Enhanced Oil Recovery with CO2 Injection

Wei Yan and Erling H. Stenby Department of Chemical Engineering Technical University of Denmark

Contents

Overview Mechanism of miscibility Experimental study of gas injection MMP calculation Summary

Recovery methods

Primary recoveryby depletion Secondary recoveryby water/gas injection for pressure maintenance Tertiary recoveryafter primary and secondary Enhanced Oil Recovery (EOR): something other than plain water or brine is being injected into the reservoir (Taber et al., SPE 35385)

EOR methods

A summary by Taber et al.

More than 20 methods

Trends in EOR with CO2

EOR production in the US

The percentage of EOR projects continues to increase CO2 injection is the only method that has had a continuous increase

CO2 vs. other gases

Supercritical extraction at reservoir conditions Easier miscibility than N2, flue gas, C1 Cheaper than liquid hydrocarbons Safer to handle and pressurize than hydrocarbon gases Reduction of GHG

CO2 sequestration + EOR

The biggest barrier for CO2 sequestration

CO2 sequestration cost: 40-60 $/ton CO2 credit: 1-20 $/ton CO2 (?)

EOR can offset the cost and even make it profitable

CO2 injected/extra oil produced (mass): 1:1 to 4:1

3:1 is carbon neutral

Net CO2 storage ratio: 0.17-0.78 tons/barrel oil

CO2 sequestration + EOR

Maximum permissible cost of carbon dioxide in $/Mscf for the North Sea (Blunt et al., 1993.)
Oil price ($/barrel) 10 2.83/1.62/1.07* 1.17/0.67/0.44 0.50/0.29/0.19 20 6.17/3.52/2.33 2.83/1.62/1.07 1.50/0.86/0.57 30 9.50/5.43/3.58 4.50/2.73/1.70 2.50/1.43/0.94

Displacement efficiency (CO2/extra oil) Volume ratio (Mscf/barrel) 3 6 10 Mass ratio 1.1 2.2 3.7

* The three numbers indicate the maximum price for rates of return r = 0/0.1/0.2

A carbon dioxide displacement would be profitable at a 10% rate of return at a gas price of over $3/Mscf (56$/ton).

Mechanisms of gas injections

Swelling of the oil phase Lowering of oil viscosity Reduction of interfacial tension Misciblility (no interfacial tension for miscible displacements)

0.0 0

Pseudo ternary system for petroleum mixtures 2

0 1.0

Three components:

Light: C1, CO2, N2 Intermediate: C2-C6 Heavy: C7+

0.5 0

0.2 5

Useful to illustrate basic concepts Cannot explain combined mechanism

1.0 0 0.7 5

(0.20,0.55,0.25)

Single phase region

5 0.7
C

Critical tie line

0 0.5

5 0.2

Two phase region

3 0.00

0.25

A 0.50

0.75

B1.00

0 0.0

First contact miscibility (FCM)

2

FCM

Single phase at any proportion

Minimum Miscibility Pressure (MMP)

Gas A
ion line

Fix Comp., change P FCM pressure (FCMP)

Oil B

t dilu

Gas A" Gas A'

Minimum Miscibility Enrichment (MME)

P'>P

Fix P, change Comp.

FCMP and swelling test

Experimental/modeling determination of FCMP

Easy to perform and provide basic information about gas injection

600 550 500 Psat (atm) 450 400 350 300 250 200 0.00

FCMP

0.20

0.40

Oil

0.60 Fraction of Gas

0.80

1.00

Gas

Multicontact miscibility

Gas and oil become miscible by multiple contacts, through which (one or both of) their compositions are changed.

Easier than FCM For 1D gas injection, 100% recovery if MCM In reality, >90% recovery for swept area Three mechanisms

Vaporizing Condensing (No such thing in a real reservoir) Combined (Zick, 1986)

Vaporizing mechanism
2

Intermediate components vaporize to gas

Oil

Miscibility achieved in the displacement front/far from the well Dry gas/oil with sufficient intermediate components
3

cr it

ica lt ie lin e

G2 G1

Gas

1
System C1/C4/C10 just above MMP

Vaporizing mechanism

Study using slimtube simulation

1.0 0.8 0.6 0.4 0.2 0.0 1 0

Gas saturation

Gas region

Gas/oil region

Oil region

Methane n-Butane

ln Ki

-1 -2 -3
n-Decane

Density (kg/m )

600 400 200 0 0.0 0.2

Liquid

Gas

0.4

0.6

0.8

1.0

Dimensionless distance

Condensing mechanism

Intermediate components condense to oil Miscibility achieved in the displacement rear/near from the well Heavy oil/enriched gas (with sufficient intermediate components)
3

cr iti ca l

tie lin e

O1

O 2

C Gas

Oil

1
System C1/C4/C10 just above MMP

Condensing mechanism

Study using slimtube simulation

1.0 0.8 0.6 0.4 0.2 0.0 1 0

Gas saturation

Gas/oil region Gas region Oil region

Methane n-Butane

ln Ki

-1 -2 -3

n-Decane

Density (kg/m )

600 400 200

Liquid

Gas

Dimensionless distance

Condensing mechanism ?

Now it is believed that there is no such mechanism in a real reservoir. Reason: the multicomponent system (reservoir fluid) contains both light intermediate and heavy intermediate. Gas tends to extract heavy intermediate, leaving the oil saturated with light and light intermediates, which are hard to be miscible with the gas. The exchange of components is two-way, both vaporizing/condensing can happen. This leads to the combined mechanism.

Combined mechanism

15 comp. (N2, C1, CO2, C2, C3, iC4, nC4, iC5, nC5, C6 and 5 C7+ comps).
Gas saturation
1.0 0.8 0.6 0.4 0.2 0.0 2 0 -2 -4 -6 -8 1000 800 600 400 200 0 0.0
Liquid Near miscible zone Gas region Gas/oil region Oil region

Density (kg/m )

ln Ki

Gas Vaporizing segment Condensing segment

0.2

0.4

0.6

0.8

1.0

Dimensionless distance

Experimental study

Swelling test

Easy to perform

Forward- and backward-contact Slimtube experiment Rising bubble apparatus

10

Forward contact

Simulate vaporizing process Provide phase and volumetric data for the process Miscibility can be achieved if P>MMP

Gas

Gas1 Oil1

Gas1

Oil

Removed

Oil

Backward contact

Simulate condensing process

Injection gas

Removed Injection gas Gas1

Oil1

Oil

Oil1

11

Slimtube experiment

Physically simulates gas injection into a 1D reservoir Standard method to determine MMP 1.2 Pore Volume Injection (PVI) at different pressures Recoveries measured Time consuming

Slimtube experiment

MMP is determined as the pressure corresponding to the break point

85 80

Recovery %

75 70 65 60 MMP 55 280 300 320 340 360 380 400 420

Pressure (atm)

12

Rising bubble apparatus

Quick but only for vaporizing mechanism

Pressure Gauge G A S O I L Air Bath

Windowed Pressure Vessel Flat Glass Tube Gas Bubble Needle

P U M P

MMP calculation method

Empirical correlations Limiting tieline method Single cell simulation Slimtube simulation (multicell/cell-to-cell simulation) Global approach by key tieline identification (semianalytical method based on intersecting tie lines)

13

Experimental correlations

Many suggestions found in the literature Expressed, e.g., as functions of pseudo critical properties of gas, specific gravity of gas Easy to use, fast predictions Accurate for reference system Inaccurate for other systems

Limiting tie line method

Negative flash to find the P when the injection tie line or the initial tie line become critical Fast, but without stability analysis only for pure vaporizing Gas /condensing

C2-C6
Initial tie-line

Critical point

Oil

Injection tie-line

C1

C7+

14

Single cell simulation

Jensen and Michelsen, 1990 Correponding to forward/backward contact (vaporizing/condensing mechanisms)

0.25 0.20 0.15

Onecell simulation
Initial tie-line

0.10 0.05 0.00 -0.05 0 20 40 60 80 100 120 140 160

P < MMP

L=

x
i =1

nc

2 i

yi2

Number of contacts

Multicell (slimtube) simulation

Multicell (cell-to-cell) simulationphysical description Injection gas

Cell 1 Cell 2 Cell n

Production

Batch i

Slimtube simulationmathematical description

+1 Cin,k = Cin,k

t n Fi ,k Fi ,nk 1 z

)
Ci Fi

n = time step k = grid block Overall molar composition Overall molar flux

15

Assumptions in slimtube simulation

The porous medium is homogenous and incompressible Instantaneous thermodynamic equilibrium Small pressure gradient compared to total pressure Capillary forces and gravity are neglected The flow is isothermal and linear Mass transfer by diffusion/dispersion is neglected

Slimtube (multicell) simulation

Directly simulate slimtube experiment Give correct MMP Time consuming Numerical dispersion if grids are too few

Simulation time proportional to Ngrid2 Extrapolation to infinity Ngrid needed, for example, determine RF(P) by plotting RF(P) vs. 1/sqrt(Ngrid) and extrapolating to zero.

16

Slimtube simulation (example)

4 2 0 -2 ln (K) -4 -6 -8 -10 -12 0 100 200 300 400 Grid number 0.2 0 500 0.8 0.6 0.4 1.2 1 Vapor molefraction

Recovery curves from slimtube simulations (numerical dispersion)

1.2 1 RF at 1.2 PVI 0.8 0.6 0.4 0.2 0 100 150 200 250 300 350
FD (100 grid blocks, 1200 time steps) FD (500 grid blocks, 6000 time steps) FD (5000 grid blocks, 60000 time steps)

Pressure (atm)

17

A MMP calculation method is needed

Can correctly account for the injection mechanism

Wrong mechanism leads to overestimation

Fast

Unlike slimtube

No numerical artifacts like numerical dispersion

Global approach by key tieline identification

Fast, semi-analtyical based on intersecting key tielines Based on the analysis of 1D multicomponent two-phase dispersion free flow using the Method Of Characteristics (MOC)

Ci Fi + =0 t x

i =1,..,nc

18

Main results from the analysis (I)

In the composition space, the analytical solution forms a composition path starting from the injection gas composition to the initial oil composition. The composition path must travel through a sequence of key tielines. For a nc component system, there are nc-1 key tielines, including

The initial tie line and the injection tie line nc-3 crossover tielines

Main results from the analysis (II)

At MMP, one of the key tie lines become critical

vaporizing and condensing mechanisms are special cases when the initial key tie line and the injection key tie line become critical

The composition path can have discontinuities known as shocks. When the path consists ONLY of shocks (the usual case), the key tie lines will intersect pairwise. For other situations (solution consisting of not only shocks but also rarefactions), intersection of key tielines is a good approximation

19

Illustration of the concepts

Semi-analytical 1D Solutions CO2

Injection gas Crossover tie line Solution path nc-1 key tie lines

Injection tie line

S
0

T,P fixed
CH4

Initial oil
C10

Initial tie line

C4

Details: find intersection key tielines

C4
Tie-line extending through injected Gas True point of intersection Wang and Orr (1997) Critical point

Gas CO2
Jessen et al. (1998)

Oil C10
Tie-line extending through initial Oil

20

Details: mathematical models (I)

Intersection equations xij +1 (1 2 j 1 ) + yij 2 j 1 xij (1 2 j ) yij +1 2 j = 0 i = 1, nc 1 Isofugacity criterion
j = 1, nc 2

i = 1, nc il yij iv = 0 , xij j = 1, nc 1 Specification of Initial and Injection composition

ziOil xi1 (1 Oil ) yi1Oil = 0 i = 1, nc 1 ziInj xinc 1 (1 Inj ) yinc 1 inj = 0

Details: mathematical models (II)

Summation of mole fractions

x
i =1

nc

yij = 0 , j = 1, nc 1

Total number of equations

N equations = 2( nc 2 1)

Newton-Raphson iteration scheme.

J +F =0

21

Details: structure of Jacobian matrix (nc=4)

X . . X . X X X X X . . . . . . . . . . . . . . . . . . . . . X . X . X X X X . X . . . . . . . . . . . . . . . . . . . . . X X . X X X X . . X . . . . . . . . . . . . . . . . . . . . . X . X X X X . . . . . . . . . . . . . . . . . . . . . X . . . X X X X X X . . . . . . . . . . . . . . . . . . . . . X . . X X X X X . X . . . . . . . . . . . . . . . . . . . . . X . X X X X X . . X . . . . . . . . . . . . . . . . . . . . . . X X X X X . . . . . . . . . . . . . . . . . . . . . X X X . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . X . . X . X X X X X . . . . . . . . . . . . . . . . . . . . . X . X . X X X X . X . . . . . . . . . . . . . . . . . . . . . X X . X X X X . . X . . . . . . . . . . . . . . . . . . . . . X . X X X X . . . . . . . . . . . . . . . . . . . . . X . . . X X X X X X . . . . . . . . . . . . . . . . . . . . . X . . X X X X X . X . . . . . . . . . . . . . . . . . . . . . X . X X X X X . . X . . . . . . . . . . . . . . . . . . . . . . X X X X X . . . . . . . . . . . . . . . . . . . . . X X X . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . X . . X . X X X X X . . . . . . . . . . . . . . . . . . . . . X . X . X X X X . X . . . . . . . . . . . . . . . . . . . . . X X . X X X X . . X . . . . . . . . . . . . . . . . . . . . . X . X X X X . . . . . . . . . . . . . . . . . . . . . X . . . X X X X X X . . . . . . . . . . . . . . . . . . . . . X . . X X X X X . X . . . . . . . . . . . . . . . . . . . . . X . X X X X X . . X . . . . . . . . . . . . . . . . . . . . . . X X X X X . . . . . . . . . . . . . . . . . . . . . X X X . . . . . . . . . . . . . . . . . . X X X . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . X X X . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . X X X

Details: search for MMP

Displacement of Zick[1] Oil by Gas A
0.6

Displacement of Zick [1] Oil by Gas B

0.6 0.5

Tie-line Length

Tie-line Length

0.5 0.4 0.3 0.2 0.1 0 120

0.4 0.3 0.2 0.1 0 120

130

140

150

160

135

150

165

180

195

210

Pressure (atm)

Pressure (atm)

Tie-line length

d=

(x
nc i =1

yi

equals 0 at MMP

22

Details: validation of the algorithm

Method / Oil Multicell [2] Slimtube [2]* Slimtube [1]** Louis Bleriot*** Key tie line Time (seconds) Zick-A 152 157 156.74 0.7 Zick-B 213.8 211 211.0 0.7 SVOC 514.2 512 7 524 519.3 1.9 SVOD 231.9 228 10 216 217.3 1.7 SVOC+D 310.9 302 10 298 295.7 1.6

Comparison of different results from literature. P (atm) *Eclipse simulation, ** Experimental, *** Multicell [1] Zick, 1986; [2] Hier, 1997

Details: validation of the algorithm

550

Calculated MMP (atm)

450

350

250

150 150

250

350

450

550

Multicell Simulator MMP (atm)

23

Influence of gas composition on MMP

Gas enrichment study when two gases are available

The rich gas is treated as solvent

Monotonic

Non-monotonic

yinj = y gas (1 E ) + ysolvent E

Extension: semi-analytical solution to 1D two-phase gas injection

Identification of key tielines MOC 1D solution to fullly self-sharpening systems (only of shocks) MOC 1D solution to systems also having rarefactions Streamline method 3D streamline based compositional reservoir simulation

24

Example
1.00 Volume fraction of gas (S) 0.80 0.60 0.40 0.20 0.00 0.00

MOC Num erical (100,450) Num erical (1000, 4500) Num erical (10000, 45000)

0.9 sec 4.4 sec 5.4 min 7.8 hr

0.20

0.40

0.60

0.80

1.00

1.20

1.40

Wave velocity (z/t)

A near miscible displacement at 365 atm and 387.45 K.

Besides phase equilibrium...

Viscosity instability

CO2 viscosity: 0.02-0.05 cP Reservoir fluids: 0.5-5 cP Inherently unstable

Gravity segregation

CO2 desnity: 1/2-3/4 water density, close to oil

Reservoir heterogeneity

Channeling

25

Summary

EOR with CO2 provides double benefits in terms of sequestering CO2 and improving oil recovery EOR with CO2 injection is mainly attributed to multicontact miscibility. Three mechanisms for MCM are discussed, only two of them (the vaporizing and the combined) are realistic In experimental study of CO2 injection, swelling test is the easiest one to perform while only the slimtube experiment can correctly determine MMP (also the standard method).

Summary

Many MMP calculation methods are available, but only two (the slimtube simulation and the intersecting tieline method) can capture the correct mechanism. The first one is time consuming and needs extrapolation, while the second one gives quick and correct solution. A useful extension of the intersecting tie line method is the semianalytical solution to 1D two-phase gas injection, which can be further used in streamlined based reservoir simulation MMP (phase equilibrium) only determines local displacement efficiency, sweep efficiency are related to other aspects (viscosity, gravity, rock heterogeneity) which must be taken into consideration.

26