Acid Treatments

Dr. Vikas Mahto

Professor
Department of Petroleum Engineering
IIT(ISM), Dhanbad-826004

Acid treatments are mainly used to remove the near-wellbore damage. There are two main types
of acidizing treatments: matrix acidizing and acid fracturing Matrix acidizing is a technique to
pump acid and other treatment fluids below the fracture pressure of formations, to stimulate
wells for improving well inflow performance. In matrix acidizing treatments, acid solution is
injected into the formation to dissolve some of the minerals to recover permeability of
sandstones (removing skin) or increase permeability of carbonates near the wellbore (creating
wormholes). Acid fracturing, on the other hand, is to create fractures in the formations first,
followed by injecting acid into fractures. Due to the uneven etching of fractures’ faces by acids,
some small channels will stay open after fractures close, which will increase the permeability of
the reservoir.
Acid Types
Currently, the main acid fluids used in acidizing treatments can be classified into three different
types: mineral acids, organic acids and retarded acids.
Mineral Acids

Hydrochloric acid (HCl) is commonly used acid for carbonate acidizing treatments, due to its
low cost and fast reaction with carbonate rock types (limestone and dolomite). It is mostly used
with the concentration of 15% (by weight) solution, to provide enough dissolving power of acid
and limit the corrosion of well tubulars. For stimulations where acid dissolving power is not an
issue, lower concentration of HCl can also be used to further reduce the corrosion. The main
disadvantage of HCl is still its high corrosivity, especially at high downhole temperature (above
250F), where the reaction rate between HCl and steel tubulars is even faster and more difficult to
control. Therefore, the concentration of HCl depends on different stimulation treatments and
wellbore conditions.
Hydrofluoric acid (HF), usually mixed with HCl, is mainly applied for sandstone acidizing.
Typically, 15% HCl and 3% HF solution is prepared. If any calcite presents in the formation,
calcium fluoride is the product due to the reaction between HF and calcite.

Calcium fluoride is insoluble in acid solutions, and may cause more damage to the porous space
of the formations. Therefore, appropriate preflush with HCl and pumping HF with HCl is
necessary to remove the carbonate minerals in sandstone formations and prevent the precipitating
reaction between calcite and HF.

Organic Acids

The advantage of organic acids is their lower corrosivity and slower reaction compared to
mineral acids. When the contacting time between acid and well tubular is long or the wellbore
down hole temperature is very high, organic acids can be used to control the corrosion.
Meanwhile, the dissolving power of organic acids is also lower than mineral acids, resulting in
less effective reaction between acid and minerals in the formation. The two main organic acids
used in acidizing treatments are acetic acid and formic acids. Both acetic and formic acids are
more expensive than HCl, and are often used as one component in retarded-acid systems or in
the formations with high temperature.

Retarded Acids

Due to the fast reaction between HCl and carbonate minerals, acid injected can be mostly spent
at a very short distance from the wellbore without penetrating deep enough into the formation.
Thus, to achieve deeper acid penetration and a successful acidizing treatment, it is necessary to
retard acid reaction by adding extra components into the acid systems. The most commonly used
retarded acid systems are gelled acids and emulsified acids.

By mixing gelling agents (polymers and surfactants) with acids, gelled acid systems can be
achieved. By increasing the viscosity of acid systems, the transportation of acid from fluid
stream to formation rocks is significantly reduced, and ultimately slows down the acid reaction.
Thus, more acid can be transported deeper into the formation and increase the chance of a
successful treatment. However, the stability of gelling agents are strongly dependent on the down
hole temperature. At high temperature, many gelling agents can degrade causing the gelling acid
system to lose its viscosity. It is recommended to use gelling acids at low moderate bottom-hole
temperature. Some other gelled acid systems depend on the pH value of the solution. Once the
acid is spent and pH of fluids is high, the viscosity of gelled acid can be significantly increased.
Meanwhile, due to the high viscosity of gelled acids, it can also be used as a diverter by
temporarily blocking the high permeability zones and divert the acids to desired zones.

Emulsified acid can be prepared by mixing acid, oil phase and emulsifier together, which
contains 20%30% of oil phase. Droplets are formed by having the oil phase as an external film
and having acid as the internal phase. The presence of external oil film reduces the diffusion rate
of acid phase to the rock surface, thus retarding the reaction rate between acid and rocks.
Stability of emulsions are also dependent on down hole temperature.

Candidate Selection
In general, acid will only penetrate several feet into the formation for matrix acidizing
treatments, resulting in removal of near-wellbore damage or slight increase of permeability. On
the other hand,acid fracturing will create fractures which can propagate much deeper into the
formation. For sandstone formations, if the permeability is moderate to high, and damage is the
main factor limiting the well production, matrix acidizing is recommended. However, if the
permeability is low, such as tight gas reservoirs or shale reservoirs, hydraulic fracturing is
recommended, since even all the damage is removed, the reservoir still cannot produce
economically due to the low permeability.

Similar rules also apply for carbonate formations. To remove or bypass the damage in the near
wellbore region in moderate or high permeability formations, the well should be stimulated by
matrix acidizing. Otherwise, acid fracturing should be applied for low-perm carbonate
formations.

Acid-Rock Interaction

Minerals that are present in sandstone pores include montmorillonite (bentonite), kaolinite,
calcite, dolomite, siderite, quartz, albite (sodium feldspar), orthoclase, and others. These minerals
can be either from invasion of external fluid during drilling, cementing, and well completion, or
from host materials that exist in the naturally occurring rock formations. The most commonly
used acids for dissolving these minerals are HCl and HF.

Chemical Reactions
Silicate minerals such as clays and feldspars in sandstone pores are normally removed using
mixtures of HF and HCl, whereas carbonate minerals are usually attacked with HCl. The
chemical reactions are summarized in Table 1. The amount of acid required to dissolve a given
amount of mineral is determined by the stoichiometry of the chemical reaction. For example, the
simple reaction between HCl and CaCO3 requires that 2 mol of HCl is needed to dissolve 1 mol
of CaCO3.

Table 1: Primary Chemical Reactions in Acid Treatments

Dissolving Power of Acids

A more convenient way to express reaction stoichiometry is the dissolving power. The
dissolvingpower on a mass basis is called gravimetric dissolving power and is defined as

V MW
β=
V MW

Where

β = gravimetric dissolving power of acid solution, lbm mineral/lbm solution

Ca = weight fraction of acid in the acid solution

Vm = stoichiometry number of mineral

Va = stoichiometry number of acid

MWm = molecular weight of mineral

MWa = molecular weight of acid.

The dissolving power on a volume basis is called volumetric dissolving power and is related to

the gravimetric dissolving power through material densities

ρa
𝑋=β
ρm

Where,
X= volumetric dissolving power of acid solution, ft3 mineral/ft3 solution
ρa =density of acid, lbm/ft3
ρm=density of mineral, lbm/ft3

SANDSTONE ACIDIZING DESIGN

The purpose of sandstone acidizing is to remove the damage to the sandstone near the wellbore
that occurred during drilling and well completion processes. The acid treatment is only necessary
when it is sure that formation damage is significant enough to affect well productivity. A major
formation damage is usually indicated by a large positive skin factor derived from pressure
transit test analysis in a flow regime of early time.

Selection of acid
The acid type and acid concentration used in acidizing treatments is selected on the basis of
minerals in the formation and field experience. For sandstones, the typical treatments usually
consist of a mixture of 3 wt% HF and 12 wt% HCl, preceded by a 15 wt% HCl preflush.
McLeod (1984) presented a guideline to the selection of acid on the basis of extensive field
experience. His recommendations for sandstone treatments are shown in Table 13.2. McLeod’s
recommendation should serve only as a starting point. When many wells are treated in a
particular formation, it is worthwhile to conduct laboratory tests of the responses of cores to
different acid strengths. Fig. 13.1 sh
shows typical acid response curves.

Acid Volume Requirement

The acid volume should be high enough to remove near
near-wellbore
wellbore formation damage and low
enough to reduce cost of treatment. Selection of an optimum acid volume is complicated by the
competing effects.
s. The volume of acid needed depends strongly on the depth of the damaged
zone, which is seldom known. Also, the acid will never be distributed equally to all parts of the
damaged formation. The efficiency of acid treatment and, therefore, acid volume also depends on
acid injection rate. To ensure that an adequate amount of acid contacts most of the damaged
formation, a larger amount of acid is necessary.

Table 2: Recommended Acid Type and Strength for Sandstone Acidizing

 Figure 1: Typical acid response curve
The acid preflush volume is usually determined on the basis of void volume calculations. The
required minimum acid volume is expressed as

𝑉
𝑉 = +𝑉 +𝑉
𝑋
Where,
Va=the required minimum acid volume, ft3
Vm=volume of minerals to be removed, ft3
VP=initial pore volume, ft3
𝑉 = 𝜋(𝑟 − 𝑟 )(1 − ∅)𝐶

𝑉 = 𝜋(𝑟 − 𝑟 )∅

ra=radius of acid treatment, ft

rw=radius of wellbore, ft
φ=porosity, fraction
Cm= mineral content, volume fraction.
Example Problem1. A sandstone with a porosity of 0.2 containing 10 v% calcite (CaCO3)is to
be acidized with HF/HCl mixture solution. A preflush of 15 wt% HCl solution is to be injected
ahead of the mixture to dissolve the carbonate minerals and establish a low-pH environment. If
the HCl preflush is to remove all carbonates in a region within 1 ft beyond a 0.328-ft radius
wellbore before the HF/HCl stage enters the formation, what minimum preflush volume is
required in terms of gallon per foot of pay zone?
Acid Injection Rate and Pressure

There is always an upper limit on the acid injection rate that is imposed by formation
breakdownfracture) pressure pbd. Assuming pseudo-steady-state flow, the maximum injection
rate limited by the breakdown pressure is expressed as

4.917 × 10 × 𝑘ℎ(𝑃 − 𝑃 − ∆𝑃 )
𝑞 = .
𝜇 (𝑙𝑛 + 𝑆)

where

qi = maximum injection rate, bbl/min

k = permeability of undamaged formation, md

h = thickness of pay zone to be treated, ft

pbd = formation breakdown pressure, psia

p = reservoir pressure, psia

Δpsf = safety margin, 200 - 500 psi

μa = viscosity of acid solution, cp

re = drainage radius, ft

rw = wellbore radius, ft

S = skin factor, ft.

The acid injection rate can also be limited by surface injection pressure at the pump available to
the treatment. This effect is described in the next section.
In most acid treatment operations, only the surface tubing pressure is monitored. It is necessary
to predict the surface injection pressure at the design stage for pump selection. The surface
tubing pressure is related to the bottom-hole flowing pressure by

psi = pwf -Δph+ Δpf

where

psi = surface injection pressure, psia

pwf = flowing bottom-hole pressure, psia

Δph = hydrostatic pressure drop, psia

Δpf = frictional pressure drop, psia.

The following approximation may be used for the frictional pressure drop calculation

518𝜌 . 𝑞 . 𝜇 .
∆ = 𝐿
1000𝐷 .

Where,

ρ = density of fluid, g/cm3

q = injection rate, bbl/min

μ = fluid viscosity, cp

D = tubing diameter, in.

L = tubing length, ft.

Example Problem 2. A 60-ft thick, 50-md sandstone pay zone at a depth of 9500 ft is to be
acidized with an acid solution having a specific gravity of 1.07 and a viscosity of 1.5 cp down
a2-in. inside diameter (ID) coil tubing. The formation fracture gradient is 0.7 psi/ft. The wellbore
radius is 0.328 ft. Assuming a reservoir pressure of 4000 psia, drainage area radius of 1000 ft,
and a skin factor of 15, calculate

1. the maximum acid injection rate using safety margin 300 psi.

2. the maximum expected surface injection pressure at the maximum injection rate.
CARBONATE ACIDIZING DESIGN

The purpose of carbonate acidizing is not to remove the damage to the formation near the
wellbore, but to create wormholes to bypass the damage region and through which oil or gas will
be produced after stimulation. Fig. 2 shows wormholes created by acid dissolution of limestone
in a laboratory

Figure 2: Wormhole created by acid dissolution of lime stone

Carbonate acidizing is a more difficult process to predict than sandstone acidizing because the
physics is much more complex. Because the surface reaction rates are very high and mass
transfer often plays the role of limiting step locally, highly non uniform dissolution patterns are
usually created. The structure of the wormholes depends on many factors including flow
geometry, injection rate, reaction kinetics, and mass transfer rates. Acidizing design relies on
mathematical models calibrated by laboratory data.

SELECTION OF ACID

HCl is the most widely used acid for carbonate matrix acidizing. Weak acids are suggested for
perforating fluid and perforation cleanup, and strong acids are recommended for other
treatments.
Table 3 lists recommended acid type and strength for carbonate acidizing.

Table 3: Recommended Acid Type and Strength for Carbonate Acidizing

All theoretical models of wormhole propagation predict deeper penetration for higher acid
strengths, so a high concentration of acid is always preferable.

ACIDIZING DESIGN FOR CARBONATE RESERVOIR

Acidizing design parameters include acid volume, injection rate, and injection pressure. The acid
volume can be calculated with different methods as mentioned earlier, such as Daccord’s
wormhole propagation model or the volumetric model, on the basis of desired penetration of
wormholes.

Based on the wormhole propagation model presented in Eq. (13.10) by Daccord et al. (1989),the
required acid volume per unit thickness of formation can be estimated using the following
equation:

/ /
𝜋∅𝐷 𝑞ℎ 𝑟 ℎ
𝑉ℎ =
𝑏𝑁

On the other hand, based on the volumetric model, the required acid volume per unit thickness of
formation can be estimated using the following equation:

𝑉ℎ = 𝜋∅(𝑟 ℎ − 𝑟 )𝑃𝑉
Example Problem 3: A 28 wt% HCl is needed to propagate wormholes 3 ft from a 0.328-
ftradius wellbore in a limestone formation (specific gravity 2.71) with a porosity of 0.15. The
designed injection rate is 0.1 bbl/min-ft, the diffusion coefficient is 1029 m2/sec, and the density
of the 28% HCl is 1.14 g/cm3. In linear core floods, 1.5 pore volume is needed for wormhole
breakthrough at the end of the core. Calculate the acid volume requirement using (1) Daccord’s
model and (2) the volumetric model.
ACID FRACTURING

Matrix acidizing in carbonate formation discussed in the previous sections targets the near-
wellbore region, one to several feet into the formation, by injecting acid into the formation rocks
below the fracturing pressure. In some of the carbonate formations, where the original
permeability is low or the damage penetrates deeper into the formation, acid fracturing
treatments can be applied. Unlike matrix acidizing, acid fracturing treatments are composed of
several pumping steps. First, a pad stage containing high viscosity fluid will be pumped to create
fractures inside the formation. Then acid is injected into the fractures, whose surfaces are etched
by acid. Unlike hydraulic fracturing, proppant is not used to keep fractures open. Instead, when
pumping stops, fractures will close. The conductivity of acid fractures depends on the
nonuniform etching pattern of rock surfaces. Due to the acid distribution in the fracture and rock
heterogeneity, the reaction and etching on rock surfaces can be uneven, which leads to small,
open channels after fracture closure. These channels can provide higher conductivity compared
to the original matrix permeability, as shown in Fig. 2

Figure 2: Conductivity of Acid fractures

The conductivity of acid fractures is decided by these open channels, which strongly depends on
acid distribution in the fractures, acid penetration depth, acid leak-off through fractures’ walls
and reaction rate of acid with carbonate rock. In general, to achieve better performance of acid
fracturing treatments, the design needs to allow acid to penetrate deeply into the fractures,
enough time for acid to react with fracture surfaces and control leak-off acid through fracture
surfaces.
To predict the conductivity of acid fractures, Nierode and Kruk (1973) developed a correlation
based on experimental results. The conductivity of acid fractures can be calculated by the
following equations:

wkf is the acid fracture conductivity in md-in, S is the fracture closure stress in psi, DREC is the
dissolved rock equivalent conductivity in md-in and RES is the rock embedment strength in psi.

However, by comparing to field-measured conductivity, the disagreement between the N-K

correlation and measured data sometimes is large, because the N-K correlation is based on
experimental data from small core samples.

A new correlation to predict the conductivity of acid fractures was developed by Deng et al.
(2012) based on statistical variations of the formation properties. The fracture conductivity at
zero closure stress for permeability-distribution-dominant cases can be presented as

where λD is the normalized correlation length, σD is the normalized standard deviation, and w is
the average fracture width in inches. λD and σD can be quantified by using the semi-variogram
model. For high leakoff coefficient ( . 0.004 ft/(min)0.5), the average width can be predicted by
For the medium leakoff coefficient (B0.001 ft/(min)0.5) with uniform mineralogy distribution

Then the correlation for overall fracture

Where σc is the closure stress in psi and E is Young’s modulus in Mpsi.