SPE 129728 Swelling/Extraction Test of a Small Sample Size for Phase Behavior Study

Jyun-Syung Tsau, University of Kansas Ly H. Bui, University of Kansas G. Paul Willhite, University of Kansas

 Swelling/extraction test is used to study phase behavior between carbon dioxide and crude oil A large size of sample volume (40 to 450 cc) requires a longer time to reach equilibrium prior to measurement

Outline of presentation
Describe an apparatus using small sample size for swelling/extraction tests Demonstrate the capability of the apparatus
Measurement of solubility of CO2, saturation pressure, swelling factor and extraction Estimation of molar volume of carbon dioxide saturated crude oil Visual observation of phase behavior Estimation of minimum miscibility pressure (MMP)

Fundamentals
Amount of CO2 dissolved in liquid (NCO2) = (Change of MassCO2 in pump - MassCO2 in line - MassCO2 in headspace ) / Molecular weight of CO2 Solubility of CO2 in liquid
Xco2= Nco2/(Nco2+Nliquid)

Phase equilibria data are obtained based on a mass balance

The pressure of CO2 is much greater than the vapor pressure of the crude oil Composition of the hydrocarbon in vapor phase is much less than that of CO2

Molar volume of CO2 saturated liquid

V = Vm /(Nco2+Nliquid)

Swelling factor = liquid volume (P) /original liquid volume

Apparatus

Water bath

View cell

Cathetometer

CO2 Pump

Verification
CO2 + Decane @ 71.10 oC (160 oF)

2000 1600 1200 800 400 0 0.0 0.2 0.4 0.6 0.8 Mole fraction of CO2 in the liquid phase 1.0
This work #1 This work # 2 Nagarajan & Robinson Jr. Jennings & Schucker

Pressure (psig)

Molar volume of CO2, decane and CO2 saturated decane

200 180 160 Molar volume (cc/mol) 140 120 100 80 60 40 20 0 0.00 0.20 0.40 0.60 0.80 1.00 Carbon dioxide (mol fraction)
y = -158.33x + 200.65 R = 0.9993

Ideal mixing
V = x C O 2 V C O 2 + (1 x C O 2 )V o or V = V o + (V C O 2 V o ) x C O

2

A straight line with a slope of (Vco2-Vo) and an intercept of Vo Molar volume of decane 200.65 cc/mol Apparent molar volume of CO2 42.32 cc/mol

Composition and properties of crude oil

0.25
Oil A

0.20 0.15

Oil B Oil C

Oil A MW 198.0 39.6 105 2.85

Oil B 228.7 33.3 110 4.95

Oil C 340.0 24.3 78 117

Mole Fraction

0.10 0.05 0.00 Carbon Number

API Gravity RT (F)

Viscosity (cp)

350 300

y = -367.13x + 402.52 R = 0.9999 Oil A Oil B Oil C Molar volume ( cc/mol) Temperature (F) y = -280.76x + 306.99 R = 0.9992 y = -235.23x + 266.12 R = 0.9995

Molar volume (cc/mol)

250 200 150 100 50 0

Oil A
105 263.41 266.12

Oil B
110 303.44 306.99

Oil C
78 399.20 402.52

Actual Estimated CO2 In oil

30.09

26.23

34.39

0.00

0.50

1.00

Carbon dioxide (mole fraction)

Typical swelling/extraction results

1.4
110 F

Swelling factor

CO2 solubility

1 0.9 CO2 solubility (mole fraction) 0.8 0.7 0.6 0.5

1.2 1 0.8 0.6 0.4 0.2 0 0 500 1000 Pressure, psig 1500 Swelling Extraction

Swelling factor

0.4 0.3 0.2 0.1 0 2000

Effect of temperature on solubility

1400 1200 1000 Pressure (psig) 800 600 400 200 105F 0 0.00 0.20 0.40 0.60 0.80 Mole fraction of CO2 in the liquid phase 1.00 115F 125F

Oil B

Effect of temperature on swelling/extraction

1.40 1.30 Swelling Factor (V/Vo) 1.20 1.10 1.00 0.90 0.80 0.70 0.60 0.50 0.40 0 500 1000 1500 Pressure (psig) 2000 2500 105F 115F 125F

Oil B

1.50 1.40 1.30 1.20 Swelling factor 1.10 1.00 0.90 0.80 0.70 0.60 0.50 0 200 400 600 800
105 F 98 F

Oil A

Pressure (psig)

1000

1200

1400

1600

1800

Three-phase region (oil A) @ 105 F

1.00 0.90 0.80 0.70 Volume % 0.60 0.50 0.40 0.30 0.20 0.10 0.00 1100 1125 1150 1175 Pressure (psig) 1200 1225 1250
Oil_rich CO2_rich_upper CO2_rich_ middle L+V L+L+V L+V

Oil C @ 78 F
296 psia 920 psia

CO2 vapor

CO2 rich liquid

Oil

Estimation of MMP (oil A) @ 105 F

1.40 1.30 1.20 1.10 Swelling factor 1.00 0.90 0.80 0.70 0.60 0.50 800 900 1000 1100 ~1240 1200 1300 MMP = 1250 psig

1400

1500

1600

1700

1800

Pressure (psig)

Estimation of MMP (oil B)

1.30 1.20 1.10 1.00 0.90 Swelling Factor 0.80 0.70 0.60 0.50 0.40 0.30 0.20 0.10 0.00 800 900 MMP = 1350 psig
~1360

110F

125F

MMP = 1650 psig

~1640

1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 Pressure [psig]

Conclusions
A new apparatus using small sample sizes is suitable for swelling test Swelling of crude oil by dissolved CO2 correlated with the molar volume of crude oil and CO2 over the range of pressure where negligible oil was extracted into the CO2 phase

Conclusions
The pressure at which extraction starts by CO2 depends on the temperature tested A three phase region (VLL) equilibrium was identified with the apparatus over a narrow range of pressure MMP estimated by the swelling/extraction test graphically is close to what determined from the slim-tube experiment

Acknowledgements

Carmen Schmitt Inc.