Matrix Acidizing
of Sandstones
14.
14-l INTRODUCTION
Acidizing sandstoneformations results primarily in dis-
solution of permeability-damagingminerals rather than
in creationof new flow paths, asis the casewhen acidiz-
ing carbonates.
Besidesthebasicquartzgrains,sandstones containother
silicoaluminate compoundsthat are often located in the
pore spaceand provoke flow restrictions. Sandstonesoc-
casionally contain carbonates,metallic oxides, sulfates,
sulfidesor chlorides,and amorphoussilica. They may also
have drilling mud or cement filtrates from invasion.
Hydrofluoric acid (HF) is the only common acid that
dissolvessiliceousminerals. Therefore, all formulations
used in matrix sandstoneacidizing involve hydrofluoric
acid or its precursors.The mostcommonlyusedacid sys-
tem is “mud acid,” a mixture of hydrochloric and
hydrofluoric acids in variable proportions. These com-
positionsarepreparedeither by diluting concentratedfor-
mulations or by reacting ammonium bifluoride with
hydrochloric acid.
This chapterdiscusseshydrofluoric acid from a chem-
ical point of view andoutlines issuessuchas dissolution,
reprecipitation,andkinetics.Physically,reactionsare cou-
pled with injection into the porousmedium. Other acidiz-
ing systemsminimize someof the drawbacksof standard
mud acid solutions; they perform functions such as:
l retardinghydrofluoric acid spendingto achievea suffi-
cient acid penetration around the wellbore, especially
in high-temperaturewells;
l avoiding precipitation of reactionbyproductstoo close
to the wellbore;
l avoiding deconsolidationof the injection zone for very
reactive formations;
l providing stabilizationof fine particlesthat may other-
wise causenew formationdamageafter they arereleased
from the rock through the dissolution of their cement-
ing materials.
Bernard M. Pi& and Her& G. Perthuis
Dowel1 Schlumberger
These other systemsand their particular fluids are dis-
cussedonly briefly.
14-1.1 Need For Fluid Tailoring
All too often, an acid formulation, whether mud acid or
one of the HF-basefluids, is pumpedinto the formation
without design considerations.It may appearsuccessful
when, in fact, it failed. The basic mechanismsinvolved
in acidizingareknown, but the couplingof thesephenome-
na with conditionssuchasreservoirheterogeneities,natu-
rally occurring impure minerals, and distribution of
mineralsinto the reservoiris extremelycomplicated.This
explains why matrix acidizing hasbeen considereduntil
now asmore an art thana science,andwhy simple recipes
that work well in one areamay fail completelyin another.
Selecting the treatment fluid is an important step in
designing a matrix treatment. The processof selecting a
fluid is complex becausemany parametersare involved,
andeachparametermay vary widely. Theremay be sever-
al fluids that are appropriatefor a givenproblem,but some
may have advantagesover others.
This chapter provides a comprehensivediscussion to
help designersselectthe optimum fluid to solve a given
problem. Although all parametersrelevantto fluid selec-
tion are discussed,the mineralogyof the formation is em-
phasized,particularly in the caseof sandstonereservoirs.
The decisionpathsarebasedon experienceandon merg-
ing expertisein the fields of chemistry,geochemistry,and
geology. This selectionprocessis basedon tailoring the
fluid not only to the damagebut also to the conditions
that causedthe damageitself.
14-1.2 Job Design
Having chosenthe proper treatmentfluid, selectionsof
fluid sequence,fluid volumes, pumping rates, and other
job parametersmust be made.Whenthe acid reactionand
14-l
RESERVOIR STIMULATION

injection modeling are not available for simulating the determinethe characteristicsof the treating fluid and the
process,volumeselectionis basedonly on experiencewith techniqueused to reach the damageand remove it. The
the given problem and formation. Job evaluation tech- location of the damageis important becausethe treating
niques, discussedin Chapter16, are extremelyimportant fluid contactsseveralother substrates(i.e., rust from tubu-
for assessingthe validity of the design. lar goods or carbonatecementingmaterial from the for-
mation) before it reachesthe damage.It must still be ef-
14-2 CRITERIA FOR FLUID SELECTION fective when it reachesthe damagedarea. Additionally,
14-2.1 Basic Concepts proper diversiontechniques,discussedin Chapter15, must
A matrix treatmentconsistsof removing the damagethat be used.
impairs the productivity of the well. Therefore, it is im- In sandstoneformations, hydrofluoric acid is used to
portant to know the extent and type of damage,the loca- dissolve silicates. Nonacid systemsare sometimesused
tion, and its origin. Damageis characterizedby two im- to dispersefines and allow them to be producedwith the
portant parameters:its composition and location. They treatingfluid. Fig. 14-l showsa decisiontree for designing

Silts and Clays

I

Native D&g Production Induced by Canpl&s Operations

(Sandstones Only]

I I

No Embedment

StabilV+g/ LOW Susr$ng SusE$ing S&r@

Fio&aag Temperatyre
Fluobwc %I$ Solution Solution SusjendiI!g:
Solution Acid 13.5-1.5
Solution Acid Sandstones
Solution I
Regular Sus~w&iing SuspeLding Dispersing/ I
Fly&ic s~$~~$‘g HCI Solubilityx20% HCI Solubility~ZO%
Solution Solution
r-l kz5&0 md

Fe,dspamsz20% Chlorite-2 10%

, , , T22,30° DWell mWe,l

Chlorite 5 10% ChloriteziO% water or water or

Oil Well Oil Well
T<i30°F Tzl3OOF

Mud Acid sl.5

Mud Acid 12.3

Solutk
Regular
Fluoboric
Acid
Solution
Mud Acid 3..05 Mud Acid 61.5 3-0.5
135-1s
Regular
Regula!
Fluobdc
Flu&~
Solution
Solution

Figure 14-l-Treatment fluid selection in sandstone acidking.

14-2
 MAi-RlX AUDIZING OF SANDSTONES

a treatmentfor a sandstonereservoir that is damagedby

silts and clays. The criteria for selectingthe treating fluid I. Permeabiiify Distribution Prior To Acidizing

are mineralogy, mechanismsof formation damageand its

removal, petrophysics, and well conditions. *w Wellbore radius
Damaged zone radius
g Initial permeabflhy
The treating fluid’s compatibility with the rock is an b Damaged zo”e permeabilily
important factor. Compatibility implies that permeabili-
ty does not decreasewhen the formation is contactedby 3. Permeability Distribution . Small lnjec\ion Volumes

the fluid. This conceptof compatibility appliesespecial-

J
kdam Permeabilily of precipitate
t
ly to sandstones,where many damaging reactions may 4
damaged zo”e within damaged
zo”e radius

occur. k”r Permeability of zo”e containing

only inert qua*= (precipitates re-
moved) within damaged area

3. Permeabilhy Distribution ~ lnlermediafe lnjeclion Volumes

142.2 Mineralogy Criteria 1

lke Concept Of Sensitivity k’: Permeability of precfpilate

As statedby McLeod (1984), a successfnlmatrix treat-

ment dependson the favorable responseof the formation 4. Permeabilily Distribution ~ Large fnjeclion Volumes
to the treatment fluid. Thus, the treating fluid must re-
move damageandbe completelycompatiblewith the for- Perm,eability of wne c??taining
only !“Kl q”arlz (precIpltates re
mation rock and fluids.
The sensitivity of a formation to a given fluid includes
all the detrimentalreactionsthat can takeplace when this
fluid contactsthe rock: the deconsolidationand collapse Figure 14-2-Permeability changes when acidizing a
of the matrix, the releaseof fines, or the formation of damaged well. (From Walsh et al., 1982.)
precipitates. A formation is “sensitive” if the reaction
between the rock minerals and a given fluid induces From a mineralogicalview, two factorsaffect the reac-
damageto the formation. tivity of a given mineral: chemical compositionand sur-
This concept, explained by Walsh et al. (1982), is face area(Table 14-l). The compositionand constitution
representedin Fig. 14-2. Acid penetration is described (petrography) of the rock are important factors used to
as the movementof chromatographicwaves. Damaging determine potential sensitivity. Fig. 14L3schematically
reactionscan occur both in the damagedzone and in the representsthe common constituentsof a sandstone.
undamagedformation.Theprecipitationof somedamaging
compoundscannotbe avoided.Sufficientvolumesof treat- Solubility
Minerals Surface Area HCI HCI-HF
ing and overflush fluids push potential precipitatesdeep
Quartz Low No Very Low
enoughinto the reservoir that their effectsare minimized Chert Low to Moderate No Low to Moderate
becauseof the logarithmic relationshipsbetweenpressure Feldspars Low to Moderate No Low to Moderate
drop and distancefrom the wellbore. Micas Low No Low to Moderate
The sensitivityof a sandstoneis affectedby hydrofluoric Kaolinite High No High
acid, damage,and otherfactors.Sihcon,aluminum,potas- lllite High No High
sium, sodium, magnesium, and calcium ions can form Smectite High No High
Chlorite High Low to High
precipitatesat a giventemperature,oncetheir productsolu- Moderate
bility is exceeded,anddamagethe formation. Thus, sen-
sitivity dependson the overall reactivity of the formation Calcite Low to Moderate High High, but CaFz
Dolomite Low to Moderate High Precipitation
minerals with the acid. Reactivity also dependson the Ankerite Low to Moderate High
structureof the rock andthe distribution of mineralswith- Siderite Low to Moderate High High
in the rock; i.e., the probability of the acid reaching the
soluble minerals. Table 14-l-Surface area and solubility of sandstone
minerals.

14-3
RESERVOIR STIMULATION
Typically, sandstonereservoirs are made of a frame-
work of silicategrains, quartz, feldspars,chert, andmica.
This framework is the originally depositedsand. Secon-
dary minerals, precipitated in the original pore spaces,
arethe cementingmaterialsfor the grains(mostfrequently
secondaryquartzovergrowthor carbonates)andthe authi-
genie clays. This meansthat the clays were precipitated
in the pore spacelong after the initia1 formation of the
rock. Thesenewly formed clays appeareither aspore lin-
ing (attachedto grain surfaces)or as pore filling.
Constituents Of Sandstone
Secondary ’
Cement
6 :arbonate
Quartz)
Clays
(Pore Lining
i.e., lllite)
Clays
(Pore Filling
i.e., Uaolinite)
Remainini Pore Space
Porosity *Mud Acid .SolubleKX?nsitive
Filling
Minerals*
Figure 14~3-Typkal constituents of sandstones.
Rock Struc@re
The actual solubility of minerals in a sandstonereservoir
strongly dependson their position within the rock struc-
ture. Thus, a petrographicstudyis help&t1in understanding
the responseof a rock to a treatmentduring a flow test.
It is important to note the following:
l HCl solubility
The solubility of the rock in hydrochloric acid is gener-
ally consideredto representthe carbonatecontent of
the sandstone.This assumptionmust be verified dur-
ing a.petrographicstudy becauseother minerals, such
as oxides,sulfides,andchlorite clays, are also.partially
soluble in HCl. A sandstonewith an HCl solubility
greaterthan 20 % should not be treatedwith a straight
HF acid. HF reactswith calcium carbonateto form a
calcium fluoride precipitate.When the solubility is less
than 20%, an HCl preflush helps prevent contactbe-
tween HF andthe carbonaterock. When the solubility
is higher than 20 %, an HCl-base treatment fluid can
14-4
be used;however, to avoid additional deconsolidation
problems, straight fluoboric acid treatment is often
preferred.
l Clay content
It is important to know the amountsof each type of
clay within the formation. However, it is much more
important to know the position and distribution of the
clays in the reservoir - they determine the rock’s
responseto the treatment.
14-2.3 Methodology Of Fluid Selection
Fluid selection is basedon a simple principle: the fluid
must efficiently remove the damageand increaseperme-
Quartz ability. The damagethat could result from precipitates
*Feldspars must also’be considered.
There is some controversy regarding the degree of
*Chert
damagecausedby precipitates.For instance,Shaughnessy
*Mica and Kunze (1981) have emphasizedthe damagingpoten-,
tial of Si(OH)+, whereasCrowe (1984) has shown that
k+
Framework
such precipitation may not causea serious problem.
The complexmineralogyof manysandstones encourages
the formation of severalpotentiallydamagingprecipitates.
The potential damageof precipitatesdependson several
factors:
l chemical factor: i.e., solubility of the precipitates in
the after-flush fluid and the native reservoir fluids;
0 crystallographic factor: i.e., whether the precipitates
are amorphous or crystalline;
l morphologicalfactor: relatingto the extractionof grains
that can migrate (precipitation out of solution in the
pore space),and whether they cover undissolvedpar-
ticles (precipitation on the surfaceof existing grains);
l concentrationfactor: i.e., whether the concentration
is high enoughto causeplugging of the pore system;
l reservoirfactor: the damagea given amountof precipi-
tate can causeis also related to rock properties such
as permeability, pore size, pore configuration, etc.
The possibility of precipitation and its effects on the
formation permeability can be determinedby flow tests,
and that information can be usedto developthe optimum
treating fluid. Flow testsunder realistic conditionsare the
only laboratory teststhat can detectthe effectsof incom-
patibility betweeninjected fluid and formation minerals.
Not only is a potential damageor permeability reduction
quantitatively assessed,but the nature of the damaging
processcanalsobe identified by a combinationof effluent
 MATRIX AUDIZING OF SANDSTONES

analysisand core analysisafter treatment (SEM, X-ray, affects the type and extent of damage(Gidley, 1985). A
thin section), as outlined by Bertaux (1986). highly permeableformation can easily be penetratedby
foreign solid particles or fluids, and the depth of the
14-2.4 Acids Used To Avoid Damaging Precipitates damage can be large. On the other hand, a low-
Using available data on HF acids/sandstoneinteractions permeability sandstonewill merely be damagedby inva-
(see Section 14-5 and Fogler et al., 1976; Hekim and sion of foreign particles. However, this type formation
Fogler, 1977; and Walsh et al., 1982), McLeod (1984) canbe more sensitiveto the invasion of foreign fluids be-
proposedguidelinesfor acid usein sandstonematrix treat- causethe smallporesoften containa largequantityof clays
ments. These guidelines, shown in Table 14-2, recom- that have a high reactivity toward fluids.
mend specific acid formulations to avoid or retard The permeability also influencesthe amountof damage
precipitation. Lowering the HF/HCl ratio is one way to causedby precipitates. A low-permeability formation is
retardprecipitation;HCl acid increasesthe dissolvingpow- more severelydamagedby precipitatesthan a formation
er of HF acid (Fogler et al., 1976; Hekim and Fogler, of high permeability.The sameis true for damageresulting
1977), and a low HF contentreducesthe precipitation of from water block.
silica Si(OH)dand, probably, of other compoundsas well
(Walsh et al., 1982). This explains the successfuluse of The Produced Fluids ,,
low HF acid formulations, suchas the 13.5% HCl-1.5 % In somecases,the type of produced fluids precludesthe
HF or 6.5 % HCl-1 % HF formulations. use of some treating fluids. This applies to gas wells,
whereit is preferableto minimize the useof purely water-
Condition Acid basefluids. Agentsthat lower surfacetension(surfactants,
ICI Solubility > 20% Use HCI Only alcohols)and/or gases(foams)are recommended.In other
ligh Permeability (100 md plus) cases,adversereactionsbetweenacidsand formation oils
or formation waters dictate the use of only specific acid
High Quartz (80%) low clay (< 5%) 12% HCI - 3% HF (1)
High Feldspar (> 20019) 13.5%HCl- 1.5% HF (1) formulations.
High Clay (> 10%) 6.5% HCI - 1% HF (2)
High Iron Chlorite Clay 3’Yo HCI - 09/o HF (2) Physical Conditions Of ‘TheWell
ow Permeability (10 md or less) The formation temperatureis an important factor because
it influencesthe efficiency of corrosion inhibitors and the
Low Clay (< WO) 6% HCI - 1.5% HF (3)
High Chlorite 3Yo HCI - 0.5% HF (4) reaction rates. Several treating fluids decreasereaction
rates at high temperaturesand provide,deeperlive-acid
lotes: penetration.
(I) Preflush with 15% HCI.
(2) Preflush with sequestered 5% HCI. Reservoir pressure influences the flowback of spent
(3) Preflush with 7.5V0 HCI or iO’J/o acetic acid. fluids. In order for a fluid to flow back, the pressure
(4) Preflush with 5% acetic acid. differential must exceedthe capillary pressure.Surface-
active agents are used to lower capillary pressure and
Table 14-2-Acid use guidelines-sandstone acidizing.
facilitate cleanup. Energized fluids can also be used for
(From McLeod, 1984.) this purpose.

The selectiontree proposedin Fig. 14-1 is an improve- Damage-RemovalMechanism

ment over theseguidelines and includes recent develop-
ments; particularly, fluoboric acid formulations, which
have demonstrateda very good ability to avoid damag-
ing reactions (Bertaux, 1986).
14-2.5 Other Criteria For Fluid Selection
Permeability
The permeability of the formation influences the selec-
tion of the treating fluid in two ways. First, permeability
There are several types of acid/sandstonereactions and
expectedresults:
l acid that only dissolvesthe damageand fines, such as
plain HF (or mud acid) formulations,
l fluid that dissolvesand/or dispersesdamageand fines,
such as suspendingformulations, whether acid based
or not, and
l acidthatdissolvesand stabilizesundissolvedfines, such
as fluoboric acid formulations.

14-5
RESERVOIR STIMULATION
An accuratedetermination of the type of damageis,
therefore, important. Damagecan be determinedfrom:
l type of clays and their characteristics, including
their size, and
l permeability and type of porosity in the sandstone.
Damagecanbe identified from this information because
of the migratory fines present during production. Fines
migrationrequiresan acid with a stabilizingeffect.A com-
parisonof the sizeof the particlesandthe sizeof the pores
may indicatethat a fluid with suspendingpropertiesis best.
Porethroat sizesare generally small in sandstones;there-
fore, if the formation is not fissured, such a suspending
mechanismis effective only at a very short distancefrom
the wellbore.
14.3 ORGANIZATION OF THE DECISION TREE
The selectiontree shownin Fig. 14-l can be divided into
four main parts: formations damagedfrom fines migra-
tion, fractured formations, high-permeability limy sand-
stones,and formations damagedduring drilling by inva-
sion from the wellbore.
14-3.1 Fines Migration
The upper left sectionof the tree correspondsto a forma-
tion damagedby native migratory fines. Fines migrate
whenthe productionrate is sufficiently high that the fluid
entrainsthe fines, which then block or bridge at restric-
tions in the flow line (porethroatsor throatsbetweensand
grains in gravel packs or in propped fractures).
In hydraulically ‘inducedpropped fractures, it must be
determinedthat this damageis really causedby migrato-
ry fines; i.e., a production rate-dependentprocess,which
meansthere is no embedment.
After the damagedisintegrates,the remaining undis-
solvedfmesmustbe stabilizedin place.Theuniqueproper-
ties of fluoboric acid (Thomas, 1979a and b) make it the
only formulation recomended for sandstoneformations
whoseproductionrapidly declinesfollowing conventional
mud-acidtreatments.A hydraulically fractured well that
has experienceda rapid production decline from fines
migration into the proppant pack (without embedment)
is also treated with fluoboric acid (Thomas and Suhy,
1979).
14-3.2 Fractured Formations
The lower left sectionof the tree in Fig. 14-l corresponds
to sandstoneswhere the damageis either in natural fis-
sures or in hydraulically induced fractures with severe
embedment.
14-6
Embedmentis a processby which the fracture closes
onto the prop pack. It occurs when the effective closure
stressincreasesasa result of the reservoirpressuredeple-
tion. This is a pressure-controlledprocess;it is different
from a rate-controlled process, such as fine migration
without embedment.Hydrofluoric and/or fluoboric acids
can be used, but they are not the most effective way of
treating this problem. The most effective remedial action
is refracturing.
A naturally fractured sandstonenormally corresponds
to a very hard, compact, low-porosity and low-
permeability formation. Since the reservoir productivity
comesfrom the fracture system,this, in turn, must have
been the medium invaded by drilling fluids and solids.
The presenceof silts and clays in either natural or
hydraulic fracturesmakesit necessaryto use a treatment
mechanismbasedon suspensionof the damage.Thus, a
suspending-typeacid is suitable. This part of the tree is
subdivided into two areas.
. On the left are sandstoneswith a small amount of
carbonate-cementingmaterial. The HCl-HF formula-
tion of the suspendingacid dependson the mineralogy.
l On the right are sandstoneswith a large amount of
carbonate-cementingmaterial (HCl solubility greater
than 20%). HCl fluids are used exclusively except at
very high temperatureswhere nonacid-typefluids are
recommended.At temperatureslower than 150’ C, the
exact formulation of the suspendingacids dependson
the amount of ferric iron in the system.
14-3.3 High-Permeability Limy Sandstones
The lower centerpart of the treecorrespondsto sandstones
with a large amountof carbonate-cementing material(HCI
solubility higher than 20%). The damagein the matrix
is causedby silts andclays.At temperaturesabove300°F,
suspendingor flocculating nonacid fluids (dependingon
the permeability) are recommended;at temperaturesbe-
low 300 oF fluoboric acid canbe used. If the permeabili-
ty is moderatelylow, which IScommon in gaswells, an
acid with a low surface tension must be used.
14-3.4 Damage By Solids From Wellbore Fluids
The lower right part of Fig. 14-l correspondsto sand-
stonesdamagedwithin the matrix during drilling or com-
pletion operations.Mud-acid formulations tailored to the
mineralogy are generally used. Low HF acid concentra-
tions are recommendedin low-permeability reservoirs.
Mud acid-type formulations, which contain alcohols to
minimize the introduction of water in the formation and

to increasethe vapor pressureand decreasethe surface
tension, are especiallyrecommendedfor gaswells. Fluo-
boric acid formulations are better treating fluids in sand-
stonescontaining potassicminerals (e.g., potassicfeld-
spar and illite clay).
14-3.5 Other Additives For Acid Formulations
The decisionpath for additive selectionis quite straight-
forward if the necessaryreservoir information is avail-
able. The tree provides only a generalanswer. Acid ad-
ditives have not beenincluded in the discussionhere be-
causethey are not designedto “remove” damage.In cer-
tain cases,a clay stabilizer can be a viable and economi-
cal alternative to a fluoboric acid treatment. However,
it mustbe consideredan integralpart of an acid treatment.
b Iron hydroxide precipitation is referred to in the tree
as an Fe problem or high Fe chlorite. Iron occursmainly
in the ferrousstatein minerals.Chloriteclay containssome
ferric iron but the solubility is relatively low in HCl. Be-
causemostproblematic ferric iron comesfrom rusty tub-
ing, it is important to clean tubular goods with hydro-
chloric acid prior to the real treatment.
14-4 PREFLUSH AND POSTFLUSH
The fluid selectionpath in Fig. 14-l indicates only the
main treating fluids. However, preflush and postflush
fluids maximizethe efficiencyof the treatingfluid. A typi-
cal sequencefor a conventionalmud-acid (HF) treatment
is preflush/maintreatingfluid/postflush.The sequencecan
be more complex as different preflushesare used, such
as solvent/acid or brine/acid or even solvent/brine/acid.
When fluoboric acid is used, whether asthe sole treating
fluid or as a preflush or a postflush to mud acid, it must
be separatedfrom any other fluid by a nonreactivespacer
(usually ammonium chloride brine) to prevent accelera-
tion of the reaction rate of fluoboric acid and incompati-
bility between fluoboric acid and the reaction products
from the other acids. The preflush, spacer,andpostflush
should be used according to considerationsdescribedin
the following paragraphs.
14-4.1 Preflush
An HCl solutionis usuallyusedasa preflushwhen acidiz-
ing sandstonewith mud acid, Various acid strengthscan
be used, dependingon the formation, to accomplishthe
following:
l displacebrine from the wellbore when an ammonium
chloride spaceris not used; to avoid contact between
HF acid and any formation brine containing K, Na,
or Ca;
MATRIX ACIDIZING OF SANDSTONES
l dissolvea maximum amountof carbonateto minimize
CaF2precipitation. Acetic acid canreplaceHCl to dis-
solve carbonates.It actsas a low pH buffer and com-
plexing agent, which helps minimize the tendencyof
iron compoundsto precipitate as HCl is spent (Bran-
non et al., 1986).
Aromatic solvents(suchas tolueneor xylene), with or
without HCl, can be used to remove paraffin and
asphaltenecomponents(Brannonet al., 1986).Mutual sol-
ventssuchasethyleneglycol monobutyl ether (EGMBE)
are also usedfrequently in preflush and postflush fluids.
However,theymustbe thoroughlytestedfor compatibility
with the oil in place. They are normally used in combi-
nation with HCl or ammonium chloride brine. Special
precautionsmustbe exercisedwhenusingmutual solvents.
The beneficial action of mutual solvents has been well
documentedby Gidley (1971) andHall (1975) in the case
of single phaseflow. But Muecke (1973) and Davies et
at. (1988)haveshownthat in oil andwater systems,mutual
solventscan mobilize fines and promote their migration,
resulting in formation plugging.
Other additives, such as surfactants, clay stabilizers,
and complexing agents,can be formulated as necessary.
14-4.2 Overflush
The role of the overflush is to displacethe main acid flush .
more than 4 ft from the wellbore. If this is not done,
precipitation of reactionproductsfrom the spentacid will
decreaseproduction. However, the main treatmentfluid
must still be carefully selectedto minimize the formation
of precipitatesduring the flowback. Recommendedover-
flush fluids are:
l NH&l, or 5% to 7.5% HCl, or diesel for oil wells,
l NH&l, or 5% to 7.5% HCl for gas wells.
In all cases,a surfactantand/or a mutual solvent, when
applicable,is recommendedto leavethe formation water
wet and to facilitate flowback of spent acids. Nitrogen
or nitritied fluid is recommendedin low-pressure wells
to facilitate the unloading of fluids (Gidley, 1985).
14-5 ACIDIZING SANDSTONES WITH MUD ACID
14-5.1 Stoichiometric Equations
A preflush of pure hydrochloric acid is always injected
in sandstones prior to the main flush of hydrofluoric acid.
This is doneto avoid the possibleprecipitation of insolu-
ble or slightly solublereactionproducts. Typically, these
insolublespeciesare calciumfluoride (CaF2),which forms
upon reaction of hydrofluoric acid with calcium
14-7
 RESERVOIR STIMULATION

carbonates, or sodium or potassium hexafluosilicates with

(M$iF& which would result from the reactionof cations K = 1.2 x 10mz7at 25’ C.
in formation brines with solubilized species.The disso- When the silicon concentrationincreasesin the aque-
lution of calcium or magnesiumcarbonatesby reaction ous phase,part of the hexafluorosilicateanions are also
with hydrochloric acid has been discussedin detail in transformedinto the acidic form of fluosilicic acid accord-
Chapter 13. ing to the reaction:
Reactionsof mud acid with the aluminosilicate com- SiFz- + 2H30’ + HZSiFe -I- 2HZ0,
ponentsof sandstonesare, in fact, those of hydrofluoric with
acid: 1,000 gal of 2 % hydrofluoric acid candissolve350
lb of clays (Smith et al., 1965). However, hydrofluoric
This transformation is usually limited, becausefluosi-
acid is a weak acid and, becauseof the equilibratedreac- licit acid is a rather strong acid. Aluminosilicate miner-
tion, is only slightly dissociatedwhen mixed with hydro- als generally have complex chemicalcompositions,such
chloric acid: as those mentionedin Table 14-3. Their overall dissolu-
HF + HZ0 + HsO+ + F-, tion reactionswill thus involve many simple equilibria.
with
I$ = 10F3.’ at 25O C. Minerals
It can also combineand form complexes,but this reac- Quartz
tion must be taken into account(Fogler et al., 1976)only
when the HF concentrationis high enough(i.e., > 1OM) Feldspars Orthoclase
Microcline
to allow numerouscollisions to occur betweenthe fluo-
ride species.This canonly occur in the caseof ultra mud- Albite
acid (25% HCl-20% HF) formulations: Plagioclase
HF + F- + HFZ-, Micas Biotite
with Muscovite
K = 3.86 at 25’ C.
Chlorite
The reaction of hydrofluoric acid with quartz grains
(pure silica) can be expressed in the two following Clays Kaolinite
equilibria: lllite
SiOZ + 4HF += SiFd + 2 HZ0 Smectite.
and
SiF4 + 2F- Y= SiF:: Chlorite

The intermediate silicon complex, SiF T, which is not Carbonates, Calcite

stable in aqueoussolution, is not considered. The first
Dolomite
stepof silica dissolution consistsof the chemisorptionof
the fluoride anion at the silica surface(Iler, 1979). Kline Ankerite
and Fogler (1981), on the contrary, show that it is the
molecularHF rather than the fluoride anion that adsorbs. Sulfates Gypsum
(See Subsection14-5.3.) Anhydrite
Gaseoussilicon tetrafluoride usually remainsdissolved Others Halite
in the liquid phaseunder bottomholepressure,as carbon
dioxide doesin the caseof carbonateacidization, so that Iron Oxides
the equilibrium is shiftedtoward formation of silicon hex-
afluorideanions,andthe remainingSiFadoesnot represent Table 14-3-Chemical composition of typical sandstone
q more than 1% of total dissolved silicon (Labrid, 1971). minerals.
Silicon hexafluoride anions can further be hydrolyzed
into monosilicic acid with evolution of heat: The disintegration of aluminosilicate minerals by
hydrofluoric acid can be consideredas stoichiometric in -
SiFg- + 8HZ0 + Si(OH)4 + 4H30’ + 6F-, a first step;that is, the aluminum/siliconratio is the same

14-8
 MATRIX ACIDIZING OF SANDSTONES

in the solution as in the mineral. Silicon is solubilized by

the sameprocessmentionedfor quartz, whereasalumi- + - AIFS
w--mm AIF;
num is involved in several fluorinated complexes: g loo-
--. AIF
AlF t3-d+ + AlF t4-+- + F- 3 ----- AlFz
n n .-5 . . . . . . . . . . . . . A,,Z
with /---\
-.
/

The prominent form of aluminum complexing varies

as a function of free fluoride ion concentration:the aver-
ageratio of fluorine to aluminum decreasesas the disso- IO-4 10-3 IO-2
lution reaction progresses(fewer F - fluoride anions are Fluoride ion Concentration, g ion/l
available), as shown in Fig. 14-4 (after Labrid, 1971).
The dissolution reaction of all aluminosilicate miner- Figure 14-4-Domains of existence of aluminum-fluorine
als in sandstonesfollows the previous equations,as far complexes. (After Labrid, 1973 .)
as the basic lattice atoms (Si, Al) are concerned.Other
rqetallic ions, suchasNa, K, Mg, Ca, and Fe, which are
involved in the minerals constituting the rock as substi- Secondary Product Solubility (g/l00 cm3)
tution cationsin the lattice or asexchangeable(adsorbed) Orthosilicic Acid
cations, come into solution as free ions during the reac- HJSiOJ o.oj 5
tion. In the case of iron, fluorinated complexes Calcium Fluoride
(FeF (3-zV- with 1 5 z 5 3) also are formed through CaF2 0.0016
reactTonssimilar to the onesfor aluminum. Thus, differ- ,,
Sodium Fluosilicate
ent global reactions can be written as a function of the Na2SiFe 0.65
consideredmineral. For instance: Sodium Fluoaluminate
l For kaolinite clay: Na3AlFe Slightly Soluble

A14Si40i0(OH)* + 4(n + m) HF Potassium Fluosilicate

K2SiFe 0.12
+ (28 - 4(n + m)) H30’ + Ammonium Fluosilicate
V-Ld~~~~~ 18.6~
4AlF n(3UnP-+ 4SiFm(4-m’- + (46 - 4(n + m)) HZO.
Calcium Fluosilicate
l For a sodic or potassic feldspar (M = Na or K): CaSiFG Slightly Soluble

MA&O* + (n + 3m) HF + (16 - n - 3m) H30’ + Aluminum Fluoride

AIF 0.559
Aluminum Hydroxide
WW~ Insoluble
Ferrous Sulfide
FeS 0.00062
0 5 n 5 6 and m = 4 or 6.
Table 14-4-Solubility, in water at room temperature, of HF
reaction byproducts.
14-5.2 Solubility Of Byproducts
When sandstones arebeingdissolvedby hydrofluoric acid, driving force for precipitate formation; precipitation can
byproducts form. Some can precipitate as soon as their be predicted from considerationof the sole liquid phase.
concentrationis sufficient to attain the limit of solubility The extent of precipitation should always be limited. If
(see Table 14-4). that is not possible, displace as far as possible from the
In many cases,the increasein pH of the liquid phase wellborethe precipitationzonethat would causea decrease
resulting from acid mixture spending constitutes the in permeability (Walsh et al., 1982).

14-9
RESERVOIR STIMULATION
Colloidal Amorphous Silica
This precipitatecannotbe avoided,asit resultspartly from
the greateraffinity of fluorine for aluminum than for sili-
con. This process acceleratesthe hydrolysis of SiFg-:
released F - anions are further involved in aluminum
complexes, and more monosilicic acid, Si(OH)d, is
generated.
Certainauthors(Labrid, 1971;Shaughnessy andKunze,
1981; Walsh et al., 1982) have emphasizedthe highly
damagingpotential of the precipitation of such colloidal
silica in the porous medium. However, this damagingac-
tion hasneverbeendemonstratedclearly andsatisfactorily.
On the contrary, other authors (Thomas and Crowe,
1981; and Crowe, 1984a) have shown that suchprecipi-
tation, which cannotbe avoided,doesnot inducedamage;
the depositionof silica hasbeenobservedonly as a coai-
ing on clay surfaces..whichlimits fines migration. Such
precipitation is beneficial becauseit, stabilizesclay and
fines. As a result, the mechanismof silica precipitation
would likely be as describedbelow.
When the concentrationof monosilicic acid, formed by
the hydrolysis of the silicon hexafluorideanions,becomes
important, two mechanismsoccur simultaneously:
l polycondensation(found by Labrid (1971) to encom-
passaboutone-third of total silicon), limited to oligo-
merit forms by aluminum in the solution,
l endothermic deposition of, amorphoussilica.
Precipitation begins earlier in the dissolution process
at higher temperatnres(within 10 mm at 200’ F) because
of the increasedthermal agitation. It also occurs more
quickly in montmorillonite-type clays than in kaolinite
clays becauseof the different initial Al/Si ratios in these
minerals (molar ratio of 1 for kaolinite and lessthan 0.5,
dependingon substitution extent, for montmorillonite) .
Finally, ahuninumcanbe totally removedfrom clays,with
a correlated silica deposition at the surface(topochemi- :
cal reaction).
Calcium Fluoride
Somecarbonatesmay remain after preflushing, either be-
causeof the initial amountof carbonate-cementing material
in the sandstonesor as a result of the carbonates’initial
protective siliceous coating. Also, slightly soluble, fine-
crystallinecalciumfluoride readily forms whencalcitecon-
tacts hydrofluoric acid. This can lead to substantial
damage:
CaCOs + 2HF + CaFZ + HZ0 + CO*.
14-10
When suchprecipitatehasformedbut hasnot completely
blocked the porosity of the formation, it may partially
redissolvewhenHF acid is nearcompletespendingtoward
the end of the job. At this time, the concentrationof fluo-
ride anionsin solution is so lowthat aluminum is hardly
complexedand appearsmainIy as free A13’ ions (Labrid,
1971). Thesealuminumions are then able to extractfluo-
rine from C!aFZprecipitates,asthey did for silicofluorides,
and partly redissolve calcium fluoride according to the
reaction:
3CaFZ + 2A13t & 3Ca” + 2AlF”.
This reactionmay be followed by the subsequent
equilibria
betweenthe different aluminum and fluorine complexes.
Alkali Fluosilicates And Flubaluminates
The aluminumor silicon-fluorinecomplexescanreactwith
alkali ions releasedin the solution from highly substitut-
ed clays or alkali feldsparsas soonastheir concentration
becomessufficiently high to form insolublealkali fluosili-
cates and, probably, fluoaluminates:
2Na’ + SiFg- + NaZSiFe
with
KS = 412 x 10-5;
2K’ -I- SiFz- + KZSiFh
with
KS = i x 10-s;
3Na’ + AlF3 + 3F- + Na3AlFh
with
KS = 8.7 x 10-l’;
2K+ + AlF; + F F + KZAIFs
with
KS = 7.8 x 10-l’.
Alkali fluosilicateprecipitationis favoredby a high level
of hydrofluoric acid. Fluosilicateprecipitates,which form
from the attack of mud acid on alkali feldsparsor clays,
are well crystallized and very damaging(Bertaux, 1986).
Sucha damagingprecipitateforms, also, whenthe volume
of preflush is insufficient and hydrofluoric acid contacts
formation brine containing alkali ions.
Aluminum Fluoride And Hydroxide
Aluminum fluoride (AlF3) or aluminum hydroxide

[Al(OH)J in the gibbsiteform canprecipitateupon spend-
ing of the acid. AIFs is especiallylikely to precipitatewhen
the HF/HCl ratio and HF concentrationare high (e.g.,
1:4 or higher) (Walsh et al., 1982). These precipitates
form according to the reactions:
Al3 + 3F- + AlF3,
A13+ + 3OH- + Al(OH)3,
with
K = I()--32.5
s quartz surfaceby electrostaticinteractions, for its point
Ferric Hydroxide Or Carbonates
Ferrous or ferric ions in the acidizing mixture can come
from pipe rust incorporated by shear effect of flow or
releasedfrom iron-bearing minerals (chlorite, hematite,
pyrite, and glauconite). The usual ferrous/ferric ion ra-
tio encounteredin acidicmixturesis 5-10:1 (Crowe, 1985).
This ratio takes into account.only the iron from iron-
bearingminerals.Most iron is dissolvedinto the acid mix-
turesby simplecontactwith the steelfrom tanksandpipes.
This dissolved iron occurs mainly as ferric ions (rust),
which are potentially damaging.
Someof the ferric ions from the pipe rust can be elimi-
nated during pumping through the reaction with tubing
metallic iron:
2Fe3’ + FecsOlid) + 3Fez+.
The sametype of reduction can occur naturally in sour
wells, as a result of the action of hydrogen sulfide:
2Fe3’ + H$ + 2HZ0 + S(s)+ 2Fe” + 2H30’.
In additionto the depositionof elementalsulfur, insolu-
ble ferroussulfidecaneasilybeprecipitatedat a pH greater
than 1.9 by the reaction with excessacidic hydrogen sul-
fide (H$YHS- with Ka = 10m7):
Fe” -k H$ + HZ0 + FeS + HS- + H30’.
Ferrous‘ions can hardly lead to precipitated ferrous
hydroxide in the near-wellborearea, sinceit forms when
the pH is higher than 6. Ferric iron is normally more
problematicas ferric hydroxide precipitatesabovepH =
2. However, in the presenceof fluoride anions,ferric ions
are complexedand Shaughnessyand Kunze (1981) have
shown that precipitation of ferric hydroxide doesnot oc-
cur until there is a pH of 5 to 6:
Fe3’ + 3OH- + Fe(OH)3,
which precipitates at pH > 2.2 as KS = 10m3’;
FeFzmn(complexes) + 3OH- + Fe(OH)3,
which precipitates at pH > 5.
MATRIX ACIDLUNG OF SANDSTONES
This mechanismof forming iron fluorine complexesap-
plies only to relatively clean sandstones.In the presence
of clays, the dissolvedaluminum ions have a greater af-
finity for fluorine than iron does.Thereforethe iron fluo-
rine complexeswill not form and iron hydroxide will still
precipitate at pH > 2.2.
The natureof the precipitate(crystallineor amorphous)
varies as a function of the anions present (Smith et al.,
1969). Ferric hydroxide can be strongly bound to the
of isoelectric chargelies abovepH 7. In the presenceof
excesscalcite, the dissolvedcarbon dioxide can also lead
to precipitation of insoluble ferric carbonates(siderite or
ankerite).
Iron-bearingprecipitatescanbe preventedby maintain-
ing a low pH in the damagedzone, by reducing anaero-
bic conditions, and by using clean equipment. If a large
quantity of iron is present, adding suitable complexing
agents in acid can prevent ferric hydroxide formation
(Crowe, 1984b). Usual complexing agentsare:
. acetic acid (up to 150’ F),
l citric acid (up to 275 ’ F),
l tetrasodium salt of ethylenediaminetetraceticacid
(EDTA) or nitrilotriacetic acid (NTA) (up to 350 ’ F);
more stablecomplexesareformed with EDTA andiron
than with EDTA and aluminum.
The possibleprecipitation of organic acid calcium salts
often usedat high temperaturesmust be consideredwhen
using theseagents.The addition of strongreducingagents
is also a good means of preventing ferric hydroxide
precipitation (Crowe, 1985).
l EDTA plays this role above 250’ F.
l Erythorbic acid works up to 400 oF with an efficiency
of 7 to 10 times that of citric acid.
14-5.3 Kinetics: Factors Affecting Reaction Rates
This subsection summarizes qualitatively the results
describedin detail in Chapter13. Sincetheoreticalaspects
were covered in Chapter 13, only practical implications
are discussedhere.
Kinetically controlled reactions (surface reaction-
limited) are effective during the acidization process of .
sandstones,and factors affecting reaction rates are dis-
cussed to complete previous thermodynamic
considerations.
Hydrofluoric Acid Concentration
Dissolution reaction rates are proportional to the
hydrofluoric acid concentration(Fogler et al., 1976;Kline
14-11
RESERVOIR STIMJLATION
et al., 1981) for most sandstoneminerals, except smec-
tite. This explains why formations with low competence
(weak cementation, potentially mobile fine particles)
shouldbe treatedwith a reducedstrengthmud acid (1.5%
HF) to avoid crumbling, especially at bottomhole tem-
peraturesgreater than 200 ’ F. Fluoboric acid performs
similarly becauseof the very low concentrationof HF
present at any time.
Hydrochlotic Acid Concentration
Dissolution reaction rates generally increasein a more
acidic medium, as the leachingof constitutivesurfaceca-
tions involves their replacementby protons, but the de-
pendency on HCl concentration is not straightforward
(Gdanski, 1986). The principal role of hydrochloric acid
is to prevent secondaryprecipitations by maintaining a
low pH. The other main effect of hydrochloric acid is to
catalyzethe attack of sandstonemineralsby hydrofluoric
acid. The mechanismand degreeof catalysisdependon
the type of mineral, as shown below.
l For instance,the reaction rate measuredat 35 ’ ‘C for
pure quartzhasthe following expression(Fogler et al.,
1976):
= 9.2 x lo-’ (1 -I- 0.8 [H+]) [HF]
c?quartz
(moles quartz/cm2/s). (14-l)
l , In the caseof a feldspar having the Na - 0.72K -
0.08Ca - 0.2Al - 1.2Si - 2.80g overall formula,
the following expressionhasbeen determined(at 25 o
C under 275 kPa pressure)asthe reactionrate (Fogler
et al., 1976):
qfeldspar = 1.3 x lo-’ (1 + 0.4 [H+]) [HF]
(moles feldspar/cmVs). (14-2)
An elementalmechanismhasbeenproposedto explain
the previous variation. It involves the adsorptionof pro-
tons on the surfacethat weakensthe siloxane bandings,
followed by the reaction of hydrofluoric acid molecules
that createsunstablesilicon-fluorine bondsat the surface,
according to the scheme:
H the previous feldspar, it is about 8 kcal/mole (Fogler et
I al., 1976).
-x -0 -Si- +Ht - -X- 0 . ..Si’ - + HF -
-X -I- FSi- + H20
where
X = Al or Si.
14-12
This is the acid (proton) catalysismechanismproposed
by Kline (1980) for feldspar.
l Dissolutionreactionis a first-orderreactionwith respect
to HF concentrationfor most aluminosilicate miner-
als. Nevertheless, dissolution kinetics is better
representedby a Langmuir-Hinshelwood type law in
the caseof sodiummontmorillonite (Kline and Fogler,
1981):
KKadsP-W
R= (14-3)
1 + KadsD-1 ’
in which KOdsis the equilibrium constant of the ex-
othermic adsorptionof HF moleculesat surfacereac-
tive sites. This adsorptionconstantis independentof
the total acidity, while K increaseswith proton con-
centration (acid catalysis). KadJis especiallyhigh for
a mineral having a high cationexchangecapacity,such
assodiummontmorillonite. For mostother clay miner-
als the value of this adsorptionconstantis small.There-
fore, when 1 B KadJHF] the expressioncan be sim-
plified to the experimentallydeterminedfirst-order ki-
neticslaw. An elementalmechanismdifferent from that
mentionedfor feldsparscanbe proposedto explain the
kinetics and to take into account solely the HF
adsorption:
F
I
~0 OH HO H OH HO OH
I I Ill I I
-X-O-X- +HF+ -X-O-X- Y=-X-F+HO-X-
where
X = Al or Si.
Temperature
Dissolutionof mineralsis a thermally activatedphenome-
non; thus, the rates increasedrastically as a function of
temperature(approximatelymultiplied by two for quartz
for a 25 ‘C increment), and the penetrationdepthsof live
acid diminish accordingly. In the caseof quartz, the acti-
vation energy is about 5.2 kcal/mole, and in the caseof
Fig. 14-5showsthe variationof the reactionrateof mud
acid with vitreous silica (more reactive than quartz) as
a function of both HF concentration and temperature
(Smith andHendrickson,1965).Aluminum andiron solu-
biIities also increaseslightly with a rise in temperature.
 MATRIX AUDIZING OF SANDSTONES

Pressure
A pressure increase speedsup the overall dissolution reac-
tion slightly, as dissolved silicon tetrafluoride can be trans-
formed partially into an acidic speqies (HZSiFh) and can
quickly initiate further reactions. For quartz, a rise of 24 %
in reaction rate was noticed between the two extreme con-
ditions (Smith et al., 1965).
In a radial injection situation, the mineral pore space
texture that determines flow partition around the wellbore
(most live acid flows through the large pores) is also a
Reaction Time, 60 min relevant parameter; clay clasts can be bypassedby the acid
flow (Williams, 1975).
‘0 1 2 3 4 5 6 7 8 9 10
HF (O/o)
14-5.4 HF Acid Reaction Modeling
The parameters that affect the reaction rate of HF acid
Figure 14~5-Reaction rate of HCI-HF on silicate glass. (Af- on sandstoneminerals are incorporated into a model that
ter Smith and Hendrickson, 1965.) predicts the evolution of formation parameters when acid
is injected.
Mineralogical CompositionAnd AccessibleSurfaceArea
In terms of surface reaction rates, sandstonesare typi-
The total specific surface area of sandstone rocks is rela- cally considered a two-component system:
tively high, and mud-acid spendingis determinedprimarily
l a slow reacting pseudocomponent,comprising the crys-
by this parameter becauseof the heterogeneous nature of
talline quartz fraction,
the dissolution reaction. However, if the contribution of
each mineral to the total accessible surface area is consi- l a fast reacting pseudocomponent, comprising all other
dered, great discrepancies between the reaction rates of species; i.e, clays, feldspars, and poorly crystallized
pure phases can be predicted and observed as shown in silica.
Table 14-5. For both pseudocomponents,the overall kinetics, which
includes the diffusion of HF-reactant species to the sur-
face; the surface reactions; and the diffusion of reacted
I Minerals I Wecific Area I products back to the bulk solution; is governed by the sur-
Quartz CO.1 cmYg face reactions because they are the slowest step. There-
Feldspars Few mz/g fore, matrix acidizing (HF) of sandstonesis often called
Kaolinite 15-30 mYg
“surface reaction-limited. ”
Mite 113 mz/g
Smectite 82 m2lg This is the major difference with matrix acidizing of
limestones, where the process is ‘ ‘diffusion-controlled. ’ ’
Table 14-5-Relative specific areas of sandstone minerals. In sandstones, the increase in permeability results from
damage removal and is correlated with a small increase
Clays react much faster than feldspars, and feldspars in rock porosity. Quartz reacts very slowly with
react much faster than quartz especially in the presence hydrofluoric acid; reactions with most aluminosilicates
of high proton (H+) concentrations. Thus, most of the provoke a rapid spending of the acid. A pseudostation-
quartz matrix can be considered as inert with respect to ary state reflects the much faster variation in species con-
the dissolution reaction (about 95 %), and the mineralog- centration (chemical modifications) than the one within
ical nature of accessible rock components determines the the rock porosity (resulting in physical modification). The
overall reaction rate. Calcite reacts at the highest rate of HF acid progresses and dissolves homogeneously every
all sandstone minerals with HF microchanneling, but in pore (and never forms conductive channelsor wormholes).
this case the mechanism of attack is not comparable be- The flow is stable and sharp fronts are formed to illus-
cause protons coming from either hydrochloric or trate the dissolution of different mineral species as acid
hydrofluoric acid can provoke the dissolution. injection progresses radially (McCune et al., 1975).

14-13
RESERVOIR STIMULATION
Severalauthorshavetried to model sucha process.Taha
et al. (1986) use the reaction model developedby Fogler
and various coworkers (see particularly Hekim et al.,
1982). Such a simplified, two-pseudocomponentmodel
and macroscopicdescription can be usedbecauseFogler
has shownthat the order of reactionof HF acid with each
pseudocomponentis equalto unity relative to the concen-
trations of HF and of the pseudocomponent.The flow is
consideredstable.
In such a model, the mineral dissolution fronts can be
computed and the concentrationof remaining clays (or
fast reactingmaterials)canbe calculated.Then, the perme-
ability increasecanbe estimatedfrom the changein porosi-
ty (or amountof material dissolved). The velocity of the
mineral dissolution front dependson the “acid capacity
number,’ ’ which is a function of the volume of clays (or
fast reacting dissolvable material) and of the acid
concentration.
The acid concentration (or spending) front can be
modelled similarly. The thickness of the front depends
on the Damkohlernumber,which is a functionof the reac-
tion rate andthe acid velocity. Suchsimulationsshowwhy
the HF acid does not penetratedeeply into the reservoir
before spendingunlessunrealistically large volumes are
used.(Thesewould almostdissolveeverythingaroundthe
wellbore and thus leave the reacted formation totally
unconsolidated.)
14-6 OTHER ACIDIZING FORMULATIONS
Problemsrelatedto the useof mud acid to removedamage
in sandstoneformations include:
l Rapid spendingprovides only a short penetration, es-
pecially at high temperatures(maximum depth about
30 cm).
l Fines, composedof either mostly quartzor mostly clay
minerals,canbe generatedduring the acid reactionand
can migrate with fluid flow. Destabilization of fines
can leadto a quick production decline after treatment.
Gravel-packedgaswells canexhibit a 50% productivity
reduction.
l The high dissolving power of mud acid destroysrock
integrity at the formation face.
New sandstoneacidizing systemsare designedto al-
leviate these shortcomings.
14-6.1 Fluoboric Acid
Fluoboric acid has been recommendedby Thomas and
Crowe (1981) as an alternative to mud acids. It doesnot
contain large amountsof hydrofluoric acid at any given
14-14
time and thus has a lower reactivity. However, it gener-
ates more HF, as HF is consumed,by its own hydroly-
sis. Therefore, its total dissolving power is comparable
to a mud-acid solution. Fluoboric acid solutionsare used
as a preflush before treating formations sensitiveto mud
acid; this avoids fine destabilizationand subsequentpore
clogging. They are also used as a sole treatment to re-
move damagein a sandstonematrix with carbonatece-
ment or in fissuresthat containmany clay particles. Fluo-
boric acid is also used as an overflush after a mud-acid
treatmentthat hasremovednear-wellboredamage(up to
0.5 ft) to allow an easierpenetrationof the fluoboric acid
solution (a few ft). Fluoboric acid is also particularly
recommendedwhenthe sandstonecontainspotassicminer-
als by avoiding damagingprecipitatesand in the caseof
fines migration due to its fines stabilization properties.
In the field, it is easily preparedby mixing boric acid
(HsBO.J, ammoniumbifluoride (NHdF. HF) , and hydro-
chloric acid. Ammonium bifluoride, an acidic salt of
hydrofluoric acid, reacts first with hydrochloric acid to
generatehydrofluoric acid:
NHdF. HF + HCl - 2HF + NH&l.
Tetrafluoboric acid is formed as a reaction product of
boric acid with hydrofluoric acid, according to:
HjBOs + 3HF - HBFsOH + 2HZ0 (quickreaction),
and
HBFsOH + HF + HBFd + HZ0 (slow reaction).
Hydroxyfluoboric acid (HBF30H) probably does not
exist in aqueoussolutionsunlessit is in equilibrium with
fluoboric acid (Wamser, 1948). The last reaction above
is of an order equalto unity with respectto both HF and
H13F30H.For this reaction,equilibriumis attainedat room
temperatureafter nearly 40 minutes for a resulting 1M
HBF4 solution. Since the equilibrium constantat 25 ’ C
is KZ = 2.3 x low3 (Wamser, 1948), about 6% (molar)
HBFd is convertedinto HBFjOH at equilibrium for a 1M
HBF4 solution. These equilibrium considerationsmean
that at any giventime andplacethereis only between0.1%
and 0.2 % (weight) of free HF at ambienttemperatureand
100’ C (212’ F) respectively.
Fluoboric acid is a strong acid of strengthcomparable
to that of hydrochloric acid (Maya, 1977); thus, the fol-
lowing reaction occurs in the solution:
HBFd + HZ0 - H30+ + I3F;.
In the following text, reactionsare written using BFF
insteadof HBF+ Acid strength diminishesin this order:

fluoboric, hydroxyfluoboric [the strength of which can
be comparedto that of trichloroaceticacid (Maya, 1977)],
and boric acid (pKnsuOs = 9.2 at 25 ’ C).
The dissolvingpower of fluoboric acid resultsfrom the
generationof hydrofluoric acidthroughits hydrolysis;i.e.,
BF; + HZ0 * BF30H- + HF.
The BF30H- anionscanbe further hydrolyzed succes-
sively into BF*(OH)L, BF(OH)l andH3BOswith the cor-
relatedHF formation,but thesereactionsmustbe takeninto
accountonly when the BF30HV concentration is lower
than 3 x lOL3 at 25’ C (Wamser, 1948). In the follow-
ing text, BF30H- hydrolysis hasbeenneglectedat usual
acid concentrations.
The hydrolysis reaction kinetics of fluoborate ions is
affected by:
l the concentrationof the fluoborate ions,
l the medium acidity that has a catalyzing effect (reac-
tion is proportional to the proton concentration),
l andthe temperature,throughtheusualactivationenergy
effect.
Thus, the reaction rate, assumingthe reversereaction
is negligible, can be expressed,after Kunze et al. (1983),
as:
d VLI
q=- = K [H30+] [BFd-] (14-4)
dt
in moles/lit/min,
with
26,183
K = 1.44 x 1017exp - 1 987T
1 (14-5)
in (mol/lit) - ’ min- ‘,
and T = temperaturein K ‘.
Thus, the reaction rate is increased300-fold when the
mixture is heatedfrom 25 ’ C to 65 ’ C and is increased
12,000-fold when heatedfrom 25 o C to 105o C. Since
the hydrolysis reaction kinetics is not affected by clays,
fluoboric acid is not considereda strongly retarded acid
in normal use. In the presenceof excessbentonite, pure
0. 1M initial fluoboric acid is spentwithin 30 minutes at
150’ F (Kunze and Shaughnessy,1983).
The reaction of fluoboric acid in sandstonesinvolves
at the sametime the hydrolysis reactionof fluoboric acid,
the classicalreactionsof the generatedhydrofluoric acid
with minerals,and additionalslow reactionsrelatedto the
fluoborate ions in liquid phase.As expected,the dissolu-
MATRlX ACIDIZING OF SANDSTONES
tion reaction of clays with fluoboric acid is a first-order
reaction with respectto the fluoborate concentration, as
it is for mud acid with respectto HF concentration.
The spendingrate of fluoboric acid on glass slides at
150’ F is one-tenththat of a mud acid having the same
total HF content(ThomasandCrowe, 1981). Sinceamor-
phous silica reactsfaster than quartz, limited deconsoli-
dation of coresnear the injection face is observedduring
flow testswith fluoboric acid. This is comparedto com-
plete crushing with mud acid. (The decreasein compres-
sive strength of the treated cores is reducedby 30% to
50%.)
The unique advantageof fluoboric acid is that it pro-
vides an efficient clay/fine stabilizationthrough reactions
relatedto borateand fluoborate ions. Swellableclays are
desensitizedby fluoboric acid: a strong decreasein ca-
tion exchangecapacity (e.g., minus 93% after 18 hours
in fluoboric acid at 150’ F for a Wyoming bentonite)was
noticed ‘by Thomas and Crowe (1981).
After a fluoboric acid treatment, migrating clays and
other fines stabilize as a result of the rock’s exposureto
acid. This is the reasonfor the long shut-in time recom-
mendedin fluoboric acid treatments. During injection,
while the acid spendsnormally, coresjust treated with
fluoboric acid exhibit a normal increasein permeability.
However, there is no long-term stabilization after treat-
ment becauseonly part of the clays dissolved; the rest
did not havetime to stabilize. Additional shut-in time al-
lows this stabilization.
When treated by fluoboric acid, montmorillonite
progressively decreasesin aluminum content and then
progressively incorporatesboron atoms; silicon precipi-
tatesfrom the solution. Coresoriginally containing 30 %
silicoaluminatesat 150’ F attainedmaximum static solu-
bilities after only 24 hours in the presenceof 1M HBFd.
(4 hours in the caseof mud acid), whereasthe maximum
increasein permeability is obtainedafter only 4 hours un-
der dynamicconditions.Theseresultsprove thedissociated
effectsof mineraldissolutionby the generatedhydrofluoric
acid (essentiallykinetically controlled) and of the parti-
cle stabilization resulting from slow complex dissolu-
tiomreprecipitation mechanisms(toward thermodynam-
ic equilibrium) during the shut-in period.
Original kaolinite clay platelets-pure aluminosilicates-
that are not dissolved by fluoboric acid appear welded
together and to the quartz grains when examinedunder
a scanningelectron microscope. A type of chemical fu-
sion of any fines seemsto take place slowly onto the sili-
ca surface.The formation of borosilicate“glass” hasbeen
assumedto account for this reaction.
14-15
RESERYOIR STIMULATION

Bertaux (1986) observedthat in silicoaluminatescon- l This processsupposesthe initial adsorptionof H30t

taining potassium, such as illite, potassium fluoborate hydronium ions on the clay surface,then its exchange
forms after treatmentwith fluoboric acid; potassiumhex- with NH:, so that HF is generatedin situ. Such ex-
afluosilicate forms after treatment with mud acid. This changeand replacementof H30t by NH4’ depends
showsthat nondamagingbyproductsare formedin the case on manyparametersand cannotbe ascertained.There-
of fluoboric acid, whereasformation plugging by alkali fore, ,eventhe generationof HF is dubious.
fluosilicatescan occur with mud acid. This is anotherad-
vantageof using fluoboric acid in some“acid-sensitive”
formations.
During the injection period, fluoboric acid behaveslike
a weak hydrofluoric acid solution, but one where the HF
is constantly replenished.The small amount of fluoride
ions availableat any time limits the dangerof precipitat-
ing aluminum species.Only the first acidity is useddur-
ing this step.Hydroxytrifluoboric acid, HBF30H, buffers
the solutionandpreventsother undesirableprecipitations.
During the shut-in HBF30H continuesto react, but at
a slow pacebecauseits hydrolysis is minimal. The HF,
thus liberated, reactsfurther with mineral species.It also
reacts by topochemical reactions, where the aluminum
from the undissolvedclay structure is put into solution
by forming one of the fluoaluminate complex ions (de-
pendingon [F-l), and the surfaceof the mineral is there- Figure 14-8-SEM picture showing kaolinite and illite clays
fore enrichedin silicon and boron. An amorphouscoat- in a pore, before attack.
ing of silica andborosilicate “glass” is then formed over
the remainingsilicateand fine silica grains, welding them
to the framework and thus preventing their migration.
This effectis clearly seenin Figs. 14-6and 14-7, where
the samepore, containing two different clays (kaolinite
and illite), is shownbefore and after reaction with a fluo-
boric acid solution. The quartz is hardly etched, while
the high surfacearea, fast reactingillite is completelydis-
solved.The kaolinite plateletsare abouthalf dissolvedand
anamorphousmaterialis coatingthe undissolvedkaolin&e,
welding themtogetherandto the underlying quartzgrain.

14-6.2 Sequential Mud Acid

This systeminvolvesthe in-situ generationof hydrofluoric
acid, occurringfrom the alternateinjectionof hydrochloric
acid and of ammonium fluoride (Hall et al., 1981). The
reactionsof hydrofluoric acid are thoughtby someto take
place at the rock surfaceby adsorption followed by ion
exchange,but the yield of this heterogeneousprocess
seemshighly doubtful for several reasons.
l If HF acidwere to be generatedthrough sucha process,
it would be a very small quantity, hardly enough to
etch the surface of the clay material.
l As this process is based on the CEC of the clays,
migrating kaolinite would hardly be touched.
Figure 14-7-SEM picture of the same pore after an 8%
HBFh treatment.
14-6.3 Alcoholic Mud Acid
Alcoholic mud-acid formulations are a mixture of mud
acid and isopropanolor methanol(up to 50%). The main
application is in low-permeability dry-gas zones. Dilu-
tion with alcohollowers the acid/mineralreactionrate and
provides a retarding effect,

14-16

Cleanup is also facilitated; acid surface tension is
decreasedby the alcoholswhile the vapor pressureof the
mixture is increased, which improves gas permeability
by reducing water saturation.
14-6.4 Mud Acid Plus AlC13 For Retardation
An acidizing systemto retard HF-minerals reactionshas
beenproposedin which aluminum chloride (AK&) is ad-
dedto mud-acidformulationsto complexsomeof the fluo-
ride ions in the injected mixture, according to the reac-
tions (Gdanski, 1985):
AlC& + 4HF + HZ0 $ AIFd- + 3HCl + H30+,
AlF‘,- + 3H30+ F+ AIF; + 3HF + 3HZ0.
However, this procedure is tantamountto adding dis-
solutionreatitionproductsto the mixture beforethesereac-
tions occur. In theory this should slow down the rates.
However, the retardationof clay dissolution hasnot been
proved experimentallybecauseof the prime importance
of the high surfaceareason clay reactivity, much more
important than a slight depletion of acid at high tempera-
tures. The risk of earlyprecipitationof damagingproducts,
such as aluminum fluoride (AIFS) or fluoaluminates, is
probably increasedby the use of an acid, already con-
taining aluminum ions, before reaction. Flow testshave
showna smallereffectivelive acid penetrationthan in the
case of mud acid.
14-6.5 Organic Mud Acid
As total acidity speedsup mineral dissolution with mud
acid, organic mud acid involves the replacementof 12%
HCl by organic acids (typically 9 % formic acid, a weak
acid only partially dissociated),mixed with 3 % HF, to
retard hydrofluoric acid spending.This systemis particu-
larly suitedfor high-temperaturewelIs (200O-300oF) , for
which pipe-corrosion rates are diminished accordingly.
This systemalso reducesthe tendency to form sludge.
14-6.6 Self-Generating Mud-Acid Systems
These acidizing systemswere originally developed by
Templeton et al. (1974), and their application has been
widenedrecently by Abrams et al. (1983). They involve
the hydrolysis of organic estersinto the corresponding
carboxyIic acids, followed by the reaction of theseacids
with ammonium fluoride to yield hydrofluoric acid. As
the hydrolysis reaction is activated by temperatureand
the acidity obtained is not as strong as with mud acid,
a low corrosion rate of tubular goodsas well asa delayed
reaction of the progressivelygeneratedhydrofluoric acid
are expected.The latter would allow deeppenetrationof
live HF.
MATRIX ACIDIZING OF SANDSTONES
Dependingon the bottomholetemperature,different or-
ganic esters are used:
methyl formate between 130’ F and 180o F, with the
reactions:
HCOOCH3 + HZ0 * HCOOH + CH30H
slow, rate-controlling reaction
HCOOH + NH4F $ NH: + HCOO- + HF
ammonium salt of monochloroacetic acid between
180’ F and 215” F:
NH; ClCH$OO- + HZ0 e HOCHJJOOH +
NH: + Cl-
methyl acetatebetween I90’ F and 280’ F.
Reagentchoiceis intendedto limit at 30% (maximum)
the generationof hydrofluoric acid during pumping of the
mixture in the tubing; thus, a minimum of 40 minutes of
spendingtime seemsnecessary.However, field tests of
these systemshave not been conclusive. Many precipi-
tatesform in theselow acidic systems,suchas ralstonite
(NHaMgAIFJ , and other fluoaluminates(silicates)upon
spendingof thesemixtures on clays; thus, the useof com-
plexing agentsor acids, such as citric acid, is suggested.
Besides,formation sensitivity after treatni?nthasnot been
tested, and handling problems arise from the high flam-
mability of methyl formate.
Overall, these systemshave many drawbacks. Based
on the hydrolysis of various organic esters,they are tem-
peratureactivated.Unlike fluoboric acid; where new HF
is generated only upon spending, no equilibrium is
reached.This meansthat more HF is geheratedas tem-
perature increasesand the ester can eventually be com-
pletely hydrolyzed long before reaching-the final depth
of damage.The true degreeof retardationdependson tem-
peratureandpumping time. Theseestersare more expen-
sive and more dangerousto handlethan HCl or inorgan-
ic salts (flammability). More precipitatesare formed as
a result of the poor solubility of the organic byproducts.
The orily advantageover the reduced-strength HF is lower
corrosion rates.
14-6.7 Buffer-Regulated Hydrofluoric Acid Systems
Other high-pH acidizing systemsproposedfor use up to
360’ F involve the buffering effect of an organic acid and
its ammonium salt, mixed with ammonium fluoride, as
a hydrofluoric acid precursor (Abrams et al., 1983). To
minimizecorrosion,the useof the sameuninhibitedbuffer,
without ammoniumfluoride as a preflush,hasbeenrecom-
mendedup to 350 ’ F. The ammoniumsalt of the organic
acid is generatedfrom the partial neutralizationof the acid
with ammonium hydroxide. The different proposed
buffered systemsare:
14-17
RESERVOIR STIMULATION
l formic acid/ammoniumformate with pH = 3.5 to 4,
l acetic acid/ammoniumacetateand citric acidlarnmo-
nium citrate with pH = 4.5 to 5.
To extend the application to higher temperatures(up
to 550 ’ F), an excessof ammonium salt is formed by us-
ing a higher ammoniumhydroxide/organicacid ratio. As
the kinetics of clay dissolution increaseswith the fluo-
ride ion concentration,more ammoniumfluoride is added
to compensatefor the pH increase(Scheuerman,1985).
Successfulin-depthstimulationhasbeenobservedwith
this systemonly for bottomholetemperatureslower than
54 ’ C. In mostcases,many damagingprecipitatesareno-
ticed when using this system(fluosilicates,fluoaluminate
often involving ammonium), the formation of which is
relatedto the weakacidity in the near-wellborearea.These
systems suffer from the same drawbacks as the self-
generatedmud-acid system.
14-7 MATRIX ACIDIZING DESIGN
A typical designfor a stimulationjob should involve the
following major steps:
Ensurethat the well is a candidatefor matrix stimu-
lation; i.e., clearly establishthat the well is damaged.
Much of this hasbeencoveredin detail in Chapter1.
21 Establish the cause of damage, its severity, and
location.
3) Selectthe proper formulation of treating fluids, in-
cluding additivesthat will removethe damagewithout
damagingthe rock through formation of secondary
precipitates, sludge, etc. This may require laborato-
ry tests.
4) Determinethe pressureand/or rate for injection with-
in matrix flow regime; i.e., without fracturing the
formation.
Determinethe volume of treating fluid to be injected
per foot of perforated interval.
If the reservoir is multilayered or if the pay zone is
very thick, determine a placementtechniqueto en-
sure each foot of the reservoir receives the proper
amount of fluid.
7) Determine possible shut-in times, plan diverter
cleanup,andmakerecommendations for returningthe
well to production or injection.
Assessprofitability of treatment by estimating in-
creasesin productivity or injectivity vs the cost of
the treatment itself.
14-18
Design engineersmust recognizethat every one of the
abovepoints is equally importantandnonecanbe exclud-
ed. Failurescanoccurby leavingout anysinglestep.Other
factors must be consideredbefore finalizing a proposal
for a pumping schedule:
l circulating out wellbore fluids that could be damaging
to the formation,
* constraints, imposedby completion, that prevent the
use of certain fluids (e.g., corrosion) or techniques
(e.g., mechanicaldiversion), and
l availability of materials.
As for any other design problem, the quality of the
proposal strongly dependson the quality of the informa-
tion collectedon the well condition,laboratorytests,reser-
voir parameters,and completion description.
It is assumedhere that the first three stepshave been
completed; i.e., a comprehensivereservoir justification
of the treatmenthasbeendoneand that stimulation fluids
have been selectedaccording to recommendationssuch
as those described in Sections 14-2 and 14-3.
14-7.1 Pressure For Injection
Matrix acidizing is defined as the injection of fluids at
pressuresbelow fracturing pressure. The injected fluid
flows either through the existing porous medium or
through new passagewayscreatedby the fluid itself.
Any “matrix” treatmentthat exceedsthe fracturepres-
sure is undesirablebecausethe acid may not dissolve or
dispersewellbore damage.While fractures are essential
in low-permeability reservoirs, in higher permeability
reservoirs the newly formed fractures may bypass the
damagedarea and may not clean the formation around
the wellbore. The createdpermeabilitycontrastwould not
be adequate,and the bypasseddamagewould remain.
Fracturesmay also extendthrough zone boundariesand
lead to an increase in water or gas production.
A major step in designing a matrix acidizing job is to
determinethe conditionsfor matrix flow regime.To avoid
fracturing the formation, the bottomhole pressuremust
not exceedthe fracturingpressure.The calculationof frac-
turing pressurehasbeendemonstratedin Chapter2. De-
termining bottomhole pressuresfrom wellhead data is
shown in detail in Chapter 16.
14-7.2 Determination Of Maximum Injection Rate
The maximum possibleinjection rate that doesnot frac-
ture the formation is derived from Darcy’s radial flow
equation:

4.917 x lO-6 kh [(Q x H) - Aps‘+ - p]
q.WIOX=
pB (ln ~JJ-,~+ s)
(14-6)
whereqirnmis the injection rate (BPM), k is the effec-
tive permeability of the undamagedformation (md); 11is
the net thicknessof the formation (ft); gfis the fracture
gradient (psi&); H is the depth (ft); Apsafeis the safety
pressuremargin (200 to 500 psi); p is the reservoir pres-
sure (psi); p is the viscosity (cp); re is the drainageradius
(ft); r,,, is the wellbore radius (ft); and s is the skin fac-
tor (dimensionless).The formation volume factor, B, is
very near unity.
Eq. 14-6 is a simplified inflow performancerelation-
ship; it doesnot accountfor transient effects, multiphase
flow, or reservoir heterogeneities.The injected fluid is
assumedto be incompressible.The effective permeabili-
ty is the permeabilityto the injectedfluid. Theseconcepts
are reviewedin detail in Chapter 16. The value obtained
from Eq. 14-6with the initial skin value can be usedonly
as a guideline for determining the initial rate.
14-7.3 Fluid Volumes: Experience
Acid flows through sandstonesin a uniform and stable
manner.As a consequence,unlike HCI treatmentsof car-
bonates, it is not the purpose of mud-acid treatmentsto
createnew permeability by dissolving part of the forma-
tion. This, in fact, would deconsolidatethe formation. In-
stead, they are intended to dissolve damagingmaterials
plugging the pore channels and thereby increase
permeability.
Acid reactionswith sandstoneformations are complex
sinceHF could reactwith feldspars,clays, and other sili-
cate and carbonateminerals, often of undefined chemi-
cal compositionandwidely variable physicaldistribution.
When acid reaction modeling is not available, volumes
used are the ones experiencehas shown to be most cost
effective,
In general,the mosteffectiveacidizingtreatmentis com-
posedof three parts: namely, a preflush, the acid formu-
lation, and an overflush.
- Prejlush Volumes
The preflush servesseveral important functions. It
l provides a separationbetweenconnatewater and HF
to help prevent the formation of potentially damaging
sodium or potassiumfluosilicates, and
l reactswith carbonateminerals in the formation to pre-
vent their reaction with HF.
MATRIX ACIDIZING OF SAh’DSTONES
Thesefunctions can be satisfiedby hydrochloric acid.
Dependingon the carbonateand clay contentsof the for-
mation and its permeability, 5 % to 15% HCl or 5 to 10%
aceticacid is used. The volume of this acid preflush also
dependson the carbonatecontent, but certain minimum
volumescanbe derivedbasedon the displacementof con-
natewater andinter-mixingof fluids while they arepumped
down the tubing.
The volume required to displaceformation fluids to a
radial distance, rS, can be estimatedby
Vp = 7.48 [t$ (rj? - t-i) x] (14-7)
where r,,, is the wellbore radius (ft); rS is the depth of
damage(ft); and l$ is the pore volume (gal&t).
The volume requiredto dissolveall acid-solublemateri-
als up to a radial distance, rS, is given for HCI by:
where VHcl is the volume of HCI required (gal/ft); XHcl
is the weight fraction of formationmaterialsolublein HCl;
/3is the dissolving power of the acid (gallon of rock dis-
solvedper gallon of acid); rS is the radius of damage(ft);
and r,,, is the wellbore radius (ft). :,
When the carbonatecontentof the sandstonereservoir
is very low, it may seemthat only a small volume of HCl
preflush, or no HCI at all, is necessary.It may appear
that a solventand/orbrine preflushis sufficient.However,
a substantialHCl preflushvolumeis still necessaryto com-
pletely exchangethe cations of the clays by protons. If
this step is not done, clays will be abIe,to exchangeand
extract protons from the main HF acid flush. This will
increasethe pH of this fluid and will certainly induce un-
desirable precipitations (Gdanski and Peavy, 1986).
Acid Volumes
The acid formulation generally usedis a 12%-3% mix-
ture of hydrochloric and hydrofluoric acids plus inhibi-
tor and any other special additives required for the for-
mation to be treated, including diverting agents. Other
strengthsof acidsand other ratios of HCl to HF acidscan
be usedto help prevent secondaryprecipitationproblems.
The HCl acid maintains a low pH to avoid deposition of
CaFz, AlF3, and other complex reaction products. This
issuehasbeenaddressedin Sections14-2, 14-3, and 14-5.
The optimum designfor regular mud-acidvolumes ap-
pears to be 125 to 200 gal per foot of formation. This
value is basedon many treatmentsthroughout the world
and on a statisticalanalysisof 174treatmentsin the Texas
14-19
RESERVOIR STIMULATION

Gulf Coast by Gidley et al. (1976). It is consistentwith spendingand correspondingmineral-concentrationpro-

figures quotedby Lafleur andJohnson(1973)in the North
Seaand by Smith et al. (1965). However, a recent study
by Gidley (1985) showsthat many successfulsandstone
acidizing treatmentshave been performed with smaller
volumes of acid.
Since the purposeof sandstoneacidizing formulations
is damageremoval, the amount and location of which is
poorly known, sometrial-and-error or onsite injectivity
measurementsare used to optimize the volume.
In order to limit such trial-and-error exercise, a real-
time onsite treatment evaluation method (Prouvost and
Economides, 1987and 1988) is usedto determinewhen
the damagehasbeenremovedand decide if enoughfluid
has been used. This techniqueis detailed in Chapter 16.
Oveflush Volumes
The overflush for mud acids canbe either 3 %- 10% HCI,
NH&l, or a light hydrocarbon, such as diesel oil. For
a gas well, nitrogen may be used. Other overflush for-
mulations can be consfderedfor special purposes, such
as to facilitate diverter cleanup.
The volume of overflush used successfullyhas ranged
from 50 gal& to 1.5 times the volume of the acid formu-
lation. Sincethe primary purposeis to displacepotentially
damaging precipitates deep into the reservoir, a 4-ft
penetration radius is usually sufficient. The required
volume may be calculated using Eq. 14-7.
Flowback
Flowbackof spentfluids from conventionalmud-acidtreat-
files after attack. To do that, rock mineralogic composi-
tion is required and minerals are lumped into two
categories:quartzor slow reactingspeciesandall the other
mineralsthat are fast reacting. An exampleof suchsimu-
lation is given in Figs. 14-Sto 14-10, where the attack
of a lOO-md,15% porosity sandstonereservoiris modeled.
In this example,the wellbore radius is 2 in. and the for-
mation is composedof 75% quartz and25 % other miner-
als. A standardmud-acidsolution(3 % HF) is injectedinto
the formation at a rate of 0.01 BPM/ft. The acid-spending
profile on the nondamagedformationis shownin Fig. 14-8
for various volumes of acid. The relative concentrations
of the fast reactingminerals and of the quartz framework
are shownin Figs. 14-9and 14-10for the samedata.These
data demonstratethat large volumes of acid are needed
to achievemoderatepenetrationwith such a homogene-
ous dissolution process.
The objectiveof matrix acidizing is to removedamage,
but the simulation requires damageparametersobtained
from well testing.When parametersareunknown, differ-
ent simulationruns canbe madewith varying parameters.
A = 150 iai/ft
0 =200 gal/ft
+ = 250 gaMt

ments should be accomplished as soon as possible.

Detrimental reaction products will be formed within the
formation if spentmud-acid formulations remain for an
extendedperiod of time. To assistsuchflowback it is be-
coming commonpractice to usenitrogen and coil tubing
for lifting spent fluids.
In productionwells that havebeentreatedfor deepclay
damage,a slow “beaning-up” processis recommended:
the wells are brought back into production very slowly
by graduallyincreasingthe sizeof the chokesover a period
of several weeks and thus keeping fine migration to a
minimum.
Usually, no attemptis made to flow back water injec-
tion wells. Rather, the well is immediately injected and
the spentfluids are pushedout farther into the formation,
away from the critical wellbore area. Radial Distance (in.)

14-7.4 Fluid Volumes: Mathematical Simulation

Only the reactionof plain hydrofluoric acid is considered Figure 14-8-HF acid spending profile in an undamaged
in this section. Using the mineral dissolution models sandstone.
described in Section 14-5.3, one can compute HF acid-

14-20
 MATRIX AUDIZING OF SmDSTONES

Using the samereservoir dataasin the previous exam-

ple, assumethat the well has beendamagedby invasion
of solids. A well test gives a skin of +8 for this forma-
tion and a depth of damageequal to 3 in. is assumed.
Therefore, the permeability of the damagedzone is cal-
culatedas 10 md. The dissolutionmodel assumesthat the
decreasein permeability in the damagedzone is due to
an increasein the concentration(invasion) of fast react-
ing species(clays).This resultsin a new, decreasedporosi-
ty of 12%, compared with the original 15%.
Injecting the sameHF acid at the samerate results in
a new HF spending,fast reactingmineral concentration,
and slow reactingmineralprofiles asshownin Figs. 14-11
to 14-13.The penetrationis evenlessthan in the first case
becausemore acid is lost to dissolvethe damagingmateri-
als in the first 3 in. of the formation. Such simulation is
useful to adapt the treatment volumes to the severity of
the problem. The capability of quickly simulating such
Radial Distance (in.) a complex processis extremely valuable in helping field
engineersto designtreatmentstailoredto the well situation.
Diversion is usually necessarywhen more than 5 to 7
ft of formation treated. Diversion designis dealt with ex-
Figure 14-g-concentration profile of fast reacting formation
minerals after HF attack, undamaged case. tensively in Chapter 15.

,E 0.96
gj
zl
E
is 0.92
cu
3
E
5
g 0.88
2
5
‘ci
5
g 0.84
. = ,200gavfl
+=250 gal/II

‘0.804 I
2 4 6 8 IO 12
Radial Distance (in.) Radial Distance (in.)

Figure 14-lo-Concentration profile of slow reacting forma-

tion mineral after HF attack, undamaged case. Figure 14-11-HF acid spending profile in a damaged
sandstone.

14-21
RESERVOIR STIMULATION
2 4 6 a
Radial Distance (in.)
Figure 14-l 2-Concentration profile of fast reacting forma-
tion minerals after HF attack, damaged case.
0.64 , Boyer, R.C., and Chia-Hsin, Wu: “The Role of Reservoir Lithol-
2 4 6 a
Radial Distance (in.)
Figure 14-13-Concentration profile of slow reacting forma-
tion mineral after HF attack, damaged case.
14-22
14-S CONCLUSIONS
Matrix acidizingof sandstones startswith the carefulevalu-
ation of the well and the accuratedetermination of the
natureandseverityof the problem. Then, a possibletreat-
ment fluid is selected.The first selectioncriterion is the
nature and location of the damage. Then, the potential
compatibility problemsbetweenthe rock mineralsand the
fluid are examined.The composition of the fluid is fur-
ther defined by performing flow tests and checking the
absenceof damaging reactions.
As the standardhydrofluoric acid has somelimitations
in terms of too fast reaction and short penetrationand of
byproductsprecipitation, other acid solutions, still using
50 gavfl HF as the dissolving agent, have beendevisedto allevi-
ate these shortcomings. ,’
Oncethe treating fluids andthe sequenceof fluids have
beendefined,treatingparameters,suchasvolmes , rates,
and pressure,are estimatedor calculatedand simulated.
10 If the extensionand severity of the damageare knoyn,
an economicevaluation (production prediction vs treat-
ment cost)canbe performed andthe treatmentresulhscan
be optimized.
At this stageit is assumedthat the acid is injectedwhere
there is damage. Placement and diversion techniques,
which are an integral and mandatorypart of every treat:
merit, are discussedin Chapter 15. Thesetechniquesal-
low injection into eachindividual layer of just the volume
of treatmentfluids necessaryfor a given distribution of
damagein eachlayer. Finally, a comprehensivemonitor-
ing of the job effectivenessand a post-treatmentevalua-
tion are necessaryand are describedin Chapter 16.
REFERENCES
Abrams, A., Scheuerman, R.F., Templeton, C.C., and Richard-
son? E.A.: “Higher-pH Acid Stimulation Systems,” JPT (Dec.
1983) 2175-2184.
Almon, W.R., and Davies, D.K.: “Clay Technology and Well
Stimulation,” Truns., Gulf Coast Association of Geological Soci-
eties (1978) XXVIII, l-6.
Bertaux, J.: “Treatment Fluid Selection for SandstoneAcidizing:
Permeability Impairment in Potassic Mineral Sandstones,” paper
SPE 15884, 1986.
10 ogy in Design of an Acidization Program: Kuparuk River Forma- -
tion, North Slope, Alaska,” paper SPE 11722, 1983.
Brannon, D.H., Netters, C.K., and Grimmer, P.J.: “Matrix Acidiz-
ing Design and Quality Control Techniques Prove Successful in
Main Pass Area Sandstone,” paper SPE 14827, 1986.
Crowe, C.W.: “Precipitation of Hydrated Silica from Spent

Hydrofluoric Acid-How Much of a Problem Is It?” paper SPE
13083, 1984.
Crowe, C.W.: “Evaluation of Agents for Preventing Precipitation
of Ferric Hydroxide from Spent Treating Acid,” JPT (April 1985)
691-695.
Davies, D.R., Lievaart, L., and Nitters, G.: “The Effects of Cor-
rosion Inhibitors and Mutual Solvents on Matrix Acidizing Treat-
ments,” paper SPE 17153, 1988.
Doerler, N,, and Prouvost, L.P.: “Diverting Agents: Laboratory
Study and Modeling of Resultant Zone Injectivities,” paper SPE
16250, 1987.
Fogler, H.S., Lund, K., and McCune, C.C.: “Predicting the Flow
and Reaction of HCl/HF Acid Mixtures in Porous Sandstone
Cores,“, SPIY (Oct. 1976) 248-260.
Gabriel,’ G.A., and Erbstoesser, S.R.: “The Design of Buoyant
Ball Sealer Treatments,” paper SPE 13085, 1984.
Gdanski, R.D.: “Ah& Retards HF Acid for More Effective Stimu-
lations,” OGJ (Oct. 28, 1985) 111-115.
Gdanski, R.D., and Peavy, M.A.: “Well Return Analysis Causes
Re-Evaluation of HCl Theories,” paper SPE 14825, 1986.
Gidleyl’ J.L.: ’ ‘Acidizing SandstoneFormations: A Detailed Ex-
amination of Recent Experience,” paper SPE 14164, 1985.
Gidley, J.L.: “Stimulation of SandstoneFormations with the Acid-
Mutual Solvent Method,” JPT (May 1971) 551-558.
Gidley, J.L., Ryan, J.C., and Mayhill, T.D.: “Study of the Field
Application of Sandstone Acidizing,” paper SPE 5693, 1976.
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RESERVOIR STIMULATION

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