Acidizing
Physics
13
13-l INTRODUCTION
Matrix acid&&g is a stimulationtreatmentusedto remove
damagenear the wellbore. It involves the injection of a
reactive fluid (normally an acid) into the porous medium
at a pressurebelow the fractoring pressore.The fluid dis-
solvessomeof theporous mediom and, consequently,ti-
creasesits permeability. In this chapter,physical aspects
of various phenomenainvolved in thesetreatmentsare
presentedwith a description of how they are modeled.
A detailed study of chemical hydrodynamics can be
found in Levich (1962). More general information on
acidiiing appearsin the SPEmonograph(Williams et sl.,
1979).
The design of a treatment requires a basic knowledge
of all the phenomenainvolved. These include:
* a chemicalreactionbetweena fluid and various solids.
. the flow of a liquid through a porous medium. Its iti-
tial statemustbe known (composition,permeabilitypro-
file, water satoration, wettability).
l possible instabilities; i.e., nonpistonlike displacement
of the satmating liquid by the treatment fltid. Well-
known manifestationsof such instabilities are viscous
fmgering and wormholing. They may occur as a result
of:
. the natural permeability gradient of the rock (the
damageis concentratedaround the wellbore),
. hydrodynamic and/or capillary forces (viscous fin-
gering of the low-viscosity acid through the high-
viscosity oil and/or imbibition of the wetting acid
into the water-wet rock),
- the permeabilitygradientinducedby the dissolution.
l In manycases,a comvmationof the abovephenome-
na may occur.
Discussedin Section 13-2 is the reaction itself and its
kinetics. Its coupling with flow is presentedin Section
G&ard Daccord
Dowel1 Schlumberger
13-3. At that point a model of sandstoneacidiziig can
be built. The problem of instabiities occurring during
thesetreatments(k&abilities that appearmainly in car-
bonate acidizing) is addressedin Section 13-4. Practical
applicationsto sandstoneand carbonateacid?& are dis-
cussedin later sections.
It is commonfor shorttreatmentssuchasthese(thenor-
mal duration is a few hours) to negl&t gravity and any
flow causedby concentrationgradients. The samesim-
plitications are made here.
13-2 SOLID-LIQUID REACTION UNDER
NO-FLOW CONDITIONS
A chemical reaction betweenhvo moleculestakes place
when they come in contact and have enough energy to
overcome. the activation barrier. Two extreme casescan
be identified.
The activationenergybarrier is very low andevery col-
lision success~y resultsin a reaction. The global rate
of the reaction is then limited only by the number of
contacts.
In the caseof a very high activationenergy,only a small
number of moleculesin contact will react. The kinet-
ics of the reaction is then directly limited by the ener-
gy bar&r.
The first caseis applicablein most gas-phasereactions
becausetheBmwnianenergyof themoleculesis very high.
The molecular diffosion is then controllmg the kinetics
andthesereactionsare saidto be diffosion limited or mass
transfer limited.
On the otherhand,manychemicalreactionstaking place
in the liquid phasehave a very high activation energy.
Molecular diffision, although it is slowed substantially
in comparisonwith the gasphase,is no longer the limit-
ing step. This type of kinetics is called reaction limited.
13-l
 Heterogeneousreactions(a solid reacting with a fluid)
do not display any particular differencesexceptthat only
one of the two reactingmoleculescan mow. The overall
kinetics may be either masstransferlimited (whenthe ac-
tivation energyis small)or reactionlimited. Smcethe reac-
tion must takeplaceat the interfacebetweenthe solid and
the liquid, this secondtype of reaction is often referred
to as surface reaction limited.
13-2.1 Surface-Reaction-Limited Kinetics
The rate of the reaction,expressedasthe numberof moles
of reacting molcculcs per unit of time, qS (in mole.
see-‘), is
qs=kjACm (13-l)
where C is the concentrationof the reactantin the liquid
phase(mole/liter), kj is the reactionrate constant[moleYm
1iP cm-’ set-‘1, A is the area of the solid (cmz), and
rn is the order of the reaction (dimensionless).
This relation is valid if molecular diffusion is not ins
portan%i.e., when the concentration is uniform every-
where: Ciactime= CbulkThe simplestreactionshave an
order rn equalto unity: the rate is simply proportional to
the concentration. Orders different from unity indicate
complexreactionmechanisms,which are outsidethe scope
of this writing.
More complex situations occur when the reaction is
reversible; i.e., the conversion of the reactants into
products is not complete as a result of the accumulation
of theproducts.This is especiallyimportantfor carbonates
and organic acids (e.g., acetic acid):
caco3 + x!n~ coon + ca (cl-l2 coo)2 + co2 + n2 0.
Carbon dioxide (COz) is a weak acid in water and pre-
vents the complete dissociation of acetic acid, which is
also a we& acid. Thus, Eq. 13-1, describing the reac-
tion kinetics, must be modified accordingly.
13-2.2 Mass-Transfer-Liited Kin&a
Nernst (1904) tirst wrote the equationdescribing the ki-
netics of mass-transfer-limitedheterogeneousreactions:
where qd is the nmber of moles reactingper unit of tie
(mole. SC-‘), C is the concentration of the reactant
(mole/liter),D is the diflGion constantof the rea&nt (cm2
see-‘), A is the area (cmz)and 8 is a characteristiclength
constant (cm).
13-2
Nernst’s law assumesimplicitly that the concentration
at the interface is equalto zero. The constant6 represents
the thicknessof the zonesurroundingthe solid where the
concentrationvaries from C (in the bulk) to zero (at the
interface);i.e., the distancethroughwhich moleculardiffi~-
sion is the main phenomenon.
Writing the mass conservationequation for the reac-
tant leads to the diffision equationthat governsthe local
concentration (Levich, 1962):
-cac DV’C. (13-3)
at
13-2.3 Mixed Kinetics
In a generalizedcase, the concentration is not uniform
nor doesit go down to zero at the solid/liquid interface.
Both phenomena,molecular diffusion and surfacekinet-
ics, must then be considered.This caseof intermediate
or mixed kinetics can be quantified by a dimensionless
kinetic parameterP, defmed as the ratio of the flux of
moleculesprovided by molecular diffusion (Q) over the
flux of moleculesconsumedby tie surfacereaction (qJ:
D
p= ~ qd = (13-4)
qs
Mass-transferkinetics correspondsto P - 0, and sur-
face kinetics correspondsto P - OJ.The reciprocal of
P is known in chemicalengineeringas the Thiele module.
13-2.4 Actual Rocks
Acti rocks display a large range of reactivities with
acids. On the other hand, the molecular diffusion con-
stant, D, is always of the same order (around IO-’
cm%ec in water). Thus, P varies dependingon kf Ta-
ble 13-I summarizesP values for common systemsof
rock/acid%calculatedfrom m and kj data found in litera-
ture, and for a pore of radius 1 mm fdled with a normal
acidic solution.
From the resultsshownin Table 13-1, it canbe deduced
that:
- the reaction of liiestone is limited by masstransfer (P
< 1);
. for dolomite, the kinetics is surface reaction limited,
but an increaseof temperatie switchesit to masstrans-
fer limited (refer to next subsection);
* for claysandquarlz,thekineticsare almostalwayslimit-
ed by surface reaction.
 4 References
Lim&one/HCl 7 x 10-e
9.4 x 10-S.
1.25 X lo-’
3x10-8
1.5 x10-9
1.5 x 10-10
3.7 x 10-e
*Value extrapolated from published data.
**The rea.Uivitv for ouartz is taken as one-v&h
Table 13Ml-Exam~le of dimensionless reaction param&r
with D = 5 x lo- cm%x?c, 6 = 1 mm, and C= 1 N.
13-2.5 Temperature Effects
Temperatore has a dramatic effect on P becauseit is
proportional to the ratio D/k? Both constantsobey ap-
proximately an Arrhcnius-typerelation. However, the ac-
tivation energiesassociatedwith each phenomenonare
very different: for chemical reactions, it is between 10
and20 kcal mole-‘; it is muchlower for mok?culardiffw
sion (a few kcal mole-‘). Thus, the ratio D/kj decreases
strongly when the temperatureincreases:at low ternper-
mm, surfacereactionmay limit the kinetics,but at higher
temperahuesthe kinetics may becomemasstransferlimit-
ed. The best example is the system dolomiWHC1, for
which P > 1 at room temperatureandP < 1 at high tem-
peratares.
13-2.6 Stoichiometry
Until now, only the kinetic aspectof the reactionhasbeen
discussed. Stoichiometry describes the number of
moleculesrequired for the dissolution of a given amount
of solid; i.e., the limiting sitaation at equilibrium - the
kinetics describesthe way this equilibrium is reached.
The stoichiometic coef&ients can be easily obtained
when the solid andliquid are well defined, asin the reac-
tion behveenlimestoneor dolomiteandhydrochloric acids
CaCOs+ 2 HCl - CaCl* + CO2+ Hz0
CaMg(CO& -4.4HCl - Car& -I MgCl* + 2 CO2+ 2 HZO.
Knowing that the molecularweightsof CaC03 andHCl
are 100 and 36.5, respectively, it can easily be calculat-
ed that 1 ltr of 15% hydrochloric acid (by weight) can
dissolve 220 g of pure limestone.
P
N&ode and I 0.07
Williams (1973)
Lund et al. (1973) 0.005
Lund et al. (1973) 4
Busenberg and 13
Plummer (1982)
Lund et al. (1973) 3Q0
** 3000
Williams et al. (1979) 0.13
that of feldsoar. 1Lund et al., 19731.
P values for different systems at 25%
For more complex minerals, suchas mixtares of clays
that form various products on reaction with hydrofluoric
acid, avenge v&es for the stoichiometriccoefficien&are
used. For example, the global reaction for kaolin& can
be written:
AlzSiOs(OH)4 + 6 HF + H.&O4 i- 2 AIFY + HzO.
Many other chemical species,such as AlFnc3-“)’ or
fluorinated silicic acids, are in equiliitium with the
productsindicatedby the simple stoichiome&icequation.
13-3 SOLDLIQUID REACTION WITH
A MOVING FLUID
During an actual treatment, the reactive fluid is injected =
at a finite rate through the porous medium. In the two
limiting casesdescribedabove(P = 0 andP = OJ),there
may be different results in imposing a mean velocity u
becausethe basicphysical mechanismsare different. The
primary effectof the flow is to decreasetheboundarylayer
thickness[a rough approximation from Levich (1962) is
6 - ll- with 0.5 < n < 11. The kinetic parameterP
is thusallowedto increasein sucha way that systemsobey-
ing at-rest diffusion-limited kinetics may become con-
trolled by surface reaction.
The latter case is typical of sandstoneacidiiing by
hydrofluoric acid (or mud acid). However, despitethe in-
creasein P, it may still remain very small and molecular
diffusion may sGllbe the limiting phenomenon.This case
is applicableduring carbonateacidiiing and is discussed
later.
13-3
RESERVOlRSl?MlLUZ’ON
13-3.1 Surface-R~ction-L~ted Kim&s
Experimental shxiies on sandstoneacidizmg with linear
coresdo not showany instabilities. Thus, the flow is con-
sideredpiston&e. Since tie kinetics is limited by sur-
face reaction, the reaction rate constant$ is independent
of the velocity. These two facts enable a macroscopic
formulation.
Severalmodels consider either a unique reactive spe-
cies (Lund andFogler, 1976, Fogler andMcCune, 1976)
or severalspecieswith different reactivities(H&m et al.,
1982; Taha et al., 1984). Hii et al. (1981) developedr~
different type of model, but resultswere poor when their
prediction was comparedwith experiments.The main ob-
jective of thesefast modelsis to predict the permeability
profile after the treatment. The main assumptionsare:
1. The porosity ($) changeslittle and for massconser-
vation considerationsit is assumedto be constantand
equal to the initial value, &.
2. Severaldifferent chemical reactionsare considered.
Theseincludethe reactionof a “fast” reactingmineral
(clays)anda “slow” reactingmineral (quarlzmatrix).
The kinetics of eachis surfacelimit&, i.e., the rate
constantskj are independentof the local velocities.
3. The local permeability is related to the local porosi-
ty through an empirical relation of the form:
Or
where ki is the undamagedpermeability. This last as-
sumptionis relevantfor uniform damages;i.e., when the
damagingmaterialcoversuniformly the walls of the pores
and throats of the porous medium. For other types of
damages,s&h asthroatsblocked by bridges of particles,
it may not be applicable.
The rate of variation in conceimation resulting from
convection and reaction is describedby (Hekim et al.,
1982):
,$s+u
at
ac= - 7 kyjqc
YET (13-6)
where u is the mean velocity (fnnction of .x and t), zj is
the sum of the reaction rates over all mineralsj, vj is the
stoichiometriccoefficient for mineralj, and Cj is the con-
centration of mineral j, which obeys a kinetic equation
of the form in Eq. 13-l. (Note that the deli&ions of $
in Eq. 13-l and 13-6 are different).
All initial quantitiesare subscriptedi. Severaldimen-
sionlessparametersmay then be delined.
13-4
. Damkholer numbers (Hekim et al., 1982), Dy>
describingthe kinetics of the reactionbehveenthe acid
and the mineralj. This is the ratio of the reaction rate
over the convection rate (with L being a macroscopic
length andtypically equalto the length of the sample):
kjvjCfL
Daj = ~
l An acid capacitynumber (Hekim et al., 1982),Acj, for
eachmineral describing the stoichiometry of the res.c-
tion between the acid and the mineral j:
Acj = +&-.
1 u
The effect of thesenumbers on the final permeability
profde can be predicted qualitatively. Consider a single
reactive mineral deposited inside a nonreactive matrix
(high reactivity clay inside a low reactivity quartzmatrix).
The permeabilityvariescontinuouslybetweena maximum
value at the wellbore (where Cc&,,= 0) down to the ini-
tial value far from the wellbore (where Cc@ = Cic+,).
Thus, there is a “front” of given thicknessXfiontwith
averageposition.xfim: for x < (xtiW - A&J2), the clay
is completely dissolved. For x > (zG~~~~ + A&&2), no
live acid haspenetrated,only spentacid, s.sshownon Fig.
13-I.
F,q. 13-l suggeststhat a contacttime t on the order of
l/kj (for first-order reactions; i.e., m = 1) is required
for an almost completedissolution. The distancethe acid
hasadvancedduring this time is ut. This length represents
the front thicknessXfiom (at the beginning of this zone,
most of the mineral is dissolved,while at its tip, the con-
tact time is zero and the mineral just begins to be
dissolved):
Xfio,,c - ut - Da-‘. (13-9)
Fast reactionrates(high Xkz)result in r~sharptiont, and
slow reactionratesproducemore &se ones(Fig. 13-2).
The meanposition of front xfiontis almostindependent
of Da but dependson AC. Considering the sameshnpli-
fied casefor a given Da, a low concentrationacid pene-
trateslessthan an acid of high concentration(Fig. 13-2).
In fW J&“t is the most usefnl variable becauseit cor-
respondsto the size of the acidiied zone. It is not sensi-
tive to the pumping rate (Da).
However, a cl&se front hasadvantageswhenit is relat-
ed to the gained permeability. Fig. 13-3 displays the
permeability profile calculaWi* from the porosity
*Sherwood,J.D.: PersonalComnicaion, 1984

Figure 13-l-predicted acid concentration profile for sand-
stone acidizing and linear flow with a nonraactiw? matrix
(Dacuam = 0). (After Sherwood, 1984.)
Figure 13-Z-Predicted clay and acid concentration profiles
for sandstone acidizing and linear flow, with a nonreactive
matrix (Daquam = 0). a) Effect of varying the acid capacity
number Acc/aY (Dac[ay = IO); b) Effect of varying the Damk-
h&r number Da+ (Ac~/~~ = 1). (After Sherwood, 1984,)
AClDliZW PHYSICS
Distance
Figure 13-3-Clay concentration profile (solid line) and car-
responding permeability profile (dashed line) for linear flow
with Dq,,,=* = 0, Da&,, = 10, and AL&,, = 1. (After Sher-
wood, 1984.)
profile using Eq. 13-4: the averageposition of the form
er is shifted farther from the wellbore than that of the lat-
ter. Thus, in terms of permeability betweenhw porosity
fronts with the samemeanposition, the more diffose front
is the more efficient
More complex and realistic situations (several miner-
als, radial geomehy)requirethe nmnerical,solutionof Eqs.
13-1, 13-5, and 13-6, but the same qualitative trends
remain.
13-3.2 Mass-Transfer-Limited Kinetics
The most interestingoccurrencesof thesephenomenaare
in carbonaterocks that are dissolvedby water at low pH.
Two distinct applications exist:
1. Surfacecarbonaterocks that are dissolvedby ground
water (with a variable samration in COJ produce
caves.This is of prime importanceto hydrogeAogists.
2. The petroleumindustryacid&s carbonateformations.
Molecular diffusion now becomesthe main phenome-
noa. The description of the situation at the solid/liquid
interface is given by the general diffision equation
(Levich, 1962):
+ + uVC = DV*C. (13-10)
Eq. 13-10 neglects the dependenceof the diffusion
coefficientoreconcentration.The key dimensionlessgroup
is now the ratio of the flux of molecules carried by the
flow over the flux of moleculesdiffusedby Brownian mo-
tion. This is calIed the Peclet number, Npe:
Npe = -$ (13-11)
13-5
 This problem has been solved analytically for certain
specialcases,c.g., cylj&ical capiIlary, singleplate, rotit-
ing disk (Levich, 1962). This last gcomctry is usedas an
example in the following paragraphs.
Rotating Disk Apparam
The rotatingdisk apparatusconsistsof a disk of rock spin-
mng III a large vol~e of reactive fluid at a constantan-
gular velocity u (Fig. 134). The concentrationof products
in the bulk is measured,and this concentrationplotted vs
tie gives a global dissolution rate .I (extrapolatedat t
= 0) as a function of u. The analytic solution (Lcvich,
1962) of Eq. 13-10 for this geometry predicts a depen-
dence of the form: .7 - u%.
Reactive Liquid
T tus. J is a function of the square root of the speed of rotation
Figure 13~4-Rotating disk apparatus: a) representation of
the apparatus, b) schematic distribution of streamlines at the
swface of the disk. (After Levich, 1962.)
This apparatoshasbeen extensivelyusedin the last 20
yearsfor measuringthe kinetics of dissolution of various
minerals under various conditions, both by hydrogeolo-
gists and researchersin the petroleumindustry (Compton
andDaly, 1984; Lund et al., 1973). Of particular interest
are the results for carbonatesin water at different pHs.
Fig. 13-5 displays typical experimental data. The most
remarkableresult is the very good agreementwith the the
vv- w’~) for low, angular velocities. At higher an-
gular velocities, the dissolution rate tends toward an
asymptoticlimit. This deviationis explainedby the cross-
over from mass-transfer-limited kinetics to suface-
reaction-limited kinetics. This is discussedin more de-
tail in the next section.
13.6
I
3
2
1
0
2 4 6 6 10
Figure 13-5-Example of data from the rotating disk appara-
of the electrode for different solutions. The dashed curves
correspond to theoretical prediction for !n = I and m c 0.5,
(From Levich, 1962.)
Porous Media - Qualitative Analysis
Despite.several experimentalstodies(e.g., Hoefncr and
Fogler, 1988),no generaiandconsistentdescription(even
qualitative)of the experimentalresultsexists.In addition,
becauseof the randomnessof porous media, no exact
microscopic description of the solid/liquid interface is
possible.
A model by Schechteret al. (1969)describestheporous
medium as representedby a bundle of capillaries with a
given distribution of cross sectionsIV. The model allows
the pores (capillaries) to grow according to a law that is
an approximate solution of the diffusion equation @q.
13-10) in a straight tube. In addition, two neighboring
pores can coalesceif they are sufficiently enlarged. The
authors could predict the developmentalbehavior of the
port distribution, IV, anddemonstratethe unstablecharac-
ter of the phenomenon:the large pores grow faster than
the small ones, which initiates “catastrophic” behavior.
This result has been known experimentally for a long
the (NierodeandWilliams, 1973;Williams et al., 1979):
the dissolution of the limestone by hydrochloric acid
produceslong and empty channelscalled ‘?vormholes”

(Fig. 13-6). This wormholing phenomenonhasboth prac-
tical advantagesand drawbacks.
. In matrix acidizing, the near-wellbore damagecan be
bypassedand the “effective” treated zone becomes
much larger thau iu sandstoneacidizing (for the same
amount of rock dissolved) or in the matrix acidizing
of carbonatesusing slow reacting acids when the ki-
netics is limited by surface reaction. In addition,
problem of nonconsolidationof the near-wellborearea
ax. less severe.
l In fmchue acidizing, wormholing is due to the fluid
loss of the acid (from the fracture into the formation).
Figure 13~6-Molding of an experimental three-dimensional
radial wormhole pattern. (After Daccord and Lenormand,
1987.)
ACIDIZNG P”XSICS
Consequently,its main effect is to reducethe fracture.
length, This decreaseiu the fracture length results in a
significant reduction in the well performancein spite of
increasedpermeability of the fractured walls.
Wormholes have been shown to be characteristic of
mass-transfer-limitedkinetics (Schecteret al., 1969). It
was observedexperimentally that their diameter ranges
from the pore sizeup to macroscopicsizes(severalmm).
Therefore, a large wormhole is the result of the eularge-
merit and collapse of seveml initial pores.
Porous Media - Quantitative Results
And Phy.Gcal Explumkm
It is only recentlythat somephysicalandbasicunderstand-
ing of this phenomenonwas achievedthrough a careful
experimentalstudy. DaccordandLenormaud(1987)have
demonstratedthat:
l the pattern formed by the etchedchannelsis a fractal,*
characterizedby a fmctal dimension, u&~,~~;
l when considering the hydraulic properties of this eu-
sembleof wormholes, au “equivalent wellbore radius”
r-L can be defined. This radius is such that, injecting
in a well of radius rw in the presenceof wormholes
leadsto injectivity conditionssimilar to thosethat would
be produced by injecting in a well of radius r;. This
effect is similar to the skiu effect, describedin Chap-
ter 1, where r; = r,,,e?.
A similar quantity can also be defmed for sandstone
acidizing: if the permeability of the acidizedzoneis much
higherthanthat of the damagedmoue,the equivalentradius
is iu the order of the tneanposition of the front xfiOnt,and
then S = ln r&cPOn,
However, the rem&able resultis thatthe s&indecreases
muchquickerunder mass-trausferkineticsthan under sur-
face reaction kinetics (Dxcord et al., 1987). Indeed:
AS -+lV (13-12)
where V is the volume of acid injected and d = dfiaCtai
= 1.6 for mass-transfer-limitedkiuetics and d = 2 for
surface-reactionkinetics (for radial geometries).
*Fractal objectsareinxxiantby changing theirscaleby anyfactor
(self-similarity).
ID fact, in physics,thisis not possibleandthis
self-similarbehavioris observedonly betweenhvo limits called
cutoffs. They a.% due to other phenomtxawhich become
predominant a.tsmallandlargescales.An importantpropertyof
fractalobjectsis thatwhenonemeasures themassm of thestrut-
turecomprised insidea boxof size1,onegetsnz= Cow &Q@Q~
with +OcrOllessthantheEuclidiandimension of thespace.
13-7
RESERVOIR ,Y,WUIAnON
Following an extensiveexperimental study oo differ-
ent rock/fluid systems,Eq. 13-12 could be transformed
into a quantitative form:
As = - -$ In (1 + AC Npe-’ r;wd) (13i3)
whereAC is the acid capacitynumber (Eq. 13% Npethe
Pecletnumber for radial flow (Npe=@z, with CJthe in-
jection rate and h the formation height), and rw the well-
bore radius. The constantb is equal to 1.7 X 104md-‘.
Fig. 13-7 illustrates the effect of changingthe flow rate
on the skin andacid penetrationaspredictedby Eq. 13-13.
The break on the skin curvescorrespondsto the “break-
through” of the wormho!.ingpatternthrough the damaged
zone.Eq. 13-13hasbeenshownto agreewith a&al field
treatments(Lietard and Daccord, 1988).
Volume (gal/ft)
---,a.5 wbl
-.~~~-2o.o
*PM
0 10 20 30 40 50 60
Volume (gal/ft)
-a) Predicted skin decreasefor a typical set of
conditions and three different injection rates. The damage
is assumed to be homogeneously distributed around the well-
bore,The lightdotted curve corresponds to the skin decrease
for an undamaged well. The break on the curves corresponds
to the penetration reaching the damage radius. b) Acid
penetration corresponding to the same situation as for a).
13-8
Understandingthis behavioris madeeasierby compar-
ison with recentstatisticalmodelsandexperimentalresults
similar to thosedescribedabovebut obtainedin completely
diierent areas@accordandLenormand,1987;Daccord,
1987). This discussionlimits the comparisonto viscous
fingetig of a low-viscosity fluid displacing a more vis-
cousone in a porous medium. Viscous fingering appears
at the interface between the two fluids, and as soon as
a perturbation develops,it is enhanced.As the pressure
drop is lessimportant in the low-viscosity fluid, the local
velocity increasesat the e*penseof the other parts of the
interface (Fig. 13-8). The same reasoning applies for
wormholes exceptthat the high-permeability wormholes
take the place of the low-viscosity fluid.
Distance
Figure 13-S-Schematic explanation of viscous fingering
instability.
Wormholing is a muchmore unstablephenomenonthan
viscousfmgering. This canbe appreciatedby calculating
the permeability ratio betweena pore and a wormhole,
which is roughly proportional to the fourth power of the
ratio of their diameters.A l-mm wormhole is 10stimes
more conductive than a lo-pm pore.
Jn both systems,the fluid velocity obeysDarcy’s law.
For incompressibleflow, ta!singinto accountthecontinuity
equation, the pressure must obey the equation:
Eq. 13-14 is the we&known Laplace equation. If the
viscosiw ratio is important (or the permeabiity ratio is
small), the pressure can be assumedto be constant
throughoutthe low-viscosity fluid (all the dissolvedthan-
nels). III addition, initial perhnbationsin tlx flow veloc-
ities wme from local differencesbetweenadjacentports:
there is a microscopic sourceof perhubation or “noise”
becauseof the local randomnessof the porous medium.
These three elements(the Laplace equation, constant
pressurewithin the flow pattern,andmicroscopicrandom
noise)aretie basicingredientsof a model&led diffasion-
Iiited aggregation(DLA) DLA is a statistical nameri-
cal model that reproducesthe aggregationof randomly
diffusing particles which stick on a “seed” (seeMeakin,
1988, for areview). It is easyto show that the probabili-
ty of findiig a randomly diffusing particle at a given point
and at a given time obeys the Laplace equation. The ir-
reversible sticking of the particles as sooa as they touch
the seedor the growing clusteris equivaIentto the bound-
q condition of constantpressureoa the pattern. The last
ingredient (noise)comesjust from the randomnessof the
Figure 13-9-Dissolution patterns obtained with a network
diffusion (Brownian motion). model. The width of the bonds is plotted proportionally to the
This reasoningis equivalentto that of Paterson(1984) amount of material removed for six orders of magnitude in
who pointed out the similarity behveenviscousfingering N,+ (1 = lowest N,+, 6 = highest). Flow is from top to bot-
and DLA. tom. There is no flow from left to right. (After Hoefner and
Fogler, 1988.)
A breakthroughin the stidy of chaotic stmch~es was
the experimentalverificationandsubsequent understanding Limits Of Ihis Behavior
of the parallelism behveenDLA and viscous fmgering. The cutoffs that limit this fractal behavior correspondto
All thesestructuresare visually very similar and, quan- the caseswhen:
titatively, they are t&t& with a fractal diiension of the . at low velocity, moleculardiffusion is predominantand
order of 1.7 (for radial geometries). the solution becomessaturatedbefore any appreciable
volume can enter the pores (quantitatively, it cor-
respondsto Npe - 1);
Further understandingof wormbolingis provided by com- . at high velocities, the boundary layer thickness6 be-
puter network simulations (Hoefner and Fogler, 1988): comes so small that P approachesunity (the.kinetics
the pc~rousmedium is representedby a two-dimensional crossesover to surface reaction, leadiig to uniform
nehvork of capillaries, In eachpore, the flow obeysKir- etching).
chaff’s laws (local equivalentto the global Laplace law), Thesehvo limiting casesarequalitativelyevidentin Fig.
andthe growth of eachpore is assumedto follow a given 13-9.
function. 13-3.3 Mixed Kinetics
Thesetwo-dimensionalmcdelsare extensiotuof the one-
The tbeoreticaJtreatmentof this intermediatecaseis more
dimensional analytical model of Schechterand Gidley complex than the pure mass-transferlimit, which is pos-
(1969)and Guin and Schechter(1971). Similar resultsare sible under very limited conditions. Analytical or namer-
obtained (Fig. 13-9) with regard to the developmentof ical solutions of the problem are available for the rotat-
unstablepatterns. Their main advantageis that it is easy ing disk apparahu(Levich, 1962)or for the pamllel plates
to changethe dissolution function and the parametersof (Williams et al., 1970).It is thenpossible,with the rotadng
the flow (,4c,Npe,pore sizedistribution) in a much wider disk method, to stidy not only the mass-transferregime
range than experimentally possible. but also the surface-reactionregime as illustiated on Fig.
13-5.

13-9
 In porousmedia, it hasbeenshownexperimentallythat
this transition is characterizedby complexpatterns,mix-
ing short and wide wormholes and uniform attack of the
matrix (Williams et al., 1979;HoefnerandFogler, 1988).
This hass@ongimplicationssince,asan example,the reac-
tion of dolomiteandHCl obeysthis type of kinetics.Thus,
a more detailed discussionis us&l.
The tmnsitionbehveenthe two mechanisms(masstrans-
fer andsurfacereaction)occurswhenthekinetic parameter
P iquals unity. In Eq. 13-4 (whereP is defined), the im-
portant qua& is 6 which is the distance over which
molecular diffision is important; i.e., the boundary lay-
er thickness. As this distancechangeswith time (asit does
for growing wormholes where 6 = radius of the worm-
hole), P also changesand a dissolution initially governed
by surfacereaction may, becauseof the enlargementof
the pores,tarn to masstransferandthusbecomeunstable.
The characteristic distance 6 can vary from place to
place: at the tip of long wormholes, it is of the order of
the pore size (= lpm); closer to the injection, it has a
macroscopicsize (= lmm), severalordersof magnitade.
larger. Hence, the local P is also a fanction of the dis-
tance from the wellbore.
In smmnary, when trying to identify the rate-limiting
stepof the dissolutionof a mineral, rememberthat it may
changewith the size, the time, and the temperatare.
13-4 OTHF,R INSTARILITIES
Severalfactors can causea nonuniform final dissolution
zone, which leads to nonuniform damageremoval. The
instabilityliied to the dissolutionphenomenonits&, rele-
vant in carbonateacidizinghasbeendiscussed.However,
the sametype of instability may occnr in sandstoneacidiz-
ing, and it will be describedby comparisonwith the car-
bonatecase.Two other factors linked to the flow condi-
tions may alsopromoteinstabiliti~. They are viscousfin-
gering (occurring at high viscosity ratios and high capil-
lary nmbers) and capillw lingerjng (occurring at low
capillary numbers,whenthe invading fluid wetsthe rock).
Another causeis the nonuniform initird permeability pro-
tile. It is presentedin parallel with viscousfingeriog when
there is a continuous gradient of viscosity. It is worth-
while to begin with viscousfingering, which is by far the
best known unstable phenomenon.
13-4.1 Viscous Fingering
The displacementof a high-viscosity fluid by one of low
viscosity is fundamentallyunstable, and it can be under-
stoodby writing Darcy’s law and initiating a small per-
13-10
turbation (Fig. 13-8). The local growth rate is propor-
tional to the pressoregradient and, thus, a local lower
viscosiq will causea local increasein velocity. However,
there could be stabilizing effects counterbalancingthe
destabiiizing ones. They come mainly from the interfa-
cial tensionbetweenthe displacedandthe displacingfluidz
a local excessof pressurep arises from the local curva-
tnre of the interfaceaccordingto Laplace’slaw, p = 2dr,
where u is the interfacial tension and r is the curvatore
radius. In the absenceof viscousforces (low flow rates),
this intexfacialeffectis predominantandthe interfacemust
have a constantcurvatore. One can understandthat for
a ftite ratio betweenviscousforces and capillary forces
(a ratio called the capillary number NcG= ~u/u), there
is an eqoilibrimn curvatareleadingto a tite finger width.
This effect has been stadiedin “Hele-Shaw cells” for
a long time, as a simplified model of porous media and
is ca&d the Saffman-Taylorinstability (SaffmanandTay-
lor, 1958). It is only very recently that it was completely
understood (Combescotet al., 1986).
For a porous medium where the distanceof action of
capillary forces is limited to the pore size, no theory can
yet predict the averagefinger width, exceptin the limit-
ing case (Nca - co), and very high viscosiq ratios. In
this caseDLA-like patterns are found and are theoreti-
cally well understood.The finger width here is equal to
the pore diameter.
13-4.2 Instability Cmked To
The Dissolution Phenomenon
This instability canbe understoodby comparisonwith vis-
cousfingering. A more d&led understandingis required
for predicting the minimum size of theseinstabilities. For
wormboles, this size is given by the minimum distance
at which the instableprocessacts; e.g., the diffosion lay-
er thickness,6, which is in the order of thepore size.Thus,
the minimum size of the wormhole is in the order of the
pore diameter.
For surfacereactiondissolution,the sameinstabilitymay
arise. The difference is that the minimum size is much
larger: the distanceacrosswhich an appreciablechange
of permeability occurs is equal to the front thickness
qom Thus, we can also expectit to be the mioimmn size
of the instabilities. This idea is supportedby calculations
by Sherwood(1987), who found similar results. An im-
portant practical applicationis that qOnr is usually rather
large (several centimeters),much larger than laboratoq
samples.This may explain why no suchinstabilitieshave
been observed experimentally.

13-4.3 Nonunifcrm Damage Around The Wellbore
This case may be understood in a way similar to that
describedfor ssndstoneacidizing.Considera flow through
a porousmediumwith a gradientof permeabilitysuchthat
it increaseswith distanceX (for the moment, do not con-
sider any other causeof instability, dissolution, or vis-
cousfingeriug). The equationgovemingthe flow is, again,
Darcy’s equation, but now the permeability k is a fnnc~
tion of X. This problem is similar to that of viscous fm-
gering when the interface betweenthe hvo fluid displays
a continuouschangein viscosity: p is a continuousfnnc-
tion of X. This latter case, often called “graded viscosity
banks” in the enhancedoil recoveryliterature,was stndied
by Chang and Slattery (1986) and Hickernell and Yort-
sos(1986). They showedthat the displacementis still un-
stablebut the minimum size of the instabilities is in the
order of the width of the transition zone. Thus, here also,
expect the minimum size of the instabilities to be in the
order of the thickness of the zone through which the
damageis concentrated.If the gradient of permeability
is small or zero (uniform damage),it will not promote
any instability. On the contrary, a sharppermeabilitygra-
dient (like the onearising from surfacefiltiation) can cause
small-scaleflow instabilities.
13-4.4 Imbibition Of A Wettkg Fluid
When acid&&g oil reservoirs, the rIow rates in the near-
wellbore area are high and the viscous forces are
predominant (AJc4> 1OK’). As a result of the radial ge-
ometry, the velocity of the displacementfront decreases
and, consequently,the relative importanceof the viscous
forces also decreases.For capillary numbers less than
10e4, capillary effectsbecomepredominant.In addition,
most reservoirsare water wet andthe injectedfluid is nor-
mally water based. This type of displacementis called
imbibition (Payatakesand Dias, 1984). The geometty of
the displacementfront is linked to the heterogeneityof
the porous medium; high-permeabilityzonesare bypassed.
Theseare filed with oil, which becomescompletely sur-
roundedby the treating fluid. These“ganglia” of oil are
disconnectedfrom the bulk and tray lead to two results:
. a nonuniform acidizing and damageremoval;
l a decreaseof the relative permeability in the near we&
bore area.
This last point may be of particular importancewhen the
oil in place has a high viscosity.
Instabilitiesmay alsodevelopunderdrainageconditions;
i.e., when the injected fluid does not wet the reservoir
(Lenonnand and Zarcone, 1985; Lenormand, 1986).
AClDE,NG P,=TXSICS
13-4.5 Combination Of Several Phenomena
In a real situation of damage removal, several of the
phenomenacausinginstabilitiesmay appeartogether.Two
main questionsarise:
* In the case of several unstablephenomenaoccnrring
together and with eachhaving its own minimum limit,
is therea synergisticeffectleadingto larger instabiities?
l If the answer to the first question is yes, what is the
minimum size of the instabiities?
The answerto the fast question is expectedto be yes
and that of the secondto be that the minimmn size will
be smaller or equal to the smallest limit. Experimental
or theoreticalverification of thesesuggestionsis awaited.
13-5 PRACTICAL IMPLICATIONS IN
SANDSTONE ACIDIZIh’G
The designof a sandstoneacidizingtreatmentis comprised
of two parts: the selection of the appropriate fluid and
the predictionof its efficiency.The modelspresentedearli-
er in this chapterarebasedon the sameapproachandhave
beenvalidatedagainstlaboratory experiments.Thus, they
are reliable enoughto be used in the design and the op-
timization of the efficiency (damageremoval)to costratio.
Although high flow rates achievethe deepestpenetra-
tion, especially when the reactivity of the quartz cannot
be neglected, certain liitations must be kept in mind.
1. The reactivitiesof all specieshaveto be low (surface-
reaction kinetics); i.e., kj is independentof U. This
assumptionmay not be valid at high temperataresfor
highly reactive clays if the diiensionless kinetic
parameterP becomesclose to unity. In such cases
moleculardiffnsion must be considered.Qualitatively,
this results in a decreaseof the effective reactivity
and thus a broadening of the front.
2. The changein permeability is related to the change
in porosity through a relationship such as shown in
Eq. 13-5. The permeability may display a less con-
tinuousbehaviorin the caseof poresblockedby tines,
which makesthe prediction of the behavior extreme-
ly difficult.
3. No instabilities take place, althoughthe reservoir can
be heterogeneouslydamaged.If instabilities actually
take place and if their averagesize is Iarge enough
when comparedwith the sizeof the treatedarea,their
effectwill be marginal.The more seriousfactorscaus-
ing theseinstabilitiesinclude a high-viscositysaturat-
ing oil, high injection rates, high temperatures(high
reactivities), and highly heterogeneousrocks.
13-11
13-6 PRACTICAL IMPLICATIONS IN
CARRONATE ACIDIZING
Practically, thereare very few parametersto adjustin car-
bonate acidizing. The fluid is hydrochloric acid, some
times viscositied, and the range of flow rates is techni-
cally limited: low rates may not be economicaland high
rates may produce pressureshigher than the fractoring
pressore, especially for low-permeability reservoirs.
Another practical liitation is to keep the near-wellbore
area strong enough; i.e., severeetching will unconsoli-
date it. This may be especially crucial for low-strength
rocks, such as chalks (HartIey and Bosma, 1985; Simon
et al., 1982).
13-6.1 Effects Of Pumping R&e
Experimental studieshave demonstratedthat the highest
penetrationis achievedwhen the kinetics is masstrans-
fer limited; i.e., under wormhormg conditions (N&ode.
and Kruk, 1973; Hoefner and Fogler, 1988; Daccord et
al., 1987). Under theseconditions, the flow rate hasonIy
a marginal effect on the final skin (Fig. 13-7). However,
low flow rates lead to compact dissolution patternsand
then to possible nonconsolidation of the wellbore area,
The ideal etchedpatternconsistsof the smallestamount
of etching close to the wellbore but with the maximum
permeabiliv. Thus, a limited nmber of wide wormholes
is the bestcompromise(for the sameamountof rock dis-
solved, a few large channelspresenta higher permeabil-
ity than several small ones). This is achievedby initiat-
ing the dissolution at low rates (thus creatig only a few
channels)and progressively increasingthe pumping rate
to limit their size.close to the wellbore and obtain more
homogeneousetcKmg at the tips (Daccord, 1987).
Cmxntly, the injection rate is increasedcontinuously
while keepingthebottomholepressurehelowthe fractoring
pressure.
13-6.2 Use Of Microemukions
Microemulsionshavebeenproposedas a meansof retard-
ing the acid-rock reaction to increase the penetration
(Hoefner et al., 1987). This effect is thoughtto takeplace
through the decreaseof the ditision constant.However,
there are experimental indications that microemulsions
may not behavein porous media as simply as hydroch-
loric acid, hencemaking a direct comparisonhnpossible.
On the other hand, decreasingD (or increasingN& does
not lead to an hxrease in the penetration if P is initially
lower thanunity. In other cases(P closeor slightly higher
than unity), the decreasein Ll may result in the crossover
from surface-reaction to mass-traosfer-limitedkineticswith
13-12
the dramatic increaseof penetrationassociatedwith the
latter.
13-6.3 Effects Of Fhid Viscosity
In the equationspresentedin this chapter, the fluid vis-
cosity does not appearexplicidy. In fact, it appearsim-
plicitly through:
. the molecular difision constant,D, which is inverse-
ly proportional to the viscosity;
l the implicit assumptionthat the fluid is Newtonian.
The viscosity may be increasedby dissolving a high
amountof small molecules(i.e., C&l2 or a small amount
of a polymer. In the former case,the liquid remainsNew-
tonian andD decreasesinverselyandlinearly with the vis-
cosity with the only consequenceof increasingthe Peclet
mnnber. The final effect is then identical to that produced
by an increase of the flow rate. In the latter case,three
new effects may arise.
. The molecular diffosion constantremains almost on-
changed(Muhr and Blanshard, 1982): it is the viscosi-
ty of the solvent that matters.
* The liquid may hecome non-Newtonian and, hence,
modify the velocity profile in the pores. The general
diffision expression,as given by Eq. 13-10, must be
moditied consequently.
Thus, althoughD is unchanged,the masstransfer may
increase (and thus the overall reaction rate) as a result
of the higher shear rate at the wall, causedby non-
Newtonian fltid rheology.
l Interactions(mechanical,chemical,or physical)between
the polymer andthe rock may result in a local decrease
of the porous medium permeability since polymer
moleculescan plug small pores adjacentto the worm-
hole walls. The polymer acts as a “fluid-loss agent.”
The local flow velocities arc deeply affected, and this
results in a very complex behavior that was studiedby
N&ode and Kruk (1973). In their stody, the worm-
hole growth velocity displays a maximum for a small
concentration of fluid-loss agent.
13-7 CONCLUSIONS
Reservoirrocks are classicallydivided into two categories:
l slow reacting rocks, suchas sandstones,for which the
reaction kinetics is surface reaction Ytited;
l fast reacting rocks, such as limestone, for which the
dissolution kinetics is limited by molecular diffusion.
This distinction is an oversimplification since both
processes may coexist at different places or scales.
 However, the first caseallows a macroscopicapproach,
which has beenused successfullyin modeling of acidii-
ing treatments.Severalunstablephenomenamay limit the
validity of this approach, but little is known about their
actoal importance.
On the contrary, fast reacting systemsare intrinsically
unstableandhaveresistedquantitativeanalysisuntil very
recently. Phenomenaoccurring at the microscopic level
(describedby the general diffusion equation) have been
indescribableby a macroscopicapproach.However, Fe-
centprogressin statisticalphysicshasallowed the under-
standing of the mechanismof wormhole formation and
thus a quantitativedescription at a macroscopicscaleus-
ing the concept of the &in effect. The two main
parameters,pumping rate and fluid viscosity, have only
marginal effects on the final skin.
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13-13