Sandstone acidizing

Dissolving power on mass basis is termed as gravimetric dissolving power

stoichiometry number of
mineral
molecular weight of mineral
weight fraction of acid in the
acid solution
molecular weight of acid

Gravimetric dissolving power of acid stoichiometry number of

solution, lbm mineral/lbm solution acid

For the reaction between 15 wt% HCl solution and CaCO3, Ca =0.15, νa = 2, νm =1
MWm = 100.1, and MWa = 36.5.
 Volumetric dissolving power of acid density of acid, lbm/ft3
solution, ft3 mineral/ft3 of solution

density of mineral, lbm/ft3

Generally, the reaction rate is affected by the characteristics of mineral, properties of acid,
reservoir temperature, and rates of acid transport to the mineral surface and removal of
product from the surface.

1. Selection of Acids

• The acid type and acid concentration is selected on the basis of minerals in the formation
and field experience.
• For sandstones, usually - a mixture of 3 wt% HF and 12 wt% HCl, preceded by a 15 wt% HCl
preflush.
• Conduct laboratory tests on the cores to analyse response to different acid strengths
 Acid volume requirement (Guo et al.)
• Volume of acid should be high enough to remove near wellbore formation damage
and low enough to reduce cost of treatment.
• Volume of acid depends on depth of damaged zone (rarely known)
• Acid treatment efficiency and acid volume depends on acid injection rate.
• On the basis of void volume calculations , minimum acid volume is given by
Va = the required minimum acid volume, ft3
Vm = volume of minerals to be removed, ft3
VP = initial pore volume, ft3

ra = radius of acid treatment, ft ; rw = radius of wellbore, ft

φ = porosity, fraction ; Cm = mineral content, volume fraction.
Remark:
1. Economides and Nolte (2000) suggested taking the initial pore volume within the radius of treatment
as the minimum required acid volume for the main stage of acidizing treatment. Additional acid volume
should be considered for the losses in the injection tubing string.

2. For calculating minimum acid volume required, commonly used method is the two-mineral model
(Hekim et al., 1982; Hill et al., 1981; Taha et al., 1989). This model requires a numerical technique to obtain
a general solution. Schechter (1992) presented an approximate solution that is valid for Damkohler number
being greater than 10.
Example:
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?

(Volume of CaCO3 to be removed)

0.42 ft3 CaCO3/ft pay zone

0.082 ft3 CaCO3/ft3 15 wt% HCl solution

6.48 ft3 of 15wt% HCl solution/ft pay zone

Effect of acid injection rate on acid concentration and reaction front.
 Acid injection rate:

Note:
• There is always an upper limit on the acid injection rate that is imposed by formation
breakdown (fracture) pressure Pbd. Assuming pseudo–steady-state flow, the maximum
injection rate limited by the breakdown pressure is expressed above.
• The acid injection rate can also be limited by surface injection pressure at the pump
available to the treatment.
Acid injection pressure:

The surface tubing pressure is related to the bottom-hole flowing pressure by:

(Economides and Nolte, 2000)

psi = surface injection pressure, psia

pwf = flowing bottom-hole pressure, psia
∆Ph = hydrostatic pressure drop, psia
∆Pf = frictional pressure drop, psia
A 60-ft thick, 50-md sandstone pay zone at a depth of 9,500 ft is to be acidized with an
acid solution having a specific gravity of 1.07 and a viscosity of 1.5 cp down a 2-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 4,000 psia, drainage area radius of 1,000 ft,
and a skin factor of 15. Determine:
(a) the maximum acid injection rate using safety margin 300 psi.
(b) the maximum expected surface injection pressure at the maximum injection rate.

??

Solve above problem using

Safety margin of 400 psi.
Carbonate Acidizing

Hydrochloric acid is a strong acid, meaning that when HCI is dissolved in water, the acid
molecules almost completely dissociate to form hydrogen ions, H+, and chloride ions, Cl-.
The reaction between HCI and carbonate minerals is actually a reaction of the H+ with
the mineral. With weak acids, such as acetic or formic acid, the reaction is also between
H+ and the mineral, with the added complication that the acid is not completely
dissociated, thus limiting the supply of H+ available for reaction. Because H+ is the
reactive species, the kinetics for the HCI reaction can also be used for weak acids by
considering the acid dissociation equilibrium.
Wormholes form in a dissolution process when the large pores grow at a rate substantially
higher than the rate at which smaller pores grow, so that a large pore receives an
increasingly larger proportion of the dissolving fluid, eventually becoming a wormhole.
This will occur when the reactions are mass transfer limited or mixed kinetics prevail, that
is, the mass transfer and surface reaction rate are similar in size. For flow with reaction
in a circular pore, the relative effects of mass transfer and surface reaction rates can be
expressed by a kinetic parameter, P, the inverse of the Thiele modulus, defined as the ratio
of the diffusive flux to the flux of molecules consumed by surface reaction (Daccord,1989).
The natural tendency for wormholes to form when reaction is mass transfer limited has
been demonstrated theoretically by Schechter and Gidley (1969). In this model, the
change in the cross-sectional area of a pore can be expressed as

where A is the pore cross-sectional area, t is time, and I is a pore growth function that
does depend on time. If n > 0, smaller pores grow faster than larger pores and
wormholes cannot form; when n < 0, larger pores grow faster than smaller pores, and
wormholes will develop. From an analysis of flow with diffusion and surface reaction in
single pores, Schechter and Gidley found that n = 1/2 when surface reaction rate
controls the overall reaction rate, and n = -1 when diffusion controls the overall
reaction rate.
On the basis of desired penetration of wormholes the acid volume can be calculated
with two methods:
(1) Daccord’s wormhole propagation model
(2) Volumetric model
Using Daccord’s model, the required acid volume per unit thickness of formation can be
estimated
 Volumetric model

(PV)bt = number of pore volumes of acid injected at the time of wormhole

breakthrough at the end of the core. Apparently, the volumetric model requires
data from laboratory tests.
Example:
A 28 wt% HCl is needed to propagate wormholes 3 ft from a 0.328-ft radius 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 10-9 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 (a)
Daccord’s model and (b) the volumetric model.

Note: If the acid volume is constrained, a

slower injection rate may be preferable. If a
sufficient acid volume is available, the
maximum injection rate is recommended for
limestone formations. However, a lower
injection rate may be preferable for dolomites.
This allows the temperature of the acid
entering the formation to increase, and thus,
the reaction rate increases.

??
Solve for dolomite formation.
 Fracture loss limit
In this section, aim is to describe wormhole geometry when fluid loss is critical feature of the
process. In case of high fluid loss rates, it is established for acid fracturing that diffusion of
the acid can be neglected.
Equations given below provides estimation of wormhole radius and length at a given time
in the limit of high fluid loss. Considered model is circular wormhole of uniform radius R and
Length l. Both depend on time.
Volume of acid entering the wormhole per unit time is qo
Rp is the initial pore radius
CR is fluid loss coefficient
t is time

Example:
Acid fracture Conductivity

• The conductivity (kf w) of an acid fracture is difficult to predict (empirical approach).

• The amount of rock dissolved in an acid fracture is represented by a parameter called
the ideal width, wi, defined as the fracture width created by acid dissolution before fracture closure.
• If all the acid injected into a fracture dissolves rock on the fracture face (i.e., no
live acid penetrates into the matrix or forms wormholes in the fracture walls), the average ideal width
is simply the total volume of rock dissolved divided by the fracture area.

X = volumetric dissolving power of the acid

V = the total volume of acid injected
h = fracture height,
Xf = is the fracture half-length
By Nierode and Kruk (1973) based on extensive laboratory studies:
From the ideal fracture width, the conductivity of an acid fracture is determined
Correlates conductivity with ideal width ,the closure stress ( ) and the rock embedment
strength( ).

Kf w is in md-ft, wi is in inch., and are in psi.

The rock embedment strength - is the force required to push a metal

sphere a certain distance into the surface of a rock sample.
Economides, M.J., Hill, A.D., and Ehlig-Economides, C. Petroleum Production Systems. Englewood Cliffs,
NJ: Prentice Hall, 1994.
Economides, M.J. and Nolte, K.G. Reservoir Stimulation, 3rd edition. New York: John Wiley & Sons, 2000.
Fogler, H.S. et al. Predicting the flow and reaction of HCl/HF mixtures in porous sandstone cores. SPEJ
Oct. 1976, Trans. AIME, 1976;234:248–260.
Hekim, Y. et al. The radial movement of permeability fronts and multiple reaction zones in porous media.
SPEJ Feb. 1982:99–107.
Hill et al. Theoretical and experimental studies of sandstone acidizing. SPEJ Feb. 1981;21:30–42.
Guo et al. Petroleum Production Engineering. Elsevier Science & Technology Books.

For teaching purpose only