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William D. McCain, Jr., Texas A&M University

Copyright 2002, Society of Petroleum Engineers Inc.

This paper was prepared for presentation at the SPE Annual Technical Conference and

Exhibition held in San Antonio, Texas, 29 September –2 October 2002.

This paper was selected for presentation by an SPE Program Committee following review of and

information contained in an abstract submitted by the author(s). Contents of the paper, as

presented, have not been reviewed by the Society of Petroleum Engineers and are subject to

BoSb

Bo = ( BoD )

correction by the author(s). The material, as presented, does not necessarily reflect any

position of the Society of Petroleum Engineers, its officers, or members. Papers presented at at p<pb , . . . . . . . . . . . . . . . . . . . . . (2b)

SPE meetings are subject to publication review by Editorial Committees of the Society of BoDb

Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper

for commercial purposes without the written consent of the Society of Petrol eum Engineers is

prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300

words; illustrations may not be copied. The abstract must contain conspicuous are correct.

acknowledgment of where and by whom the paper was presented. Write Librarian, SPE, P.O.

Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.

This paper presents a brief discussion of the laboratory

procedures, which will lead to the derivations of Eq. 2b and a

correct replacement for Eq. 1.

Abstract

Combinations of data from two laboratory procedures, Laboratory Procedures

differential liberation and separator test, are used to determine

The two laboratory procedures that provide the necessary

values of oil formation volume factors and solution gas-oil data are the differential liberation (sometimes called

ratios for pressures below the bubblepoint pressure of the differential vaporization or differential distillation) and the

reservoir oil. The equation commonly used to calculate the

separator test (sometimes, incorrectly, called flash test). Each

solution gas -oil ratio is incorrect: the correct equation is of these laboratory procedures will be described briefly. What

derived. The equation used to calculate the oil formation will be seen is that each procedure starts with a quantity of

volume factors is correct; however, a derivation illustrating the

reservoir oil in the laboratory cell at its bubblepoint pressure at

underlying assumptions has not been published. This the reservoir temperature. In each procedure, gas is removed

derivation is also examined. in a sequence of flash vaporizations, with the resulting liquid

ending up at atmospheric pressure and 60°F

Introduction (standard conditions).

The bad news is that the equation usually used in the

petroleum industry to calculate solution gas -oil ratios from

Differential Liberation. Theoretically, the differential

black oil PVT reports, liberation starts with a liquid at some pressure and

temperature, then the liquid is partially vaporized, and each

BoSb

R s = R sSb − (R sDb − R sD ) , . . . . . . . . . . . . . . . . . . (1) small increment of vapor is at once removed from the contact

BoDb with the liquid.1 Thus, the liquid is in equilibrium at any

instant with a small amount of vapor. This procedure is

is incorrectly formulated. somewhat tedious, so the petroleum industry emulates the

The good news is that the errors at high pressures, where differential liberation with a series of flash vaporizations in

solution gas -oil ratios are more often used, are not severe. A which a definite fraction of a batch of liquid is vaporized and

correct formulation of the equation will improve estimates of kept in intimate contact with the liquid until the gas is

solution gas -oil ratio throughout the full range of withdrawn at the end of each step in the series.

depletion pressures. In practice, the process starts with a sample of reservoir

Further good news is that the equations used to calculate oil at its bubblepoint pressure in the laboratory cell with the

oil formation volume factors from black oil PVT reports, temperature controlled at reservoir temperature. A dozen or

so steps (the exact number depends on the starting bubblepoint

pressure) consisting of flash vaporizations are carried out.

Each step starts with a pressure reduction at constant reservoir

temperature. This causes gas to be vaporized. The gas is

2 WILLIAM D. MCCAIN, JR. SPE 77386

allowed to come to equilibrium with the liquid at the lower bubblepoint is the starting point of both processes and is

pressure and reservoir temperature, and then the gas is independent of the process. Table 2 shows this comparison

removed, and its quantity and specific gravity are measured. for the data of Table 1. The quantity of oil resulting from the

The volumes of the liquid remaining at the end of each step separator test is eighteen percent higher than the oil resulting

are determined. The last flash vaporization step ends at from the differential liberation. The quantity of gas resulting

atmospheric pressure. Then the temperature of the remaining from the separator test is fifteen percent lower than the gas

liquid is reduced to 60°F and the liquid volume is adjusted to from the differential liberation. And compositions and

maintain the pressure at 0 psig. This final liquid is called the properties of the resulting oils and gases differ significantly, as

residual liquid from the differential liberation or, simply, represented by the different API gravities of the oils and

residual oil. specific gravities of the gases.

The volumes of gas removed in all steps are added; this is

the amount of gas in solution at bubblepoint pressure. The gas Calculation of Oil Formation Volume Factors

volumes are decremented to determine the gas remaining in The ratio

solution at the pressure at the end of each step.

Finally, the volumes of gas in solution (in standard cubic 1 residual bbl

feet, scf) and the volumes of the oil in the cell (in reservoir BoDb res. bbl @ p b B oSb residual bbl

barrels, res. bbl) at the end of each step are divided by the = . . . . . . . . . . . (3)

1 STB BoDb STB

volume of the residual oil (at atmospheric pressure and 60°F).

These are presented in the laboratory report as gas in solution, BoSb res. bbl @ p b

scf/residual barrel, and relative oil volume, reservoir

barrel/residual barrel. Other properties, such as reservoir oil provides a convenient relationship between residual barrels

density, incremental gas specific gravity, and gas from the differential liberation and stock-tank barrels from the

compressibility factor, are also measured and reported. separator test. The term reservoir barrel at bubblepoint

pressure (at reservoir temperature), which appears twice on the

Separator Test. The separator test starts with a sample of the left-hand side of Eq. 3, can be eliminated since both laboratory

reservoir oil at its bubblepoint pressure in the laboratory cell at procedures start with the reservoir oil in the laboratory cell at

reservoir temperature (same as the start of the differential its bubblepoint pressure at reservoir temperature.

liberation). A measured volume of the reservoir oil is expelled The change in volume of oil in the reservoir during

through a sequence of two (usually, though sometimes three) pressure depletion can be written as

flash vaporizations. In the first, at separator temperature and

pressure, the gas that was vaporized is removed, and the liquid BoSb

goes to the second flash at stock-tank temperature and BoSb − Bo = ( BoDb − BoD ) . . . . . . . . . . . . . . . . . . . (4)

BoDb

atmospheric pressure. The volume of resulting liquid is

determined at atmospheric pressure and 60°F; this liquid is

The units of this equation are

usually called stock-tank oil and the volume is reported in

stock-tank barrels, STB, which also could be interpreted as

change in res bbl of oil change in res bbl of oil residual bbl

standard barrels. =

The volumes and specific gravities of the gases from the STB residual bbl STB

two flash vaporizations are measured. The two gas volumes

are added, and the sum is reported as solution gas-oil ratio at Under the assumption that the change in volume (res. bbl) of

the bubblepoint, scf/STB. The volume of reservoir oil that oil in the reservoir is the result of a differential liberation

was expelled at the start of the test is divided by the volume of process, the “change” units in the numerator of each side of

stock-tank oil (at standard conditions) and reported as oil the equation are identical. Thus, the equation is correct.

formation volume factor at the bubblepoint, res. bbl/STB. The Eq. 4 can be rearranged as

density of the stock-tank oil is measured and usually reported

in °API. BoSb

Bo = BoD , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (2b)

BoDb

Example Laboratory Data

Table 1 shows selected data from a differential liberation

which is the equation generally used in the petroleum industry

and a separator test for a black oil. The bubblepoint pressure

to calculate oil formation volume factors from differential

is 3043 psig at a reservoir temperature of 262°F.

liberation and separator test data.

The quantity and properties of oil and gas produced by the

Note that the use of Eq. 2b requires that the ratio of the

two procedures are different. However, this is difficult to see

volumes of residual oil to stock-tank oil remains constant (for

in the formats in which the data are presented. A comparison

a particular oil sample), regardless of the starting pressure.

of the results of the two procedures may be made by placing

The limited experimental data that are available show that this

the data on a basis of one barrel of reservoir oil at bubblepoint

is true.2

pressure and reservoir temperature. The oil in place at the

SPE 77386 ANALYSIS OF BLACK OIL PVT REPORTS REVISITED 3

There are very limited data to test the results of Eqs. 2a The correct formulation is as follows. The equation must

and 2b against measured oil formation volume factors. calculate the gas remaining in solution in the reservoir oil at a

However, Dodson, et al.,2 provided one set of data. Dodson, pressure after pressure depletion from p b to some p, Rs ,

et al., proposed a laboratory procedure for determining oil scf/STB. Further, Rs should be the amount of gas to be

formation volume factors (and solution gas -oil ratios) that is liberated through a separator/stock-tank sequence.

generally considered more accurate than the differential RsSb is the gas originally in solution in the reservoir oil at

liberation/separator test procedure usually used and discussed its bubblepoint pressure as measured in a separator test, scf of

in this paper. Unfortunately their “composite liberation,” gas from sep. test/STB. RsDb –RsD is the volume of gas

although considered a superior method,3 requires a large liberated in the reservoir during a differential liberation from

sample of reservoir fluid and is very time consuming in the p b to p, scf of diff. lib. gas/residual bbl.

laboratory. Thus, it is not used in routine laboratory analysis. The ratio

But Dodson, et al., did provide one example of a routine

laboratory report and the results of a composite liberation for scf of gas from sep. test

the same black oil. Fig. 1 shows values of oil formation R sSb STB

volume factor calculated with Eqs. 2a and 2b compared with RsDb scf of gas from diff. lib.

the more accurate results of the composite liberation.

residual bbl

The small differences between the results of Eq. 2b and

the data from the composite liberation are approximately one

takes into account both the difference in the two oils, residual

percent, well within experimental accuracy. The composite

bbl/STB, and the difference in the two gases, scf of gas from

liberation is an entirely different laboratory procedure; the sep. test/scf of gas from diff. lib.

differential liberation/separator test discussed here is the

Thus,

industry’s (less expensive) method of approximating the

composite liberation. R sSb

( R sDb − R sD )

RsDb

Calculation of Solution Gas-oil Ratios

Eq. 1 is used commonly in the petroleum industry to combine scf of gas lib. by diff. lib. scf of gas from sep. test, residual bbl

data from differential liberation and separator tests to calculate residual bbl scf of gas from diff. lib., STB

solution gas -oil ratios. The validity of this equation can be

examined easily by rearrangement: is the gas differentially liberated converted to scf of sep.

gas/STB. The difference between the gas originally in

BoSb

R sSb − R s = ( RsDb − R sD ) . . . . . . . . . . . . . . . . . . . (5) solution and the gas liberated during depletion from pb to p is

BoDb the gas remaining is solution at p.

R sSb

The units are R s = R sSb − (R sDb − R sD ) . . . . . . . . . . . . . . . . . . (6)

R sDb

gas liberated in sep test, scf gas libera ted in diff lib, scf residual bbl

=

STB residual bbl STB Again, there is the assumption that the differential liberation

mimics the depletion in an oil reservoir, i.e., the gas remaining

in solution is that left after gas has been removed by

Eq. 5 shows that the gas volume liberated during the differential liberation.

separator test has been set equal to the gas volume liberated Eq. 6 can be rearranged into a simpler form

during the differential liberation. If the sources of the data are

not taken into account, the units, scf/STB, appear to be R sSb

correct. However, Table 2 shows that the gas liberated during R s = R sD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (7)

R sDb

a separator test is significantly different in quantity and quality

from the gas liberated during a differential liberation. The

ratio BoSb /BoDb in Eq. 5 takes into account the differences in The use of Eq. 7 implies that the ratio of the gas liberated

the oils from the separator test and differential liberation, but by separator test to the gas liberated by differential liberation

the differences in the gases are ignored. be constant (for a particular oil sample), regardless of the

Thus, the material balance expressed in Eq. 5 must be starting pressure. The limited available data from Dodson, et

incorrect. It follows that values of solution gas-oil ratio al.2 show this to be true.

calculated with Eq. 1 must be in error! In fact, this is Again, the Dodson, et al.2 data are the only data available

illustrated every time the equation is used because calculated to use in comparing the results of Eq. 1 and Eq. 7 with

values of solution gas -oil ratio are generally negative at experimental solution gas -oil ratios measured at pressures

low pressures. below bubblepoint pressure of the oil.

4 WILLIAM D. MCCAIN, JR. SPE 77386

Fig. 2 shows the results of Eqs. 1 and 7 using the data RsDb = Solution gas-oil ratio at bubblepoint

from the routine laboratory report compared with the more pressure measured in a differential

accurate results of the composite liberation. Eq. 7 gives liberation, scf from differential

values of Rs , which fit the composite liberation more closely liberation/residual bbl

than the results of Eq. 1. Further, the values of Rs from Eq. 7

converge to zero at 0 psig (as required by the definition of Rs ), References

while the values from Eq. 1 are negative at low pressures. 1. Dodge, B.F.: Chemical Engineering Thermodynamics,

The small differences between the results of Eq. 7 and the McGraw-Hill, New York (1944), 592.

composite liberation data in Fig. 2, as well as the good 2. Dodson, C.R., Goodwill, D., and Mayer, E.H.:

comparison of the results of Eqs. 2a and 2b in Fig. 1, show “Application of Laboratory PVT Data to Reservoir

that the simpler, less costly, routinely used PVT procedures Engineering Problems,” Trans., AIME (1953) 198, 287–

give results adequate for reservoir engineering work. 298.

The difference between the results of Eq. 7 and Eq. 1 in 3. Moses, P.L.: “Engineering Applications of Phase

Fig. 2 are not very dramatic. However, notice that the Behavior of Crude Oil and Condensate Systems,” J. Pet.

Dodson, et al.2 oil does not have much dissolved gas, with Rsb Tech. (July 1986) 38, 715– 723.

of about 600 scf/STB. Fig. 3 shows that the oil of Table 1,

which has about 1000 scf/STB originally in solution, shows a TABLE 1. SELECTED DATA FROM DIFFERENTIAL LIBERATION

much larger difference between the results of the two AND SEPARATOR TEST OF A BLACK OIL

equations, about thirty percent at a reservoir pressure of Differential Liberation at 262°F

1100 psig. Incre-

mental

Conclusions Gas in Relative Oil Gas

Eqs. 2a, 2b, and 7 are the correct equations for calculating oil Pressure, Solution, Volume, Specific

psig scf/residual bbl res. bbl/residual bbl Gravity

formation volume factors and solution gas-oil ratios at 3043 1401 2.022

reservoir pressures below the bubblepoint pressure when 2900 1307 1.965 0.822

combining the data from differential liberation with separator 2600 1140 1.866 0.867

test data. 2300 998 1.783 0.858

The use of differential liberation data for these 2000 868 1.709 0.853

1700 751 1.644 0.856

calculations is nearly as accurate as the more costly composite

1400 642 1.584 0.861

liberation data and is certainly adequate for reservoir 1100 537 1.526 0.881

engineering calculations. 800 436 1.468 0.922

500 331 1.407 1.008

Nomenclature 263 235 1.339 1.197

Bo Oil formation volume factors at pressure, 143 176 1.290 1.432

=

0 0 1.111 2.194

res. bbl/STB 0 at 60°F = 1.000

BoSb = Oil formation volume factor at bubblepoint

pressure measured in a separator test, res. Gravity of Residual Oil = 43.2°API @ 60°F

bbl @ p b /STB

BoD Oil relative volumes at pressures less than SEPARATOR TEST

=

Oil

bubblepoint pressure measured in a Forma-

differential liberation, res. bbl/residual bbl tion

BoDb = Oil relative volume at bubblepoint pressure Volume Stock-

measured in a differential liberation, res. bbl Factor, tank Oil

Flash Pres- Temper- Gas-oil res. Gravity, Gas

@ p b /residual bbl Vapori - sure, ature, Ratio, bbl/ °API @ Specific

BoE = Oil relative volume at pressures above zation psig °F scf/STB STB 60°F Gravity

bubblepoint pressure measured in a constant Separator 100 70 935 0.775

mass expansion, res. bbl/res. bbl @ p b Stock

Tank 0 72 102 1.714** 48.0 1.309

Rs = Solution gas-oil ratios at pressures less than 1037*

bubblepoint pressure, scf/STB

*Solution gas-oil ratio at bubblepoint pressure

RsSb = Solution gas-oil ratio at bubblepoint

pressure measured in a separator test, scf **Oil formation volume factor at bubblepoint pressure

from separator test /STB

RsD = Solution gas-oil ratios at pressures less than

bubblepoint pressure measured in a

differential liberation, scf from differential

liberation/residual bbl

SPE 77386 ANALYSIS OF BLACK OIL PVT REPORTS REVISITED 5

TABLE 2. THE VOLUMES AND PROPERTIES OF THE OIL AND Fig. 2 Comparison of solution gas-oil ratios calculated

GAS RESULTING FROM THE TWO LABORATO RY PROCEDURES from routine laboratory PVT data using Eqs. 1 and 7 with

ARE QUITE DIFFERENT (DATA FROM TABLE 1)

Differential

data from composite liberation showing that Eq. 7 has a

Liberation Separator Test better fit.

Volume of oil at standard residual bbl STB

conditions at end of 0.495 0.583

res. bbl @ P b res. bbl @ P b 700

process

Gravity of oil at standard

conditions at end of 43.2°API 48.0°API 600

process

Volume of total gas at scf scf

692.9 605.0 500

standard conditions

liberated during process res. bbl @ P b res. bbl @ Pb

Weighted average specific 400

gravity at standard 1.0931 0.8252

conditions of total gas

300

liberated during process

200

Fig. 1 Comparison showing excellent fit of oil formation

volume factors calculated from routine laboratory PVT

100

data using Eqs. 2a and 2b with data from composite

liberation.

0

1.3

-100

0 500 1000 1500 2000 2500 3000 3500 4000

Reservoir pressure, psig

1.25

data from composite liberation calculated with Eq. 7 calculated with Eq. 1

Oil formation volume factor, res. bbl/STB

from routine laboratory PVT data using Eqs. 1 and 7,

showing that the deviation between the results is greater

1.15 when initial solution gas-oil ratio is large.

1200

1.1

1000

1.05 800

Solution gas-oil ratio, scf/STB

600

1

0 500 1000 1500 2000 2500 3000 3500 4000

400

Reservoir pressure, psig

-200

0 500 1000 1500 2000 2500 3000 3500

Reservoir pressure, psig

Eq. 7 Eq. 1