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SPEH)OE
aoolstyof
Potrolwn Er@rrasra
U.S. Oapmtmant
of Ermrgy
SPE/DOE 20238
Design and Optimization of Alkaline Flooding Formulations
T. Ft. French and T,E, Burchfield,
SPE Membsrs
This paper waa prepared for preamlatlon at the SPE/DOESevanlh Sympoalumon EnhanoadOil Raooveryheld In Tulsa, Oklahoma,April 22-25, 1SS0.
Thla paper was aeleotedfo- preaarrtatlonby an SPE ProgramOommlffeefollowing review of information contained in an abatract submitted by the author(s).Contelt, of the paper,
ae prewnted, have not bean eviawad by the Sooletyof PetroleumEndnwrs and aro subleof to mmectlon bYthe author(a).The materfalt ~ PreWnf@ does not n~~*~lY ~fl~t
ormembara.ParmrafxewnteddtspE mwtinware8ubl@towbli~tionre~ewWEdltofialQJmminwbof fhe ~lav
anYpoaitlonof the Sooietyof Pmolaum Englnwra,ireofficers,
of PetroteumEnglnwra. Perrniwionto oopyis rwtrlotd to anabatrwf of not morethan SWwords.Illustration maynot be 00PIed.Theabafraotshouldoontainoormplouousacknowtadgment
of where and by whom the papar is presented. Write Publlcationa Manager, SPE, P.O. Box S3SSS6,Richardson,TX 75CSXWSS.Telex, 7S09S9SPEDAL.
Referertoss
andiiiusfrationa
at endof paper
616
Oii Dis@eoementTeats
t P~
Phase Be;wior
Equal volumes (4 mL) of Wilmingtonoil A and aqueous phase
were sealed in 10-mL grsduated ampoules. The samples were
placed in an oven at 52 C. Observationswere made after 1 week.
The sampleswere obsewed et that the and evaluated. The aan@es
were then evatuatedwhile being shaken. Finally, the sampleswere
evaluated again after 1 more day. The observation while shaking
provided infonnatbn about the type of emutsionformed (oil-!n.water
or water-ln+ii), the ease of emufaifbatlon,the stabilityrd the emulsbn
(while shaking), and the amount (qualitative) of 011em~dslfied. The
final evak@on (1 day after shaking) provides wfditional data on
emulsbn stability.
Surfactarrt
Anaiytbal methods used for measurement of surfaotant
oonoentratbn were two-phaee titretbn and HPLC. The two-phase
titratbn was described by Rosen and t30fdsmith,4and the HPLC
prooedureis sirnliarto that desoribedby Hofmanand Angstadt,6 The
wavelength used for absorbenoe measurement of Petmatep B-100
surfactant was 222 nm, whbh is very close to the wavelength
selectedby Hofmanand Arrgatadt.
No visible emuisifkation
Blaokemulsbn
Brown emulsbn
SPE/DOE20238
Alkalinity
Effiuent sampleewere oolleoted in 5-ml incrementsand oerrtrituged
before the volume of oil ooifeoted was determined. The aqueous
phasewas then eeparatedand anaiyzedfor alkalinityby titratbn to pH
4 with 0,1 N HCL
ElementalAnalysis
The effluents were anaiyzed for siiloon with atomic absorption
spectroscopy,
Interglacial
Tensbn
Irrterfacialpropertiesof seleotedsystemswere measuredwith a
spinning drop interfaclal tensbmeter at 52 C. The transient iFT
behavior of nonequilibriated samples was monitored over a time
intervalof severalhours.
Acidic Crude
I
I
I
I
616
SPE)DOE 20238
Low-Ackt Crude
The second example is for a light o!! %omDelsware-Chikfera
(OK), fkdd, (See Tabfe 1,) The alkali used was a pfi 9.5 mixture of
0.049 N NaHCO~,0.0078 N Na2C03, ml 0.0325 N Na2HP04, The
experiments were conducted % S2 C, the same temperature that
was used for the heaviercFJde. The Delswara.Chllderaoil is stightfy
acidicand relativelyunreacifveto akall. Fig,3 sh6w8that afkaliabn3
producedonfy a small reductbn in in.
Sciubilfty
AnoNrerway surfactant bases may ocour in a M88rvok is by
filtratbn.8 This effect shcukf be consideredwhen dsslgnlng @kalltWsurfactanffbode. Many EOR eurfecfants@ comptex mixturesthat
are sparfngly soluble in aqueous solutions. Many popular EOR
surfactants have bw aoiutrflttiesin brines. Forrnutstbne made wltrr
these surfactants are of,m cloudy dlsperebne, instead of tme
aolutlone. For example, the fittersbilfty of 0.1% Petroetep B-1OO
surfactarrtat 50 C was greatfy reducedwhen mixedwith a reletfvefy
high Ionk strength alkaline eotutbn. At 50 C, in 0.3% NaCl (fonk
strength = 0.051), 98.lA of the aurfactant worJtdpass through a
0.45 pfifter, However,when a mbrfureof 0.032NN@HP04 +0.032N
NaHC03 + 0.016N Na2C@ wtfh a pH of 10 waa added to the 0.3%
NaCl (total bnlc strength = 0.155), the fractbn of surfactant that
passedthrough the filter was reducedto 22.1%.
Adsorption
Surfacfantlevels In an injectedsolutbn can also be reducedby
adsorption onto reaewoir rock. Numerous researchers have
meaaured the adsorption of anionio aunactants under alkaline
condltiorre. These reauftscan be summarized by stating that alkali
reducedthe adsorptbn of anbnk surfactantsonto pure clay minerals
as much as 93% and reduced adsorption 7 to 49% when reservoir
sandstones were used.8*lo~12.13
Gypsum
SPE/DOE 20238
?dontrnorillonite
Montmorillonite,whkh is leasreactivewith atkalie,la detrimental
to alkaline fboding processes because of tts high surface area arxl
vety high catbn exchangecapacity. High CEC velueeare asacciated
with high montmorillontfe content. If divalenf Ions OCCUPY
the
exchange eltes, much of the injected alkali can be consumed by
adverse precipitation reactions. The screening criterion for ion
exohange capacity Is 5 meqkg. This corresponds rcughly with the
presenceof 1% montrncrilbnite and 0.4 wl % of diva[ent bns in the
brine,1116
Limestone
High pH alkalis are reactive with limestone and should be
avoided in dolomitic reservoirs. Low (Nai-iC03) and mcderate
(Na2C03) pH carbonates have been shown to be compatible with
dobmitlc cores.1718
AddJ@M&
Tne acid number of crude oil was previouslythought to be an
important parameter for alkaline flooding processes.
The
exparimentadescrfbed in the first section of this paper showed that
oil acid number may not bean extremely impcrtarrtparameter. The
detaiied study of 24 alkaline field projects that was menticned above
failed to chow a correlation between oil acid number and project
success.
m
wi ~nsumW Kg&f!o~kxpmk
dug size(PV)
--(1)
alkali consumed
...................(2)
alkali concentration x a
61s
:PRAX3E
20238.
-.
,.
_,---
Trov. R. French
the ACC). The size of a 0.095 N Na2C03 slug is 0.51 PV. The larger
value for Na2C03 reflects the increased reactivity of the Na2C03.
The sandpack flood results snow that only 0,22 PV of the 0.19 N
equinormal mixture of carbonates would be needed to satisfy
This value reflects the higher
consumption requirements.
concentratbn of the solution more than the shorter residencetime In
the cores.
ebMmBsFwQmmwwl
One of the mechanisms for mobllizatbn of residual oil is IFT
reduction, and phase behavior tests can be used to optimize the
parametersthat will producelow IFT. The experimentalpmcadurefor
performing these tests was described above and in previous
p*,51ications,2-3,7-8Sinm the 10W-pl-falkalis such as NaHC03 and
Na2C03 dc not produce the uitra-bw IFT valuea of the higher-pH
alkalis,small amountsof syntheticeurfactantswere addedto the alkali
to promotefurther Iowerfngof IIT. Wilmingtonoil A was used for the
phase bahavbr tests.
-------
1.
2.
----
--
.-.
3.
4.
5.
.-.r
The authors wish to thank Dr. Philip B. Lorenz for his work on
definingthe screeningcriteria that were describedIn this paper. The
authorsalSCwlahto thank Kerr.McGeeChemicalCorpcratbn and the
U.S. Departmentof Energyfor sponeortngthe work,
1.
2.
3.
4.
5.
6.
7.
8.
9.
-----
--------
---,
--------
-.
-,
-v-
---.
I o.
11,
12.
13.
14.
15.
18,
17.
18.
19.
20.
21,
22,
Elaevler
SPE 20238
oil
Gravity,0 APl
Deiaware-Chikier
33.0
0.13
Wiknlngton011A
12.9
3.40
Wilmington011B
18.0
1.59
Permeability,
Chemical
Chemioal
ini fLCt8s#~-
vo:~,
pH
Final
Inittal
23
0.47
1.05
10.17
508
331
21.89
0.301
1.91
0.198
52
0.59
1.40
10.17
502
400
28.57
0.477
1.31
0.186
52
0.55
1.31
6.3
554
435
0.408
0.375
1Per kg of rook.
Alkali
Sandstone
Surfaotant
Experiment
meq. adsorbecfl
kg sandstone
.0325NNa2HP04
.0162NNa2C03 +
.032NNaHC03
(0S% NaCl)
crushed
Berea
Petroatep B-1OO
Batch
0.834
,0325NNa2HP04+
.0162NNa2Cm +
,032NNaHC03
(0.3%NaCl)
Berea
Petroatep B-1OO
Coreflood
0.198
0.28N NaHC03
(1.48%NaCl)
Wiimingm
sand
Petrostep B-105
Batch
2.18
0.14NNaHC03 +
0,14N Na2C03
(1.26%NaCl)
Wilmington
eand
Petroatep B-105
0.085N NaHCOa
(2.4%NaCl)
Wiiminf$on
aand
Naodol 25-3S
slimtube(40 ft)
0.869
0.067N Na2C03
(2.4%NaCl)
Naodol 25-3S
Slimtube(40 ff)
0.622
sand
621
2.26
spaoifiogravity@ 60/~OF
API gravity, de9rees
KinernatioVISOOSW
@ 1250F,*
Total add nutir, rn@gm
Nitrogen (ohemiluminescem), wt %
Carton, wt %
Hydrogen,WI%
Brine
26,600
322
625
7.4
74
23
trc
trc
3
tro
18
5
Quartz,%
Feldepar,%
Gypsum,%
Kaolinite,%
illite/mioe,%
Mixed-layerilliieMneotiie, %
Plagioolesefetdepar,L
FektsparK, %
Resewoirparameters
52
100 to 3,000
850
320
Temperature,C
Permeabilii, rnd
Gross zone thickness,ft
Net zone thickness,ft
pH
Experiment
Slim tube 1
Slim tube 2
Slim tube 3
0.087N NaHC03
0.067N Na2CQj
0.065 N Ne4Si04
SandpaokWil 1
SandpaokWil 2
Sandpackwit 3
Sariip20k Wil 4
meqlkg
8.24
10.79
11.72
3.1
6.4
16.0
9.3
9.3
9,3
9.3
5.3
6.3
10.9
4.9
ReSdence
time,
days
30
30
30
.8
.8
.8
.6
SPE 20238
,.
TASLE6.- Reeuke
ofSSHMY
r~lremti teeflng
et0.1%eurfeofent
ooncenfmfbn
Neodol Petmetep
S-102 12-15-3S
229
Neodol
22-9
N-+
Na~
5103
12.15-3s
2.9
5.3
3<0
N82C03
N4Pd
3,000
PPX2,000
Wm 1,000
ppm
Teel
Prefluzih
W1.,1
no.
Wifl
POfW)W
Veklme,
Wmr
W12 0.25
W23 0.25
W24 0.26
w-is 0.25
1~~ ~
2M ~ne~
volume
0.2s
0.?5
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
~
chase
P@Y&
PvPv
Pv
Pv
SW,
Meffrw
oensumptk.n Reff0,4 lFr,
%
Mum
Km,
Pv%lmqmg
0.26
0.25
0.26
0,25
0.25
1.s
1.0
1.0
1.0
1.0
44.0 102I0.0053
41.5 1050 0.0083
42.4 460 0.0109
4s.s 975 0.0049
41.3 1400 MA.
41.8
39.9
55.0
30.0
36.9
o.(fg5
N N@.fQ,o,~ N ~~, and3.394
N@l,eX~ W 6W0fIWWW
25% MCI, and FbcOn 4S00
O.WN-,
o,~ Nf.&#q, 0.1%wt@mrii,
AsP
eoMbn
eutimaM2
3.3 Necdof
25.9
3.5 Pelroetep S.105
3.3 Neodol
25.9
%2.0 None
2S2.0Neodel26-S
AsP
t@fbn
atkei#
N@fQ+f@@2
~+
Na#%
f@+=2+w&
m+
f%wl
none
m aF@L
CX b@ZO~r.
VillStl sS@
wee
OKitfadfrOm
- (OUF401MW tine
ohamkd
tbrmu
reeking
amer weremd)xloo.
Soo.
23eoy
2400-
NOSURFACTANT
o 0.$%NEODOL26-9ETNOXYLATE
ec4-
ZiOO.
mOO-
4oQ-
1200.
g
%mg
&
13cQ -
~1400-
~.
/
m
o*
o
<~.~
10
20
30
TIME, mm
100
TIME, mhr
200
SPE 20258
4000
E
g
3000-
~~
NO2URFACTANT
o o.1%PETROWEP3-100
1000
1
9
800
600
400
200
TIME, mln
0 ~400
o
TIME, Mln
Preflueh
-3% Naci
0.5
1.5
2.5
634
S= 20238
O.ooc
2345678
Pore volume, PV
-i
[
o
0.2
0.4
0.6
0.6
I
1.0
Flgura7. -ScMtyrequir
omentdla
ramforananlonlo au~actantand
w:hrmaarbonats(PH1! .8) or mixtureof sodiumcarboneto
r@aodlumbloerborwt.(PH9.3) t 5% C.
I
o
0.5
1,0
1.5
2.0
2.5
3.0
AES 1215-2SCONCENTRATION, wt %
12
10
aQ
.I ,
0.5
1.0
1.5
2.0
2.5
3.0
NE,...>OI.25-9 CONCENTRATION. wt %
Ffgure9.- Ssllrrftyrqu&nantdl
agrsmfor a nonlonlesurfastsntand
sodium osr nsts (@f 10.8) ors mfxturs of sodiumcarbonata
andsodiumWuhonsts (#f 9.s)ats% C.