IN THE NAME OF GOD

Petroleum Production Engineering1

Acidizing
M.H.Ghazanfari
Introduction
 It is a technique to stimulate wells for improving well inflow
performance.
 Most wells are stimulated either as part of initial completion or
later in production life.
 Productivity is improved by:
 Removing formation damage and increasing permeability in
near wellbore area.(Matrix Acidizing or Matrix Treatment)
 Creating a conductive fracture extending from the wellbore
into the reservoir.(Fracturing or Acid Fracturing)
 Acid acts by dissolving minerals that make up the original
formation matrix, as well as pore‐plugging materials that
result from mud invasion or fines migration.
Introduction
 In matrix acidizing, acid is injected into the formation below
formation fracturing pressure, resulting in radial flow into
formation.
 Acid reacts with pore walls and throats, enlarging them and
also dissolves acid soluble clay and other fines.
 Acidizing is usually designed to create a reacting front that
will reach the estimated radius of formation damage.
 The aim is to restore the original formation permeability or
enhance existing permeability.
 The acid volume should be high enough to remove possible
near wellbore damages.
Acidizing Carbonate Reservoirs
limestone and dolomite
 HCl is generally used alone, and the acid dissolves the rock
matrix, allowing dispersion of plugging materials.
 Normally 15% HCl by weight acid is used However,
concentrations of 5 to 37 % can be used.
 Volumes of 50 to 250 gal/ft. are usually sufficient to remove
damage 3‐5 ft. from the wellbore.
 Penetration of acid into carbonate reservoirs is usually
non‐uniform because of the heterogeneous nature of the
formations.
 Pore space in carbonates is a combination of vugs and hairline
fractures.
 HCl is sometimes added to water thickened with polymer to
increase viscosity
Acidizing Sandstone Reservoirs
 In sandstone reservoirs treatment Is usually performed with a mixture
of hydrofluoric(HF) and hydrochloricacids(HCl) , typically 3% HF
and12%HCl.
 This is called mud acid by Dowell/Schlumberger.
 The HF reacts with the quartz(silicondioxide), and other
silicates(including feldspars and clay minerals present in the
sandstone).
 The HCl reacts with any carbonate materials present such as the
cementing agents commonly found in sandstone.
 The acid reacts to a great extent , with plugging materials , rather
than with the rock matrix because of the large surface area of the
plugging materials.
 Usually , injection of 50 to 250gal/foot of production interval is
sufficient to remove damage near the wellbore.
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
hydrochloric acid (HCl) and hydrofluoric acid (HF).
 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.
Carbonate –Acid 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.
 A. HCl + Carbonate Rock
 B. 2HCl + CaCO3 ←→ CaCl2 + H2O + CO2↑ (calcite)

 C. 4HCl + CaMg(CO3)2 ←→ CaCl2 + MgCl2 + 2H2O+

2CO2↑ (dolomite)
 D. 2HCl + MgCO3 ←→ MgCl2 + H2O + CO2↑ (dolomite)

 E. 2HCl + FeCO3 ←→ FeCl2 + H2O + CO2↑ (siderite)

Sandstone Acid Reactions
 A. HF + sandstone matrix minerals
 1. SiO2 + 4HF ←→ SiF4 + 2H2O (quartz) SiF4 + 2HF
←→ H2SiF6 (fluosilicic acid)
 2. NaAlSi3O8 + 22HF ←→ 3H2SiF6 + AlF3 + NaF +
8H2O (sodium feldspars)
 B. HF + calcireous minerals
 1. 2HF + CaCO3 ←→ CaF2↓ + CO2↑ (calcite)
Primary Chemical Reactions in
Acidizing
Potential HF Acid Issues
 Fluosilicicacid H2SiF6 produced by the reactions may
subsequently react with ions of sodium (Na+) and
potassium (K+) to produce insoluble salts.
 When concentration of HF becomes very low, the
fluosilicicacid can decompose yielding silicon tetra
fluoride SiF4which undergoes hydrolysis to yield
precipitation of silicic acid Si(OH)4.
 Salt precipitation occurs when HF contacts calcium ions
Ca++producing insoluble calcium fluoride CaF2.
Deep Penetration with HF Acid
 Where damage in sandstone reservoirs is due to
migration of clay particles, acid may need to
penetrate deep into the formation. Fluoboricacid may
be used as it forms HF slowly as it is hydrolyzedin
aqueous solution (HBF4).
 Alternatively, a staged injection of NH4F followed by
HCl causes gradual generation of HF. In either case,
HF is formed slowly and the reaction can proceed
deeper into the formation.
Considerations for a Matrix Acid
Treatment
 Acids must react with specific rock matrix and
plugging materials to yield soluble products
 Products resulting from primary acid-rock reactions
do not react with each other or with formation
materials to create insoluble precipitates.
 The reaction rate should be controlled to yield a
desirable acid penetration and favourable porosity
and permeability distribution.
Common Acid Problems
 When ferric ions (Fe3+) are present, they can
precipitate from spent acid solutions as Fe(OH)3when
the pH is greater than 2. Ferric ions may result from
dissolution of iron‐bearing formation minerals or may
derive from the dissolution of rust in the tubing by the
acid solution.
 Sequestering agents, normally EDTA, can be added
to the acid solution to prevent precipitation of Fe(OH)3
but these must be used with caution as they can cause
precipitates of their own.
 Corrosion inhibitors should be used to prevent
damage to tubing and casing.
Common Acid Problems
 Mutual solvent –usually ethylene glycol monobutylether
EGMBE, added to the post flush to remove corrosion
inhibitor absorbed on formation surfaces and to restore
water‐wet conditions
 In some reservoirs, contact of crude oil by acid can cause the
formation of asphaltenic sludges.
 Simple bottle tests can be done in the lab prior to acidizing
to check for incompatibility between the formation crude
and the planned acid treatment solution.
 When sludge formation is a problem, emulsions of acid in
aromatic solvents or surfactants have been used to prevent
asphaltene precipitation.
Dissolving Power of Acids
 A convenient way to express reaction stoichiometry is with the
dissolving power , wish expresses the amount of mineral that
can be consumed by a given amount of acid on a mass.
 The dissolving power on a mass basis is called gravimetric
dissolving power and is defined as:

 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
Dissolving Power of Acids
 The dissolving power on a volume basis is called volumetric
dissolving power and is related to the gravimetric dissolving
power through material densities:

 Where:
X: volumetric dissolving power of acid solution , ft3 mineral/ft3
solution
ρa: density of acid , lbm/ft3
ρm: density of mineral , lbm/ft3
Example
Dissolving Power of Acids

For the reaction between 15 wt% HCl solution and

CaCO3, Ca= 0.15, Vm=1, Va= 2, MWm= 100.1,
and MWa= 36.5 . Thus,
β100= 1.37 lbm CaCO3/lbm HCl
β15= 0.21 lbm CaCO3/lbm HCl 15%
Sandstone Acidizing Design
Selection of Acid
 Remove the damage near the wellbore that occurred
during drilling and well completion processes.
 Acidizing is only necessary when it is sure that formation
damage is significant 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
 The acid type and acid concentration is selected on the
basis of minerals in the formation.
 For sandstones , the typical treatments usually consist of
a mixture of 3wt%HF and12wt%HCl , preceded by
a15wt%HCl preflush.
Sandstone Acidizing Design
Selection of Acid
 Recommended Acid Type and Strength for Sandstone
Acidizing: (McLeod, 1984, presented a guideline to the
selection of acid on the basis of extensive field experience):
Sandstone Acidizing Design
Acid Volume Requirement
 The acid volume should be high enough to remove near wellbore
formation damage and low enough to reduce cost of treatment.
 Selection of an optimum acid volume is complicated by the
competing effects . The volume of acid needed depends strongly on
the depth of the damaged zone , which is seldom known.
 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.
Sandstone Acidizing Design
Acid Volume Requirement
 The acid preflush volume is usually determined on the basis of
void volume calculations . The required minimum acid volume is
expressed as:

 Where:
Va : the required minimum acid volume , ft3
Vm : volume of minerals to be removed , ft3
Vp : initial pore volume , ft3
Sandstone Acidizing Design
Acid Volume Requirement

 Where:
Cm : mineral content , volume fraction
ra : radius of acid treatment , ft
rw : wellbore radius , ft
φ: porosity , fraction
Example
 A sand stone with a porosity of 0.2
containing10v%calcite(CaCO3) is to be acidized with
HF/HCl mixture solution . A preflush of 15wt%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 within1ft 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 payzone?
Example
 Solution:
 Volume of Caco3 to be removed:

 Initial pore volume:

 Gravimetric dissolving power of 15%wt HCL solution:

Sandstone Acidizing Design
Acid Injection Rate
 Acid injection rate should be selected on the basis of mineral
dissolution and removal and depth of damaged zone.
 In producing wells, spent acid should be produced back
immediately to minimize precipitation of reaction products
 High rate gives less reaction time to remove materials
causing damage, but also moves spent acid rapidly away so
as to minimize potential damage from insoluble precipitates.
 Selecting an optimum injection rate is a difficult process
because the damaged zone is seldom known with any
accuracy and the competing effects of mineral dissolution
and reaction product precipitation.
Sandstone Acidizing Design
Acid Injection Rate
 The maximum injection rate limited by the breakdown(fracture)
pressure is expressed as:

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 pressure , 200 to 5000 psia
Sandstone Acidizing Design
Acid Injection Pressure
 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
Psi : surface injection pressure , psia
Pwf : flowing BHP , psia
ΔPh : hydrostatic pressure drop , psia
ΔPf : frictional pressure drop , psia
Sandstone Acidizing Design
Acid Injection Pressure

ρ: density of fluid , g/cm3

q: injection rate , bbl/min
μ: fluid viscosity , cp
D: tubing diameter , in.
L: tubing length , ft
Example
 A 60‐ft thick , 50‐md sandstone pay zone at a depth
of 9,500ft is to be acidized with an acid solution
having a specific gravity of1.07 and a viscosity
of1.5cp down a2‐in.Inside diameter(ID) coiltubing .
The formation fracture gradient is 0.7psi/ft . The
wellbore radius is 0.328ft . Assuming a reservoir
pressure of 4,000psia , drainage area radius of
1,000ft , and a skin factor of 15 ,calculate:
 (a)the maximum acid injection rate using safety
margin 300psi.
 (b)the maximum expected surface injection pressure
at the maximum injection rate.
Example
 Solution:
 The minimum acid injection rate:

 The maximum expected surface injection pressure:

Carbonate Acidizing Design
Acid Injection Pressure
 The purpose of carbonate acidizing is not to remove the
damage to the formation near the wellbore , but to create
wormholes through which oil or gas will flow after
stimulation.
 Reactions much more rapid than sandstones . Often a few
large channels are opened up(wormholes) in which size and
orientation of these difficult to predict or control.
 The surface reaction rates are very high and mass transfer
often plays the role of limiting step locally.
 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.
Carbonate Acidizing Design
Acid Injection Pressure
 Below you can find the figures of wormholes created by acid
dissolution of limestone(Hoefner and Fogler,1988) HCl most
often used–no precipitation reactions
occur in carbonates as found
in sandstones.
 Other weaker acids can be
used if corrosion is a problem
eg.acetic and formic acid.
Carbonate Acidizing Design
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 .
All theoretical models of wormhole propagation predict deeper
penetration for higher acid strengths , so a high concentration of
acid is always preferable.
 Recommended Acid Type and Strength for Carbonate Acidizing are
as(McLeod,1984):
Carbonate Acidizing Design
Acid Volume Requirement
 The acid volume can be calculated using :
(1) Daccord’s wormhole propagation model:

Vh : required acid volume per unit thickness of formation , m3/m

φ : porosity , fraction
D : molecular diffusion coefficient , m2/s
qh : injection rate per unit thickness of formation , m3/sec-m
rwh : desired radius of wormhole penetration , m
df =1.6 , fractal dimension
b=1.05*10-5 in SI units
Carbonate Acidizing Design
Acid Volume Requirement

Nac : acid capillary number , dimensionless

γa : acid specific gravity
γm : mineral specific gravity
Carbonate Acidizing Design
Acid Volume Requirement
 The acid volume can be calculated using:
(2) the volumetric model , on the basis of desired penetration
of wormholes.
 Based on the volumetric model , the required acid volume per
unit thickness of formation can be estimated using the following
equation:

Where (PV)bt is the number of pore volumes of acid injected at

the time of wormhole breakthrough at the end of the core.
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 10‐9m2/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.
Example
 Solution:
(a) Daccord’s model:
Example
(b) Volumetric model:
THE END