Chapter 21

Crude Oil Properties and Condensate Properties and Correlations

Paul Buthod,
U. of Tulsa*

Introduction
All crude oils are composed primarily of hydrocarbons, which are made by the combination of the elements carbon and hydrogen. In addition, most crudes contain sulfur compounds and trace quantities of oxygen, nitrogen, and heavy metals. The difference in crude oils is caused by the amount of sulfur compounds and by the types and molecular weights of the hydrocarbons making up the oil. The hydrocarbons found in crude oil range in size from the smallest molecule, methane, which contains 1 atom of carbon, to the largest ones, which contain nearly 100 atoms of carbon. The types of hydrocarbon compounds are paraffin, naphthene, and aromatic, found in raw crude, and olefin and diolefin, which are sometimes found in refined products after thermal treatment. Since any crude oil will have several thousand different compounds in it, it has been impossible so far to develop exact analyses of the actual compounds present. Three methods of reporting analyses are available-ultimate analysis, chemical analysis, and evaluation analysis. Ultimate analysis lists the composition in percentages of the elements carbon, hydrogen, nitrogen, oxygen, and sulfur. This tells very little about the type of compounds present or the physical characteristics of the oil. It is useful, however, in determining the amount of sulfur that must be removed. Table 21.1 shows the ultimate analysis of several crude oils. Chemical analysis gives composition in percentage of paraffin, naphthene, and aromatic-type compounds present in the crude. This type of analysis can be determined with fair accuracy by means of chemical reaction and solvency tests. An analysis of this sort gives an idea of the usefulness of refined products but does not give any
This author also wrote the tiginal chapter on this topic in the 1962 edation.

means of predicting the amount of various refined products. Table 2 1.2 gives the chemical analysis of several fractions of four crude oils. The crude-oil evaluation consists primarily of a fractional distillation of the oil followed by physicalproperty tests (for parameters such as gravity, viscosity, and pour point) on the distillation products. Since the primary means of separating products in the refinery is fractionation, this analysis makes it possible to predict yields of refined products and physical properties studied in the evaluation. The evaluation curves shown in Fig. 2 1.1 make it possible to predict the physical properties of the refined products. As an example of the use of evaluation curves, Table 2 1.3 shows product yields and properties when a refinery is operated for maximum gasoline yield, and Table 2 1.4 shows product yields and properties when the objective is to produce lubricating oils and diesel fuel. Since the early 1970s, much research has-been performed on the use of the gas chromatograph to generate simulated distillations. This has the advantage of producing crude-oil evaluation curves with very small samples of crude and in a period of about an hour, compared with about a gallon of crude for a fractional distillation column and about 2 days for the analysis. The simulated distillation is called ASTM Test Method D2887. I

Base of Crude Oil

Since the beginning of the oil industry in the U.S., it has been convenient to separate crude oils into three broad classifications or bases. These three, paraffin, intermediate, and naphthene, are useful as general classifications but lead to ambiguity in many instances. Because a crude may exhibit one set of characteristics for

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TABLE Pl.l-ULTIMATE Specific Gravity -r 0.862 0.897 0.912 0.951 0.91 0.97 0.897 0.948

CHEMICAL ANALYSES

OF PETROLEUM Component WI N 0 3.6 0.37 0.76 0.60 0.70 4.30 1.5 0.54

Petroleum Pennsylvania pipeline Mecook, WV Humbolt, KS Healdton, OK Coalinga, CA Beaumont, TX Mexico Baku, USSR Colombia, South America
Combined mtrogen and oxygen.

Temperature PC) 15 0

15 15 20

C 85.5 83.6 85.6 85.0 86.4 85.7 83.0 66.5 65.62

H 14.2 12.9 12.4 12.9 11.7 11.0 11 .o 12.0 11.91

--

Base paraffin paraffin mixed mixed

naphthene

1.14 2.61 1.7*

naphthene naphthene

TABLE 21.2-CHEMICAL
Grozny (High Paraffin) 45.3% at 572OF Aromatic 3 z 14 18
17

ANALYSES OF PETROLEUM, %
Oklahoma California (Huntmgton Beach), 34.2% at 57ZF Paraffin 73 65 55 55 52 51
-A

Fraction (0 140 to 203 to 252 to 302 to 392 to 482 to 203 252 302 392 482 572

Grozny (ParaffinFree Upper Level), 40.9% at 572OF Paraffin 72 65 56 57 59 61 Aromatic 4 8 13 21 26 35 Naphthene 31 40 52 55 63 57 Paraffin 65 52 35 24 11 8 Aromatlc 5 7 12 16 17 17

(Davenport),
64% at 572OF Naphthene 21 28 33 29 31 32

Naphthene 25 30 35 29 23 22

Aromatic i
11

Naohthene 46 31 64 61 45 40

Paraffin 46 65 25 22 30 31

17 25 29

TABLE 21.3-EVALUATION

WHEN OPERATING PRIMARILY FOR GASOLINE Percent Distilled Gravity (OAPI) 56 28.8 6.4$ 32.0

Material Gas loss Straight-run gasoline (untreated) Catalytic charge V&breaker Crude oil charge or asphalt

Basis 54.5 octane number 900F cut remainder

Range 0 to 1.3 1.3 to 32 32 to 80.5 80.5 to 100

Midpoint ~16.6 56.2

Yield 1.3 30.7 48.5 19.5 100.0

Other Properties 390DF ASTM endpoint7 165OF aniline point or 47.5 diesel index 110 penetration 11.65 characterization factor

Topping follwed by YaWUrn flashing to produce a gas 011for catalflic cracking. breaker chargestock.

The Cycle stcck IrOm catalytic cracking is thermally cracked along wtth the asphalt or vis-

Average gravity from instantaneouscurve of API gravity. ?At about 400aF endpoint the truebOiling.pCint cut point is about 2PF higher than the ASTM end point
*By a material balance.

TABLE 21.4-EVALUATION

WHEN OPERATING PRIMARILY FOR LUBRICATING-OIL

Percent Distilled API Gravity 61.2C 41.3e 32.1 25.9 19.1 32.0 Viscosity, SUS

STOCK0

Material Gas loss

Basis 300 EPb 445 EPb 156 aniline point

Range 0 to 1.3 lo 21 .O to 38.5 to 56.5 to 74.9 to 80.9 to

Midpoint

Yield 19.7 17.5 18.0 18.4 6.0 19.1

100.0

Other Properties

Light gasoline (untreated) Reforming naphtha Diesel fuel Light lube or cracking stock Lube stock (untreated) Asphalt Crude oil

remainder
100 Ws viscosity at 2lOOF

100 penetration

-13 1.3 21.0 10.5 38.5 29.7 56.5 47.5 74.9 65.7 80.9 77.9 100.0

63.8 octane numberd 0.16% sulfur 41 (estimated) 50 diesel Index; 0.82% sulfur 145 at 100F 1.49% sulfur 100 at 210F

100 penetration at 77OFg

CRUDE-OIL & CONDENSATE

PROPERTIES & CORRELATIONS

21-3

TABLE 21.5-BASES

OF CRUDE OILS Approximate LowBoiling 12.2+ 12.2+ 12.2 + 11.5 to 12.0 11.4 to 12.1 11.4 to 12.1 11.511.511.4UOP* * HighBoiling 12.2+ 11.4 to 12.0 11.412.2+ 11.4 to 12.1 11.411.4 to 12.1 12.2+ 11.4-

API Gravity at 60F Low-Boiling High-Boiling Key Fraction

Characterization Factor

Part paraffin baraffin

paraffin intermediate intermediate intermediate naphthene naphthene naphthene

Part
paraffin intermediate naphthene paraffin intermediate naphthene intermediate paraffin naphthene

1
40+ 40+ 40+ 33 to 40 33 to 40 33 to 40 333333-

Key Fraction 2 30+ 20 to 30 2030+ 20 to 30 2020 to 30 30+ 20-

USBM, Repon3279 (Sept.1935).

Universal Oil Products Co.. Chicago

its light materials and another set for the heavy-lube fractions, the USBM has developed a more useful method of classifying oils. Two fractions (called key fractions) are obtained in the standard Hempel distillation procedure. Key Fraction 1 is the material that boils between 482 and 527F at atmospheric pressure. Key Fraction 2 is the material that boils between 527 and 572F at 40 mm absolute pressure. Both fractions are tested for API gravity, and Key Fraction 2 is tested for cloud point. In naming the type of oil, the base of light material (Key Fraction 1) is named first, and the base of the heavy material (Key Fraction 2) is named second. If the cloud point of Key Fraction 2 is above 5F, the term wax-bearing is added. If the pour point is below 5F, it is termed waxfree. would mean Thus, paraffin-intermediate-wax-free a crude that has paraffinic characteristics in the gasoline portion and intermediate characteristics in the lube portion and has very little wax. Table 21.5 shows the criteria used in establishing bases of oil by the USBM method. Several attempts have been made to establish an index to give a numerical correlation for the base of a crude oil. The most useful of these is the characterization factor K developed in Ref. 2,

TABLE 21.6-TYPICAL CHARACTERIZATION FACTOR VALUES Characterization Factor 12.1 11.8 11 .o 11.5 10.5 10.0 9.8 to to to to to to to 12.5 12.0 11.6 11.8 11.5 11.0 11 .O

Product Pennsylvania stocks (paraffin base) Mid-Continent stocks (intermediate) Gulf Coast stocks (naphthene base) Cracked gasoline Cracking-plant combined feeds Recycle stocks Cracked residuum

number of worldwide crudes and products and typical hydrocarbon compounds that have the same characterization factor as the oil in question.

Physical Properties
Fig. 21.2 shows the relationship of carbon-tohydrogen ratio, average molecular weight, and mean average boiling point as a function of API gravity and characterization factor. The API Technical Book3 Data has published a number of correlations for physical properties of petroleum. For the most accurate data, this reference should be consulted. When oil is heated or cooled in a processing operation, the amount of heat required is best obtained by the use of the specific heat. Fig. 21.3 shows the specific heat of liquid petroleum oils as a function of API gravity and temperature. This chart is based on a characterization factor of 11.8, and if the oil being studied is other than that, there is a correction shown at the lower right side of the chart. The number obtained for the specific heat should be multiplied by this correction factor. Certain paraffin hydrocarbons are also shown on the chart. No correction need be applied to these. If vaporization or condensation occurs in a processing operation, the heat requirements are most easily handled by the use of total heats. Fig. 2 1.4 gives total heats of petroleum liquid and vapor, with liquid at 0F as a reference or zero point. This eliminates the necessity of selecting a latent heat, specific heats of both vapor and liquid, and deciding at what temperature to apply the latent heat. Certain corrections must be applied for characterization factor and for pressure.

K=- 3% Y

in which TB is the molal average boiling point (degrees Rankine) and y is the specific gravity at 60F. This has been used successfully in correlating not only crude oils, but refinery products both cracked and straight-run. Typical numerical values for characterization factors are listed in Table 2 1.6. In addition to the relationship between the characterization factor and the specific gravity and boiling point defined above, a number of other physical properties have been shown to be related to the chamcterization factor. Among these properties are viscosity, molecular weight, critical temperature and pressure, specific heats, and percent hydrogen. Table 21.7 shows characterization factors for a

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TABLE 21.7-CHARACTERIZATION
Characterization Factor 14.7 14.2 13.85 13.5 to 13.6 13.0 to 13.2 12.8 12.7 12.6 12.55 12.5 12.1 to 12.5 12.2 to 12.44 12.0 to 12.2 11.9 to 12.2

FACTORS OF A FEW HYDROCARBONS,

PETROLEUMS,

AND TYPICAL STOCKS

Hydrocarbons propane propylene isobutane butane butane-l and isopentane hexane and tetradecened P-methylheptane and tetradecane pentene-1, hexene-1, and cetene 2,2,4-trimethylpentane hexene-2 and 1.3-butadiene 2,2,3,3tetramethyl butane 2,l l-dimethyl dodecadiene

Typical Crude Oils

Miscellaneous Products

94.5 API adsorption gasoline Four Venezuelan paraffin waxes paraffin wax*: MC. 82.2 API natural gasoline CA 81.9 API natural gasoline Cotton Valley (LA) lubes Pennsylvania-Rodessa Big Lake (TX) Lance Creek (WY) Mid-Continent (MC.) Oklahoma City (OK) (LA) debutanized E. TX natural gasoline San Joaquin (Venezuela) wax distillate Panhandle (TX) lubes Six Venezuelan wax distillates

paraffin-base gasolines
Middle East light products cracked gasoline from paraffinic feeds E. TX gas oil and lubes light cycloversion gasoline from M.C. feeds Middle East gas oil and lubes cracked gasoline from intermediate feeds E. TX and IA white products cracked gas oil from paraffinic feeds catalytic cycle stocks from paraffinic feeds cracked gasoline from naphthene feeds Tia Juana (Venezuela) gas oil and lubes naphthenic gasoline: catalytic (cracked) gasoline catalytic cycle stocks from MC. feeds cracked gasoline from hrghly naphthenrc feeds high-conversion catalytic cycle stocks from parafbnic feeds typical catalytic cycle stocks liaht-ail coil thermal feeds catalytic cycle stocks from 11.7~characterization-factor feeds gasoline from catalytic re-forming

11.9 11.8 to 12.1 11.85 11.7 to 12 11.75 11.7 11.6 11.5 to 11.8 11.5

hexylcyclohexane Fullerton (W. TX) Illinois; Midway (AR) W. TX; Jusepin (Venezuela) Cowden (W TX) Santa Fe Springs (CA) Slaughter (W. TX); Hobbs (NM) Colombian Hendrick and Yates (W. TX) Elk Basin, heavy (WY) Kettleman Hills (CA) Smackover (AR) Lagunillas (Venezuela) Gulf Coast light distillates

butylcyclohexane octyl or diamyl benzene

11.45 11.4 11.3to 11.6 11.3

ethylcyclohexane and 9-hexyl-l l-methylheptadiene methylcyctohexane

cyclobutane and 2,6,10,14tetramethyl

hexadiene

12.66 (range 12.1 to 13.65) calculated lrom factors of raw and dewaxed lube stocks

(YIELD1

*.-

IO

20

30 40 50 60 i-0 PERCENTAGEDISTILLED

80

90 I

100 I

Ftg. 21 .l-Evaluation curves of a 32.0API intermediate-base crude oil of characterization factor 11.65.

CRUDE-OIL 8 CONDENSATE

PROPERTIES & CORRELATIONS

21-5

9.0

8.0

7-o

1100

6.0

1000

900

800

700

600

500

400

300

200

100 IO 20 30 40 50

Fig. 21.2-Petroleum properties as a function of API gravity and characterization factor. Note: the parameters in the curves refer to the characterization factor.

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PETROLEUM ENGINEERING

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III

200

400 600 TEMPERATURE,F

000

Fig. 21.3-Specific heats of Mid-Continent liquid oils with a correction factor for other bases of oils.

7 / L o-

o-

o-

o9 3-

1,.,!,,,,,,.,
K=CHARACTEklZATION FACTOR = 3MOLAL AVG. BOILINGPOINT,R / SPEClF(CG.,ilTYf~ /
1,100 I I 000 , OF I 900 I 1,000 I 1,200

34 0

Fig. 21.4-Heat

content of petroleum fractions including the effect of pressure.

CRUDE-OIL

& CONDENSATE

PROPERTIES

& CORRELATIONS

21-7

TABLE 21.8-TRUE-BOILING-POINT

CRUDE OIL ANALYSES Location

Smackover, AR Gravity, API Sulfur, % Viscosity, SUS at lOOoF Date Characterization factor At 25OF At 450F At 550F At 750DF Average Base Loss, % Gasoline % at 300F Octane number, clear Octane number, 3 cc TEL % to 400F Octane number, clear Octane number, 3 cc TEL % to 450F Quality Jet stock % to 550F API gravity Qualitv Kerosene distillate %, 375 to 500F API gravity Smoke point Sulfur, % Quality Distillate or diesel fuel %, 400 to 700F Diesel index Pour point Sulfur, O/O Quality Cracking stock (distilled) %, 400 to 900F Octane number (thermal) API gravity Quality Cracking stock (residual) % above 550F API gravity API cracked fuel % gasoline (on stock) % gasoline (on crude oil) Lube distillate (undewaxed) % 700 to 900Fc Pour point Viscosity index Sulfur, % Quality Residue, % over 900F Asphalt quality 20.5 2.30 270 413139 11.62 11.48 11.47 11.55 11.53 I 0 6.0 73.2a a9.0a 11 .o 66.0b 14.4 good b 24.1 41.9 good 9.5 38.0 16.0b 0.29b

Atlanta, AR (limestone) 44.5 0.48c 35

Kern River, CA 10.7 1.23 6,000 +

Santa Maria, CA 15.4 4.63 368 812154 11.90 11.42 11.29 11.11 11.48 IN 0 7.0

Coalinga (East), CA 20.7 0.51 178

Coalinga, CA 31.1 0.31 40

11.82 12.05 12.08 12.25 12.05 IP 1.5 25.2d

11.13 11.15 11.15 N 0 0

11.28 11.20 11.23 N 3.0 1.2d

11.5 11.53 11.59 11.72 11.58 I 1.1 21 .6d 72.ob 31 .6d 66.7b 35.6d excellent b 46.2d 46.0d good Il.Od 37.0 17.0b 0.06b

39.2d

1.2d

48.5b 45.3d 2.P

13.2 59.8e 70.30 17.0

9.6d 67.0 b 15.6d good b 29.3d 36.9

56.3d 57.4

6.1 d 29.5b

25.0 43.0 good 8.5 34.5 1.8d

15.0d 46.0 27.0b 0.06b excellent 35.0d 76.0d high 0.15b

2.7d 32.5d 13.0b 0.38b

16.0d 34.0d 14.5b o.ub

29.2

43.0b Ob 0.82 b

19.7d mob - 30.0b

0.8b

23.8 33.0 - 3.0 2.56

38.4d 33.0b -25.ob 0.35b

28.0d 48.5 20.0b 0.W

48.2 71.4b 25.7

51.4d 64.5 b 35.5

41.8d 7.5.6b 20.0 good 93.9d 9.1

39.8 75.6d 22.8

59.46 22.3 excellent 67.7d 11 .o 4.2 27.5 18.6 13.06

45.6d 70.4b 28.0 good 52.P 18.2 5.0 42.2 22.2 17.6d 56.0b 0.43b 21.7d good

75.9

42.2d

75.0 i:: 15.0 11.0

14.7 4.8 35.5 27.0 19.0 37.0b 2.45 b 40.8 good

27.1 9.6 54.9 23.2 16.4d 113.0b 0.8b excellent 7.9d

22.2d

16.0

1.5b 57.0d excellent 47.0 excellent

0.67b 28.0d excellent

a Simply aviation gasoline, not always 300-F cut point Esbmated from general cotrelat~ons. Sour oils (1.e.. oils containing more than 0.5 cu ft hydrogen sulfide per 100 gal before stabilization.) dApproximat.+d from data on other fractions of same oil. Research method Octane number

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TABLE 21.9-ANALYSIS

OF CONDENSATE LIQUID AND GAS FROM SELECTED TEXAS ZONES

Carthage Upper Pettite Zone 607 70 19.62 16.23 18.25 0.695 1.480 89.045 4.691 1.393 0.401 0.394 0.283 0.191 0.379 1.098 100.00 61.0 91.51 OAPI 74.8 59 2 48.1

Chapel Hill Palusy Zone Sampling pressure Sampling temperature Total fluid mol wt Liquid/gas ratio, bbl per million scf Gas mol WI Gas analysis, mol% Carbon dioxide Nitrogen Methane Ethane Propane i-butane n-Butane i-pentane n-Pentane Hexanes Heptane plus Total Liquid gravity, OAPI Llquld mol wt Liquid analysts Light gasoline Naphtha Kerosene dtstlllate Gas oil Nonviscous lube Residuum and loss 645 82 25.03 88.74 20.18 0.794 1.375 76.432 7.923 4.301 1.198 1.862 0.937 0.781 1.415 2.992 100.00 71.8 68.64 Vol % ---__ 55.1 37.2 21.1

Carthage Lower Pettile Zone 63267 20.19 29.28 18.25 0.646 1.967 88.799 3.363 1.536 0.335 0.583 0.302 0.254 0.574 1.641 100.00 64.8 81.55 Vol % 40.7 47.0 79 API 76.6 59.3 47.6

Old Ocean Chenault Zone 752 85 20.76 29.33 18.70 0.448 0.370 87.584 5.312 2.302 0.584 0.630 0.416 0.207 0.505 1.642 100.00 54 0 85.93 Vol % 21.2 55.3 15.0 3.8 4.7

Old Ocean Larson Zone 702 85 20.51 28.71 18.17 0.468 0.414 90.162 4.067 1.616 0.464 0.390 0.274 0.123 0.418 1.604 100 00 47.6 110.07 API 70.9 52.2 42.1 36.6 29.8

Seellgson 21 D Zone 810 80 20 64 29.88 18.42 0.130 0 075 89.498 4 555 1 909 0 465 0 493 0.286 0209 0 385 2015 100.00 52.7 94.49 Vol % 22.6 47.7 15.9 7.3 6.5

Seeligson 21 A Zone 410 85 20.63 24.48 18.69 0.200 0.253 88.731 5.224 1.795 0.488 0.452 0.172 0.241 0.414 2.032 100.00 52.1 103.22 API 68.4 53.1 43.0 37.0

Saxet 1087 88 21.34 41.33 18.89 0.299 0.281 86.733 4.816 2.873 0.836 0.788 0.583 0.256 0.633 2.102 10000 60.0 68.73 Vol % 35.7 47.6 10.0 2.4 4.3 OAPI 73.6 55.9 44.9 38.2

OAPI Vol % 82.9 60.5 50.8 29.1 48.4 18.2

5.6

4.3

4.4

=APl Vol % --71.2 14.7 52.9 36.9 42.6 17.4 37.8 21.3 74 2.3

OAPI Vol % 70.1 53.4 43.8 37.4 20.7 49.5 16.1 7.2 6.5

An important physical property of petroleum necessary in studying flow characteristics is viscosity. Viscosity of petroleum is often reported in Saybolt Universal Seconds (SUS), derived from one of the common routine tests for oils. For engineering calculation, however, the viscosity should be obtained in centipoise. The relation between these two systems, according to the U .S Bureau of Standards, is 5 =0.219ts Yo --, 149.7 tsu

where FL0 = viscosity, cp Yo = specific gravity of oil at measured temperature, and tSU = Universal Saybolt viscosity, seconds. An accurate correlation for viscosity is difficult, especially for viscous oils, but an estimate of viscosity may be obtained from Fig. 21.5. Four characterization factors are given, and interpolation must be made for other factors.

True-Boiling-Point

Crude-Oil Analyses

Fig. 21.5-Approximate relation between viscosity, ture, and characterization factor.

tempera-

A number of true-boiling-point crude-oil analyses are included in Table 21.8. In addition to the gravity, viscosity, sulfur content, and characterization factor, there is a breakdown of typical products made from each crude. This table may be used either to estimate the value of the products listed or to plot and evaluate any set of products obtained (see Fig. 21.1). The table is separated first according to state, and within each group according to gravity.

CRUDE-OIL

& CONDENSATE

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& CORRELATIONS

21-9

When the quality of a product is indicated as good or excellent, it means not only that the quality is good but that it is present in normal amounts and that a salable product can be made without excessive treatment. Table 21.9 shows the analysis of the gas and liquid phases after a stage separation of several condensates. Nelson4 gives a compilation of 164 crudes and lists the gravity, characterization factor, sulfur content, and viscosity of each. Those tables include yields of typical refined products, along with their physical properties and an indication of their quality. A true-boiling-point curve can be generated by plotting the end points of these products against the cumulative volume percent yield. If the characterization factor is plotted on the same graph, the characterization factor at any instantaneous boiling point can be calculated. When instantaneous temperatures and characterization factors at different percents are known, specific gravity, API gravity, and viscosity curves may be estimated. Thus, evaluation curves such as those in Fig. 21 .l may be produced for any of the 164 crudes listed. A typical page of these data is shown in Table 21.8. More recently, a series on evaluations of non-U.S. crude oils was published. 5 The format is similar to those in Nelsons compilation, 4 but the physical properties are usually more complete. An example of an analysis from this series is shown in Table 21.10. The USBM in Bartlesville, OK, began making distillation analyses before 1920. This laboratory [U.S. DOE Bartlesville Energy Technology Center (BETC)] has continued to evaluate crude oil up to the present time and has two publications6,7 that show the distillation data along with gravity and viscosity of the distilled fractions. They also show the percentage composition of the fractions in terms of paraffins, naphthenes, and aromatics. This set of tables uses the correlation index rather than characterization factor as a correlating number. In general, low correlation index (1,) numbers indicate highly paraffinic (pure paraffin hydrocarbons, I, =O). High numbers indicate a high degree of aromaticity (benzene, I,. = 100). The correlation index is defined as follows.
1,=413.7 y-456.8+87552/T~,

TABLE Pl.lO-TYPICAL CRUDE OIL EVALUATION, EKOFISK, NORWAY Crude Gravity, API Basic sediment and water, vol% Sulfur, wt% Pour test, OC Viscosity, SUS at lOOoF Reid vapor pressure, psi at 1OOF Salt, lbm/l,OOO bbl Nitrogen compounds and lighter, ~01% Gasoline Range, OF Yield, VOWI Gravity, OAPI Sulfur, wt% Research octane number, clear Research octane number, - 3 mL tetraethyl lead per gallon Gasoline Range, OF Yield, ~01% Gravity, OAPI Paraffins, ~01% Naphthenes. vol% Aromatics, ~01% (0 + A) Sulfur, wt% Research octane number, clear Research octane number, + 3 mL tetraethyl lead per gallon Kerosene Range, OF Yield, ~01% Gravity, OAPI Viscosity, SUS at lOOoF Freezing point, OF Aromatics, VOW (0 + A) Sulfur, wt% Aniline point, OF Smoke point, mm Liaht Gas Oil Range, OF Yield, ~01% Gravity, OAPI Viscosity, SUS at lOOoF Pour point, OF Sulfur, wt% Aniline point, OF Carbon residue, Ramsbottom, wt% Cetane index TopPed Crude Range, OF Yield, ~01% Gravity, OAPI Viscosity, SUS at 122OF Pour point, OF Sulfur, wt% Carbon residue, Ramsbottom, wt% Nickel, vanadium, ppm 650 + 38.8 21.5 80.25 -85 0.39 4.0 5.04, 1.95 500 400 to 500 13.5 40.2 32.33 -38 13.1 <0.05 146.2 21 60 to 400 31.0 60.1 56.52 29.52 13.96 0.0024 52.0 76.0 60 36.3 1 .o 0.21 +20 42.40 5.1 14.5 1.0

to 200
10.7 77.2 0.003 74.4 90.0

to 650
15.7 33.7 43.83 -25 0.11 164.3 0.08 56.5

where y is the specific gravity of the fraction at 60F and T, is the average normal boiling point in degrees Rankine . All U.S. DOE analysis data have been built into the BETC Crude Oil Analysis Data Bank.8 The data retrieval system, Crude Oil Analysis System (COASYS), is available by telephone hookup, and customers may search, sort, and retrieve analyses from the file. More than 30 keywords are available for searching; for example, YEAR, APIG, LOC, GEOL and SULF, allow a search on year analyzed, API gravity, location by state and country, geological formation, and percent sulfur in the oil, respectively. Table 21.11 shows the type of information obtained in a typical analysis retrieved from a computer search by COASYS.

Bubblepoint Pressure Correlations*

In the study of reservoir flow properties, it is important to know whether the fluid in the reservoir is in the liquid,
The rematnder of this chapter was written by M.0 Standing in the 1962 editon.

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TABLE 21.11-ADAPTATION

OF BETC COMPUTER SEARCH PRINTOUT

Crude Petroleum Analysis: BETC Sample-B75008 lndentification Webb W Field, Grant County, OK Red Fork, Des Moines, Middle Pennsylvanian-4,464 General Characteristics Gravity, specific [OAPI] Sulfur, wt% Viscosity, SUS at 77OF at 1 OOF Pour point, OF Nitrogen, wt% Color Distillation. USBM Method (First droo at 79OF) Stage l-Distillation Fraction Cut Number (OF) Vol% -1221
2 3 4 5 6 7 8 9 10 167 212 257 302 347 392 437 482 527 0.820[41.1] 0.24 42

to 4,482 ft

39
<5 0.054

brownish-black

at Atmospheric Pressure 746 mm Hg Cumulative VOW0

3.7 9.2 16.6 22.4 29.1 35.1 41.0 47.8 52.9

Gravity at 6OOF
Specific API

Correlation
Index 7 17 21 22 23 22 23 24 25

Refraction Index Specific at 20C Dispersion

1.38560 1.39755 1.41082 1.42186 1.43039 1.43770 1.44415 1.45102 1.45771 126.3 131.1 133.0 134.0 134.7 135.2 135.5 137.6 138.0

Viscosity Cloud at lOOoF point

(SW

~~-

(OF)

wwo Residuum Crude

-1.5 1.5
2.2 5.5 7.4 5.8 6.7 6.0 59 6.8 5.1

0.639
0.670 0.712 0.738 0.757 0.773 0.785 0 798 0.812 0.823

89.9 79.7
67.2 60.2 55.4 51.6 48.8 45.8 42.8 40.4

Stage 2-Distillation
11 12 13 14 15 392 437 482 527 572 7.2 6.2 5.6 4.8 5.1

continued at 40 mm Hg
60.1 66.3 72.1 76.9 82.0 99.0 0.842 0.851 0.863 0.874 0.887 0.934 38.6 34.8 32.5 30.4 28.0 20.0 7.1 0.67 0.235 1.4 30 30 33 35 38 1.46481 1.47017 1.47736 141.2 148.4 145.6 40 i: 96 179 14 ii 76 98

Restduum Carbon Sulfur

Nitrogen

17.0

Approximate Summary

Light gas Gas+ Naoh

Kerosend

9.2 35.1
17.8

0.690
0.743 0.311 0.845 0.854 to 0.875

Gas oil Non viscous lub Med viscous lub

Viscous lub Restdue Loss

11.6 10.3
6.0 1.3 17.0 1.0

73.6 58.9 43.1 35.9 34.3 to 30.3 5oto 100 loot0 200 >200

0.875 to 0.890 30.3 to 27.4 0.890 to 0.894 27.4 to 26.8 0.934 20.0

vapor, or two-phase state. With crude oils, the fluid may be subcooled liquid, but with some dissolved gas. Upon reduction in reservoir pressure, a point where the gas starts to come out of solution, called bubblepoint pressure, is reached. At this point the flow characteristics change. Some of the earliest work in this field was done by Lacey , Sage, and Kircher. 9 Several empirical correlations have been developed to predict the bubblepoint pressure, and some of these arc presented later.

Dewpoint-Pressure Correlations
The dewpoint, like the bubblepoint, is characterized by a substantial amount of one phase in equilibrium with an infinitesimal amount of the other phase. At the dew-

point, the liquid phase is at its minimum. In general, petroleum-reservoir systems that involve dewpoint behavior at reservoir conditions are characterized by (1) surface gas/oil ratios (GORs) greater than 6,000 cu ft/bbl in most instances; (2) lightly colored tank oils, usually straw-colored to light orange for reservoir systems at 3,000 to 5,000 psi but grading to brown for systems at 7,C00 psi and greater; (3) tank oil gravity usually greater than 45API; and (4) methane content usually greater than 65 mol% . Few dewpoint-pressure correlations of reservoir systems have been published. Sage and Olds published a very general correlation of the behavior of several San Joaquin Valley, CA, systems. A correlation developed by Organick and Golding I1 is discussed in

CRUDE-OIL & CONDENSATE

PROPERTIES & CORRELATIONS

21-11

TABLE 21.11-ADAPTATION

OF BETC COMPUTER SEARCH PRINTOUT

(continued)

Hvdrocarbon-tvpe Analvsis for Crude Petroleum Analvsis 875008 Fraction Number 1 2 3 4 5 a 7 a 9 10 11 12 vow0 of Crude 1.5 2.2 5.5 7.4 5.8 6.7 6.0 5.9 6.8 5.1 72 6.2 Specific Gravity 0.639 0.670 0.712 0.738 0.757 0.773 0.785 0.798 0.812 0.823 0.842 0.851 Correlation Index Aromatics (VOW0 of Fraction) 0.0 2.4 5.9 7.5 9.1 10.2 10.6 10.7 11.5 10.4 13.0 16.2 P-N * (vol% of Fraction) 100.0 97.6 94.1 92.5 90.9 89.8 89.4 89.3 88.5 89.6 87.0 83.8 Correlation index of P-N Gravity of P-N 0.639 0.665 0.702 0.727 0.746 0.761 0.772 0.784 0.796 0.809 0.825 0.831

7 17 21 22 23 22 23 24 25 30 30

5 13 16 17 17 16 16 17 18 22 21

Analvsis of Naotha Fractions Fraction Number 2 3 4 5 6 7 Vol% of P-N ANaphtha 7.1 23.7 38.6 44.0 43.6 43.6 Paraffin 92.9 76.3 61.4 56.0 56.4 56.4 Vol% of Fraction Naphtha 6.9 22.3 35.7 40.0 39.2 39.0 Paraffin 90.7 71.8 56.8 50.9 50.7 50.4 Fraction Number 12 14 Number of Total 1.4 1.7 Aromatic Rings 0.3 0.6 Naphthenes per mol 1.1 1.1

Summarv Data for Blends Naphtha Blend (Fractions 1 through 7) VOW of Crude in Blend Aromatic, VOW of Blend Paraffin-Naphthene, vol% of Blend Naphthene, ~01% of Blend Paraffin, ~01% of Blend Naphthene, ~01% of P-N in Blend Paraffin, vol% of P-N in Blend Naphthene Ring, wt% of P-N in Blend Paraffin + Side Chains, ~1% of P-N in Blend
Parafbn-Naphtha

Gas/oil Blend (Fractions 8 through 12) 31.2 12.5 07.5

35.1 7.9 92.1 32.6 59.5 35.3 64.7 20.0 80.0

28.3 71.7

detail. Calculation of the dewpoint pressure by means of the composition and equilibrium ratios is discussed in Chap. 23.

Sage and Olds Correlation

Laboratory studies on five San Joaquin Valley systems resulted in the correlation shown in Table 21.12. The basis for the 160F data presented in this table is shown in Fig. 21.6. Although the five systems correlate within themselves, it is not known how representative the correlation is of systems from other fields. The data are reproduced here more as a guide to dewpoint-pressure behavior than as a means of estimating precise values of dewpoints. Organick and Goldings Correlation This correlation relates saturation pressure of a system directly to its chemical composition by geans of two generalized composition characteristics TB, the molal average boiling point, and W,, a modified weight average equivalent molecular weight. The saturation pressure may be either bubble-point pressure, dewpoint pressure, or the very special case of critical pressure. The 15 working charts (Figs. 21.7 through 21.21) cover

primarily conditions that pertain to dewpoints, and it is in this capacity that they will be discussed. The reader should be aware, however, that the charts also may be used to estimate critical pressure and temperature of the more volatile systems. The correlation has limited usefulness as a bubblepoint-pressure correlation because it covers primarily high-volatility systems. system. The short-cut method suffices for most calculations. Calculation of Ts. The molal average boiling point of the system is defined as TB=CyxTa, . . . . . . . . . . . . . . . . . . . . . . . . . . ...(l)

where y is the mole fraction and T, the atmospheric boiling point. Boiling points of the pure compounds (methane, ethane, nitrogen, carbon dioxide, etc.) are listed in Chap. 20. The boiling point of the CT + fraction is taken as the Smith and Watson I2 mean average boiling point (MABP). The MABP can be calculated from the ASTM distillation curve, the procedure being first to calculate the ASTM volumetric average boiling point (VABP, F) and then to apply a correction factor to obtain the

21-12

PETROLEUM ENGINEERING

HANDBOOK

TABLE Pl.lZ--RELATION OF DEWPOINT PRESSURE OF CALIFORNIA CONDENSATE SYSTEMS Tank-Oil Gravity (API) lOOoF 52 54 56 58 60 62 64 16OOF 52 54 56 58 60 62 64 220F 54 56 58 60 62 64 4,440 4,190 3,970 3,720 3,460 3,290 3,080 4,760 4,400 4,090 3,840 3,610 3,390 3,190 4,410 3,990 3,700 3,430 3,150 2,900 4,140 3,920 3,730 3,540 3,340 3,190 3,010 4,530 4,170 3,890 3,650 3,430 3,240 3,060 4,230 3,780 3,480 3,210 2,970 2,740 3,000 3,710 3,540 3,380 3,220 3,070 2,920 4,270 3,950 3,690 3,470 3,280 3,100 2,930 4,050 3,600 3,280 3,030 2,800 2,590 3,680 3,540 3,390 3.250 3,100 2,970 2,840 4,060 3,760 3,520 3,320 3,150 2,990 2,820 3,890 3,440 3,110 2,880 2,670 2,470 3,530 3,410 3.280 3,140 3,010 2,880 2,770 3,890 3,610 3,380 3,200 3,040 2,090 2,740 3,750 3,300 2,970 2,760 2,570 2,380 3,420 3,310 3,180 3,060 2,930 2,800 2,700 3,650 3,490 3,270 3,110 2,960 2,810 2,670 3,620 3,180 2,850 2,660 2,480 2,300 GOR (cu ft/bbl) 15,000 20,000 25,000 35,000 30,000 -~ 40,000

9 2
hi 4500 5
z E ; z x i x GAS-OIL RATIO, CU FT/EEiL 3000 3500 4000

Fig. 21.6-Influence of gas/oil ratio and tank-oil gravity on retrograde dewpoint pressure at 160F.

TABLE 21.13-CORRECTION TO ADD TO ASTM VOLUMETRIC AVERAGE BOILING POINT TO OBTAIN MEAN AVERAGE BOILING POINT Slope of ASTM Curve (OF/%) 10 to 90% points 2.0 2.5 3.0 3.5 4.0 4.5 ASTM VABP (OF) 200 -13-17 -22 -27 -33 300 -11.5 - 15.5 -20 -25 - 30.5 400 - 10.5 - 14 - 18.5 -23 - 28.5 - 34.5 500 -9.5 _._ -13 -17 -21.5 -26.5 -32.5

TABLE 21.14-VALUES OF EQUIVALENT MOLECULAR WEIGHTS FOR NATURALGAS CONSTITUENTS Methane Ethane Propane i-butane n-Butane i-pentane n-Pentane Hexanes Ethylene Nitrogen Carbon dioxide Hydrogen sulfide 16.0 30.1 44.1 54.5 58.1 69.0 72.2 85 26.2 28.0 44.0 34.1

TABLE 21.15-CORRECTION TO ADD TO ASTM VOLUMETRIC AVERAGE BOILING POINT TO OBTAIN CUBIC AVERAGE BOILING POINT Slope of ASTM Curve (oF/%) 10 to 906/o points 2.0 2.5 3.0 3.5 4.0 4.5 ASTM VABP (OF) 200 - 5.0 - 6.5 -8.0 - 10.0 - 12.5 - 15.0 400 -4.0 - 5.5 -7.0 -8.5 -10.0 -12.5 600 -3.5 -4.5 - 5.5 - 7.0 - 8.5
10.0

MABP. The VABP is the average of the temperatures at which the distillate plus loss equals 10, 30, 50, 70, and 90% by volume of the ASTM charge, that is,
y, = TlOW + T30% + Tsox + T70% + T90% 5 ) . . . . (2)

where TI/ is the ASTM volumetric average boiling point. The correction to add to TV to obtain the mean average boiling point is given in Table 2 1.13 as a function of TV and the slope of the ASTM curve between the 10 and 90% distilled points. In the correlation, r, is in degrees Rankine (i.e., F+460). Calculation of W,. The modified weight average equivalent molecular weight, W,, is a more complex function to evaluate. It is defined as the equivalent molecular weight multiplied by the summation of the weight fractions. The equivalent molecular weight of a paraffin hydrocarbon compound is its true molecular

weight. For other than straight-chain paraffin compounds (isoparaffns and olefins), the equivalent molecular weight is defined as the molecular weight that an n-paraffin would have if it boiled at the same temperature as the isopamftin or olefin in question. Values of the equivalent molecular weights for naturalgas constituents are given in Table 21.14. The equivalent molecular weight of the C 7 + fraction is determined by calculating the Watson characterization factor, Kw , and using Fig. 21.7. Use of the characterization factor permits some account to be taken of the paraffinicity of the heavy-end material.

Kw=

........................(3)

where Tc is the cubic average boiling point, R. The cubic average boiling point (Fc) is obtained by adding the corrections in Table 21.15 to the ASTM TV, F.

CRUDE-OIL & CONDENSATE

PROPERTIES & CORRELATIONS

21-13

SLOPE

OF

ASTM lo%-90%,

DISTILLATION OF/%

CURVE TEMPERATURE.F

Fig. 21.7-Equivalent Organick correlation.

molecular weight of C, + fraction. and Golding dewpointlpressure

Fig. 21.10-Saturation pressure vs. temperature Parameter T,

at W, =80.

POOC

TEMPERATURE, TEMPERATURE.F

Fig. 21.8-Saturation pressure vs. temperature Parameter Ta.

at W,

= 100.

Fig. 21 .ll-Saturation pressure vs. temperature Parameter T,.

at W, = 70.

v 3

E a
6 ;: 2 2 TEMPERATURE, F

5000\
400030002000-

TEMPERATURE,F

Fig. 21.9-Saturation pressure vs. temperature Parameter Ta

at W, = 90.

Fig. 21 .12-Saturation pressure vs. temperature Parameter Ts.

at W, =60.

21-14

PETROLEUM ENGINEERING

HANDBOOK

8000 $ g 4 g a 5 F i 3 & m 7000 6000 5000 4000 3000 2000 0 100 TEMPERATURE.F 200 300 TEMPERATURE.F

Fig. 21.13-Saturation pressure vs. temperature Parameter T,

at W, = 55.

Fig. 21.16-Saturation pressure vs. temperature Parameter T,

at W,

=40.

L O-50 TEMPERATURE.F

I 0

I 100

I 200 OF

I 300

TEMPERATURE,

Fig. 21.14-Saturation pressure vs. temperature Parameter T,.

at W,

= 50

Fig. 21.17-Saturation pressure vs. temperature Parameter T,.

at W,

=35.

I
O-50 TEMPERATURE.F

I
0 100 TEMPERATURE,F 200 10 C

Fig. 21.15-Saturation pressure vs. temperature Parameter i;,

at W, = 45.

Fig. 21.18-Saturation pIessure vs. temperature at W, =X.5. Parameter T,.

CRUDE-OIL & CONDENSATE

PROPERTIES & CORRELATIONS

21-15

TEMPERATURE,

OF

TEMPERATURE,

Fig. 21.19-Saturation pressure vs. temperature Parameter T,.

at W, =30.

Fig. 21.20-Saturation pressure vs. temperature at W, = 27.5. Parameter 1,.

Example Problem 1. The dewpoint pressure at 200F for a well effluent having the composition shown in Table 21.16 is predicted as follows. 1. Calculating first the properties of the separator liquid CT+, we have TV= and 497 -232 lo-90% slope= 80 =3.31. 232+260+313+383+497 5 =337F

nw 2 4000
9 g 6 c 2 2 :: 1000 0 130 TEMPERATURE,OF 200 300 3000 2000

Fig. 21.21-Saturation pressure vs. temperature Parameter Ts

at W, =25.

From Table 21.13, MABP is 337-22.5=315F or 775R. From Table 21.15, CABP is 337-8.3=329F or 789R, giving

Kw=

3vTiG
0.7535

= 12.3.

Accuracy of Organick-Golding Correlation. About 50% of the 2 14 points that form the basis for the correlation were in error less than 5 % and 82 % were in error less than 10%. Standard deviation of all points is about 7.0%.

From Fig. 21.7 the W, for the CT + material from the separator liquid is estimated to be 142. Properties of the C 7 + material from the separator gas are assumed to be equal to those of n-octane (i.e., Tg=718R, W, = 114). 2. Calculating values of TB and W, for the well effluent, we obtain the results shown in Table 2 I. 17. 3. Having calculated Ts and I@, for the well effluent, we can now determine the desired dewpoint pressure at 200F by interpolation between Figs. 21.14 and 21.15. At TB =240F, the dewpoint pressure is w, =50 w, =45 4,850 4,ooO

Total Formation Volume Correlations

The total formation volume factor (FVF) defines the total volume of a system regardless of the number of phases present. Vink et I3 have shown that it is possial. ble to have more than two hydrocarbon phases in equilibrium when the system contains an excessively large amount of one component. Naturally occurring systems usually exist in either one or two phases. For this reason, the term two-phase formation volume has become synonymous with total formation volume. The relationship of specific volume and density to the total formation volume is the same as indicated in the preceding section for the oil-formation volume. Total Formation Volume Factors of Gas-Condensate Systems Total formation volume factors, specific volumes, and densities of gas-condensate systems may be calculated by use of the ideal gas-law equation with the proper compressibility factor applied provided that the liquid phase present does not amount to an appreciable fraction of the

and the calculated dew point (at W, =49)is 4,680 psia. It will be noticed that at 4,680 psia and 200F the material is about 200F and 900 psi above the critical temperature and pressure of the system. (From Figs. 21.14 and 2 1.15, the locus of critical states line gives Tc=OF and pc=3,800 psia.)

21-16

PETROLEUM ENGINEERING

HANDBOOK

TABLE 21.16-WELL

EFFLUENT COMPOSITION Mole Fraction

heavier components. These values can be obtained by the chart shown in Fig. 21.22. The following example illustrates the calculation of M, and v, . Example Problem 2. The specific volume of a gascondensate system at reservoir conditions given the system molal analysis shown in Table 21.18 is calculated as follows, assuming 1 pound mole of system. 460 + 199 Tpr = 370.7 =1.78,

Component co*
N2

Separator Gas 0.0060 0.0217 0.8986 0.0131 0.0461 0.0043 0.0043 0.0019 0.0017 0.0019 0.0004
-

Separator Liquid 0.0988 0.0350 0.0201 0.0382 0.0495 0.0313 0.1284 0.5606 1 .oOOo

Effluent 0.0056 0.0204 0.8498 0.0454 0.0146 0.0053 0.0064 0.0048 0.0035 0.0096 0.0004 0.0342 1 .oooo

c: 3 i-C, n-C 4 i-C 5 n-C 5 C6

c,+ c,+ l l *

0.0381

2,500 -=3.75, Ppr= 666.0 z=O.885 (from Fig. 20.2) and at 2,500 psia and 199F

1 .oooo

Properties of C, + *separator gas C, + mOfeclar we,gtlt= 114 Separator liquid C, + Molecular weight = 139 Density= 0.7535 g/cc=56.3API ASTM distillation BP (%) 21WF 10 232 20 245 30 260 40 269 50 313 60 349 70 363 60 416 90 497 95 Endpoint tEffluen1 composition calculated on the basis of separator liquid/gas ratio 3.0 gal/lo3 cu H.

vro zRT - 0.885 10.73~659 _ x 19.39x2,500 MP

=O. 129,

system volume. Usually, at reservoir pressures and temperatures and for systems whose composition can be expressed as having a surface GOR greater than 10,000 cu ft/bbl, the presence of 10 ~01% liquid phase will not cause errors greater than 2 or 3% when the two-phase mixture density is calculated as though the mixture existed in only a single phase. This comes about because the partial volumes of components in the liquid phase are substantially the same as the partial volumes of the same components in the vapor phase. Calculations from Composition of the Condensate System. As outlined previously, the formation volume (total or single phase) can be calculated from the relation
B=Mm vro L M,,v,, .,,.,..................~ . . .

where Tpr is the pseudoreduced temperature, ppr the pseudoreduced pressure, z the compressibility factor, and v, the specific volume (cu ftilbm) at reservoir conditions. In the above solution, two phases ale present at 2,500 psia, as the dewpoint pressure calculated by the method of Organick and Golding is 2,690 psia at 199F. Probably no correlation will indicate directly the amount of liquid present at pressures less than the dewpoint pressure, although it can be calculated by use of suitable equilibrium-ratio and density data. Calculations from GOR and Produced Fluid Properties. A second method of calculating specific volume or formation volume on the basis of the gas-law equation was developed by Standing. I4 This method uses a correlation (Fig. 21.23) to obtain the gravity of the well effluent (or reservoir system) from the condensate liquid/gas ratio, gas gravity, and the stock-tank-oil gravity of the surface products. The effluent gravity is then used to obtain values of pseudocritical temperatures and pressures and, by means of these, to evaluate compressibility factors for the entire effluent. The condensate curve of Fig. 2 1.24 should be used when employing this method. Example Problem 3. The total formation volume of a gas-condensate system at reservoir conditions given the parameters in Table 21.19 is calculated as follows, assuming 1 bbl of stock-tank condensate. 3,700x0.65+170x1.20 Yg 3,700+170

where

M, = molecular weight of reservoir system,

RJ = specific volume of reservoir system, M,, = molecular weight of stock-tank oil, VSI = specific volume of stock-tank oil, and L = moles of stock-tank oil per 1 mole of reservoir system.

=0.675

L can be calculated by use of equilibrium ratios and the methods outlined in Chap. 23. To use the pseudoreduced-temperatuatureipseudoreduced-pressure/compressibility chart in the calculation of vrO, it is necessary to determine suitable pseudocritical temperature and pressure values for the heptanes and

and 1 bbl condensate per million cubic feet is 325 3.70+0.17 where yp is the gravity of total surface gas. =84,

CRUDE-OIL & CONDENSATE

PROPERTIES & CORRELATIONS

21-17

TABLE 21 .17-CALCULATED

VALUES OF 7, and W, Weight Fraction Times Equivalent Molecular Weight 0.47 0.68 9.33 1.76 1.21 0.72 0.92 1.03 0.77 3.03 0.22 28.90 w, = 49.04

Component
co2 F2 c: C3

Fraction 0.0056 0.0204 0.8498 0.0454 0.0146 0.0053 0.0084 0.0048 0.0035 0.0096 0.0004 0.0342 1 .oooo

i-C 4 n-C, i-C 5 n-C,

c6

C, + separator gas C, + separator liquid

Boiling Point (W 350 139 201 332 416 471 491 542 557 600 718

Fraction Times Boiling Point (W 2.0 2.8 170.8 15.1 6.1 2.5 3.1 2.6 1.9 5.8 0.3 26.9 7s = 239.9

Fraction 0.0107 0.0244 0.5831 0.0586 0.0274 0.0133 0.0158 0.0150 0.0107 0.0356 0.0019 0.2035 1.0009

Equivalent Molecular Weight 44 28 16.0 30.1 44.1 54.5 58.1 69.0 72.2 85 114 142

TABLE 21.18-CALCULATION

OF SPECIFIC VOLUME OF GAS-CONDENSATE Critical Temperature of Components, 7, vu 548 227 344 550 666 733 766 830 847 915 1,090.

SYSTEM

Component

Mole Fraction, y 0.0059 0.0218 0.8860 0.0460 0.0134 0.0045 0.0048 0.0026 0.0021 0.0037 0.0084

Molecular Weight, M 44.0 28.0 16.0 30.1 44.1 58.1 58.1 72.1 72.1 86.2 138

Weight, ybf Ubm) 0.26 0.61 14.18 1.39 0.59 0.26 0.28 0.19 0.15 0.32 1.16 19.39

yT, (OR) 3.2 4.9 304.8 25.3 8.9 3.3 3.7 2.2 1.8 3.4 9.2 370.7

Critical Pressure of Components, pc (wia) 1,072 492 673 709 618 530 551 482 485 434 343

YPC 6.3 10.7 596.3 32.8 8.3 2.4 2.6 1.3 1 .o 1.6 2.9 666.0

co2 N2 Cl c,
i-Cd n-C, i-C 5 n-C, C6 c,+

C,

Reservoir iemperature Molecular weight of Specific gravity of C, *Pseudocrttical values

= 19&F C, b = 138. f = D 7535. from Fig 21.22

1.5

GAS

060 GR

1.4

0.70 GAS GR.

ri $
F d

Id0

120

140 160 180 200 MOLECULAR WEIGHT SPkIFIC:GRAVliY

220

240 1

BOOM.&+--+

60&O

-j

hw 1
iz k

lo3 120

220

J
240 CFB 20 40 60 El0 ICC

140 I60 180 hxl MOLECULAR WEIGHT

Sbl Condensate per IO C ft

temperatures Fig. 21 .Z?-Pseudocritical heptanes and heavier.

and pressures

for

Fig. 21.23-Effect of condensate volume on the ratio of surface-gas gravity to well-fluid gravity.

21-18

PETROLEUM ENGINEERING

HANDBOOK

TABLE 21 .l g--DATA FOR CALCULATING TOTAL FORMATION VOLUME OF A GAS-CONDENSATE SYSTEM Reservoir pressure, psia Reservoir temperature, OF Stock-tank-condensate production, B/D Stock-tank condensate gravity, OAPl Tank vapor rate, IO3 cu ft/D Tank vapor gravity (air = 1) Trap gas rate, lo3 cu ft/D Trap gas gravity, (air = 1 .O)
0as1s 1 bbl of stock-tank condensate

3,000 250 325 45 170 1.20 3,700 0.65

TABLE 21.21-DATA FOR CALCULATING TOTAL FORMATION VOLUME OF THE GAS-CONDENSATE SYSTEM DESCRIBED IN EXAMPLE PROBLEM 4 Reservoir pressure, psia Reservoir temperature, OF GOR (condensate total), cu ft/bbl Gas gravity (total) Tank-oil gravity, OAPI 3,000 250 11,900 0.675 45

TABLE 21.20-DATA FOR CORRELATION FOR OBTAINING TOTAL FORMATION VOLUME FACTORS OF DISSOLVED GAS AND GAS-CONDENSATE SYSTEMS SHOWN IN FIG. 21.25 Pressure, psia GOR, cu ft/bbl Temperature, OF Gas gravity Tank-oil gravity, OAPI 400 to 5,000 75 to 37,000 100 to 258 0.59 to 0.95 16.5 to 63.8

TABLE 21.22-DATA USED TO CALCULATE TOTAL FORMATION VOLUME FACTOR IN EXAMPLE PROBLEM 5 Reservoir pressure, psia Reservoir temperature, OF GOR, cu ftlbbl Separator Tank Total Gas gravity Tank-oil gravity, OAPI 1,329 145 566 37 603 0.674 36.4

From Fig. 21.23, at 45API ~&~~=1.367 and yl,,=1.367x0.675=0.923, where Ylw = well fluid gravity, ysr = trap gas gravity, and Ylwr = well fluid reservoir gravity. From Fig. 21.24,

From Fig. 21.23 the molecular weight of stock-tank condensate, M, , is 140, moles of stock-tank condensate per barrel is 281/140=2.00, moles of surface gas per barrel of stock-tank condensate is l/325 x (3,870x 103) x l/379=31.4, and total moles per barrel of stock-tank condensate is 2.00+31.4=33.4. From gas law,

y=-=

n*T P

33.4~0.845~ 10.73~710
=71.7 3,000

and 71.7 V=-= 5.615

Tpc =432
and

12.8,

ppc=647.
At reservoir conditions of 3,000 psia and 250F, 460+250 Tpr = 432 PPr and from Fig. 20.2 z=O.845. By using 350 lbm/bbl for water, the weight of stocktank condensate per barrel is 350x 141.5 131.5+API =281. 3,000 =------4.64, 647 =1.64,

where the first value of V is in cubic feet and the second in barrels, giving a formation volume B, of 12.8 bbllbbl of stock-tank condensate. Total Formation Volume Factors of Dissolved Gas Systems A suitable correlation for obtaining total formation volume factors of both dissolved gas and gas-condensate systems was developed by Standing. t5 This correlation is shown in Fig. 21.25, and the graphical chart for simplified use of the correlation is given by Fig. 2 1.26. The correlation contains 387 experimental points, 92% of which are within 5% of the correlation. Range of the data comprising the correlation is given in Table 2 1.20. Example Problem 4. The total formation volume of the gas-condensate system described in Example Problem 3 is calculated as follows, given the data in Table 2 1.2 1.

CRUDE-OIL & CONDENSATE

PROPERTIES & CORRELATIONS

21-19

675 a 4 650

aw 2 625 i 2 u t 5 g 3 ; 4 a 600 575 550 525 500

F. 475 E
: 2 f 450 425

: - 400 2 z 8 2 I a 375 350 325 3oo 060 I I 080 ~ ~ 100 j I / 120 I 1 I / 140 I 1 I I 160 I I 160

Fig. 21.24-Pseudocritical well fluids.

properties of gases and condensate

Fig. 21.25-Formation volume of gas plus liquid phases from GOR, total gas gravity, tank-oil gravity, temperature, and pressure.

Fig. 21.26-Chart for calculating total formation Standings correlation.

volume by

21-20

PETROLEUM

ENGINEERING

HANDBOOK

141.5 Yo= =0.802 131.5+45

Tc = Tm = Tm =
TV = vro = -vst = w, = Y=

and

=11,90()

(250)o5

x~~~~~~~~.~X~-~ooo27x~wo

(0.675) o.3 15.8 =11,900 x(O.802).O 0.877 =1.72x105

z = Ye =
ygt =

Ylw Ylwr Yo p

= = = =

cubic average boiling point, K (R) mean average boiling point, K (R) mean average boiling point, K (R) volumetric average boiling point, F specific volume of reservoir system specific volume of stock-tank oil modified weight average equivalent molecular weight mole fraction compressibility factor gas specific gravity trap gas gravity well fluid gravity well fluid reservoir gravity tank-oil specific gravity viscosity, Pa. s (cp)

where y0 is the tank-oil specific gravity. From Fig. 21.25, B,=13+bbl/bbl oftank oil. From Fig. 21.26, B, = 13.7 bbl/bbl of tank oil. Example Problem 5. The total formation volume of well production at reservoir conditions given the data in Table 21.22 is calculated as follows. From Fig. 21.26, B,= 1.72 bblibbl of tank oil. Experimental value calculated from PVT test results is 1.745 bbl/bbl of tank oil.

References
1. ASTM Standards on Petroleum Products and Lubricants, Part 24, ASTM, Philadelphia (1975) 796. 2. Watson, K.M., Nelson, E.F., and Murphy, G.B.: Charactetization of Petroleum Factions, Ind. and Eng. Chem. (Dec. 1935) 1460-64. 3. Technical Data Book-Petroleum Refining, API, Washington, D.C. (1970) 2-11. 4. Nelson, W.L.: Petroleum Refinery Engineering, fourth edition, McGraw-Hill Book Co. Inc., New York City (19X3), 910-37. 5. A Guide to World Export Crudes, Oil and Gas J, (1976). 6. Ferrem, E.P. and Nichols, D.T.: Analyses of 169 Crude Oils fmm 122 Foreign Oil Fields, U.S. Dept. of the Interior, Bureau of Mines, Bartlesville, OK (1972). 7. Coleman, H.J. et a[.: Analyses of 800 Crude Oils from United States Oil Fields, U.S. DOE, Bartlesville, OK (1978). 8. Woodward, P.J.: Crude Oil Analysis Data Bank, Bartlesville Energy Technology Center, U.S. DOE, Bartlesville, OK (Oct. 1980) 1-29. 9. Lacey, W.N., Sage, B.H., and Kircher, C.E. Jr.: Phase Equilibrja in Hydrocarbon Systems III, Solubility of a Dry Natural Gas in Crude Oil, Ind. and Eng. Chem. (June 1934) 652-54. Gas 10. Sage, B.H. andOlds, R.H.: VolumetricBehaviorofOiland from Several San Joaquin Valley Fields, Trans., AIME (1947) 170, 156-62. 11. Organick, E.I. and Golding, B.H.: Prediction of Saturation Pressures for Condensate-gas and Volatile-oil Mixtures, Trans., AIME (1952), 195, 135-48. 12. Smith, R.L. and Watson, K.M.: Boiling Points and Critical Pmperties of Hydrocarbon Mixtures. Ind. and Enn. Chem. (19j7) 1408. 13. Vink, D.J. er al.: Multiple-phase Hydrocarbon Systems, Oil and Gas J. (Nov. 1940) 34-38. 14. Standing, M.B.: Volumetric and Phase Behavior of Oil Field Hydrocarbon Systems, Reinhold Publishing Corp., New York City (1952). 15. Standing, M.B.: A Pressure-Volume-Temperature Correlation for Mixtures of California Oils and Gases, Drill. and Prod. Prac., API (1947), 275.

Nomenclature
B= formation volume, m3 (bbl) I, = correlation index K= characterization factor L, = moles of stock-tank condensate per barrel L, = moles of stock-tank oil per 1 mole of reservoir system, kmol/m3 (lbm moligal) M= molecular weight Mm = molecular weight of reservoir system Mst = molecular weight of stock-tank oil n= total moles PC = critical pressure, psia (lbflsq in.) Ppr = pseudoreduced pressure R= universal gas constant tsu = Universal Saybolt viscosity, seconds T= temperature, F T, = critical temperature, C (F) Tpr = pseudoreduced temperature
Ta = atmospheric boiling point, K (R) TB = molal average boiling point, K (R)