CO2 Enhanced Oil Recovery

Reservoir Growth
From CO2 Enhanced Oil
Recovery
The Fundamentals
Mark H. Holtz

US CO2 driven EOR Projects and

Infrastructure-Today and
Tomorrow

CO2 Enhanced Oil Recovery

Source: Denbury Resources, Inc., 2004

Outline
CO2 Enhanced Oil Recovery

Fluid Characteristics
Rock fluid interaction
Flooding methods
Flooding project design

Potential Solvents

CO2 Enhanced Oil Recovery

Alcohols
Nitrogen
Air
Flue gas
Various petroleum gases
(C3)
Methane
Carbon dioxide

Classifying Solvent
Displacements...

CO2 Enhanced Oil Recovery

Minimum Miscible
Enrichment (MME)

Minimum Miscibility
Pressure (MMP)

CO2 Miscible Flooding Mechanisms

CO2 Enhanced Oil Recovery

Large density at reservoir conditions makes the CO2 a good solvent for
light hydrocarbons
The formation of a single phase diminishes the capillary forces
Miscibility with the CO2 lowers the viscosity of the oil and increases its
mobility.
Miscibility Region
(CO2 and Oil Form Single Phase)

Pure CO2

CO2 Vaporizing
Oil Components

Direction of Displacement

CO2 Condensing
Into Oil

Original Oil

Selection of Candidates Suitable for CO2

Miscible Flooding
CO2 Enhanced Oil Recovery

Minimum Miscibility Pressure (MMP) within an achievable range

CO2 Minimum Misciility Pressure

% Recovery at 1.2 HCPV of CO2

Injected

100
95

CO2 Thermodynamic MMP

90
85
80
75
70
65
60
55
50
1000

1100

1200

1300

1400

1500

Test Pressure, psia

1600

1700

1800

Ways to Estimate MMP...

CO2 Enhanced Oil Recovery

Experimental.
Slim tube experiments
Rising bubble method
Vanishing interfacial
tension

Calculation
Mixing cell method
Method of characteristics

Correlation.

Ways to Estimate MMP

Experimental

CO2 Enhanced Oil Recovery

Slim tube experiment: Isothermal crude displacement by carbon

dioxide in the absence of water. The apparatus consists of a large
aspect ratio tube or spiral coil containing beads or unconsolidated sands.
(Rutherford 1962, Yarborough and Smith 1970, Holm et al 1974)

Ways to Estimate MMP

Experimental

CO2 Enhanced Oil Recovery

Rising bubble method: Visual observation experiment and

photography of rising gas bubbles in the oil. An empirical pressure
dependence of the rising gas bubbles is established to infer the
MMP (Christiansen and Kim 1984; Hagen and Kossack 1986)

Ways to Estimate MMP

Analytical

CO2 Enhanced Oil Recovery

Mixing cell method: Simulated container in which oil and gas are
mixed and equilibrium vapor and liquid phases are formed. Two versions:
single-cell methods (Kuo 1985; Nouar et al. 1986) and multiple-cell methods
(Metcalfe et al.1973; Pederson et al. 1986; Neau et al. 1996)

Ways to Estimate MMP

Analytical

CO2 Enhanced Oil Recovery

Tie line analysis and method of characteristics (MOC): Negative

flash simulated to find the pressure when the injection tie line or
the initial tie line become critical. In other words, the MMP would be the
pressure at which the critical tie line passes through the crude
composition. (Wang and Orr 1984)

Ways to Estimate MMP

CO2 Enhanced Oil Recovery

Correlations
Many correlations are found in the literature that are largely based on slim
tube test data. Most of them are functions of API gravity, C5+ molecular
weight,
and temperature.
Correlation for CO 2 M inimum Pressure as a Function of T emperature
(M ungan, N., Carbon Dioxide Flooding Fundamentals, 1981)
6000

Molecular Weight C5+ vs. Oil gravity (Lasater, 1958)

20

Oil Gravity, oAPI

Miscibility Pressure, psi

5000
MOLE W EIGHT C 5 + =

340

300

280

260

240

220

200

4000
180
3000

2000

1000

0
0.00

100.00

200.00

300.00

Molecular Weight C5+

400.00

500.00

0
70

110

150

190
o

Te m pe rature , F

230

270

Effect of Impurities in CO2

CO2 Enhanced Oil Recovery

MMP decreases if the impurity has a

greater critical temperature than CO2
Increasing MMP

Decreasing MMP

Critical Properties of Common

Elements/Compounds
CO2 Enhanced Oil Recovery

Critical temperature
Substance
Sulfur
dioxide
SO2
Ammonia
(NH3)

(oF)

(oC)

315.8

Critical pressure
(psi) (lb/sq
.in)

(atm)

1143

Boiling temperature
(oF)

(oC)

14.11

266

130

1691

115

-27.4

-33

706-716

375-380

3,200

217.8

212

100

88.2

31

1132

77

-110

-79

Carbonmonoxid
e (CO)

-222

-141

528

35.9

-310

-190

Air

-220

-140

573

39

Hydrogen
(H)

-402

-242

294

20

-423

-253

Nitrogen (N)

-236

-149

514

35

-321

-195

Nitric Oxide
(NO)

-94

Oxygen (O2)

-180

-297

-183

Water (H2O)
Carbondioxide
(CO2)

65
-118

735

50

MMP Correction for Impurities

CO2 Enhanced Oil Recovery

Pmmp = PmmpCO2(1 (0.00213(Tpc Tc) + (0.000251(Tpc Tc)2 2.35E7 (Tpc Tc)3

Where: Pmmp

= MMP of mixture

PmmpCO2 = MMP of CO2

Tpc

= Psudo critical temperature of mixture

Tc

= Critical temperature of mixture

(From Sebastian et al. 1984)

Key Physical Properties

CO2 Solubility in Aqueous Phase, Constant
Temperature
CO2 Enhanced Oil Recovery

CO2 Concentration in Aqueous Phase, mole

fraction

0.1
5,800 psi

2,900 psi

Temperature
= 140 F
T=140F

0.01
1,060 psi

0.001

1,400 psi

91
91 psi
psi

0.0001
0

50,000

100,000

150,000

200,000

Salinity, ppm NaCl

250,000

300,000

350,000

Outline
CO2 Enhanced Oil Recovery

Fluid Characteristics
Rock fluid interaction
Flooding methods
Flooding project design

Residency of CO2 in An EOR Flood

CO2 Enhanced Oil Recovery

CO2 dissolved in
produced oil

CO2 as separate
residual phase
Rock
Grain
CO2
Rock
Grain
Rock
Grain
CO2 dissolved in water

CO2 dissolved in
residual oil

Flow & Saturation

Definitions
CO2 Enhanced Oil Recovery

160

Capillary pressure (psi)

140
120

Drainage, wetting phase being

replaced by non wetting phase

100
80

Imbibition, wetting phase

replacing nonwetting phase

60
40

Swirr

20

Sor

0
0

10 20 30 40 50 60 70 80 90 100

Wetting-phase water saturation

(percent)

Formation of Residual Saturation

CO2 Enhanced Oil Recovery

Moore and Slobod, 1956

Pore Doublet model

Capillary force holds nonwetting phase in larger pore

Formation of Residual Saturation

CO2 Enhanced Oil Recovery

Oh and Slattery, 1976

Snap-off model
Pore radius
Aspect ratio =
Pore throat radius
Capillary force cause nonwetting
phase to snap-off into pore

Geologic Effects on Residual

Saturation

CO2 Enhanced Oil Recovery

Modified from Stegemeier, 1976

Prediction of non-wetting phase

saturation for intergranular pore space
CO2 Enhanced Oil Recovery

Residual non-wetting phase saturation (fraction)

Gas Residual saturation to water (fraction)

Frio Barrier bar

N = 143

Log. (Gas Residual saturation to water

(fraction))

0.8

Frio (Port Neches field)

0.6

0.4

0.2

y = -0.3136Ln(x) - 0.1334
R2 = 0.8536

0
0

0.1

0.2

0.3

0.4

Porosity (fraction)

0.5

0.6

Reported Residual Oil Saturation

Frio Fluvial Deltaic Sandstone Play
CO2 Enhanced Oil Recovery

Representative Probability Function

Sor Distribution

1.0
12

100%

10

80%
70%

Frequency

60%
50%

40%
4

30%
20%

10%
0%

0
0-19 19-24 24-2929-34 34-39 39-44 44-49 49-54 54-59 59-64

Residual oil saturation ( % )

Cumulative frequency

90%

Input data
0.5

Lognormal function
(28.76, 8.34)
0.0
15

24

34

43

53

Residual oil saturation ( % )

62

Residual oil saturation characteristics of carbonate

enhanced oil recovery projects
CO2 Enhanced Oil Recovery

Deep water cherts

6

Karst modified

Frequency

Reefs

Restricted to
open platform

3
2
1
0
15

20

25

30

35

40

45

50

55
QAc4240c

Average reservoir residual oil saturation (percent)

Port Neches Water-Oil Relative

Permeability Curves
CO2 Enhanced Oil Recovery

0.8

0.6
kr

krw
krow
0.4

Cross over 0.53

Swi = 0.18

0.2

Sor = 0.34

0
0
From Davis, 1994, SPE paper # 27758

0.2

0.4

0.6
Sw

0.8

Reported Residual oil Saturation

in Gulf Coast CO2 EOR Pilots

CO2 Enhanced Oil Recovery

Reservoir

Residual oil to water (fraction)

Quarantine Bay

0.38

Timbalier Bay

0.29

Weeks Island

0.22

Port Neches

0.3

Little Creek

0.21

Bay St. Elaine

Paradis

0.1 to 0.4
0.26

St Elaine Bay Field Residual Oil

Saturation Measurements
CO2 Enhanced Oil Recovery

Sor (fraction)

Porosity
(fraction)

Pressure cores

0.137

0.277

Sidewall cores

0.208

0.279

Log-inject-log waterflood

0.207

--

Conventional logs

0.079

0.299

0.35

--

Measurement type

Partitioning tracer test

Flooding Methods
CO2 Enhanced Oil Recovery

Huff-n- Puff
Water after gas (WAG)
Gravity stable
Continuous injection

Single Well Cyclic or Huff n Puff

CO2 EOR Method
CO2 Enhanced Oil Recovery

Definition

A method by which CO2 is injected into a single well, the

well is shut-in, and then CO2 is produced back from the
same well along with oil.

General procedure
1)
2)
3)
4)
5)
6)
7)

Measure reservoir temperature and pressure

Pressure test the tubing the make sure that the CO2 will go
where it is interned
Inject designed CO2 slug size
Shut in the well for designated soaking period
Produce the well and monitor oil, gas, water, and CO2
production
Analyze data for utilization factor (Mscf/STB), CO2
sequestered, oil production rate change, Incremental oil
recovery, cost to benefit analysis
Repeat procedure if successful

Huff n Puff CO2 Recovery Methods

CO2 Enhanced Oil Recovery

Swelling of oil
CO2 dissolves in the oil causing the oil to swell. This
increased both oil saturation and relative permeability.

Viscosity reduction
When CO2 dissolves in the oil, oil viscosity is reduced
increasing oil mobility.

Water blocking
Oil and gas saturation are increased around the effected well
area which decreased water relative permeability.
This gives the added benefit of reducing lifting and water
disposal costs.

Huff n Puff CO2 Design

CO2 Enhanced Oil Recovery

Set up wellhead to connect to CO2 tanks.

Consider per wellhead CO2 heater to keep CO2 from
flashing to gas in well tubing.
Bottom-hole injection pressure
Design below frac pressure but high so reservoir pressure
gets near initial pressure.

Choose soak time. Note that soaks times greater

than 4 weeks has not been found to have a strong
impact on recovery.
Set up separator system to capture CO2 for reuse.
( may choose to reuse the CH4 + CO2 gas stream)

Single Well Cyclic or Huff n Puff

CO2 EOR Method

CO2 Enhanced Oil Recovery

Huff n Puff
Example 28 Texas projects (Haskin &Alston,
1989), 106 LA and Kentucky wells (Thomas &
Monger, 1991)
Results 3,233 to 29,830 stb/well
Design 8 MMscf CO2 injected, 2-3 week soak
times
CO2 utilization 0.71 2.73 Mscf/stb, Average 1.3
Mscf/stb

Huff n Puff Oil Recovery

CO2 Enhanced Oil Recovery

Incremental Oil Production,

STB

Incremental Oil Recovery as a function of Slug Size

100000

10000

1000

100

10

10

100

1000

CO2 Slig Size, ton

10000
Johns edt., 2000

Water After Gas

CO2 Enhanced Oil Recovery

The Water after gas method is used to reduce

the fingering of CO2 between injector and
producer to obtain better sweep efficiency.
WAG ratio the ratio of the amount of water
injected to the amount of CO2 injected
Water Cycle length
Typically in the units of hydrocarbon pore volume.

WAG Injection Rule of Thumb

CO2 Enhanced Oil Recovery

Let pre CO2 water injection rate be X

Average water-cycle injection rate =
0.5X (based on West Texas WAG)
CO2 injection rate = 2 to 3)X

Relative Cost For a CO2 EOR

WAG Project
CO2 Enhanced Oil Recovery

Field equipment
10%
22%
CO2 Cost

68%

Recycling
plant

Gravity Stable Design

CO2 Enhanced Oil Recovery

CO2 Miscible
Critical Velocity ( velocity at which CO2 will
finger)

Reservoir dip
Permeability
Fluid viscosities
Fluid densities
Additional solvents can be added to optimize
density

Determine injection rate and bottom

hole pressure.

Continuous injection
CO2 EOR Processes Tested on the Gulf
Coast
CO2 Enhanced Oil Recovery

Continuous injection

Example little Creek

Results 17 % of OOIP recovered
Design continuous injection, recycling total gas stream
CO2 Utilization ? Mscf/stb, ? Average Mscf/stb

Denbury as a Corporate
Model

CO2 Enhanced Oil Recovery

Added CO2 flood proved reserves of

35.3 MMBOE ( 12/31/03)
West Mallalieu field (2001) $ 4 million investment
10.4 MMBOE proved reserves $2.60/bbl cost
McComb Field (2002) $ 2.3 million investment 8.4
MM BOE proved reserves $3.57/bbl cost

Little Creek, Ms 17% recovery

1974 pilot
1985 2 phase project implemented

Project Design
CO2 Enhanced Oil Recovery

Injection facilities

Storage
Compression

Well Design
Wellhead
Tubing
Corrosion inhibitors
Stainless steel gravel pack

Production Oil
facilities

Separation
Storage
CO2 recycle
system
Suction scrubber
Filter separator
Dehydrator

CO2 recycling

CO2 Injection Well Design

CO2 Enhanced Oil Recovery

Example from
Bay St. Elaine
Field

Palmer et al., 1984)

CO2 Production Well Design

CO2 Enhanced Oil Recovery

Inhibitor

Inhibitor string

Inhibitor packer fluid

Gas lift valve mandrel

Inhibitor string strap

Check valve

Casing

Perforations

Hydraulic packer

Production tubing

Catcher Sub

Methods to Reduce Corrosion

Problems
CO2 Enhanced Oil Recovery

Use of corrosion inhibitors

Separate CO2 injection lines
Stainless steel wellheads
Fiber glass gathering systems