S

SPE 1511
126
B
Best Prac
ctices forr Conducting CO2-EOR
Lab
b Study
F
Fawaz M. Al-O
Otaibi, SPE, Saad
S
M. Al-M
Mutairi, SPE, Sunil
S
L. Kokall, SPE, Jamess J. Funk, SP
PE and
JJassi F. Al-Qa
ahtani, SPE, Saudi
S
Aramco
o

C
Copyright 2012, Society
y of Petroleum Enginee
ers
T
This paper was prepare
ed for presentation at the SPE EOR Conferen
nce at Oil and Gas We
est Asia held in Muscatt, Oman, 1618 April 2
2012.
T
This paper was selected for presentation by an
a SPE program comm
mittee following review of information containned in an abstract subm
mitted by the author(s)). Contents of the pape
er have not been
re
eviewed by the Society
y of Petroleum Engine
eers and are subject to
o correction by the autthor(s). The material ddoes not necessarily re
eflect any position of the Society of Petroleu
um Engineers, its
officers, or members. Electronic
E
reproduction
n, distribution, or stora
age of any part of thiss paper without the wrritten consent of the S
Society of Petroleum E
Engineers is prohibite
ed. Permission to
eproduce in print is res
stricted to an abstract of
o not more than 300 words;
w
illustrations mayy not be copied. The abbstract must contain co
onspicuous acknowled
dgment of SPE copyrig
ght.
re

A
Abstract
Energy dem
mand has been escalating and
d is predicted to increase furrther in the cooming decades. The dialoguee on global
cclimate changee has the world
d abuzz on thee primary greeen house gas, ccarbon dioxidee. Both of thesse factors havee created a
pperfect storm for
fo the use of carbon
c
dioxide for enhanced oil recovery. T
The petroleum industry is ideeally suited forr disposing
oof this green ho
ouse gas. Each oil company (and others) has therefore steppped up its effo
forts in carbon dioxide utilizaation, either
ffor EOR or seq
questration. Th
he injection of CO2 into a reservoir is not nnew. Indeed C
CO2 injection hhas establishedd itself as a
vvery efficient mechanism
m
for increasing oil recovery.
To design a CO2-EOR or CO2 sequestraation project, one
o requires a llarge set of apppropriate expeerimental data ffor a given
rreservoir/fluid system. Wheree does one starrt? Even if thee data have to bbe generated iin a service labb, a good desiggn requires
ssome thought and
a effort. A seearch of the litterature revealss no best practtices for generaating this datasset. This paperr presents a
ccomprehensive experimental design for conducting a CO2 laboratory stuudy.
The essentiaal components of a laboratory
y study for CO
O2 injection incclude measurinng fluid-fluid innteractions andd fluid-rock
innteractions. Flluid-fluid studiies include miiscible displaceement tests, m
measurement off minimum miiscibility presssures, fluid
pproperties of CO
C 2-oil or CO2-brine mixturees including viscosity and ddensity, asphalttene precipitatiion, and swellling. Fluidrrock interaction
n studies typiccally include coreflooding
c
teests for determ
mining the oil rrecovery potenntial, three-phaase relative
ppermeability, crritical gas satu
uration, gas trap
pping and wetttability changees. Each of thesse sets of experriments will bee described
inn light of their best practice. The ultimate goal
g is to establlish a procedurre for generatinng a reliable annd accurate dattaset.
Introduction
EOR (tertiaary recovery) iss a process to recover the oill left behind affter primary annd secondary rrecovery methoods. There
aare many appliied EOR techn
niques includin
ng thermal, gaas injection, chhemical, etc. S
Selecting an aappropriate meethod for a
pparticular reserrvoir depends on
o a number of
o factors. The screening criteeria is mostly based on the ffluid and rock properties.
T
Thermal EOR methods invollve the injectio
on of heat and are the most ccommon. Gas injection is onne of the mostt promising
E
EOR methods and
a it involves the injection of
o gases such as
a CO2, N2 or hhydrocarbons.
The best gas
g for injection is CO2 fo
or several reassons: lower m
miscibility presssures, better solvent propeerties, CO2
ssequestration, and
a higher oil recoveries. CO
C 2 increases oil
o recovery thhrough its favoorable propertiies including m
miscibility,
sswelling, and lo
owering oil visscosity. The inccrease in recov
very by CO2 inj
njection is also attained by maaintaining (or iincreasing)
thhe reservoir pressure,
p
displaacing the oil, and by elimin
nating the interrface betweenn the oil and C
CO2. By eliminating this
innterface and hence
h
the interfacial forces, it
i is possible to
o theoreticallyy recover mostt of the oil in pplace. To undeerstand the
pprocess of enhaanced oil recov
very by gas injeection, it is firsst necessary to understand thee concepts of m
miscibility.
The term m
miscibility is referred to thee ability of two
o or more fluidds (CO2 and oill) to form a sinngle phase wheen they are
m
mixed in any proportion.
p
An
n important con
nsideration in miscible proc esses is the ellimination of tthe interface between the
ooriginal fluids.. If an interfaace is formed at some prop
portion of onee fluid in the other, then thhe fluids are considered
immiscible. In
I petroleum reeservoirs, CO2 that is miscib
ble with the resservoir fluid inn any proportioon are called fiirst-contact
m
miscible fluids. They form a single phase with
w the reservo
oir fluid. An innjection gas (C
CO2) which is not first-contact miscible
w
with the reserv
voir oil can bee made misciblle (for certain compositions only) with thhe reservoir oill by a processs known as
m
multiple-contacct or dynamic miscibility.
m
Th
his process can
n be either the vvaporizing gass drive (CO2 caan extract or vaaporize the
inntermediate co
omponents from
m reservoir oill) or the condensing gas drivve (the reservoiir oil at the mixing front is m
made richer
bby condensing the intermediaates from the in
njected solvent into the oil).

SPE 151126

CO2-EOR is a well-known method that has been applied in the field extensively. The initial pilots were conducted in the
US in the late 1940s. The first full scale immiscible carbon dioxide flooding process was conducted in Bartlesville in
Oklahoma in 1958 (Dyer and Farouq, 1989). The first pure carbon dioxide gas injection was conducted in the Ritchie field of
southern Arkansas in 1969 (Khatib and Earlougher, 1981). Today, most of the CO2-EOR commercial projects are located in
the Permian Basin of west Texas. CO2-EOR has added increasing amounts of oil production capacity in the US (Jarrell et al.,
2002). The American Petroleum Institute stated that the oil and gas industry has over 35 years of continuously developing
experience in transporting and injecting CO2 for enhanced oil recovery (EOR). CO2-EOR is now being commercially
exploited in the rest of the world including Canada, Europe, Asia, Middle East and the Far East. Immiscible carbon dioxide
flooding has been conducted in the Bati Raman in Turkey in 1980 (Khatib and Earlougher 1981, Karaoguz et al. 1989, Sahin
et al. 2007). This project is considered one of the most successful EOR applications in the history for heavy oil fractured
carbonate reservoirs. In recent years, a lot of interest in CO2 injection is stemming from the CO2 sequestration in reservoirs.
Due to the recent interest in CO2 from environmental issues, the interest in CO2-EOR has grown substantially. CO2-EOR
is being field tested around the world. There are numerous pilots and commercial field projects either in the implementation
phase or on the drawing board. Many other companies are contemplating CO2-EOR. Before a further decision can be made
on whether to apply it in field or not, generally some laboratory experiments are needed to be done. The lab experiments or
studies generally cover fluid-fluid and fluid-rock interactions. To generate a reliable and accurate CO2-EOR dataset we have
to establish a procedure for conducting such lab studies. A complete set of data for a CO2-EOR lab study includes MMP
measurements, fluid properties of CO2-oil mixtures, asphaltene precipitation, swelling, oil recovery potential, three-phase
relative permeability, critical gas saturation, gas trapping and wettability changes. These data are critical input for any
reservoir simulation that follows the initial laboratory study to evaluate the feasibility of the process for a given reservoir.
Experimental Studies
Two sets of experimental studies need to be conducted for any given CO2-EOR prospect: fluid-fluid and fluid-rock
interactions. Fluid-fluid studies involve the oil and CO2 interactions while fluid-rock studies involve reservoir fluids and rock
samples. The first and perhaps the most important step towards getting accurate and reliable experimental data is acquiring
representative samples. The representative fluid sample for a CO2-EOR study is generally a recombined sample of the
pressurized separator gas and liquid samples targeting the average fluid composition of the original well stream. The other
important parameters in the experimental study are procedures, and calibrated and reliable instruments. These will be
discussed under each laboratory experiment. Specific experiments that are generally conducted in any CO2-EOR studies
involve minimum miscibility pressure (MMP) measurements, fluid properties of CO2-oil mixtures, asphaltene precipitation,
swelling, oil recovery potential, three-phase relative permeabilities, critical gas saturation, gas trapping and wettability
changes. These will be discussed in the following sections.
Fluid-Fluid Interactions
An understanding of reservoir oil and CO2 interactions is perhaps the most important for any CO2-EOR project. It
involves the measurement of miscibility of CO2 with the reservoir oil, PVT phase behavior, swelling, enrichment, reduction
in viscosity and mixing. Another important aspect of these interactions is the precipitation of asphaltenes from live crude oil
when it comes in contact with CO2. Fluid-fluid interactions should also include reservoir brine and CO2 behaviors. These
measurements and procedures to measure them are outlined below, and should constitute an important part of any CO2-EOR
laboratory study.
MMP Measurements:
MMP is an important parameter for the design of gas injection-EOR processes and is defined as the lowest pressure at
which a gas can develop miscibility, through a multicontact process, with reservoir oil at reservoir conditions. When the
MMP is above the reservoir pressure, the gas injection flood will be immiscible with generally lower ultimate oil recoveries.
Conversely, when the MMP is below the reservoir pressure, the gas flood will be miscible with higher oil recoveries.
Miscibility can be achieved through a vaporizing process, a condensing process, or a combined vaporizing-condensing
process. The MMP can be obtained experimentally either by the slim tube system (Danesh, 1998), a rising bubble apparatus
or through the use of correlations. The gold standard for MMP measurement in the industry is the slim tube apparatus. A
schematic representation of the slim tube apparatus is given in Fig. 1. The tubing is tightly packed with glass beads and
coiled to give a certain permeability and porosity. The specifications for slim tube are rather stringent and are provided
elsewhere (Elsharkawy, Suez, Poettmann and Christiansen, 1992).

S
SPE 151126

Visual
Cell

Figure 1: Sllim Tube App

paratus
The proced
dure for MMP
P measuremen
nt includes thee following steeps. The slim
m tube is first filled with tooluene and
ppressurized to the desired test
t
pressure. The oven is then heated aand set to thee desired reserrvoir temperatture. After
sstabilization, th
he slim tube iss flooded with two pore volu
umes (PVs) off live reservoirr oil at a consstant flow rate (2-4 cc/hr
ddepending on th
he slim tube volumes and sp
pecification). After
A
stabilizati on, the slim tuube is flooded w
with 1.2 PVs oof CO2 at a
cconstant flow rate
r
(6-8 cc/hr)). The effluentt oil is collecteed in a burettee where it is continuously m
measured usingg an optical
ssensor. The gass is measured using
u
a continu
uous gasometerr. A digital cam
mera takes picttures of the oill passing throuugh a visual
ccell at the outleet of the slim tube
t
periodicallly. An online densitometer continuously m
measures the ddensity of the eeffluent oil
m
mixture after oil
o passes through the visuall cell. The rem
maining oil in the slim tubee is extracted bby flooding tooluene at a
cconstant flow rate (10-20 ccc/hr). Sufficient quantities of
o toluene aree injected untiil the effluentt becomes cleaar, usually
rrequiring 3-4 PV
P of toluene. The amount of extracted oil
o in toluene iis measured ussing UV specttroscopy technniques. The
sshrinkage facto
or is calculateed from the deensity of the live oil measuured at test prressure and reeservoir tempeerature and
ccompared to the volumes and
d density at 60oF. The formatiion volume facctor is also calcculated accorddingly. The voluume of oil,
vvolume of gas, oil density, sy
ystem pressuree and temperatture are recordded periodicallyy during gas fl
flooding. From
m these data
thhe cumulative gas injected (%
%PV), cumulaative oil recoveered (%PV), deensity of produuced oil and cuumulative GOR
R produced
aare calculated. The ultimate oil recovery at
a 1.2 PV injeected gas is caalculated from
m the measuredd oil collected and using
aappropriate formation volumee factor. An ex
xample plot is shown in Fig.. 2. The presennce of bubbles is monitored iin the sight
gglass over the entire
e
injection
n history. Bubbles are generallly observed inn an immisciblee case (Fig. 3).

Figure 2: Cum
mulative CO2 injected vers
sus oil recov
very (%PV)

Figu
ure 3: Bubble
es are generrally observe
ed in an imm
miscible case
These stepss are repeated for
f at least six test
t pressures at
a the given resservoir temperrature (three in miscible and tthree in the
im
mmiscible region). The perceent oil recoverry calculated att 1.2 PV of CO
O2 injected at eeach pressure iis plotted as a ffunction of
ppressure. From
m this plot (Fig.. 4) the MMP is
i estimated ass the point of ddiscontinuity, aas well as the oobservation off bubbles in
thhe effluent streeam.

S
SPE 151126

Figure 4: Ulttimate oil rec

covery at diffferent test prressures
A
As mentioned before,
b
the MM
MP can be also obtained exp
perimentally bby using a risinng bubble appaaratus, or RBA
A, that was
ddeveloped in th
he early 1980s. A partial flow
wsheet for the RBA
R
appears inn (Fig. 5). Thee most essentiaal feature of thee apparatus
is a flat glass tu
ube mounted vertically
v
in a high
h
pressure sight gage in a temperature coontrolled bath. The glass tubee is flat for
bbetter viewing of bubbles rissing in opaquee oils. The RBA is a consideerably faster m
means of measuring the MM
MP for both
vvaporizing and
d condensing systems than the slim tube. The RBA taakes 1-2 hourrs per MMP ddetermination (excluding
ppreparation tim
me), while thee slim tube taakes one to tw
wo weeks per MMP determ
mination. Asphhaltene precipiitation can
ccompletely plug
g slim tubes, whereas
w
such precipitation
p
is only a minor hhindrance in thhe RBA. (Elshaarkawy, Suez, Poettmann
aand Christianseen, 1992). Therre is no recoverry data or fluid
d samples availlable during a R
RBA test.

Figure 5: Schematic
S
of the Rising--Bubble Apparatus
S
Swelling and Fluid
F
Propertiies of CO2-Oill Mixtures:
Slim tube teests do not pro
ovide phase beh
havior and fluiid property datta needed for ccompositional ssimulation, esppecially for
tuuning an equattion of state. To
T generate theese data experim
mental simulattion is often coonducted in a bbatch mode in static PVT
ccells at differen
nt injected gas--reservoir oil mixture
m
ratios. During these ttests, a fixed am
mount of the innjected gas is m
mixed with
rreservoir oil an
nd the swelling
g of the oil, deensity and viscosity of the m
mixture, and com
mpositions aree measured. Thhis suite of
tests is generallly referred as the
t swelling or solubility tests. The objectivve of conductinng these tests is to observe annd measure
thhe change in oil
o properties when
w
it is mixeed with the injeected gas in terrms of reductioon in reservoirr oil density, reeduction in
vviscosity, oil swelling
s
in thee reservoir, ch
hange in saturration pressuree and change in GOR. A sw
welling test iss generally
pperformed in a high pressure-high temperatture PVT wind
dowed cell. A known volumee of reservoir fluid (~40 cc) is charged
innto a cell at 50
000 psig (shou
uld be higher th
han the reservo
oir pressure) annd heated to reeservoir temperature. The dennsity of oil
ssample is meaasured at thesee conditions. A constant com
mposition exppansion (CCE) is performedd to determine saturation
ppressure, relativ
ve volume, and
d liquid density
y for the origin
nal oil. In the C
CCE experimeent, the pressurre is reduced inn steps and
thhe volume at each
e
step is reccorded. The firrst oil-injected gas mixture iss prepared by aadding a certaiin amount of innjected gas
too target a desirred mole% of injected
i
gas in
n the mixture. Again
A
a CCE i s performed too determine satturation pressuure, relative
vvolume, gas-oiil-ratio, and liq
quid density for
fo the oil-injeccted gas mixtuure. This test is repeated seeveral times foor different
m
mixtures (usuallly 10, 20, 40 and 60 mole%
% injected gas). A typical CC
CE plot for diffferent mixturees is shown in Fig. 6 and
sswelling data iss plotted in Fig
g. 7.

S
SPE 151126

Figu
ure 6: Swellin
ng test summ
mary (Satura
ation Pressurre and GOR))

Figure 7: Sw
wollen volum
me versus am
mount of CO2 added.
CO2 injection reduces thee oil viscosity. Using PVT apparatus
a
we ccan find the visscosity reductiion of oil in eaach step of
ppore volume inj
njected. A typiccal viscosity plot for differentt mixtures is shhown in Fig. 8..

O viscosity
y versus amo
ount of CO2 a
added.
Figure 8: Oil
O
Onset of Asphaltene Precipiitation:
Whenever a gas is injected into an oil reservoir, esp
pecially CO2, a potential exists for the preecipitation of aasphaltenes
((Kokal and Say
yegh, 1995). The onset of asp
phaltene precip
pitation can bee measured from
m live crude ooils using solidds detection
ssystem (SDS) (Hammami,
(
Ch
hang-Yen, Nig
ghswander and
d Strange, 19955). A schematiic representatioon of the solidds detection
ssystem is given
n in Fig. 9. Thee SDS apparatu
us consists of a laser power ssource, a fiberr optic bundle tthat carries thee laser light
innto the PVT ceell, the actual PVT
P
cell contaaining the crudee at pressure annd temperaturee, another fiberr optic bundle tthat carries
thhe received laser light from the PVT cell, and a power meter
m
that meaasures the amoount of light reeceived. The P
PVT cell is
m
mounted insidee a temperaturee-controlled ov
ven and has an effective volum
ume of 110 cm3 . The PVT celll is a windoweed cell that
ppermits visual observation
o
off the oil inside the cell. A varriable volume ddisplacement ppump controls the volume annd pressure
oof the fluid insside the cell. The
T PVT cell also
a
has a speccially designedd magneticallyy coupled impeller mixer thaat provides

S
SPE 151126

ppowerful mixin
ng and maintaiins equilibrium
m in the fluid system. The P
PVT cell is dessigned for opeeration at presssures up to
110,000 psig and
d temperatures up to 360F.

Figure 9: Solids Detectio

on System (S
SDS) (Courte
esy Oilphase/
e/DBR-Schlum
mberger)
A certain volum
me of reservoirr oil is charged
d into the PVT cell at a relativvely high presssure. It is then titrated slowlyy with CO2.
T
The proceduress for detecting the onset of assphaltene preciipitation from ccrude oils is deescribed elsew
where (Hammam
mi, ChangY
Yen, Nighswan
nder and Stran
nge, 1995). An
A example plo
ot of a titratinng experimentt is shown in Fig. 10. The laser light
trransmittance in
ncreases initiallly as the CO2 dilutes
d
the crud
de and then staarts to decline aafter ~0.75 cm
m3 of CO2 injecction (Point
A
A). This is the point
p
of asphalltene onset. Ass more CO2 is added
a
the amoount of asphalteene precipitatioon increases annd the light
trransmittance declines
d
monotonically. Afteer 3.7 cm3 of CO2 addition the amount oof light passingg through the cell is not
m
measurable (Po
oint B). As more CO2 is addeed the light tran
nsmittance starrts to increase (~4.2 cm3) inddicating a diluution effect,
oor a re-dissoluttion effect (Point C). After ~5.0
~
cm3 of CO2 addition thhe transmittancce declines agaain as the bubbble point is
rreached (Point D).

Fig
g 10: Titration
n of reservoiir oil with CO
O 2.
B
Bulk Depositio
on:
The experim
ments describeed previously provide
p
the onset of asphalteene precipitatioon; they do noot quantify the amount of
aasphaltenes preecipitated. Thee precipitation quantity can be measured using a separrate PVT cell. It is essentiallly a highppressure filtratiion apparatus and it consistts of two floaating piston puumps as show
wn in Fig. 11. One of the ccylinders is
cconnected to a pump. The sample
s
is takeen in one of the cylinders aand equilibrateed for ~48 hoours. The sampple is then
trransferred into
o the second em
mpty cylinder through a filteer assembly. T
The experimentt is conducted at constant prressure and
temperature rep
presenting reseervoir condition
ns. The deposiited asphaltenees are trapped oon the filter asssembly that arre removed
aat the end of th
he experiment and
a weighted. The amount off asphaltenes pprecipitated is ccalculated in pppm or as a perrcent of the
tootal oil chargeed. The experim
ment is conduccted at differen
nt gas-reservoirr oil ratios andd the amount precipitated measured and
thhe trend plotted (Fig. 12).

S
SPE 151126

Figu
ure 11: Bulk Asphaltene Precipitation
n Apparatus (Schematic))

B
Asphalttene Precipittation Data (ttypical)
Figure 12: Bulk
F
Fluid-Rock In
nteractions
Fluid-rock interactions arre equally important in a CO
O2-EOR projecct. The oil recoovery potentiaal should be simulated in
tyypical, but welll thought out coreflooding
c
ex
xperiments. Otther experimennts that need too be conductedd include three--phase (oilw
water-gas) relattive permeabiliity, critical gass saturation meeasurements, annd wettability aalteration meassurements.
Another con
ncern during CO
C 2 injection iss its interaction
n with reservoirr rock and the subsequent disssolution of thee rock. The
ddissolution of rock can havee both positiv
ve (increase in
n injectivity, rreduced pressuure for injectioon) and negattive effects
((plugging of po
ores, scale precipitation). Beesides the poten
ntial benefits oout of the CO2 flooding in teerms of oil reccovery, the
innteraction betw
ween CO2/brin
ne and carbonaate rock is cruccial. Carbon ddioxide dissolvves in water to form the weaak carbonic
aacid (H2CO3):

CO2 + H2O H2C

CO3

H2CO3 + H2O H3O+ + HCO3HCO3- + H2O H3O+ + CO32T

The weak carbo
onic acid reacts with carbonaate rocks releassing calcium annd magnesium
m ions. This iniitial dissolutionn is usually
ffollowed by seccondary precip
pitation of calciium carbonate due to increasee in pH value:

CaCO
C
C 3 Ca2+ + 2HCO33 + H2CO
CaMg(C
CO3)2 + H2CO
O3 Ca2+ + Mg2+ + 2HC
CO3T
The deposition
n of interaction
n products of CO
C 2/brine/rock
k has been fouund to cause a decrease in thhe well injectivvity during
ddifferent CO2-E
EOR operation
ns. According to Grigg and Svec
S
(2003), ssignificant calccium carbonatee was noted duuring WAG
innjection of CO
O2 in limestone cores, while no
n deposition was
w observed inn dolomite corees.
Appropriatee studies shoulld be conducted that address the impact of CO2 on carboonate (or sandstone) rocks as a result of
C
CO2 injection (CO
( 2-EOR). It should investiigate factors (ee.g., pressure, flow rate, watter saturation, and other) thatt affect the
C
CO2/rock interractions. This aspect of flu
uid-rock interaactions is not covered and the reader is referred to tthe several
ppublications (Isssever et al. 1993, Stalkup 19
978, Simon and
d Graue 1965, M
Mungan 1991, Hadlow 1992).

S
SPE 151126

O
Oil Recovery Potential:
P
There can be
b significant difference
d
in oil
o recovery bettween misciblee and immiscibble gas injectioon. The oil reccovery will
bbe enhanced when
w
CO2 is miscible witth oil under reservoir
r
condditions. Munggan (Mungan, 1991) has ccompiled a
ccomprehensive review of CO
O2 flooding und
der different in
njection scenarrios. Basicallyy, CO2 floodingg has been stuudied in the
laaboratory or applied
a
in the field in the fo
ollowing modees: CO2 stimuulation, continuuous CO2 injeection, CO2 sluug process,
ssimultaneous in
njection of CO
O2 and water, alternating injecction of CO2 aand water (WA
AG), injecting H
H2S or SO2 w
with CO2 to
loower the minim
mum miscibilitty pressure, injjecting CH4 wiith CO2 to takee advantage of gravity stabilizzation, flue (coombustion)
ggas injection, injecting LPG and CO2 mixtures, and LPG
G followed by CO2. Almost aall the commeercial miscible gas floods
tooday employ the
t WAG meth
hod (Hinderakeer, Utseth, Husstad, Kvanvik and Paulsen, 11996). Gas injeection projectss contribute
aabout 40% of the
t total US-EO
OR production
n: most of whicch are WAG flloods. Most off the WAG floood projects in the US are
rreported to be an
a economic su
uccess (Hadlow
w, 1992).
The oil recovery potentiaal can be meassured experimeentally by coreeflooding systtem. A schemaatic representaation of the
ccoreflooding sy
ystem is shown
n in Fig. 13. Ty
ypical corefloo
oding apparatusses can operatee at overburdenn pressures up to ~10,000
ppsi, pore pressu
ures up to 9,500
0 psi and temp
peratures up to 150C (higherr specification are also possibble). All pore fl
fluid wetted
pparts should bee constructed from
f
inert mateerials such as Hastelloy
H
C-2776, Viton, andd Teflon. Larrge volumes oof oil, brine
aand CO2 are generally suppllied from high-pressure floatting piston acccumulators thaat are driven bby external higgh-pressure
ppumps. System
m pressure can be
b maintained by a back presssure regulator (BPR) at the ccore outlet. Thee core floodingg apparatus
is equipped witth a three phasse separator th
hat is used to measuring
m
the recovered oil during waterfllooding. The sseparator is
pplaced inside th
he oven in a mounting
m
brackeet and operatess at reservoir ppressure and tem
mperature. Thee separator hass two bores
oone of which iss used for acqu
uiring level meaasurements forr the water-oil iinterface positiion that measuured with a trannsducer.

Figure 13: Core Floo

oding Appara
atus (Schematic)
The core flooding proced
dure starts with
h selecting a laarge number off core plugs foor screening. T
The screening consists of
rroutine analysiss, computerized tomography (CT) scan an
nd nuclear maggnetic resonannce (NMR) meaasurements. Thhe CT scan
is to make suree that there is no fracture orr permeability barrier withinn the plugs. Thhe NMR is to determine the micro and
m
macro porosity
y distribution and
a to ensure that the comp
posite core pluugs are of the same rock tyype. In the corre flooding
are filled with
aapparatus, all accumulators
a
h the correct fluids
f
(dead o il, live oil, brrine and CO2). A typical cooreflooding
eexperiment con
nsists of the folllowing steps:
1. Saaturate the coree plugs with reservoir brine.
2. Sttart dead oil flooding
f
to measure the oriiginal oil in pplace (OOIP). This is norm
mally conducteed at room
tem
mperature. Th
he dead oil fllooding will continue
c
till thhe pressure ddifference betw
ween inlet andd outlet is
staabilized.
3. Raaise the temperrature in the ov
ven to reservoirr temperature. Inject several pore volumes of dead oil.
4. Sttart live oil floo
oding and keep
p flooding till th
he pressure diffference betweeen inlet and ouutlet is stabilizeed
5. Ag
ge the core forr some time (ty
ypically 10-15 days).
d
6. Th
he composite is
i now fully saaturated with live
l
oil and thhe pore pressurre is at averagge reservoir prressure and
tem
mperature and ready for wateer flooding.
7. Sttart water flood
ding initially att constant flow
w rate (typicallyy 1 cc/min andd later at 2 andd 4cc/min) and collect the
prroduced oil in the
t separator. The
T separator is
i at reservoir cconditions andd the collected ooil is live oil. K
Keep water
flo
ooding until no
n more oil produced, until the water cut reach ~99% ((Usually 2 4 pore volumees of brine
injjection).
8. Fo
or the continuo
ous CO2 injectiion experimentt: Start continuuous CO2 floodding at constannt flow rate of 00.5 cc/min,
recovered oil will be collected in fraction colllectors at atmoospheric condittions. The colllected oil here is dead oil.
g until no moree fluid is producced (usually 1--2 pore volumee of CO2 injecttion).
Keeep continuouss CO2 flooding
9. Fo
or WAG modee CO2 injection
n experiment: Start injectingg CO2 at consttant flow rate oof 0.5 cc/min for 0.2 PV
fo
ollowed by 0.2
2 PVs of waterr injection. Th
his cycle (0.2 PV CO2 and 0.2 PV waterr) is repeated for several

S
SPE 151126

cy
ycles. The reco
overed oil is co
ollected in fracction collectorss at atmospherric conditions. The collected oil here is
deead oil. Keep continuous CO2 flooding untill no more fluidd is produced.
10. Co
ollect the data and perform th
he recovery callculations.
A typical WAG
W
type coreflooding experriments results are shown in F
Fig. 14.

Figure 14:
1 Cumulatiive PV CO2 in
njected versu
us cumulativ
ve % OOIP re
ecovered and
d pressure d
drop
T
Three-Phase Relative
R
Permeability:
Another im
mportant aspect of CO2-EOR lab
l studies and
d experiments is three-phase relative permeeability data. T
The flow of
aall three phasees, oil, gas an
nd water shou
uld be consid
dered in gas iinjection, gas cap expansioon and thermaal flooding
aapplications. Ex
xtensive researrch has been co
onducted on th
hree-phase relattive permeabillity to understaand the hydrodyynamics of
ffluid flow in po
orous medium during gas injjection. The litterature review
w shows that thhe gas always bbehaves as a nnon-wetting
pphase while oill and water cou
uld be wetting or intermediatee wetting (Levverett and Lewiis, 1940, Coreyy et al., 1956, S
Saraf et al.,
11982). It was also noted that the
t relative perrmeability of the wetting andd non-wetting pphase is primaarily a functionn of its own
ssaturation and relative permeeability of the intermediate-w
wetting phase iis strongly afffected by the ssaturation histoory and the
ssaturations of other
o
two phasees (Pejic, Dragan and Maini, 2003).
Three-phasee relative perm
meability data can
c be obtained
d by conductinng special SCA
AL experimentts. The nature oof such lab
eexperiments is lengthy and expensive
e
leadiing to limited number of labb experiments reported in thee literature forr the threepphase flow (Oaak 1990, Main
ni et al., 1990, Larsen and Sk
kauge, 1995, E
Eleri et al., 19995 and Baker 1999). To oveercome the
oobstacle of con
nducting such lab experimen
nts, predictive models
m
have bbeen used wideely to estimatee the three phaase relative
ppermeability daata.
Ahmadloo et
e al. (2009) reeviewed a wid
de range of exp
perimental resuults reported onn three-phase rrelative permeeability and
pprovided guidelines on the seelection of pred
dictive models for generationn of three-phasee relative perm
meability isoperrms. It was
ffound that therre is no single available three-phase predicctive model th at can be conssidered reliablee and comprehhensive for
aaccurate predicction of isopeerms because these predicttive models hhave been devveloped basedd on two-phase relative
ppermeability daata.
An alternative technique that overcomees the experimental difficultyy is the use off pore networkk models (Piri and Blunt,
22002, Suicmez et al., 2006). The simulation
ns for both carrbonate and sanndstones proviide quantifiablle data includinng trapping
m
models (Spiterii, et. al., 2005) as well as a pllatform for optimal sensitivityy testing. An eexample is shoown in Fig. 15.

Figure 15
5: Experimen
ntal and pore
e network sim
mulated thre
ee phase rela
ative permea
ability (SPE95
5594)
W
Wettability Ch
hanges:
Wettability alteration is an
n effective app
proach to enhan
nce oil recoverry significantlyy. The main facctors affecting wettability
aalteration are oil
o composition
n, brine chemisstry, rock surfaace mineralogyy and the systeem temperaturee, pressure andd saturation
hhistory (Buckleey et al., 1995)). The adsorptio
on of polar com
mpounds and/oor the depositioon of organic m
matter that wass originally
ppresent in the crude oil can
n alter most of
o the rocks surface chemiistry. Polar coompounds conntain a polar end and a

10

S
SPE 151126

hhydrocarbon en
nd. The polar end
e adsorbs on
n the rock surfface, exposing the hydrocarbbon end and making the surfa
face oil wet
((Anderson, 198
86). Brine chem
mistry plays a major
m
role in altering
a
the weettability of thee rock where thhe brines salinnity and pH
sstrongly affect the charge of the rock surfaace. The rock surface becom
mes positively ccharged when the pH is deccreased and
nnegatively charrged when the pH is increased. Also, raisin
ng the temperaature and presssure tends to ppromote the soolubility of
w
wettability-altering compoun
nds. In an oil-b
bearing formaation, the wetttability can vaary with depthh where a greaater waterw
wetting prefereence is seen neaar the bottom of
o the transition zone and a ggreater oil-wettting preferencee is observed nnear the top
((Okasha et al., 2007). Zones higher in the structure havee a greater cappillary pressurre, which can ccounteract the disjoining
ppressure and destabilize
d
the water film, alllowing surface-active compponents in the oil to contactt the solid. Loower in the
sstructure, the so
olid surfaces mostly
m
retain the water film (O
Oil and Gas Jouurnal, summer 2007).
Wettability alteration durring CO2 flood
ding process is investigated extensively inn the literaturee. Researcherss measured
w
wettability befo
ore and after CO
C 2 flooding to
o track any chaanges (Lin andd Huang, 1990;; Stalkup, 19700; Shelton and Schneider,
11975; Tiffin an
nd Yellig, 1983
3). Schneider and
a Owens (19
976) conducted laboratory eexperiments onn more than 199 preserved
ccores. The resu
ults showed thaat oil bypassed by the solventt bank increaseed the gas saturration trapped during the lateer period of
w
water injection
n. Also, it was found that waater mobility was
w reduced dduring later peeriods of waterr injection. Potter (1987)
cconducted expeeriments study
ying the effectss of CO2 flooding on the wetttability of Weest Texas dolom
mitic cores. Thhe selected
ccores representted three types of wettability states: intermeediate oil-wet, intermediate aand intermediaate water-wet. C
Changes in
rrelative permeaability were ex
xamined initiallly before and after CO2 floooding. Then, roock wettabilityy was monitored through
cchasing the ch
hanges in relaative permeabiility behaviorss. The results showed that the cores beccame slightly water-wet
ssuggesting extrraction of the rock surface caaused by CO2. Chalbaud et al
al. (2007) addreessed the role oof wettability dduring CO2
fflooding. Coree experiments were conduccted on a carrbonate reservvoir for two w
wettability connditions: wateer-wet and
inntermediate-w
wet. CO2 flooding was perfo
ormed in glasss micro-modelss to trace the distribution oof fluids underr the same
cconditions. Botth results show
wed that CO2 diid not contact the
t solids for w
water-wet media. On the otheer hand, the CO
O2 partially
w
wetted the solid
ds if the mediaa were intermed
diate-wet. Zek
kri et al. (2007)) conducted a llaboratory studdy evaluating thhe possible
aalteration of wettability
w
for tight limeston
ne cores. Chan
nges in relativve permeabilitty due to CO2 injection weere used to
rrecognize the wettability
w
alterration. The ressults suggested
d that CO2 floooding changed the water-wett limestone corres to more
ffavorable condiition of wettab
bility, i.e., moree water-wet co
ondition. Also, CO2 flooding reduced the IF
FT between thee employed
ccrude oil and itts brine which was a favorab
ble effect. Gup
pta and Mohannty (2008) testted oil sampless obtained from
m fractured
ccarbonate reserrvoirs to study the effects som
me of the fluid
d properties on wettability altteration. The teest results show
wed that as
ssalinity increassed, wettability alteration decreased.
d
Also
o, it was founnd that the w
wettability alterration increaseed at high
temperature leaading to higherr oil recovery from
fr
fractured carbonate
c
reserrvoirs.
Wettability changes durin
ng and after CO
C 2 injections are difficult tto determine qquantitatively. With NMR ttechniques,
cchanges in the T2 relaxation time
t
distributio
on and calculaation of surfacee relaxavity caan often be useed for wettabiliity indices.
IIn conventionaal testing, repeaat measuremen
nts of the Amo
ott our USBM before and affter CO2 injecttion provide onne point of
ccomparison as do more sophisticated observ
vations based on
o ESEM imagges (Okasha, 20007).

Figure 17: Water

W
distribu
ution and inttermediate wetting
w
chara
acteristics off grains, Arab
b-D carbona
ate rocks
(SP
PE 105114)
C
Conclusion
The design of a CO2-EOR
R or CO2 sequeestration projecct requires a laarge set of expeerimental and modeled data for a given
rreservoir/fluid system. These data are criticcal input for an
ny reservoir sim
mulation studyy that may be conducted to eexplore the
ffeasibility of such
s
a project.. A comprehensive experim
mental design ffor conductingg a CO2 laborratory study reequires the
eessential compo
onents of meassuring fluid-flu
uid interactionss and fluid-rockk interactions.
Fluid-fluid studies includ
de miscible dissplacement inccluding the meeasurement off minimum miiscibility presssures, fluid
pproperties of CO
C 2-oil or CO2-brine mixturees including viiscosity and deensity, asphalteene precipitation, and swelliing. Ideally
ssuch experiments should bee conducted with
w
live reserv
voir fluids at reservoir connditions. It is important to design the
eexperiments weell to obtain accurate and reprresentative datta that can be uused in simulatoors and fluid characterizationn.
Fluid-rock interaction
i
studies typically include coreflo
ooding tests foor determiningg the oil recoveery potential, tthree-phase
rrelative permeaability, critical gas saturation, gas trapping and wettabilityy changes. Theese tests providde the key com
mponents to

SPE 151126

11

address flow regime and displacement sensitivities. An accurate set of data is key to successfully modeling and validation
larger pilot and field scale projects.
Acknowledgements
The authors would like to thank Saudi Aramco for permission to publish this paper. Special thanks go to Ali Al-Meshari
for his help in the development of experimental procedure.
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