uniform, nor does it go down
to zero at the solid liquid interface, and as a result both molecular diffusion and surface
kinetics must be considered. The dimensionless kinetic parameter P can therefore be
defined as:
qd D
Equation 3 P= = ⋅ 10 − 3
qs k j ⋅ δ ⋅ Cm − 1

Reactions with Rocks

Actual rocks display a large number of reactivities with acids. Thus P will vary depending
on k j. Table 1 below summarises common P values for various rock acid combinations.
Table 1. Values of Dimensionless Reaction Parameter P.
System m kj P
-6
Limestone / HCl 0.2 7 x 10 0.07
-7
Dolomite / HCl 0.44 1.25 x 10 4
-9
Feldspar / HF 1 1.5 x 10 300
-10
Quartz / HF 1 1.5 x 10 3000
-6
Vitreous Silica / HF 1 3.7 x 10 0.13

From the table above, it can be deduced that:

• Reaction with limestone is limited by mass transfer (P<1);
• Reaction with Dolomite is surface reaction limited;
• Clays and quartz are surface reaction limited.

© IIT Madras 2011 2

 Acid Stimulation

Stoichiometry

Stoichiometry describes the number of molecules required for the dissolution of a given
amount of solid. These effects can be obtained when the solid and liquid are well
defined, as in the reaction between limestone and hydrochloric acid:
Equation 4 CaCO3 + 2HCl → CaCl 2 + CO 2 + H2O

Knowing that the molecular weights of CaCO3 and HCl are 100 and 36.5 respectively, it
can be calculated that one litre of 15% hydrochloric acid can dissolve 220 grams of pure
limestone.

Practical Implications

The design of a sandstone acidising treatment is comprised of two parts:

• the selection of the appropriate fluid;
• prediction of the fluids efficiency.

Acidising in Sandstone Reservoirs

In sandstone reservoirs, treatment is usually performed with a mixture of hydrofluoric

(HF) and Hydrochloric (HCl) acids – typically 4% HF and 12% HCl. The acid reacts with
quartz, silicates and the carbonates that may be found as cementicious materials. The
acid reacts predominantly with plugging materials rather than with the rock matrix, and
an injection of fifty to two hundred and fifty gallons per foot will remove the near wellbore
damage.
Certain sandstone acid reactions may produce insoluble salts that tend to precipitate
and plug flow channels. To minimise the damage of precipitating salts, sandstone
acidising is commonly performed in three stages:
• an HCl pre-flush to displace formation brines and remove carbonate materials;
• an HF-HCl treatment to react with the rock matrix and plugging materials;
• a post flush with either HCl or mutual solvent that displaces the reaction product
away from the wellbore.

In certain cases where damage in the sandstone reservoir is due to particles, the acid
may need to penetrate deep into the reservoir. In these cases chemicals are used to
retard the HF reaction.
Matrix acidising is defined as the injection of fluids at pressures below the fracture
pressure. The injected fluid flows either through the existing porous medium or through
new passageways created by the fluid itself. The maximum possible injection rate that
does not fracture the formation can be derived from Darcy’s radial flow equation:
4.917 ⋅ 10 −6 ⋅ k ⋅ h ⋅ [(gf ⋅ H) − ∆p safe − p]
Equation 5 qmax =
µ ⋅ B ⋅  ln e + s 
r
 rw 
Where:
qmax maximum injection rate
k permeability
h formation height
gf fracture gradient
H depth
∆psafe safety pressure margin (200 to 500 psi)
p reservoir pressure

© IIT Madras 2011 3

 Acid Stimulation

µ viscosity
B formation volume factor
re drainage radius
rw wellbore radius
s skin factor
However, it is important to note that this equation does not account for transient effects,
multiphase flow or reservoir heterogeneities. The injected fluid is assumed to be
incompressible. As such the value obtained from the equation can only be used to
provide a guideline for determining the initial rate.
Depending on the carbonate and clay content of the formation and its permeability, 5%
to 15% HCl is used for preflush. The volume required to displace formation fluids to a
radial distance, rs, can be estimated from the following equation:
Equation 6 [ ( ) ]
Vp = 7.48 ⋅ φ ⋅ rs2 − rw2 ⋅ π

Where:
Vp pore volume
φ porosity
rs depth of the damage
rw well bore radius
However, the volume required to dissolve all acid soluble material to a radial distance rs
is given for HCl by:

Equation 7 VHCl = 7.48 ⋅

(
π ⋅ (1 − φ ) ⋅ X HCl ⋅ rs2 − rw2 )
β

Where:
VHCl HCl volume required
XHCl is the weight fraction of formation material soluble in HCl
β dissolving power of the acid

Acidising in Carbonate Reservoirs

In carbonate reservoirs (limestones and dolomites) HCl is used alone and in this case
the rock itself dissolves, rather than the plugging materials, which cause the formation
damage. The dissolved carbonate rock disperses plugging particles and enlarges the
flow passages. Normally a 15% HCl acid is used and 50 to 250 gallons per foot will
remove 3 to 5 feet from the wellbore radius.
The penetration of acid in carbonate rock is typically non-uniform, since the pore
structure is formed by vugs and microfissures. The resulting channels created by the
acid are known as wormholes.

Predicting Acidising Results

Various methods have been suggested to predict acidising results. They are all based
on essentially the same procedure: Simulate the acid reaction and calculate the
resultant permeability increase. The prediction models use highly idealised assumptions
and thus lack the practical value for effective treatment selection.
Only a post-acidising well test or close monitoring of production history may establish
the degree of treatment success. The standard transient test for treatment evaluation is
a pressure build up, performed shortly after the acid job is completed. Test data are
used to calculate post acid skin, which can be compared with the design skin.

© IIT Madras 2011 4