Production Engineering

Some Aspects on Acidizing

Part II
Acid-Mineral Reaction Kinetics
 Matrix Acidizing
AcidMineralReactionKinetics

Thekineticsofareactionisadescriptionoftherateatwhich
the chemical reaction takes place once the reacting species
thechemicalreactiontakesplace,oncethereactingspecies
havebeenbroughtintocontact.

Acidmineralreactionsaretermed"heterogeneous"reactions
because they are reactions between species occurring at the
becausetheyarereactionsbetweenspeciesoccurringatthe
interfacebetweendifferentphases,theaqueousphaseacid
andthesolidmineral.

Thereactionbetweenanacidandamineraloccurswhenacid
reachesthesurfaceofthemineralbydiffusionorconvection
fromthebulksolution.
 Matrix Acidizing
AcidMineralReactionKinetics

Theoverallrateofacidconsumptionormineraldissolutionwill
depend on two distinct phenomena:
dependontwodistinctphenomena:
therateoftransportofacidtothemineralsurfacebydiffusionor
convection,and
theactualreactionrateonthemineralsurface.
h l i h i l f
Often,oneoftheseprocesseswillbemuchslowerthantheother.In
thiscase,thefastprocesscanbeignored.
Forexample,thereactionratefortheHClCaC03reactionis
extremelyhigh,sotheoverallrateofthisreactionisusually
controlled by the rate of acid transport to the surface the
controlledbytherateofacidtransporttothesurface,the
slowerofthetwoprocesses.
Ontheotherhand,thesurfacereactionratesformany
, y
HFmineralreactionsareveryslowcomparedwiththeacid
transportrate,andtheoverallrateofacidconsumptionor
mineral dissolution is reaction rate controlled
mineraldissolutionisreactionratecontrolled.
 Matrix Acidizing
AcidMineralReactionKinetics

Therateofacidtransfertothereactivesurfacebydiffusion,
flow induced mixing (forced convection) mixing resulting from
flowinducedmixing(forcedconvection),mixingresultingfrom
densitygradients(freeconvection),orfluidlossintothe
formation is the first step.
formationisthefirststep.

The
Thesecondstepisthereactionratedeterminedbythekinetics
second step is the reaction rate determined by the kinetics
ofthesurfacereactiononcetheacidreachestherocksurface.

Finally,thereactionproductsmustbetransportedawayfrom
thesurface.

Tounderstandtheoverallreactionprocess,itisnecessaryto
developanunderstandingofeachindividualstep
 Matrix Acidizing
AcidMineralReactionKinetics

Schematicdiagramofsysteminwhichaddreactionoccurs
 Matrix Acidizing
AcidMineralReactionKinetics

Areactionrateisgenerallydefinedastherateofappearanceinthe
solution of the species of interest in units of moles per second.
solutionofthespeciesofinterestinunitsofmolespersecond.

Asurfacereactionratedependsontheamountofsurfaceexposed
toreaction,sothesereactionsareexpressedona
h d perunitsurface
f
areamanner.

Ingeneral,thesurfacereactionrateofanaqueousspeciesAreacting
withmineralBis:RA =rA *SB

whereRA istherateofappearanceofA(moles/sec),rA isthesurface

areaspecificreactionrateofA(moles/secm
p ( / 2),
),andSB isthesurface
areaofmineralB.

Wh
WhenAisbeingconsumed,thereactionrates,r
Ai b i d h i A andR
d A ,are
negative.
 Matrix Acidizing
AcidMineralReactionKinetics

Considertheheterogeneousreactionofanacidwithcalcium
carbonate (limestone) as
carbonate(limestone)as

Insymbolicform

Forthisreactionageneralrateexpressionis

whereCi isthesurfaceconcentrationofcomponenti,E
f f f andER
aretheforwardandbackwardreactionrateconstants,
respectively and exponents are order of reaction respect to
respectively,andexponentsareorderofreaction,respectto
componenti.
 Matrix Acidizing
AcidMineralReactionKinetics

Forareactionthatis orderinhydrogenionconcentration,
the general rate expression is
thegeneralrateexpressionis

Experimentaldatashowthatthisreactiongoesessentiallyto
completion.
completion

Therefore
Therefore,thebackwardratewillbenegligibleinmost
the backward rate will be negligible in most
applicationsofstrongacidsincarbonatesandtherate
expressionthusreducesto
p
 Matrix Acidizing
Reactions of HCI Acid with Carbonates
ReactionsofHCIAcidwithCarbonates

ThereactionbetweenHCl andcarbonatemineralsisactuallya
reactionoftheH+ withthemineral.Lundetal.(1973,1975)
measuredthekineticsoftheHCICaIcite/dolomitereactions,as

Theconstants,Ef,andE/RaregiveninTable.SIunitsare
usedintheseexpressions,soCHCI hasunitsofkgmole/m3 andT
is in K
isinK.
Thereactionrateconstantdependsontemperatureand
sometimes on the concentration of chemical species other than
sometimesontheconcentrationofchemicalspeciesotherthan
A.
 Matrix Acidizing
Reactions of HCI Acid with Carbonates
ReactionsofHCIAcidwithCarbonates

Lundetal.(1973,1975)measuredthekineticsoftheHCI
CaIcite/dolomitereactions,as
 Matrix Acidizing
Reactions of Weak Acids with Carbonates
ReactionsofWeakAcidswithCarbonates

Withweakacids,suchasaceticorformicacid,theequilibrium
constantofacidshouldbeused.

IfbothHCl andformicacidreactas orderinhydrogenion

concentrations,thekineticsofaweakacidcarbonatemineral
reactioncanbeobtainedfromtheHCl
ti b bt i d f th HCl reactionkineticsby
ti ki ti b
(Schechter,1992)

whereKd isthedissociationconstantoftheweakacidandEf is
the reaction rate constant for the HClmineral reaction
thereactionrateconstantfortheHClmineralreaction
 Matrix Acidizing
AcidMineralReactionKinetics
LaboratoryMeasurementofReactionKinetics
Inordertomeasurethesurfacereactionrateofacidmineral
reactions,itisnecessarytomaintainaconstantmineralsurface
area,andtoensurethattherateofacidtransporttothe
mineralsurfaceisfastrelativetothereactionrate.
i l f i f t l ti t th ti t
Themostcommonmethodisrotatingdiskapparatus.Inthe
rotating disk apparatus a disk of the mineral is placed in a
rotatingdiskapparatus,adiskofthemineralisplacedina
largecontainerholdingtheacidsolution.Thediskisrotated
rapidly,sothattheacidmasstransferrateishighrelativeto
p y, g
thesurfacereactionrate.
 Matrix Acidizing
AcidMineralReactionKinetics
LaboratoryMeasurementofReactionKinetics
Becauseoftherotation,thereisacentrifugaleffectthatwill
causethefluidtoflowinaradialdirectionalongthediskand
reducethethicknessofthestagnantfluidlayernearthe
surface(oftencalledthediffusionboundarylayer).
f ( ft ll d th diff i b d l )

IIndesigningarotatingdiskreactorsystem,thediskradius
d i i t ti di k t t th di k di
mustbemuchlargerthantheboundarylayerthickness(often
about 0 01 cm) and flow in the system must be laminar In
about0.01cm)andflowinthesystemmustbelaminar.In
theory,thesystemisdesignedsothatthediskspinsinan
infinitevolume;however,inaliquidsystem,ifthevessel
diameterisatleasttwicethediskdiameter,theobservedrate
isindependentofthevesseldiameter.
 Matrix Acidizing
AcidMineralReactionKinetics
LaboratoryMeasurementofReactionKinetics
thefollowingequalitybetweenreactionrateandmasstransfer
ratemustapply.

cAs istheacidconcentrationnearthesurfaceand isthe

diffusionboundarylayerthickness.

Atsmall,angularvelocities islarge,thereactionisdiffusion
controlled,andthedifferencebetweenthebulkandsurface
concentrations is large
concentrationsislarge.
Asrotationalspeedisincreased,theboundarylayerthickness
decreases thereby decreasing the mass transfer resistance
decreases,therebydecreasingthemasstransferresistance.
 Matrix Acidizing
AcidMineralReactionKinetics
LaboratoryMeasurementofReactionKinetics
Whenthereactionratenolongerincreaseswithanincreasein
rotationalspeed,theobservedreactionrateiscontrolled
entirelybythesurfacekinetics.Undertheseconditions,the
surfacekineticsareobtaineddirectly,anddiffusionratesdo
f ki ti bt i d di tl d diff i t d
nothavetobetakenintoaccountaswasdoneforparallel
plate reactors.
platereactors.
 Matrix Acidizingg
AcidMineralReactionKineticsExample
ConsiderarodofCaCO3 ,whichisrapidly(veryrapidly)rotated
inanacidsolutionsothatdiffusionandothermasstransfer
ratescanbeneglectedwithrespecttothereactionrate.The
reactionrateisthentheslowstep.SupposetheCaCO
ti t i th th l t S th C CO3 rodis
di
immersedinabathcontaining15wt%HCI.Iftheinitialrod
radius is 1 cm, what is its radius 15 sec after it has been
radiusis1cm,whatisitsradius15secafterithasbeen
immersedinthebath?Thebathtemperatureis4O"C.
 Matrix Acidizingg
AcidMineralReactionKineticsExample
Ifthemasstransferrateishighbecausetherodisrapidly
rotated,thesurfaceacidconcentrationwillapproximately
equalthebulkacidconcentration15%.
Sincethedensityof15wt%Hcl isabout1070kg/m3

So
 Matrix Acidizingg
AcidMineralReactionKineticsExample
If a=rodradius,CaCO3 =densityofCaC03 ,and =gramsof
calcitedissolvedpergramofHCIreacted

Therodradiusafter15sechasbeenreducedto0.83cm.
 Matrix Acidizing
Reactions of HF with Sandstone Minerals
ReactionsofHFwithSandstoneMinerals

Hydrofluoricacidreactswithvirtuallyallofthemanymineral
constituentsofsandstone.Reactionkineticshavebeen
reportedforthereactionsofHFwithquartz(Bergman,1963;
Hill t l 1981) f ld
Hilletal.,1981),feldspars(Fogler
(F l etaI.,1975),andclays(Kline
t I 1975) d l (Kli
andFogler,1981.)
Thesekineticexpressionscanallberepresentedby
These kinetic expressions can all be represented by

Theconstants,,Ef,andE/RaregivenintheTable.
 Matrix Acidizing
Reactions of HF with Sandstone Minerals
ReactionsofHFwithSandstoneMinerals

TheseexpressionsshowthatthedependenceonHFconc.isapproximately
f
firstorder(
d ( =1).Forthefeldsparreactions,thereactionrateincreases
) h f ld h
withincreasingHCl conc.,eventhoughHCl isnotconsumedinthereaction.
Thus,HCl catalyzestheHFfeldsparreactions.Also,thereactionrates
betweenclaymineralsandHFareverysimilarinmagnitude,exceptforthe
illite reaction,whichisabouttwoordersofmagnitudeslowerthanthe
others.
 Matrix Acidizing
Reactions of HF with Sandstone Minerals
ReactionsofHFwithSandstoneMinerals

RateConstants(Ef )fortheDissolutionofClayMineralsinHydrofluoricAcid
 Matrix Acidizing-Example
Reactions of HF with Sandstone Minerals
ReactionsofHFwithSandstoneMinerals

A2cmdiameterdiskofalbite (Nafeldspar)isimmersedina 3wt

%HF,12wt%HCl solutionat50oC androtatedrapidlyfor1hr.The
densityoftheacidsolutionis1.075g/cm3andthedensityofthe
feldspar is 2.63 g/cm3.Iftheacidconcentrationremains
feldsparis2.63g/cm . If the acid concentration remains
approximatelyconstantduringtheexposureperiod,whatthickness
ofthediskwillbedissolvedandwhatmassofHFwillbeconsumed?
 Matrix Acidizing-Example
Reactions of HF with Sandstone Minerals
ReactionsofHFwithSandstoneMinerals

Thechangeinthenumberofmolesoffeldspar,Mf ,isequaltothe
reactionrate,Rf :dMf/dt =Rf =rf*Sf

Th
Thespecificreactionrate,r
ifi i f,isconstant,sincetheacidconcentration
i i h id i
isapproximatelyconstant,and,neglectingthereactionattheedge
ofthediskandanyeffectsofsurfaceroughness,thesurfaceareaof
y g ,
thediskisconstant.Thus,aboveEquationisreadilyintegratedto
yield:Mf =rf *Sf *t

Thesurfaceareaofthediskis cm2 or x104 m2.Thespecific

reaction rate is obtained from rate equations using the data in the
reactionrateisobtainedfromrateequations,usingthedatainthe
Table.First,theacidconcentrationsmustbeexpressedinkg
moles/m3 ofsolution
Matrix Acidizing-Example
Reactions of HF with Sandstone Minerals
ReactionsofHFwithSandstoneMinerals
 Matrix Acidizing-Example
Reactions of HF with Sandstone Minerals
ReactionsofHFwithSandstoneMinerals

andthenumberofmolesoffeldspardissolvedin1hris:
Mf =(1.77x1O7)( x104)(3600)=2x107 kgmolesfeldspar

Thechangeinthicknessofthediskisthevolumedissolveddivided
bythesurfacearea:

=6.3x105 m=0.063mm

Theminussignindicatesthatthesurfaceisreceding.
 Matrix Acidizing-Example
Reactions of HF with Sandstone Minerals
ReactionsofHFwithSandstoneMinerals

Themassofacidconsumedisrelatedtothemassoffeldspar
dissolvedthroughthestoichiometry.Assumingthat20molesofHFis
consumedpermoleoffeldspar,theamountofacidconsumedis:

O
Only0.063mmofthefeldsparsurfaceisdissolvedin1hr.Since
y 0.063 o t e e dspa su ace s d sso ed . S ce
feldsparisoneofthefasterreactingconstituentsofsandstone,this
indicatesthatthereactionratesinsandstoneacidizingarequite
small.However,inthisexample,itwasassumedthatthefeldspar
ll H i thi l it d th t th f ld
surfacewassmooth,makingtheavailablesurfaceforreactionsmall.
Insandstonescomposedofsmallgrainsofminerals,thespecific
p g , p
surfaceareasofthegrains(thesurfaceareaperunitvolume)are
muchlarger,makingtheoverallreactionratemuchlarger.
 Matrix Acidizing-Example
Reactions of HF with Sandstone Minerals
ReactionsofHFwithSandstoneMinerals

Exercise
Asmallparticleofalbite (sodiumfeldspar)1mminradiusis
droppedintoalargevolumeofacidsolutioncomposedof
3wt%HFand12wt%HCI(acid =1075kg/m3 at25C)whichis
stirredvigorouslysothattheacidconcentrationnearthe
reactive surface is the same as that in the bulk phase; that is
reactivesurfaceisthesameasthatinthebulkphase;thatis,
diffusionisrapid.Lfthebathtemperatureis25C,howlong
willittakeforthealbite particletodissolveintheacid
p
solution?Comparethistimewiththetimerequiredtodissolve
thesamesizeparticleofaquartz.
 Matrix Acidizing-Example
Reactions of HF with Sandstone Minerals
ReactionsofHFwithSandstoneMinerals

Integratingresultsin

Andforquartz
q
 Matrix Acidizing-Example
ReactionsofHFwithSandstoneMinerals
TheRelativeReactionRatesofSandstoneMinerals
Asandstonecontains85%quartz,10%Nafeldspar,and5%
kaolinite bymass.Thespecificsurfaceareasofthemineralsare
approximately20m2/kgforthequartzandfeldsparand8000
m2/kgfortheclay.Ifthisrockiscontactedwitha3wt%HF,
/k f th l If thi ki t t d ith 3 t % HF
12wt%HCl solutionat50C,whatproportionoftheHFwill
initially be consumed by each of the three minerals?
initiallybeconsumedbyeachofthethreeminerals?
 Matrix Acidizing-Example
ReactionsofHFwithSandstoneMinerals
TheRelativeReactionRatesofSandstoneMinerals
Perunitmassofrock,thespecificsurfaceareaofeachmineral
isitsspecificsurfaceareatimesthemassfractionofthe
mineralpresentinthesandstone.Forexample,thespecific
surfaceareaofquartzpermassofsandstone,S
f f t f dt Sq,is
i
(20m2/kg)(0.85)=17m2/kgrock.Similarly,thespecificsurface
areasoffeldsparandkaolinite are 2 and 400 m2/kgrock,resp.
areas of feldspar and kaolinite are2and400m /kg rock, resp.
TheoverallrateofreactionofHFwitheachmineralis,

RHF,q=q *rq *Sq ,RHF,f=f *rf *Sf ,RHF,k=k *rk *Sk

wherei istheratioofthestoichiometric coefficientofHFto

that of mineral, the reactions show 6 moles HF/mole quartz,
thatofmineral,thereactionsshow6molesHF/molequartz,
20molesHF/molefeldspar,and24molesHF/molekaolinite.
 Matrix Acidizing-Example
ReactionsofHFwithSandstoneMinerals
TheRelativeReactionRatesofSandstoneMinerals
Usingthedatagiveninthetable,
RHF,q =9.4x108CHF, RHF,f =4.4X106CHF , RHF,k =5.1x106CHF

The
ThefractionofHFexpendedinaparticularreactionisthe
fraction of HF expended in a particular reaction is the
overallreactionrateforthatmineraldividedbythesumofthe
reactionrates,showingthat1%oftheHFisreactingwith
quartz,46%isreactingwithfeldspar,and53%isreactingwith
t 46% i ti ith f ld d 53% i ti ith
kaolinite.
Thisisatypicalresult,illustratingthatthereactionratesofHF
This is a typical result, illustrating that the reaction rates of HF
withclaysandfeldsparsareapproximatelytwoordersof
magnitudehigherthanthatbetweenHFandquartz.Because
th l
theclayandfeldsparreactionratesarerelativelyhighandthey
d f ld ti t l ti l hi h d th
generallycompriseasmallportionofthetotalrockmass,they
g q
willbeconsumedfirstinsandstoneacidizing.Thequartz
reactionbecomesimportantinregionswheremostoftheclay
andfeldsparhavealreadybeendissolved.
 Matrix Acidizing
Acid Transport to the Mineral Surface Diffusion
AcidTransporttotheMineralSurfaceDiffusion

Whenthesurfacereactionrateishigh,reactionofHCIwith
carbonateminerals,theoverallrateofreactionwillbe
controlledbytherateofacidtransporttothemineralsurfaces
b diff i
bydiffusionandbyconvection.
db ti
Thediffusional fluxofacidisgivenbyFick's law,

Thisequationshowsthataciddiffusiontothereactivesurface
is driven by the concentration gradient between the bulk
isdrivenbytheconcentrationgradientbetweenthebulk
solutionandthesurface.
TheeffectivediffusioncoefficientforHCIhasbeendetermined
The effective diffusion coefficient for HCI has been determined
byRobertsandGuin (1975)andisshownas,
 Matrix Acidizing
Acid Transport to the Mineral Surface Diffusion
AcidTransporttotheMineralSurfaceDiffusion

TheeffectivediffusioncoefficientofHCl asafunctionofT
 Matrix Acidizing
Modeling Heterogeneous Reactions
ModelingHeterogeneousReactions

Heterogeneouschemicalreactionstakeplaceatthesolution
mineralsurfaces;thusanacidbalancetakenaboutasmall
volumeentirelycontainedwithinthebulksolutionwillnot
i l d
includeanytermsrelatedtothechemicalreaction.
t l t d t th h i l ti
Theacidbalancewillthereforesimplybetheconvection
diffusion equation and chemical reactions will enter the
diffusionequationandchemicalreactionswillenterthe
analysisasboundaryconditions.
Figuredepictsavolumeelementdrawninafluidandas
Figure depicts a volume element drawn in a fluid and as
shown,thereisaflowinthexdirectionaswellasdiffusive
transportinboththex andydirections.
Diffusioninthezdirectionperpendiculartotheplaneofthe
figureisdisregarded
 Matrix Acidizing
Modeling Heterogeneous Reactions
ModelingHeterogeneousReactions

Sketchdepictingasmallvolumeelementwhollycontained
withinafluid.
 Matrix Acidizing
Modeling Heterogeneous Reactions
ModelingHeterogeneousReactions

Amaterialbalancetakenaboutthesmallelementisasfollows:

Dividingbyelementvolumeresultsasimplifiedformof
convectiondiffusionequation
 Matrix Acidizing
Modeling Heterogeneous Reactions Parallel Plate Reactor
ModelingHeterogeneousReactionsParallelPlateReactor

aparallelplatereactorcomposedofcloselyspacedmineral
slabswithacidflowingintheaxialdirection

Flowofacidislaminar,thewallsaresolidandsmooth,so
 Matrix Acidizing
Modeling Heterogeneous Reactions Parallel Plate Reactor
ModelingHeterogeneousReactionsParallelPlateReactor

Thisarrangementisnotthecurrentpreferredapproachfor
obtainingacidmineralreactionrates.Therotatingdisksystem
representsabetterapproach;however,theparallelplate
systemisaninterestingoneinthattherolesofheterogeneous
t i i t ti i th t th l fh t
reactionsanddiffusivetransporttothesurfaceareclearly
delineated.

Substitutinginthemodelequation
Substituting in the model equation

TheBCsare:
 Matrix Acidizing
Modeling Heterogeneous Reactions Parallel Plate Reactor
ModelingHeterogeneousReactionsParallelPlateReactor

IfwetakethereactiontoberepresentedbyEq.giveninslide
no8with"
h" =0.6,thenthedifferentialequationcanbe
h h d ff l b
integratedusingnumericaltechniques.
TheresultsareshowninFig.
The results are shown in Fig
Thequantitiesplottedaredefinedasfollows:

Averageconcentrationistheconatoutlet.
C0 istheinletconcentration
Pf isrepresentsthedegreeofacidreaction
LfD isaisadimensionlessdistanceorlength
alongtheparallelplates
Pf isaquantityrepresentingtherateof
chemicalreactiondividedbytherateofdiffusion
 Matrix Acidizing
Modeling Heterogeneous Reactions Parallel Plate Reactor
ModelingHeterogeneousReactionsParallelPlateReactor

Graphoffractionalordersurfacechemicalreactionsassociated
withlaminarflowbetweenparallelplates
 Matrix Acidizing
Modeling Heterogeneous Reactions Parallel Plate Reactor
ModelingHeterogeneousReactionsParallelPlateReactor

SmallvaluesofPf signalasmallreactionrateascomparedto
thediffusionrate,whereasalargePf relatestoveryrapid
reactions.
LargerPf aresaidtorepresentdiffusionlimitedreactions.and
acalculationwillshowthattheacidconcentrationnearthe
surface is quite small This is the case for most reactions
surfaceisquitesmall.Thisisthecaseformostreactions
involvingHCl andcarbonates.
Similarly,graphsforotherreactionordersandforlaminarflow
Similarly graphs for other reaction orders and for laminar flow
incirculartubesmaybepresentedbythestudents!
 Matrix Acidizing
ModelingHeterogeneousReactionsParallelPlateReactor
g g

Example:MeasurementofReactionRate
Supposethata15wt%Helsolutionismadetoflowatan
averagevelocityof0.5cm/secbetweenparallelslabsofCaCO3
thatarespaced0.5cmapart.Theslabsare100cmlong.Ifthe
outletacidconcentrationis13wt%and =0.6,whatisthe
forward reaction rate constant Ef ,Thetemperatureis25
forwardreactionrateconstant,E The temperature is 25C
C.
ForthiscaseDA=1.5x105 cm2/sec
 Matrix Acidizing
ModelingHeterogeneousReactionsParallelPlateReactor
g g

Oneeasilycouldcalculate

ReadingfromFig.wefindP
g g f =1.0.Basedonthisresult

Generally,weexpresstheacidconcentrationintermsof
kgmoles/m3.AsshowninExample1,15wt%HCIcorresponds
toaconcentrationof4.4kgmoles/m3
End