Professional Documents
Culture Documents
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
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
21-2
PETROLEUM ENGINEERING
TABLE Pl.l-ULTIMATE
Specific
Gravity
-r
Petroleum
0.862
0.897
0.912
Pennsylvania pipeline
Mecook, WV
Humbolt, KS
Healdton, OK
Coalinga, CA
Beaumont, TX
Mexico
Baku, USSR
Colombia, South America
CHEMICAL ANALYSES
Temperature
PC)
15
0
0.951
0.91
0.97
0.897
0.948
C
85.5
83.6
85.6
85.0
86.4
85.7
83.0
66.5
65.62
15
15
20
HANDBOOK
OF PETROLEUM
H
14.2
12.9
12.4
12.9
11.7
11.0
11 .o
12.0
11.91
Component
WI
N
0
--
Base
paraffin
paraffin
mixed
mixed
3.6
1.14
2.61
1.7*
0.37
0.76
0.60
0.70
4.30
naphthene
naphthene
naphthene
1.5
0.54
TABLE 21.2-CHEMICAL
Fraction
(0
140 to
203 to
252 to
302 to
392 to
482 to
203
252
302
392
482
572
Grozny
(High Paraffin)
45.3% at 572OF
Aromatic
ANALYSES OF PETROLEUM, %
Oklahoma
64% at 572OF
Naphthene
Paraffin
Aromatic
Naphthene
Paraffin
Aromatlc
Naphthene
Paraffin
25
30
35
29
23
22
72
65
56
57
59
61
4
8
13
21
26
35
31
40
52
55
63
57
65
52
35
24
11
8
5
7
12
16
17
17
21
28
33
29
31
32
73
65
55
55
52
51
3
z
14
18
17
TABLE 21.3-EVALUATION
Percent Distilled
Gas loss
Straight-run gasoline (untreated)
Catalytic charge
Range
0 to 1.3
1.3 to 32
32 to 80.5
remainder
80.5 to 100
charge or asphalt
Aromatic
-A
i
11
17
25
29
Naohthene
Paraffin
31
46
64
61
45
40
65
46
25
22
30
31
Basis
Material
V&breaker
Crude oil
California
(Huntmgton Beach),
34.2% at 57ZF
(Davenport),
Midpoint
~16.6
56.2
Yield
1.3
30.7
48.5
19.5
100.0
Gravity
(OAPI)
56
28.8
6.4$
32.0
Other Properties
390DF ASTM endpoint7
165OF aniline point or 47.5
diesel index
110 penetration
11.65 characterization factor
The Cycle stcck IrOm catalytic cracking is thermally cracked along wtth the asphalt or vis-
TABLE 21.4-EVALUATION
Material
Basis
Gas loss
300 EPb
445 EPb
156 aniline point
remainder
100 Ws
viscosity at 2lOOF
100 penetration
Range
0 to
1.3 lo
21 .O to
38.5 to
56.5 to
74.9 to
80.9 to
Midpoint
-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
Yield
19.7
17.5
18.0
18.4
6.0
19.1
100.0
API
Gravity
61.2C
41.3e
32.1
25.9
19.1
Viscosity,
SUS
STOCK0
Other Properties
21-3
TABLE 21.5-BASES
OF CRUDE OILS
API Gravity
at 60F
Low-Boiling
Part
paraffin
baraffin
paraffin
intermediate
intermediate
intermediate
naphthene
naphthene
naphthene
Approximate
UOP* *
Characterization Factor
High-Boiling
Key Fraction
Part
Key Fraction
2
LowBoiling
HighBoiling
paraffin
intermediate
naphthene
paraffin
intermediate
naphthene
intermediate
paraffin
naphthene
40+
40+
40+
33 to 40
33 to 40
33 to 40
333333-
30+
20 to 30
2030+
20 to 30
2020 to 30
30+
20-
12.2+
12.2+
12.2 +
11.5 to 12.0
11.4 to 12.1
11.4 to 12.1
11.511.511.4-
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-
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,
K=- 3%
Y
TABLE 21.6-TYPICAL
CHARACTERIZATION
FACTOR VALUES
Product
Pennsylvania stocks (paraffin base)
Mid-Continent stocks (intermediate)
Gulf Coast stocks (naphthene base)
Cracked gasoline
Cracking-plant combined feeds
Recycle stocks
Cracked residuum
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
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
DataBook3
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.
21-4
PETROLEUM
TABLE 21.7-CHARACTERIZATION
Characterization
Factor
Hydrocarbons
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
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
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
11.45
11.4
11.3to 11.6
11.3
PETROLEUMS,
HANDBOOK
Miscellaneous Products
(LA)
paraffin-base gasolines
butylcyclohexane
octyl or diamyl benzene
Lagunillas (Venezuela)
Gulf Coast light distillates
hexadiene
12.66 (range 12.1 to 13.65) calculated lrom factors of raw and dewaxed lube stocks
ENGINEERING
*.-
IO
20
(YIELD1
30
40
50
60
i-0
PERCENTAGEDISTILLED
80
90
100
Ftg. 21 .l-Evaluation
curves of a 32.0API intermediate-base
crude oil of characterization factor 11.65.
CRUDE-OIL 8 CONDENSATE
21-5
9.0
8.0
7-o
6.0
1100
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.
21-6
PETROLEUM ENGINEERING
200
400
600
TEMPERATURE,F
III
HANDBOOK
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-
1,.,!,,,,,,.,
o-
K=CHARACTEklZATIONFACTOR
=
3MOLAL AVG. BOILINGPOINT,R
/ SPEClF(CG.,ilTYf~
9
3-
I
I
000
, OF
34
0
Fig. 21.4-Heat
I
900
I
1,000
/
1,100
I
1,200
CRUDE-OIL
& CONDENSATE
PROPERTIES
21-7
& CORRELATIONS
TABLE 21.8-TRUE-BOILING-POINT
Atlanta,
AR
(limestone)
Kern
River,
CA
Santa
Maria,
CA
Coalinga
(East),
CA
Coalinga,
CA
20.5
2.30
270
413139
44.5
0.48c
35
10.7
1.23
6,000 +
15.4
4.63
368
812154
20.7
0.51
178
31.1
0.31
40
11.62
11.48
11.47
11.55
11.53
I
0
11.82
12.05
12.08
12.25
12.05
IP
1.5
6.0
73.2a
a9.0a
11 .o
66.0b
14.4
good b
45.3d
2.P
24.1
41.9
good
56.3d
57.4
6.1 d
29.5b
9.5
38.0
16.0b
0.29b
15.0d
46.0
27.0b
0.06b
excellent
43.0b
Ob
0.82 b
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
N
0
11.90
11.42
11.29
11.11
11.48
IN
0
25.2d
7.0
1.2d
21 .6d
72.ob
39.2d
1.2d
13.2
59.8e
70.30
17.0
9.6d
67.0 b
31 .6d
66.7b
15.6d
good b
35.6d
excellent b
25.0
43.0
good
29.3d
36.9
46.2d
46.0d
good
2.7d
32.5d
13.0b
0.38b
8.5
34.5
1.8d
16.0d
34.0d
14.5b
o.ub
Il.Od
37.0
17.0b
0.06b
35.0d
76.0d
high
0.15b
19.7d
mob
- 30.0b
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
39.8
75.6d
22.8
59.46
22.3
excellent
45.6d
70.4b
28.0
good
75.9
42.2d
27.1
9.6
54.9
23.2
93.9d
9.1
75.0
14.7
4.8
35.5
27.0
i::
15.0
11.0
67.7d
11 .o
4.2
27.5
18.6
52.P
18.2
5.0
42.2
22.2
19.0
16.4d
16.0
13.06
17.6d
0.67b
56.0b
0.43b
28.0d
excellent
21.7d
good
29.2
37.0b
2.45 b
40.8
good
11.13
11.15
11.15
48.5b
113.0b
0.8b
excellent
7.9d
0.8b
22.2d
1.5b
57.0d
excellent
47.0
excellent
11.28
11.20
11.23
N
3.0
11.5
11.53
11.59
11.72
11.58
I
1.1
21-8
PETROLEUM
TABLE 21.9-ANALYSIS
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
ENGINEERING
HANDBOOK
Carthage
Lower Pettile
Zone
Old Ocean
Chenault
Zone
Old Ocean
Larson
Zone
Seellgson
21 D Zone
Seeligson
21 A Zone
Saxet
67
20.19
752
85
20.76
702
85
20.51
810
80
20 64
410
85
20.63
1087
88
21.34
645
82
25.03
607
70
19.62
88.74
20.18
16.23
18.25
29.28
18.25
29.33
18.70
28.71
18.17
29.88
18.42
24.48
18.69
41.33
18.89
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
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
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
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
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
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
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
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 %
---__
55.1
37.2
21.1
5.6
632-
OAPI Vol %
OAPI
Vol %
API
Vol %
82.9
60.5
50.8
74.8
59 2
48.1
40.7
47.0
79
76.6
59.3
47.6
21.2
55.3
15.0
3.8
29.1
48.4
18.2
4.3
4.4
4.7
=APl Vol %
--71.2
14.7
52.9
36.9
42.6
17.4
37.8
21.3
74
2.3
API
Vol %
70.9
52.2
42.1
36.6
29.8
22.6
47.7
15.9
7.3
6.5
OAPI Vol %
API
Vol %
OAPI
70.1
53.4
43.8
37.4
68.4
53.1
43.0
37.0
35.7
47.6
10.0
2.4
73.6
55.9
44.9
38.2
20.7
49.5
16.1
7.2
6.5
4.3
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
Fig. 21.5-Approximate
relation
between
viscosity,
ture, and characterization factor.
tempera-
Crude-Oil Analyses
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
PROPERTIES
& CORRELATIONS
y-456.8+87552/T~,
21-9
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%
36.3
1 .o
0.21
+20
42.40
5.1
14.5
1.0
Gasoline
Range, OF
Yield, VOWI
Gravity, OAPI
Sulfur, wt%
Research octane number, clear
Research octane number, - 3 mL tetraethyl
lead per gallon
60
to 200
10.7
77.2
0.003
74.4
90.0
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
60 to 400
31.0
60.1
56.52
29.52
13.96
0.0024
52.0
76.0
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
400 to 500
13.5
40.2
32.33
-38
13.1
<0.05
146.2
21
500
to 650
15.7
33.7
43.83
-25
0.11
164.3
0.08
56.5
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
PETROLEUM ENGINEERING
21-10
TABLE 21.11-ADAPTATION
HANDBOOK
to 4,482 ft
General Characteristics
Gravity, specific [OAPI]
Sulfur, wt%
Viscosity, SUS
at 77OF
at 1 OOF
Pour point, OF
Nitrogen, wt%
Color
0.820[41.1]
0.24
42
39
<5
0.054
brownish-black
2.2
5.5
7.4
5.8
6.7
6.0
59
6.8
5.1
Stage 2-Distillation
392
437
482
527
572
Restduum
Carbon
Sulfur
Gravity at
6OOF
Cumulative
VOW0
Specific
3.7
9.2
16.6
22.4
29.1
35.1
41.0
47.8
52.9
0.670
0.712
0.738
0.757
0.773
0.785
0 798
0.812
0.823
-1.5
1.5
2
3
4
5
6
7
8
9
10
11
12
13
14
15
0.639
Correlation
API
89.9
79.7
Index
Refraction
Index
Specific
at 20C
Dispersion
Viscosity Cloud
at lOOoF point
(SW
(OF)
~~-
67.2
60.2
55.4
51.6
48.8
45.8
42.8
40.4
7
17
21
22
23
22
23
24
25
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
30
30
33
35
38
1.46481
1.47017
1.47736
141.2
40
14
148.4
145.6
i:
96
179
ii
76
98
wwo
Residuum Crude
continued at 40 mm Hg
7.2
6.2
5.6
4.8
5.1
60.1
66.3
72.1
76.9
82.0
0.842
0.851
0.863
0.874
0.887
38.6
34.8
32.5
30.4
28.0
17.0
99.0
0.934
20.0
7.1
0.67
0.235
Nitrogen
1.4
Approximate Summary
Light gas
Gas+ Naoh
9.2
35.1
Kerosend
17.8
Gas oil
Non viscous
lub
Med viscous
lub
Viscous lub
Restdue
Loss
0.690
11.6
0.743
0.311
0.845
73.6
58.9
43.1
35.9
10.3
0.854 to 0.875
34.3 to 30.3
5oto 100
6.0
1.3
17.0
1.0
loot0 200
>200
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-
TABLE 21.11-ADAPTATION
21-11
(continued)
vow0 of
Crude
Specific
Gravity
Correlation
Index
1
2
3
4
5
a
7
a
9
10
11
12
1.5
2.2
5.5
7.4
5.8
6.7
6.0
5.9
6.8
5.1
72
6.2
0.639
0.670
0.712
0.738
0.757
0.773
0.785
0.798
0.812
0.823
0.842
0.851
Aromatics
(VOW0of
Fraction)
P-N *
(vol% 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
100.0
97.6
94.1
92.5
90.9
89.8
89.4
89.3
88.5
89.6
87.0
83.8
7
17
21
22
23
22
23
24
25
30
30
Correlation
index of P-N
5
13
16
17
17
16
16
17
18
22
21
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
Vol% of P-N
ANaphtha
7.1
23.7
38.6
44.0
43.6
43.6
Vol% of Fraction
Paraffin
Naphtha
Paraffin
92.9
76.3
61.4
56.0
56.4
56.4
6.9
22.3
35.7
40.0
39.2
39.0
90.7
71.8
56.8
50.9
50.7
50.4
Fraction
Number
Number
of Total
Aromatic
Rings
Naphthenes
per mol
12
14
1.4
1.7
0.3
0.6
1.1
1.1
Gas/oil Blend
(Fractions 8
through 12)
35.1
7.9
92.1
32.6
59.5
35.3
64.7
20.0
80.0
31.2
12.5
07.5
28.3
71.7
Parafbn-Naphtha
. . . . . . . . . . . . . . . . . . . . . . . . . . ...(l)
21-12
PETROLEUM ENGINEERING
9
2
TABLE Pl.lZ--RELATION
OF DEWPOINT PRESSURE OF
CALIFORNIA CONDENSATE SYSTEMS
Tank-Oil
Gravity
(API)
hi 4500
5
z
20,000
25,000
35,000
30,000 -~
4000
40,000
lOOoF
3500
52
54
56
58
60
62
64
16OOF
4,440
4,190
3,970
3,720
3,460
3,290
3,080
4,140
3,920
3,730
3,540
3,340
3,190
3,010
3,000
3,710
3,540
3,380
3,220
3,070
2,920
3,680
3,540
3,390
3.250
3,100
2,970
2,840
3,530
3,410
3.280
3,140
3,010
2,880
2,770
3,420
3,310
3,180
3,060
2,930
2,800
2,700
52
54
56
58
60
62
64
220F
4,760
4,400
4,090
3,840
3,610
3,390
3,190
4,530
4,170
3,890
3,650
3,430
3,240
3,060
4,270
3,950
3,690
3,470
3,280
3,100
2,930
4,060
3,760
3,520
3,320
3,150
2,990
2,820
3,890
3,610
3,380
3,200
3,040
2,090
2,740
3,650
3,490
3,270
3,110
2,960
2,810
2,670
54
56
58
60
62
64
4,410
3,990
3,700
3,430
3,150
2,900
4,230
3,780
3,480
3,210
2,970
2,740
4,050
3,600
3,280
3,030
2,800
2,590
3,890
3,440
3,110
2,880
2,670
2,470
3,750
3,300
2,970
2,760
2,570
2,380
Methane
Ethane
Propane
i-butane
n-Butane
i-pentane
n-Pentane
Hexanes
Ethylene
Nitrogen
Carbon dioxide
Hydrogen sulfide
x
GAS-OIL
CU
FT/EEiL
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
3,620
3,180
2,850
2,660
2,480
2,300
2.0
2.5
3.0
3.5
4.0
4.5
300
400
-11.5
- 15.5
-20
-25
- 30.5
-
- 10.5
- 14
- 18.5
-23
- 28.5
- 34.5
500
-9.5
_._
-13
-17
-21.5
-26.5
-32.5
TABLE 21.15-CORRECTION
TO ADD TO
ASTM VOLUMETRIC AVERAGE BOILING
POINT TO OBTAIN CUBIC AVERAGE
BOILING POINT
RATIO,
Fig. 21.6-Influence
of gas/oil ratio and tank-oil gravity on
retrograde dewpoint pressure at 160F.
16.0
30.1
44.1
54.5
58.1
69.0
72.2
85
26.2
28.0
44.0
34.1
3000
TABLE 21.14-VALUES
OF
EQUIVALENT MOLECULAR
WEIGHTS FOR NATURALGAS CONSTITUENTS
y,
HANDBOOK
. . . . (2)
Slope of ASTM
Curve (oF/%)
10 to 906/o points
200
400
2.0
2.5
3.0
3.5
4.0
4.5
- 5.0
- 6.5
-8.0
- 10.0
- 12.5
- 15.0
-4.0
- 5.5
-7.0
-8.5
-10.0
-12.5
10.0
Kw=
........................(3)
SLOPE
Fig. 21.7-Equivalent
Organick
correlation.
OF
21-13
ASTM
lo%-90%,
DISTILLATION
OF/%
CURVE
TEMPERATURE.F
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,.
v
3
E
a
5000-
4000-
at W, = 70.
TEMPERATURE,
Fig. 21.9-Saturation
pressure vs. temperature
Parameter Ta
;:
3000-
2
2
2000-
TEMPERATURE,F
at W, = 90.
Fig. 21 .12-Saturation
pressure vs. temperature
Parameter Ts.
at W, =60.
PETROLEUM ENGINEERING
21-14
HANDBOOK
8000
$
7000
6000
4
g
a
5000
5
F
4000
i
3
3000
&
m
2000
0
100
200
300
TEMPERATURE.F
TEMPERATURE.F
Fig. 21.13-Saturation
pressure vs. temperature
Parameter T,
at W, = 55.
Fig. 21.16-Saturation
pressure vs. temperature
Parameter T,
L
O-50
I
0
at W,
= 50
I
200
=40.
I
300
OF
Fig. 21.17-Saturation
pressure vs. temperature
Parameter T,.
O-50
at W,
=35.
I
0
100
200
10 C
TEMPERATURE,F
TEMPERATURE.F
Fig. 21.15-Saturation
pressure vs. temperature
Parameter i;,
TEMPERATURE,
TEMPERATURE.F
Fig. 21.14-Saturation
pressure vs. temperature
Parameter T,.
I
100
at W,
at W, = 45.
Fig. 21.18-Saturation
pIessure vs. temperature at W, =X.5.
Parameter T,.
TEMPERATURE,
OF
Fig. 21.19-Saturation
pressure vs. temperature
Parameter T,.
TEMPERATURE,
at W, =30.
21-15
232+260+313+383+497
=337F
Fig. 21.20-Saturation
pressure vs. temperature at W, = 27.5.
Parameter 1,.
nw
2 4000
9
g
3000
6
c
2000
2
2
::
and
1000
130
200
300
TEMPERATURE,OF
497 -232
lo-90%
slope=
=3.31.
80
Kw=
3vTiG
= 12.3.
0.7535
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
Fig. 21.21-Saturation
pressure vs. temperature
Parameter Ts
at W, =25.
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%.
21-16
PETROLEUM ENGINEERING
TABLE 21.16-WELL
EFFLUENT COMPOSITION
Mole Fraction
Component
Separator
Gas
0.0060
0.0217
0.8986
co*
N2
c:
3
i-C,
n-C 4
i-C 5
n-C 5
C6
c,+
c,+
l *
0.0461
0.0131
0.0043
0.0043
0.0019
0.0017
0.0019
0.0004
-
1 .oooo
Separator
Liquid
-
Effluent
0.0201
0.0382
0.0495
0.0313
0.1284
0.5606
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
1 .oooo
0.0988
0.0350
0.0381
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
.,,.,..................~
=1.78,
370.7
2,500
-=3.75,
Ppr= 666.0
z=O.885 (from Fig. 20.2)
and at 2,500 psia and 199F
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.
B=-
HANDBOOK
. . .
where
=O. 129,
=0.675
3,700+170
=84,
3.70+0.17
where yp is the gravity of total surface gas.
TABLE 21 .17-CALCULATED
Boiling
Point
(W
350
139
201
332
416
471
491
542
557
600
718
Fraction
Component
0.0056
0.0204
0.8498
0.0454
0.0146
0.0053
0.0084
0.0048
0.0035
0.0096
0.0004
0.0342
co2
F2
c:
C3
i-C 4
n-C,
i-C 5
n-C,
c6
C, + separator gas
C, + separator liquid
TABLE 21.18-CALCULATION
co2
N2
Cl
c,
C,
i-Cd
n-C,
i-C 5
n-C,
C6
c,+
VALUES OF 7, and W,
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
Fraction
Equivalent
Molecular
Weight
Weight Fraction
Times
Equivalent
Molecular
Weight
0.0107
0.0244
0.5831
0.0586
0.0274
0.0133
0.0158
0.0150
0.0107
0.0356
0.0019
0.2035
44
28
16.0
30.1
44.1
54.5
58.1
69.0
72.2
85
114
142
0.47
0.68
9.33
1.76
1.21
0.72
0.92
1.03
0.77
3.03
0.22
28.90
Mole
Fraction, y
Molecular
Weight, M
Weight, ybf
Ubm)
0.0059
0.0218
0.8860
0.0460
0.0134
0.0045
0.0048
0.0026
0.0021
0.0037
0.0084
44.0
28.0
16.0
30.1
44.1
58.1
58.1
72.1
72.1
86.2
138
0.26
0.61
14.18
1.39
0.59
0.26
0.28
0.19
0.15
0.32
1.16
Critical
Temperature of
Components, 7,
(OR)
548
227
344
550
666
733
766
830
847
915
1,090.
49.04
SYSTEM
Critical
Pressure of
Components, pc
(wia)
yT,
vu
3.2
4.9
304.8
25.3
8.9
3.3
3.7
2.2
1.8
3.4
9.2
19.39
Reservoir iemperature
Molecular weight of
Specific gravity of C,
*Pseudocrttical values
w, =
1.0009
7s = 239.9
1 .oooo
Component
21-17
YPC
1,072
492
673
709
618
530
551
482
485
434
343
6.3
10.7
596.3
32.8
8.3
2.4
2.6
1.3
1 .o
1.6
2.9
370.7
666.0
= 19&F
C, b = 138.
f = D 7535.
from Fig 21.22
1.5
060
GR
GAS
1.4
ri
$
Id0
120
F
d
220
240
1
BOOM.&+--+
hw
1
iz
k
140
160
180
200
MOLECULAR WEIGHT
0.70
GAS GR.
lo3
120
SPkIFIC:GRAVliY
60&O
140
I60
180
hxl
MOLECULAR WEIGHT
-j
220
240
CFB
20
40
60
El0
ICC
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
3,000
250
325
45
170
1.20
3,700
0.65
TABLE 21.20-DATA
FOR CORRELATION FOR
OBTAINING TOTAL FORMATION VOLUME FACTORS OF
DISSOLVED GAS AND GAS-CONDENSATE SYSTEMS
SHOWN IN FIG. 21.25
400 to 5,000
75 to 37,000
100 to 258
0.59 to 0.95
16.5 to 63.8
Pressure, psia
GOR, cu ft/bbl
Temperature, OF
Gas gravity
Tank-oil gravity, OAPI
Tpc=432
ppc=647.
At reservoir conditions of 3,000 psia and 250F,
=1.64,
432
PPr
3,000
=------4.64,
647
3,000
250
11,900
0.675
45
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
n*T
33.4~0.845~
10.73~710
3,000
y=-=
=71.7
71.7
V=-=
5.615
and
460+250
and
Tpr =
TABLE 21.21-DATA
FOR CALCULATING TOTAL
FORMATION VOLUME OF THE GAS-CONDENSATE
SYSTEM DESCRIBED IN EXAMPLE PROBLEM 4
=281.
12.8,
21-19
675
a
4
650
aw
2 625
i
2
u
t
5
g
3
600
575
550
525
4a
500
F. 475
E
:
450
2
f
425
:
- 400
2
z
375
8
2
350
I
a
325
3oo
060
~
080
Fig. 21.24-Pseudocritical
well fluids.
~
100
120
140
160
160
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
141.5
Yo=
=0.802
131.5+45
Tc =
Tm =
Tm =
TV =
and
vro =
-vst =
w, =
Y=
=11,90()
(250)o5
x~~~~~~~~.~X~-~ooo27x~wo
(0.675) o.3
15.8
=11,900 x(O.802).O
0.877
=1.72x105
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)
z =
Ye =
ygt
Ylw
Ylwr
Yo
p
=
=
=
=
ENGINEERING
HANDBOOK
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
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