Matrix Acidizing

of Sandstones
14.
Bernard M. Pi& and Her& G. Perthuis
Dowel1 Schlumberger

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

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

14-4
 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- There are several types of acid/sandstonereactions and
ments; particularly, fluoboric acid formulations, which expectedresults:
have demonstrateda very good ability to avoid damag- l acid that only dissolvesthe damageand fines, such as
ing reactions (Bertaux, 1986). plain HF (or mud acid) formulations,
l fluid that dissolvesand/or dispersesdamageand fines,
14-2.5 Other Criteria For Fluid Selection
such as suspendingformulations, whether acid based
Permeability or not, and
The permeability of the formation influences the selec- l acidthatdissolvesand stabilizesundissolvedfines, such
tion of the treating fluid in two ways. First, permeability as fluoboric acid formulations.

14-5
RESERVOIR STIMULATION

An accuratedetermination of the type of damageis, Embedmentis a processby which the fracture closes
therefore, important. Damagecan be determinedfrom: onto the prop pack. It occurs when the effective closure
l type of clays and their characteristics, including stressincreasesasa result of the reservoirpressuredeple-
their size, and tion. This is a pressure-controlledprocess;it is different
l permeability and type of porosity in the sandstone. from a rate-controlled process, such as fine migration
without embedment.Hydrofluoric and/or fluoboric acids
Damagecanbe identified from this information because
can be used, but they are not the most effective way of
of the migratory fines present during production. Fines
treating this problem. The most effective remedial action
migrationrequiresan acid with a stabilizingeffect.A com-
is refracturing.
parisonof the sizeof the particlesandthe sizeof the pores
A naturally fractured sandstonenormally corresponds
may indicatethat a fluid with suspendingpropertiesis best.
to a very hard, compact, low-porosity and low-
Porethroat sizesare generally small in sandstones;there-
permeability formation. Since the reservoir productivity
fore, if the formation is not fissured, such a suspending
comesfrom the fracture system,this, in turn, must have
mechanismis effective only at a very short distancefrom
been the medium invaded by drilling fluids and solids.
the wellbore.
The presenceof silts and clays in either natural or
hydraulic fracturesmakesit necessaryto use a treatment
14.3 ORGANIZATION OF THE DECISION TREE
mechanismbasedon suspensionof the damage.Thus, a
The selectiontree shownin Fig. 14-l can be divided into suspending-typeacid is suitable. This part of the tree is
four main parts: formations damagedfrom fines migra- subdivided into two areas.
tion, fractured formations, high-permeability limy sand-
. On the left are sandstoneswith a small amount of
stones,and formations damagedduring drilling by inva-
carbonate-cementingmaterial. The HCl-HF formula-
sion from the wellbore.
tion of the suspendingacid dependson the mineralogy.
14-3.1 Fines Migration l On the right are sandstoneswith a large amount of
carbonate-cementingmaterial (HCl solubility greater
The upper left sectionof the tree correspondsto a forma-
than 20%). HCl fluids are used exclusively except at
tion damagedby native migratory fines. Fines migrate
very high temperatureswhere nonacid-typefluids are
whenthe productionrate is sufficiently high that the fluid
recommended.At temperatureslower than 150’ C, the
entrainsthe fines, which then block or bridge at restric-
exact formulation of the suspendingacids dependson
tions in the flow line (porethroatsor throatsbetweensand
the amount of ferric iron in the system.
grains in gravel packs or in propped fractures).
In hydraulically ‘inducedpropped fractures, it must be
14-3.3 High-Permeability Limy Sandstones
determinedthat this damageis really causedby migrato-
ry fines; i.e., a production rate-dependentprocess,which The lower centerpart of the treecorrespondsto sandstones
meansthere is no embedment. with a large amountof carbonate-cementing material(HCI
After the damagedisintegrates,the remaining undis- solubility higher than 20%). The damagein the matrix
solvedfmesmustbe stabilizedin place.Theuniqueproper- is causedby silts andclays.At temperaturesabove300°F,
ties of fluoboric acid (Thomas, 1979a and b) make it the suspendingor flocculating nonacid fluids (dependingon
only formulation recomended for sandstoneformations the permeability) are recommended;at temperaturesbe-
whoseproductionrapidly declinesfollowing conventional low 300 oF fluoboric acid canbe used. If the permeabili-
mud-acidtreatments.A hydraulically fractured well that ty is moderatelylow, which IScommon in gaswells, an
has experienceda rapid production decline from fines acid with a low surface tension must be used.
migration into the proppant pack (without embedment)
is also treated with fluoboric acid (Thomas and Suhy, 14-3.4 Damage By Solids From Wellbore Fluids
1979). The lower right part of Fig. 14-l correspondsto sand-
stonesdamagedwithin the matrix during drilling or com-
14-3.2 Fractured Formations pletion operations.Mud-acid formulations tailored to the
The lower left sectionof the tree in Fig. 14-l corresponds mineralogy are generally used. Low HF acid concentra-
to sandstoneswhere the damageis either in natural fis- tions are recommendedin low-permeability reservoirs.
sures or in hydraulically induced fractures with severe Mud acid-type formulations, which contain alcohols to
embedment. minimize the introduction of water in the formation and

14-6
 MATRIX ACIDIZING OF SANDSTONES

to increasethe vapor pressureand decreasethe surface l dissolvea maximum amountof carbonateto minimize
tension, are especiallyrecommendedfor gaswells. Fluo- CaF2precipitation. Acetic acid canreplaceHCl to dis-
boric acid formulations are better treating fluids in sand- solve carbonates.It actsas a low pH buffer and com-
stonescontaining potassicminerals (e.g., potassicfeld- plexing agent, which helps minimize the tendencyof
spar and illite clay). iron compoundsto precipitate as HCl is spent (Bran-
non et al., 1986).
14-3.5 Other Additives For Acid Formulations Aromatic solvents(suchas tolueneor xylene), with or
The decisionpath for additive selectionis quite straight- without HCl, can be used to remove paraffin and
forward if the necessaryreservoir information is avail- asphaltenecomponents(Brannonet al., 1986).Mutual sol-
able. The tree provides only a generalanswer. Acid ad- ventssuchasethyleneglycol monobutyl ether (EGMBE)
ditives have not beenincluded in the discussionhere be- are also usedfrequently in preflush and postflush fluids.
causethey are not designedto “remove” damage.In cer- However,theymustbe thoroughlytestedfor compatibility
tain cases,a clay stabilizer can be a viable and economi- with the oil in place. They are normally used in combi-
cal alternative to a fluoboric acid treatment. However, nation with HCl or ammonium chloride brine. Special
it mustbe consideredan integralpart of an acid treatment. precautionsmustbe exercisedwhenusingmutual solvents.
b Iron hydroxide precipitation is referred to in the tree The beneficial action of mutual solvents has been well
as an Fe problem or high Fe chlorite. Iron occursmainly documentedby Gidley (1971) andHall (1975) in the case
in the ferrousstatein minerals.Chloriteclay containssome of single phaseflow. But Muecke (1973) and Davies et
ferric iron but the solubility is relatively low in HCl. Be- at. (1988)haveshownthat in oil andwater systems,mutual
causemostproblematic ferric iron comesfrom rusty tub- solventscan mobilize fines and promote their migration,
ing, it is important to clean tubular goods with hydro- resulting in formation plugging.
chloric acid prior to the real treatment. Other additives, such as surfactants, clay stabilizers,
and complexing agents,can be formulated as necessary.
14-4 PREFLUSH AND POSTFLUSH
The fluid selectionpath in Fig. 14-l indicates only the 14-4.2 Overflush
main treating fluids. However, preflush and postflush
The role of the overflush is to displacethe main acid flush .
fluids maximizethe efficiencyof the treatingfluid. A typi-
more than 4 ft from the wellbore. If this is not done,
cal sequencefor a conventionalmud-acid (HF) treatment
precipitation of reactionproductsfrom the spentacid will
is preflush/maintreatingfluid/postflush.The sequencecan
decreaseproduction. However, the main treatmentfluid
be more complex as different preflushesare used, such
must still be carefully selectedto minimize the formation
as solvent/acid or brine/acid or even solvent/brine/acid.
of precipitatesduring the flowback. Recommendedover-
When fluoboric acid is used, whether asthe sole treating
flush fluids are:
fluid or as a preflush or a postflush to mud acid, it must
be separatedfrom any other fluid by a nonreactivespacer l NH&l, or 5% to 7.5% HCl, or diesel for oil wells,
(usually ammonium chloride brine) to prevent accelera- l NH&l, or 5% to 7.5% HCl for gas wells.
tion of the reaction rate of fluoboric acid and incompati- In all cases,a surfactantand/or a mutual solvent, when
bility between fluoboric acid and the reaction products applicable,is recommendedto leavethe formation water
from the other acids. The preflush, spacer,andpostflush wet and to facilitate flowback of spent acids. Nitrogen
should be used according to considerationsdescribedin or nitritied fluid is recommendedin low-pressure wells
the following paragraphs. to facilitate the unloading of fluids (Gidley, 1985).
14-4.1 Preflush 14-5 ACIDIZING SANDSTONES WITH MUD ACID
An HCl solutionis usuallyusedasa preflushwhen acidiz-
ing sandstonewith mud acid, Various acid strengthscan 14-5.1 Stoichiometric Equations
be used, dependingon the formation, to accomplishthe A preflush of pure hydrochloric acid is always injected
following: in sandstones prior to the main flush of hydrofluoric acid.
l displacebrine from the wellbore when an ammonium This is doneto avoid the possibleprecipitation of insolu-
chloride spaceris not used; to avoid contact between ble or slightly solublereactionproducts. Typically, these
HF acid and any formation brine containing K, Na, insolublespeciesare calciumfluoride (CaF2),which forms
or Ca; 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 When suchprecipitatehasformedbut hasnot completely

This precipitatecannotbe avoided,asit resultspartly from blocked the porosity of the formation, it may partially
the greateraffinity of fluorine for aluminum than for sili- redissolvewhenHF acid is nearcompletespendingtoward
con. This process acceleratesthe hydrolysis of SiFg-: the end of the job. At this time, the concentrationof fluo-
released F - anions are further involved in aluminum ride anionsin solution is so lowthat aluminum is hardly
complexes, and more monosilicic acid, Si(OH)d, is complexedand appearsmainIy as free A13’ ions (Labrid,
generated. 1971). Thesealuminumions are then able to extractfluo-
Certainauthors(Labrid, 1971;Shaughnessy andKunze, rine from C!aFZprecipitates,asthey did for silicofluorides,
1981; Walsh et al., 1982) have emphasizedthe highly and partly redissolve calcium fluoride according to the
damagingpotential of the precipitation of such colloidal reaction:
silica in the porous medium. However, this damagingac- 3CaFZ + 2A13t & 3Ca” + 2AlF”.
tion hasneverbeendemonstratedclearly andsatisfactorily.
On the contrary, other authors (Thomas and Crowe, This reactionmay be followed by the subsequent
equilibria
1981; and Crowe, 1984a) have shown that suchprecipi- betweenthe different aluminum and fluorine complexes.
tation, which cannotbe avoided,doesnot inducedamage;
the depositionof silica hasbeenobservedonly as a coai- Alkali Fluosilicates And Flubaluminates
ing on clay surfaces..whichlimits fines migration. Such The aluminumor silicon-fluorinecomplexescanreactwith
precipitation is beneficial becauseit, stabilizesclay and alkali ions releasedin the solution from highly substitut-
fines. As a result, the mechanismof silica precipitation ed clays or alkali feldsparsas soonastheir concentration
would likely be as describedbelow. becomessufficiently high to form insolublealkali fluosili-
When the concentrationof monosilicic acid, formed by cates and, probably, fluoaluminates:
the hydrolysis of the silicon hexafluorideanions,becomes
important, two mechanismsoccur simultaneously: 2Na’ + SiFg- + NaZSiFe
l polycondensation(found by Labrid (1971) to encom- with
passaboutone-third of total silicon), limited to oligo- KS = 412 x 10-5;
merit forms by aluminum in the solution,
2K’ -I- SiFz- + KZSiFh
l endothermic deposition of, amorphoussilica.
Precipitation begins earlier in the dissolution process with
at higher temperatnres(within 10 mm at 200’ F) because KS = i x 10-s;
of the increasedthermal agitation. It also occurs more
quickly in montmorillonite-type clays than in kaolinite 3Na’ + AlF3 + 3F- + Na3AlFh
clays becauseof the different initial Al/Si ratios in these with
minerals (molar ratio of 1 for kaolinite and lessthan 0.5,
KS = 8.7 x 10-l’;
dependingon substitution extent, for montmorillonite) .
Finally, ahuninumcanbe totally removedfrom clays,with 2K+ + AlF; + F F + KZAIFs
a correlated silica deposition at the surface(topochemi- :
with
cal reaction).
KS = 7.8 x 10-l’.
Calcium Fluoride Alkali fluosilicateprecipitationis favoredby a high level
Somecarbonatesmay remain after preflushing, either be- of hydrofluoric acid. Fluosilicateprecipitates,which form
causeof the initial amountof carbonate-cementing material from the attack of mud acid on alkali feldsparsor clays,
in the sandstonesor as a result of the carbonates’initial are well crystallized and very damaging(Bertaux, 1986).
protective siliceous coating. Also, slightly soluble, fine- Sucha damagingprecipitateforms, also, whenthe volume
crystallinecalciumfluoride readily forms whencalcitecon- of preflush is insufficient and hydrofluoric acid contacts
tacts hydrofluoric acid. This can lead to substantial formation brine containing alkali ions.
damage:
CaCOs + 2HF + CaFZ + HZ0 + CO*. Aluminum Fluoride And Hydroxide
Aluminum fluoride (AlF3) or aluminum hydroxide

14-10
 MATRIX ACIDLUNG OF SANDSTONES

[Al(OH)J in the gibbsiteform canprecipitateupon spend- This mechanismof forming iron fluorine complexesap-
ing of the acid. AIFs is especiallylikely to precipitatewhen plies only to relatively clean sandstones.In the presence
the HF/HCl ratio and HF concentrationare high (e.g., of clays, the dissolvedaluminum ions have a greater af-
1:4 or higher) (Walsh et al., 1982). These precipitates finity for fluorine than iron does.Thereforethe iron fluo-
form according to the reactions: rine complexeswill not form and iron hydroxide will still
Al3 + 3F- + AlF3, precipitate at pH > 2.2.
The natureof the precipitate(crystallineor amorphous)
A13+ + 3OH- + Al(OH)3, varies as a function of the anions present (Smith et al.,
with 1969). Ferric hydroxide can be strongly bound to the
K = I()--32.5
s quartz surfaceby electrostaticinteractions, for its point
of isoelectric chargelies abovepH 7. In the presenceof
Ferric Hydroxide Or Carbonates excesscalcite, the dissolvedcarbon dioxide can also lead
Ferrous or ferric ions in the acidizing mixture can come to precipitation of insoluble ferric carbonates(siderite or
from pipe rust incorporated by shear effect of flow or ankerite).
releasedfrom iron-bearing minerals (chlorite, hematite, Iron-bearingprecipitatescanbe preventedby maintain-
pyrite, and glauconite). The usual ferrous/ferric ion ra- ing a low pH in the damagedzone, by reducing anaero-
tio encounteredin acidicmixturesis 5-10:1 (Crowe, 1985). bic conditions, and by using clean equipment. If a large
This ratio takes into account.only the iron from iron- quantity of iron is present, adding suitable complexing
bearingminerals.Most iron is dissolvedinto the acid mix- agents in acid can prevent ferric hydroxide formation
turesby simplecontactwith the steelfrom tanksandpipes. (Crowe, 1984b). Usual complexing agentsare:
This dissolved iron occurs mainly as ferric ions (rust), . acetic acid (up to 150’ F),
which are potentially damaging. l citric acid (up to 275 ’ F),
Someof the ferric ions from the pipe rust can be elimi-
nated during pumping through the reaction with tubing l tetrasodium salt of ethylenediaminetetraceticacid
metallic iron: (EDTA) or nitrilotriacetic acid (NTA) (up to 350 ’ F);
more stablecomplexesareformed with EDTA andiron
2Fe3’ + FecsOlid) + 3Fez+. than with EDTA and aluminum.
The sametype of reduction can occur naturally in sour The possibleprecipitation of organic acid calcium salts
wells, as a result of the action of hydrogen sulfide: often usedat high temperaturesmust be consideredwhen
2Fe3’ + H$ + 2HZ0 + S(s)+ 2Fe” + 2H30’. using theseagents.The addition of strongreducingagents
is also a good means of preventing ferric hydroxide
In additionto the depositionof elementalsulfur, insolu- precipitation (Crowe, 1985).
ble ferroussulfidecaneasilybeprecipitatedat a pH greater
l EDTA plays this role above 250’ F.
than 1.9 by the reaction with excessacidic hydrogen sul-
fide (H$YHS- with Ka = 10m7): l Erythorbic acid works up to 400 oF with an efficiency
of 7 to 10 times that of citric acid.
Fe” -k H$ + HZ0 + FeS + HS- + H30’.
Ferrous‘ions can hardly lead to precipitated ferrous 14-5.3 Kinetics: Factors Affecting Reaction Rates
hydroxide in the near-wellborearea, sinceit forms when This subsection summarizes qualitatively the results
the pH is higher than 6. Ferric iron is normally more describedin detail in Chapter13. Sincetheoreticalaspects
problematicas ferric hydroxide precipitatesabovepH = were covered in Chapter 13, only practical implications
2. However, in the presenceof fluoride anions,ferric ions are discussedhere.
are complexedand Shaughnessyand Kunze (1981) have Kinetically controlled reactions (surface reaction-
shown that precipitation of ferric hydroxide doesnot oc- limited) are effective during the acidization process of .
cur until there is a pH of 5 to 6: sandstones,and factors affecting reaction rates are dis-
cussed to complete previous thermodynamic
Fe3’ + 3OH- + Fe(OH)3, considerations.
which precipitates at pH > 2.2 as KS = 10m3’;
Hydrofluoric Acid Concentration
FeFzmn(complexes) + 3OH- + Fe(OH)3,
Dissolution reaction rates are proportional to the
which precipitates at pH > 5. hydrofluoric acid concentration(Fogler et al., 1976;Kline

14-11
RESERVOIR STIMJLATION

et al., 1981) for most sandstoneminerals, except smec- This is the acid (proton) catalysismechanismproposed
tite. This explains why formations with low competence by Kline (1980) for feldspar.
(weak cementation, potentially mobile fine particles) l Dissolutionreactionis a first-orderreactionwith respect
shouldbe treatedwith a reducedstrengthmud acid (1.5% to HF concentrationfor most aluminosilicate miner-
HF) to avoid crumbling, especially at bottomhole tem- als. Nevertheless, dissolution kinetics is better
peraturesgreater than 200 ’ F. Fluoboric acid performs representedby a Langmuir-Hinshelwood type law in
similarly becauseof the very low concentrationof HF the caseof sodiummontmorillonite (Kline and Fogler,
present at any time. 1981):

Hydrochlotic Acid Concentration KKadsP-W

R= (14-3)
Dissolution reaction rates generally increasein a more 1 + KadsD-1 ’
acidic medium, as the leachingof constitutivesurfaceca- in which KOdsis the equilibrium constant of the ex-
tions involves their replacementby protons, but the de- othermic adsorptionof HF moleculesat surfacereac-
pendency on HCl concentration is not straightforward tive sites. This adsorptionconstantis independentof
(Gdanski, 1986). The principal role of hydrochloric acid the total acidity, while K increaseswith proton con-
is to prevent secondaryprecipitations by maintaining a centration (acid catalysis). KadJis especiallyhigh for
low pH. The other main effect of hydrochloric acid is to a mineral having a high cationexchangecapacity,such
catalyzethe attack of sandstonemineralsby hydrofluoric assodiummontmorillonite. For mostother clay miner-
acid. The mechanismand degreeof catalysisdependon als the value of this adsorptionconstantis small.There-
the type of mineral, as shown below. fore, when 1 B KadJHF] the expressioncan be sim-
l For instance,the reaction rate measuredat 35 ’ ‘C for plified to the experimentallydeterminedfirst-order ki-
pure quartzhasthe following expression(Fogler et al., neticslaw. An elementalmechanismdifferent from that
1976): mentionedfor feldsparscanbe proposedto explain the
= 9.2 x lo-’ (1 -I- 0.8 [H+]) [HF] kinetics and to take into account solely the HF
c?quartz
adsorption:
(moles quartz/cm2/s). (14-l)
F
l , In the caseof a feldspar having the Na - 0.72K - I
0.08Ca - 0.2Al - 1.2Si - 2.80g overall formula, ~0 OH HO H OH HO OH
the following expressionhasbeen determined(at 25 o I I Ill I I
C under 275 kPa pressure)asthe reactionrate (Fogler -X-O-X- +HF+ -X-O-X- Y=-X-F+HO-X-
et al., 1976):
where
qfeldspar = 1.3 x lo-’ (1 + 0.4 [H+]) [HF]
X = Al or Si.
(moles feldspar/cmVs). (14-2)
An elementalmechanismhasbeenproposedto explain Temperature
the previous variation. It involves the adsorptionof pro- Dissolutionof mineralsis a thermally activatedphenome-
tons on the surfacethat weakensthe siloxane bandings, non; thus, the rates increasedrastically as a function of
followed by the reaction of hydrofluoric acid molecules temperature(approximatelymultiplied by two for quartz
that createsunstablesilicon-fluorine bondsat the surface, for a 25 ‘C increment), and the penetrationdepthsof live
according to the scheme: acid diminish accordingly. In the caseof quartz, the acti-
vation energy is about 5.2 kcal/mole, and in the caseof
H the previous feldspar, it is about 8 kcal/mole (Fogler et
I al., 1976).
-x -0 -Si- +Ht - -X- 0 . ..Si’ - + HF - Fig. 14-5showsthe variationof the reactionrateof mud
-X -I- FSi- + H20 acid with vitreous silica (more reactive than quartz) as
a function of both HF concentration and temperature
where (Smith andHendrickson,1965).Aluminum andiron solu-
X = Al or Si. biIities also increaseslightly with a rise in temperature.

14-12
 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 time and thus has a lower reactivity. However, it gener-
et al. (1986) use the reaction model developedby Fogler ates more HF, as HF is consumed,by its own hydroly-
and various coworkers (see particularly Hekim et al., sis. Therefore, its total dissolving power is comparable
1982). Such a simplified, two-pseudocomponentmodel to a mud-acid solution. Fluoboric acid solutionsare used
and macroscopicdescription can be usedbecauseFogler as a preflush before treating formations sensitiveto mud
has shownthat the order of reactionof HF acid with each acid; this avoids fine destabilizationand subsequentpore
pseudocomponentis equalto unity relative to the concen- clogging. They are also used as a sole treatment to re-
trations of HF and of the pseudocomponent.The flow is move damagein a sandstonematrix with carbonatece-
consideredstable. ment or in fissuresthat containmany clay particles. Fluo-
In such a model, the mineral dissolution fronts can be boric acid is also used as an overflush after a mud-acid
computed and the concentrationof remaining clays (or treatmentthat hasremovednear-wellboredamage(up to
fast reactingmaterials)canbe calculated.Then, the perme- 0.5 ft) to allow an easierpenetrationof the fluoboric acid
ability increasecanbe estimatedfrom the changein porosi- solution (a few ft). Fluoboric acid is also particularly
ty (or amountof material dissolved). The velocity of the recommendedwhenthe sandstonecontainspotassicminer-
mineral dissolution front dependson the “acid capacity als by avoiding damagingprecipitatesand in the caseof
number,’ ’ which is a function of the volume of clays (or fines migration due to its fines stabilization properties.
fast reacting dissolvable material) and of the acid In the field, it is easily preparedby mixing boric acid
concentration. (HsBO.J, ammoniumbifluoride (NHdF. HF) , and hydro-
The acid concentration (or spending) front can be chloric acid. Ammonium bifluoride, an acidic salt of
modelled similarly. The thickness of the front depends hydrofluoric acid, reacts first with hydrochloric acid to
on the Damkohlernumber,which is a functionof the reac- generatehydrofluoric acid:
tion rate andthe acid velocity. Suchsimulationsshowwhy
NHdF. HF + HCl - 2HF + NH&l.
the HF acid does not penetratedeeply into the reservoir
before spendingunlessunrealistically large volumes are Tetrafluoboric acid is formed as a reaction product of
used.(Thesewould almostdissolveeverythingaroundthe boric acid with hydrofluoric acid, according to:
wellbore and thus leave the reacted formation totally HjBOs + 3HF - HBFsOH + 2HZ0 (quickreaction),
unconsolidated.)
and
14-6 OTHER ACIDIZING FORMULATIONS HBFsOH + HF + HBFd + HZ0 (slow reaction).
Problemsrelatedto the useof mud acid to removedamage
in sandstoneformations include: Hydroxyfluoboric acid (HBF30H) probably does not
l Rapid spendingprovides only a short penetration, es- exist in aqueoussolutionsunlessit is in equilibrium with
pecially at high temperatures(maximum depth about fluoboric acid (Wamser, 1948). The last reaction above
30 cm). is of an order equalto unity with respectto both HF and
H13F30H.For this reaction,equilibriumis attainedat room
l Fines, composedof either mostly quartzor mostly clay temperatureafter nearly 40 minutes for a resulting 1M
minerals,canbe generatedduring the acid reactionand HBF4 solution. Since the equilibrium constantat 25 ’ C
can migrate with fluid flow. Destabilization of fines is KZ = 2.3 x low3 (Wamser, 1948), about 6% (molar)
can leadto a quick production decline after treatment. HBFd is convertedinto HBFjOH at equilibrium for a 1M
Gravel-packedgaswells canexhibit a 50% productivity HBF4 solution. These equilibrium considerationsmean
reduction. that at any giventime andplacethereis only between0.1%
l The high dissolving power of mud acid destroysrock and 0.2 % (weight) of free HF at ambienttemperatureand
integrity at the formation face. 100’ C (212’ F) respectively.
New sandstoneacidizing systemsare designedto al- Fluoboric acid is a strong acid of strengthcomparable
leviate these shortcomings. to that of hydrochloric acid (Maya, 1977); thus, the fol-
lowing reaction occurs in the solution:
14-6.1 Fluoboric Acid
HBFd + HZ0 - H30+ + I3F;.
Fluoboric acid has been recommendedby Thomas and
Crowe (1981) as an alternative to mud acids. It doesnot In the following text, reactionsare written using BFF
contain large amountsof hydrofluoric acid at any given insteadof HBF+ Acid strength diminishesin this order:

14-14
 MATRlX ACIDIZING OF SANDSTONES

fluoboric, hydroxyfluoboric [the strength of which can tion reaction of clays with fluoboric acid is a first-order
be comparedto that of trichloroaceticacid (Maya, 1977)], reaction with respectto the fluoborate concentration, as
and boric acid (pKnsuOs = 9.2 at 25 ’ C). it is for mud acid with respectto HF concentration.
The dissolvingpower of fluoboric acid resultsfrom the The spendingrate of fluoboric acid on glass slides at
generationof hydrofluoric acidthroughits hydrolysis;i.e., 150’ F is one-tenththat of a mud acid having the same
total HF content(ThomasandCrowe, 1981). Sinceamor-
BF; + HZ0 * BF30H- + HF.
phous silica reactsfaster than quartz, limited deconsoli-
The BF30H- anionscanbe further hydrolyzed succes- dation of coresnear the injection face is observedduring
sively into BF*(OH)L, BF(OH)l andH3BOswith the cor- flow testswith fluoboric acid. This is comparedto com-
relatedHF formation,but thesereactionsmustbe takeninto plete crushing with mud acid. (The decreasein compres-
accountonly when the BF30HV concentration is lower sive strength of the treated cores is reducedby 30% to
than 3 x lOL3 at 25’ C (Wamser, 1948). In the follow- 50%.)
ing text, BF30H- hydrolysis hasbeenneglectedat usual The unique advantageof fluoboric acid is that it pro-
acid concentrations. vides an efficient clay/fine stabilizationthrough reactions
The hydrolysis reaction kinetics of fluoborate ions is relatedto borateand fluoborate ions. Swellableclays are
affected by: desensitizedby fluoboric acid: a strong decreasein ca-
l the concentrationof the fluoborate ions, tion exchangecapacity (e.g., minus 93% after 18 hours
l the medium acidity that has a catalyzing effect (reac- in fluoboric acid at 150’ F for a Wyoming bentonite)was
tion is proportional to the proton concentration), noticed ‘by Thomas and Crowe (1981).
After a fluoboric acid treatment, migrating clays and
l andthe temperature,throughtheusualactivationenergy
other fines stabilize as a result of the rock’s exposureto
effect.
acid. This is the reasonfor the long shut-in time recom-
Thus, the reaction rate, assumingthe reversereaction mendedin fluoboric acid treatments. During injection,
is negligible, can be expressed,after Kunze et al. (1983), while the acid spendsnormally, coresjust treated with
as: fluoboric acid exhibit a normal increasein permeability.
d VLI However, there is no long-term stabilization after treat-
q=- = K [H30+] [BFd-] (14-4)
dt ment becauseonly part of the clays dissolved; the rest
did not havetime to stabilize. Additional shut-in time al-
in moles/lit/min, lows this stabilization.
with When treated by fluoboric acid, montmorillonite
progressively decreasesin aluminum content and then
26,183 progressively incorporatesboron atoms; silicon precipi-
K = 1.44 x 1017exp - 1 987T
1 (14-5) tatesfrom the solution. Coresoriginally containing 30 %
silicoaluminatesat 150’ F attainedmaximum static solu-
in (mol/lit) - ’ min- ‘, bilities after only 24 hours in the presenceof 1M HBFd.
and T = temperaturein K ‘. (4 hours in the caseof mud acid), whereasthe maximum
increasein permeability is obtainedafter only 4 hours un-
Thus, the reaction rate is increased300-fold when the der dynamicconditions.Theseresultsprove thedissociated
mixture is heatedfrom 25 ’ C to 65 ’ C and is increased effectsof mineraldissolutionby the generatedhydrofluoric
12,000-fold when heatedfrom 25 o C to 105o C. Since acid (essentiallykinetically controlled) and of the parti-
the hydrolysis reaction kinetics is not affected by clays, cle stabilization resulting from slow complex dissolu-
fluoboric acid is not considereda strongly retarded acid tiomreprecipitation mechanisms(toward thermodynam-
in normal use. In the presenceof excessbentonite, pure ic equilibrium) during the shut-in period.
0. 1M initial fluoboric acid is spentwithin 30 minutes at Original kaolinite clay platelets-pure aluminosilicates-
150’ F (Kunze and Shaughnessy,1983). that are not dissolved by fluoboric acid appear welded
The reaction of fluoboric acid in sandstonesinvolves together and to the quartz grains when examinedunder
at the sametime the hydrolysis reactionof fluoboric acid, a scanningelectron microscope. A type of chemical fu-
the classicalreactionsof the generatedhydrofluoric acid sion of any fines seemsto take place slowly onto the sili-
with minerals,and additionalslow reactionsrelatedto the ca surface.The formation of borosilicate“glass” hasbeen
fluoborate ions in liquid phase.As expected,the dissolu- 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 Figure 14-7-SEM picture of the same pore after an 8%
place at the rock surfaceby adsorption followed by ion HBFh treatment.
exchange,but the yield of this heterogeneousprocess
seemshighly doubtful for several reasons. 14-6.3 Alcoholic Mud Acid
l If HF acidwere to be generatedthrough sucha process, Alcoholic mud-acid formulations are a mixture of mud
it would be a very small quantity, hardly enough to acid and isopropanolor methanol(up to 50%). The main
etch the surface of the clay material. application is in low-permeability dry-gas zones. Dilu-
l As this process is based on the CEC of the clays, tion with alcohollowers the acid/mineralreactionrate and
migrating kaolinite would hardly be touched. provides a retarding effect,

14-16
 MATRIX ACIDIZING OF SANDSTONES

Cleanup is also facilitated; acid surface tension is Dependingon the bottomholetemperature,different or-
decreasedby the alcoholswhile the vapor pressureof the ganic esters are used:
mixture is increased, which improves gas permeability methyl formate between 130’ F and 180o F, with the
by reducing water saturation. reactions:
HCOOCH3 + HZ0 * HCOOH + CH30H
14-6.4 Mud Acid Plus AlC13 For Retardation slow, rate-controlling reaction
An acidizing systemto retard HF-minerals reactionshas HCOOH + NH4F $ NH: + HCOO- + HF
beenproposedin which aluminum chloride (AK&) is ad-
dedto mud-acidformulationsto complexsomeof the fluo- ammonium salt of monochloroacetic acid between
ride ions in the injected mixture, according to the reac- 180’ F and 215” F:
tions (Gdanski, 1985): NH; ClCH$OO- + HZ0 e HOCHJJOOH +
NH: + Cl-
AlC& + 4HF + HZ0 $ AIFd- + 3HCl + H30+, methyl acetatebetween I90’ F and 280’ F.
AlF‘,- + 3H30+ F+ AIF; + 3HF + 3HZ0. Reagentchoiceis intendedto limit at 30% (maximum)
the generationof hydrofluoric acid during pumping of the
However, this procedure is tantamountto adding dis- mixture in the tubing; thus, a minimum of 40 minutes of
solutionreatitionproductsto the mixture beforethesereac- spendingtime seemsnecessary.However, field tests of
tions occur. In theory this should slow down the rates. these systemshave not been conclusive. Many precipi-
However, the retardationof clay dissolution hasnot been tatesform in theselow acidic systems,suchas ralstonite
proved experimentallybecauseof the prime importance (NHaMgAIFJ , and other fluoaluminates(silicates)upon
of the high surfaceareason clay reactivity, much more spendingof thesemixtures on clays; thus, the useof com-
important than a slight depletion of acid at high tempera- plexing agentsor acids, such as citric acid, is suggested.
tures. The risk of earlyprecipitationof damagingproducts, Besides,formation sensitivity after treatni?nthasnot been
such as aluminum fluoride (AIFS) or fluoaluminates, is tested, and handling problems arise from the high flam-
probably increasedby the use of an acid, already con- mability of methyl formate.
taining aluminum ions, before reaction. Flow testshave Overall, these systemshave many drawbacks. Based
showna smallereffectivelive acid penetrationthan in the on the hydrolysis of various organic esters,they are tem-
case of mud acid. peratureactivated.Unlike fluoboric acid; where new HF
is generated only upon spending, no equilibrium is
14-6.5 Organic Mud Acid reached.This meansthat more HF is geheratedas tem-
As total acidity speedsup mineral dissolution with mud perature increasesand the ester can eventually be com-
acid, organic mud acid involves the replacementof 12% pletely hydrolyzed long before reaching-the final depth
HCl by organic acids (typically 9 % formic acid, a weak of damage.The true degreeof retardationdependson tem-
acid only partially dissociated),mixed with 3 % HF, to peratureandpumping time. Theseestersare more expen-
retard hydrofluoric acid spending.This systemis particu- sive and more dangerousto handlethan HCl or inorgan-
larly suitedfor high-temperaturewelIs (200O-300oF) , for ic salts (flammability). More precipitatesare formed as
which pipe-corrosion rates are diminished accordingly. a result of the poor solubility of the organic byproducts.
This systemalso reducesthe tendency to form sludge. The orily advantageover the reduced-strength HF is lower
corrosion rates.
14-6.6 Self-Generating Mud-Acid Systems
These acidizing systemswere originally developed by 14-6.7 Buffer-Regulated Hydrofluoric Acid Systems
Templeton et al. (1974), and their application has been Other high-pH acidizing systemsproposedfor use up to
widenedrecently by Abrams et al. (1983). They involve 360’ F involve the buffering effect of an organic acid and
the hydrolysis of organic estersinto the corresponding its ammonium salt, mixed with ammonium fluoride, as
carboxyIic acids, followed by the reaction of theseacids a hydrofluoric acid precursor (Abrams et al., 1983). To
with ammonium fluoride to yield hydrofluoric acid. As minimizecorrosion,the useof the sameuninhibitedbuffer,
the hydrolysis reaction is activated by temperatureand without ammoniumfluoride as a preflush,hasbeenrecom-
the acidity obtained is not as strong as with mud acid, mendedup to 350 ’ F. The ammoniumsalt of the organic
a low corrosion rate of tubular goodsas well asa delayed acid is generatedfrom the partial neutralizationof the acid
reaction of the progressivelygeneratedhydrofluoric acid with ammonium hydroxide. The different proposed
are expected.The latter would allow deeppenetrationof buffered systemsare:
live HF.

14-17
RESERVOIR STIMULATION

l formic acid/ammoniumformate with pH = 3.5 to 4, Design engineersmust recognizethat every one of the
l acetic acid/ammoniumacetateand citric acidlarnmo- abovepoints is equally importantandnonecanbe exclud-
nium citrate with pH = 4.5 to 5. ed. Failurescanoccurby leavingout anysinglestep.Other
To extend the application to higher temperatures(up factors must be consideredbefore finalizing a proposal
to 550 ’ F), an excessof ammonium salt is formed by us- for a pumping schedule:
ing a higher ammoniumhydroxide/organicacid ratio. As l circulating out wellbore fluids that could be damaging
the kinetics of clay dissolution increaseswith the fluo- to the formation,
ride ion concentration,more ammoniumfluoride is added * constraints, imposedby completion, that prevent the
to compensatefor the pH increase(Scheuerman,1985). use of certain fluids (e.g., corrosion) or techniques
Successfulin-depthstimulationhasbeenobservedwith (e.g., mechanicaldiversion), and
this systemonly for bottomholetemperatureslower than l availability of materials.
54 ’ C. In mostcases,many damagingprecipitatesareno- As for any other design problem, the quality of the
ticed when using this system(fluosilicates,fluoaluminate proposal strongly dependson the quality of the informa-
often involving ammonium), the formation of which is tion collectedon the well condition,laboratorytests,reser-
relatedto the weakacidity in the near-wellborearea.These voir parameters,and completion description.
systems suffer from the same drawbacks as the self- It is assumedhere that the first three stepshave been
generatedmud-acid system. completed; i.e., a comprehensivereservoir justification
of the treatmenthasbeendoneand that stimulation fluids
14-7 MATRIX ACIDIZING DESIGN have been selectedaccording to recommendationssuch
A typical designfor a stimulationjob should involve the as those described in Sections 14-2 and 14-3.
following major steps:
14-7.1 Pressure For Injection
Ensurethat the well is a candidatefor matrix stimu-
lation; i.e., clearly establishthat the well is damaged. Matrix acidizing is defined as the injection of fluids at
Much of this hasbeencoveredin detail in Chapter1. pressuresbelow fracturing pressure. The injected fluid
flows either through the existing porous medium or
21 Establish the cause of damage, its severity, and through new passagewayscreatedby the fluid itself.
location. Any “matrix” treatmentthat exceedsthe fracturepres-
3) Selectthe proper formulation of treating fluids, in- sure is undesirablebecausethe acid may not dissolve or
cluding additivesthat will removethe damagewithout dispersewellbore damage.While fractures are essential
damagingthe rock through formation of secondary in low-permeability reservoirs, in higher permeability
precipitates, sludge, etc. This may require laborato- reservoirs the newly formed fractures may bypass the
ry tests. damagedarea and may not clean the formation around
4) Determinethe pressureand/or rate for injection with- the wellbore. The createdpermeabilitycontrastwould not
in matrix flow regime; i.e., without fracturing the be adequate,and the bypasseddamagewould remain.
formation. Fracturesmay also extendthrough zone boundariesand
Determinethe volume of treating fluid to be injected lead to an increase in water or gas production.
per foot of perforated interval. A major step in designing a matrix acidizing job is to
determinethe conditionsfor matrix flow regime.To avoid
If the reservoir is multilayered or if the pay zone is fracturing the formation, the bottomhole pressuremust
very thick, determine a placementtechniqueto en- not exceedthe fracturingpressure.The calculationof frac-
sure each foot of the reservoir receives the proper turing pressurehasbeendemonstratedin Chapter2. De-
amount of fluid. termining bottomhole pressuresfrom wellhead data is
7) Determine possible shut-in times, plan diverter shown in detail in Chapter 16.
cleanup,andmakerecommendations for returningthe
well to production or injection. 14-7.2 Determination Of Maximum Injection Rate
Assessprofitability of treatment by estimating in- The maximum possibleinjection rate that doesnot frac-
creasesin productivity or injectivity vs the cost of ture the formation is derived from Darcy’s radial flow
the treatment itself. equation:

14-18
 MATRIX ACIDIZING OF SAh’DSTONES

4.917 x lO-6 kh [(Q x H) - Aps‘+ - p] Thesefunctions can be satisfiedby hydrochloric acid.

q.WIOX= Dependingon the carbonateand clay contentsof the for-
pB (ln ~JJ-,~+ s) mation and its permeability, 5 % to 15% HCl or 5 to 10%
(14-6) aceticacid is used. The volume of this acid preflush also
whereqirnmis the injection rate (BPM), k is the effec- dependson the carbonatecontent, but certain minimum
tive permeability of the undamagedformation (md); 11is volumescanbe derivedbasedon the displacementof con-
the net thicknessof the formation (ft); gfis the fracture natewater andinter-mixingof fluids while they arepumped
gradient (psi&); H is the depth (ft); Apsafeis the safety down the tubing.
pressuremargin (200 to 500 psi); p is the reservoir pres- The volume required to displaceformation fluids to a
sure (psi); p is the viscosity (cp); re is the drainageradius radial distance, rS, can be estimatedby
(ft); r,,, is the wellbore radius (ft); and s is the skin fac- Vp = 7.48 [t$ (rj? - t-i) x] (14-7)
tor (dimensionless).The formation volume factor, B, is
very near unity. where r,,, is the wellbore radius (ft); rS is the depth of
Eq. 14-6 is a simplified inflow performancerelation- damage(ft); and l$ is the pore volume (gal&t).
ship; it doesnot accountfor transient effects, multiphase The volume requiredto dissolveall acid-solublemateri-
flow, or reservoir heterogeneities.The injected fluid is als up to a radial distance, rS, is given for HCI by:
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 where VHcl is the volume of HCI required (gal/ft); XHcl
as a guideline for determining the initial rate. is the weight fraction of formationmaterialsolublein HCl;
/3is the dissolving power of the acid (gallon of rock dis-
14-7.3 Fluid Volumes: Experience solvedper gallon of acid); rS is the radius of damage(ft);
Acid flows through sandstonesin a uniform and stable and r,,, is the wellbore radius (ft). :,
manner.As a consequence,unlike HCI treatmentsof car- When the carbonatecontentof the sandstonereservoir
bonates, it is not the purpose of mud-acid treatmentsto is very low, it may seemthat only a small volume of HCl
createnew permeability by dissolving part of the forma- preflush, or no HCI at all, is necessary.It may appear
tion. This, in fact, would deconsolidatethe formation. In- that a solventand/orbrine preflushis sufficient.However,
stead, they are intended to dissolve damagingmaterials a substantialHCl preflushvolumeis still necessaryto com-
plugging the pore channels and thereby increase pletely exchangethe cations of the clays by protons. If
permeability. this step is not done, clays will be abIe,to exchangeand
Acid reactionswith sandstoneformations are complex extract protons from the main HF acid flush. This will
sinceHF could reactwith feldspars,clays, and other sili- increasethe pH of this fluid and will certainly induce un-
cate and carbonateminerals, often of undefined chemi- desirable precipitations (Gdanski and Peavy, 1986).
cal compositionandwidely variable physicaldistribution.
When acid reaction modeling is not available, volumes Acid Volumes
used are the ones experiencehas shown to be most cost The acid formulation generally usedis a 12%-3% mix-
effective, ture of hydrochloric and hydrofluoric acids plus inhibi-
In general,the mosteffectiveacidizingtreatmentis com- tor and any other special additives required for the for-
posedof three parts: namely, a preflush, the acid formu- mation to be treated, including diverting agents. Other
lation, and an overflush. strengthsof acidsand other ratios of HCl to HF acidscan
be usedto help prevent secondaryprecipitationproblems.
- Prejlush Volumes
The HCl acid maintains a low pH to avoid deposition of
The preflush servesseveral important functions. It CaFz, AlF3, and other complex reaction products. This
l provides a separationbetweenconnatewater and HF issuehasbeenaddressedin Sections14-2, 14-3, and 14-5.
to help prevent the formation of potentially damaging The optimum designfor regular mud-acidvolumes ap-
sodium or potassiumfluosilicates, and pears to be 125 to 200 gal per foot of formation. This
l reactswith carbonateminerals in the formation to pre- value is basedon many treatmentsthroughout the world
vent their reaction with HF. 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 files after attack. To do that, rock mineralogic composi-
Seaand by Smith et al. (1965). However, a recent study tion is required and minerals are lumped into two
by Gidley (1985) showsthat many successfulsandstone categories:quartzor slow reactingspeciesandall the other
acidizing treatmentshave been performed with smaller mineralsthat are fast reacting. An exampleof suchsimu-
volumes of acid. lation is given in Figs. 14-Sto 14-10, where the attack
Since the purposeof sandstoneacidizing formulations of a lOO-md,15% porosity sandstonereservoiris modeled.
is damageremoval, the amount and location of which is In this example,the wellbore radius is 2 in. and the for-
poorly known, sometrial-and-error or onsite injectivity mation is composedof 75% quartz and25 % other miner-
measurementsare used to optimize the volume. als. A standardmud-acidsolution(3 % HF) is injectedinto
In order to limit such trial-and-error exercise, a real- the formation at a rate of 0.01 BPM/ft. The acid-spending
time onsite treatment evaluation method (Prouvost and profile on the nondamagedformationis shownin Fig. 14-8
Economides, 1987and 1988) is usedto determinewhen for various volumes of acid. The relative concentrations
the damagehasbeenremovedand decide if enoughfluid of the fast reactingminerals and of the quartz framework
has been used. This techniqueis detailed in Chapter 16. are shownin Figs. 14-9and 14-10for the samedata.These
data demonstratethat large volumes of acid are needed
Oveflush Volumes to achievemoderatepenetrationwith such a homogene-
The overflush for mud acids canbe either 3 %- 10% HCI, ous dissolution process.
NH&l, or a light hydrocarbon, such as diesel oil. For The objectiveof matrix acidizing is to removedamage,
a gas well, nitrogen may be used. Other overflush for- but the simulation requires damageparametersobtained
mulations can be consfderedfor special purposes, such from well testing.When parametersareunknown, differ-
as to facilitate diverter cleanup. ent simulationruns canbe madewith varying parameters.
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.
A = 150 iai/ft
Flowback 0 =200 gal/ft
Flowbackof spentfluids from conventionalmud-acidtreat- + = 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

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.
2 4 6 a 10 If the extensionand severity of the damageare knoyn,
Radial Distance (in.) an economicevaluation (production prediction vs treat-
ment cost)canbe performed andthe treatmentresulhscan
be optimized.
Figure 14-l 2-Concentration profile of fast reacting forma- At this stageit is assumedthat the acid is injectedwhere
tion minerals after HF attack, damaged case. 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.

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14-22
 MATRIX ACIDIZING OF SWDSTONES

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Smith, C.F., Crowe, C.W., and Nolan, T.J. : “Secondary Depo-
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RESERVOIR STIMULATION

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