Crude Oil Characterization

Petroleum Refining Chapter 4: Characterization
Chapter 4
Characterization & properties estimation
of crude oil and petroleum products
Introduction
There is no analytical technique available to determine
(either quantitatively or quantitatively) all the tens of
thousands of chemical species in petroleum and its
fractions.
Only the low-boiling components C1-C5 can be
completely identified using gas chromatography analysis.
For the white fractions (e.g. Naphtha), only a limited
number of components can be completely identified
using PINA, PIONA, or Detailed HC GC analyzers
(Table 2.3 2.6).
To overcome this shortcoming, petroleum refiners resort
to define (characterize) petroleum and its fractions using
global (bulk) properties.
This traditional way of oil characterization, though old, is
still being used today.
This type of characterization is used as basis for
assigning a price for crude oils and petroleum fractions
and in design of petroleum processes.
Sulfur content & API gravity have the greatest influence on the value of
crude oil, although N2 and metals content are increasing in importance.
The price of petroleum fractions is influence by other properties in
addition
4-1
Copyrights 2001 2012, Dr. Tareq Albahri, Chem. Eng. Dept., Kuwait University
API Gravity (API)

A measure of crude oil density/specific gravity.
API = 141.5 131.5

sp.gr.
(4.1)
(60F )
sp.gr. = oil
water(60F )
(4.2)
Light crude have lower density (sp.gr.) API is higher.

10 < API < 50
(or less)
(or more)
High API crude produces more distillates (valuable) than
it does residue (less valuable).
Distillation Range (Curve)

The boiling point range is an alternate method to
represent the composition of petroleum and its products.
It gives an indication of the quantities and qualities of the
various products present in crude oil (i.e. naphtha,
kerosene, diesel, gas oil, residue, etc).
Gases
- Can be used to determine the
LPG
most desirable processing
sequence to obtain the
Naphtha
required products.
Crude
Kerosene
Oil
- Can be used to determine
whether the crude is
Diesel
suitable for asphalt or
lube oil manufacture.
Residue
4-2
4-3
Types of distillation curves

1. TBP (True Boiling Point) distillation curve.
2. ASTM (D86/D1160) distillation curve.
3. EFV (Equilibrium Flash Vaporization)
4-4
TBP is the most useful.

- However, no standard test exists for measuring the
TBP.
- Most common TBP test is Hempel & D-285.
(Neither specifies # of stages or reflex ratio used).
- Trend is toward 15/5 distillation (D-2892) to stand
for TBP (assumed to be the same as TBP).
- An estimate of the composition of the butane and
lighter components is frequently added to the lowboiling end or the IBP of the TBP curve to
compensate for the loss during distillation.
ASTM is more common because it is simple to
determine in the laboratory. Kuwait refineries use ASTM
curve (Which is then converted to TBP curve).
4-5
Example 4.1:
Estimate the true boiling point (TBP) distillation curve of the
petroleum fraction having the following ASTM D86
distillation temperatures:
Vol %
T (F)
IBP
5%
10%
400
30%
420
50%
438
70%
460
90%
485 490
95%
FBP
Recovery = Solution:
Using Fig. 3A1.1 from the API technical Data Book
(1) Correct the ASTM D86 distillation temperatures above
475 F for cracking using Hadden equation.
Log D = 1.587 + 0.00473 T
where, T & D are in F
For the 90% temp. Log D = 1.587 + 0.00473 (485) =
0.707
D = 5 F
The corrected 90% temp. becomes = 485 + 5 = 490 F
4-6
(2) Find the atmospheric TBP mid (50%) temperature using

the mid temp of the ASTM D86 and the lower part of
Figure 3A1.1.
438 F on the x-axis T= 2 F on the y-axis
[correction]
Therefore, the TBP 50% T =ASTM 50% T + T = 438+2
= 440 F
(3) Find the temp for each segment of the TBP curve using
upper part of Figure 3A1.1.
Segment of
Curve (Vol
%)
0 to 10
10 to 30
30 to 50
50 to 70
70 to 90
90 to 100
ASTM T (F)
TBP T (F)
[from table above] [Figure 3A1.1]
20
18
39
31
22
30
33
40
TBP (F)
409 39 = 370
440 31 = 409
440
440 + 33 = 473
473 + 40 = 513
Vol %
IBP
10%
30%
50%
70%
90%
FBP
Note: it is possible to convert TBP temperatures to ASTM

D86 using Figure 3A2.1 from the API technical data
book, which involves a trial and error procedure.
4-7
Copyright 2001-2014 Dr. Tareq Albahri, Chemical Engineering Dept., Kuwait University, All rights reserved
4-8
4-9
Crude oil analysis are reported in 2 parts,

1. D-86, atmospheric, (IBP up to 527 F end point 760
mmHg)
2. D-1160, vacuum, (392 to 572 F end point at 40 mmHg)
equivalent to 580 to 790 F at 1 atm.
- Vacuum Distillation is necessary to prevent excessive
pot ( )temperatures, which cause cracking of the
crude oil.
- To combine the two results in one curve, the distillation
temperatures at 40 mmHg reported in the analysis must
be corrected to 760 mmHg pressure using Figure 3.6
from text.
The 572 F end point at 40 mmHg corresponds to 790 F at 760
mmHg.
4-10
Figure 4.1: Boiling point distribution curve

Estimation of the TBP curve above 790 F can be obtained by
1. Extrapolating of probability graph (Figure 3.7 in text) to
1100F or higher FBP.
4-11
Figure 4.2: Crude oil TBP Distillation Curve Probability Chart.

4-12
Example 4.2: construction of the TBP & API Curves

Draw the TBP and API curves for the following crude assay
4-13
Solution:
1. Results in the table are in TBP not ASTM so there is no need
for conversion.
2. On a graph paper, plot the sum percent (column 4) as your xaxis and the cut temperature (column 2) as your y-axis until
you reach the temperature 527 F (this is the atmospheric
distillation data).
3. To plot the vacuum distillation data on the same graph you
would need to correct the vacuum distillation temperatures
(at 40 mmHg) to atmospheric pressure (i.e. convert from
D1160 to D86 test pressure) using the following equation,
Tb (1atm) = 126.14 + 1.169 Tb (40 mmHg)
then continue plotting the curve as above.
4. Plot all the data in step 1 and 2 above on the probability
graph extending the straight line to the FBP. Read the values
of x (sum percent) and y (temperature) above 572 F and list
them in a table. Use the new values to continue the rest of
your distillation curve.
5. Plot on the same graph the API (column 6) versus cut mid%
calculated as follows;
Mid% cut 1 = 0.8/2 = 0.4
Mid% cut 2 = 0.8 + 1.0/2 = 1.3
Mid% cut 3 = 1.8 + 3.0/2 = 3.3
Mid% cut 4 = 4.8 + 3.4/2 = 6.5
4-14
API = 78.8
API = 75.1
API = 63.7
API = 55.9 etc.
2. Better results are obtained when using the probability density

function shown below instead of Figure 4.2.
T-T o = A ln 1
B 1-x
To
1/B
(4.3)
Where x is the volume fraction distilled, T is the distillation

temperature, and To, A and B are constants determined by
regression using the solver function in Microsoft Excel or any
curve fitting program. Once the constant are determined, the
function may be used in the above equation to construct the
rest of the boiling point diagram.
When applied to the crude in example 4.2 the following
values are obtained for the constants
To = 30.788
A = 4986.5
B = 2.5131
Using these constants into the above equation, the following
TBP curve is predicted.
Hints: when applying the same to your own crude oil, use the
above values as initial guess. Also, add an absolute to the
above equation to avoid getting errors
T-T o = A ln abs 1
B
1-x
To
4-15
1/B
(4.4)
vol %
0.8
1.8
4.8
8.2
11.3
15.2
20.1
26.9
34.9
53.1
60.9
67.1
72.8
79.7
85
90
95
98
99.9
T (F)
122
167
212
257
302
347
392
437
482
584
637
690
742
795
846
911
1008
1118
1394
x
0.008
0.018
0.048
0.082
0.113
0.152
0.201
0.269
0.349
0.531
0.609
0.671
0.728
0.797
0.85
0.9
0.95
0.98
0.999
20
40
T
122
167
212
257
302
347
392
437
482
584
637
690
742
795
846
911
1008
1118
1394
calculated
123.43632
158.976516
221.339965
268.288313
302.429928
339.126056
379.358772
428.88685
482.000019
596.320067
646.905867
689.704546
732.454459
791.401438
845.847377
911.151517
1008.33677
1117.85398
1393.84728
abs diff
1
8
9
11
0
8
13
8
0
12
10
0
10
3
1600
TBP Temperature (F).
1400
1200
1000
800
600
400
200
0
0
60
Vol. %
4-16
80
100
Characterization & Classification
Characterization Factors
Correlate between the yield and the aromaticity &
paraffinicity of petroleum oils.
Several correlations exist,
1. UOP or Watson characterization factor (Kw)
1
3
B
T
K w = (sp.gr.)
@60F
(4.5)
More commonly used.

TB is the normal boiling point of the pure compound or
the mean average boiling point of a petroleum fraction
in R [F+460].
Higher for lighter components and petroleum fractions
e.g. Kw 12.1 (Naphtha), Kw 11.9 (Diesel)
For petroleum fractions 10 < Kw
contain
highly
aromatic
compounds
4-17
< 15
contain
highly
paraffinic
compounds
For crude oil 10.5 < Kw < 12.9
highly
highly
naphthenic paraffinic
crude
crude
For pure hydrocarbons
Kw = 13 for paraffins.
Kw = 12 for HC with equivalent chain and ring
weights.
Kw = 11 for pure naphthenes.
Kw = 10 for pure aromatics.
2. US Bureau of Mines Correlation Index
87,552 + 473.7 (sp.gr.)

CI =
T
@60 F
456.8
(4.6)
- TB & sp.gr. as above.

- Useful in evaluating individual fractions from oils (e.g.
naphtha, kerosene, diesel, etc.).
- The CI scale starts with 0 for straight-chain paraffins
and 100 for benzene.
0
highly paraffinic
100 highly naphthenic/aromatic
- CI values are not quantitative.
Low CI values high conc. of paraffins in the fraction.
4-18
Higher CI values high conc. of naphthenes &

aromatics.
Example 4.3: Watson K for pure components

Calculate the Watson characterization factor and correlation index for npentane.
Solution:
For n-pentane, the boiling point is 97 F and sp.gr. is 0.63
Using equation (5.3) above
1
(97+460)
K w = (0.63) = 13.06
3
Using equation (5.4) above
87,552
CI = (97+460) + 473.7 (0.63) 456.8 0
Table 5.4: Comparison of Kw and CI for pure components

Compound
TB (F)
Sp.gr.
Kw
CI
n-Hexane
2-Methylpentane
Cyclohexane
Benzene
Naphthalene
155.72
140.47
177.29
176.18
884
0.664
0.658
0.7835
0.8845
1.176
12.8
12.8
11.0
9.7
8.16
0
0.7
51.7
99.8
199.2
4-19
Classification of crude oil

- Paraffinic base
- Naphthenic base
- Asphalt base
- Mixed base
- Aromatic base (up to 80% in the far east)
These classifications convey the nature of the products to be
expected and the processing necessary.
US Bureau of Mines Classification
Based on the properties of the residue left from nondestructive atmospheric and vacuum distillation tests.
Fraction (1) from 482-527 F atm. distillation (760 mmHg)1.
Fraction (2) from 527-572 F vac. distillation (40 mmHg)2.
The gravity of these two fractions, obtained from Figure 3.8,
is used to classify crude as shown in table below.
Key fractions, API
Classification
Fraction (1)
40
40
33 40
33 40
33 40
33
< 33
Paraffin
Paraffin, Intermediate
Intermediate, Paraffin
Intermediate
Intermediate, Naphthene
Naphthene, Intermediate
Naphthene
1&2
Both from TBP curve

4-20
Fraction (2)
30
20 30
30
20 30
20
20 30
< 20
Crude Suitable for Asphalt Manufacture:

There are certain characteristics of crude oils that indicate if
they are possible sources of Asphalt.
Not 100% accurate as experimental tests.
A crude oil is usually suitable for asphalt manufacture if it
meats the three following criteria:
(1) The crude oil gravity < 35 API
(2) Contains a residue (MeABP=750F) with a Watson
characterization factor < 11.8.
(3) If (KW)550F (KW)750F < 0.15
If > 0.15, the residue may contain too much
wax to meet most asphalt specifications.
4-21
Example 4.4:
Classify the following crude using the US bureau of mines classification
then specify whether it is suitable for asphalt manufacture. (See chapter 3)
Solution:
1200
90
80
1000
800
60
50
600
40
400
API Gravity
Temperature (F)
70
30
20
200
10
0
0
0
20
40
60
80
100
Percent Distilled
Figure. TBP and gravity-mid percent curves
Fraction (1) from 482-527 F atm. distillation (760 mmHg).

Fraction (2) from 527-572 F vac. distillation (40 mmHg)2.
The gravity of these two fractions, obtained from above figure, is used to
classify crude as shown in table below.
Fraction 1 33 API
Fraction 2 22 API
Equivalent to 740-790 F atm. distillation (760 mmHg).

4-22
From the table above, this crude would be classified as Naphthene,

Intermediate
For the crude oil to be suitable for asphalt manufacture it should satisfy the
following
(1) API < 35
(specified in the data sheet for crude oil)
(2) (KW)550F (KW)750F < 0.15

at 750 F API = 25 SG = 0.904
(750+460)1/3
Kw =
11.79
(0.904)
at 550 F API = 32 SG = 0.865

(550+460)1/3
Kw =
11.6
(0.865)
Kw = 11.79 11.6 = 0.19 (> 0.15)

1200
90
80
1000
800
60
50
600
40
400
30
20
200
10
0
0
0
20
40
60
Percent Distilled
4-23
80
100
API Gravity
Temperature (F)
70
(3) Residue (MeABP = 750 F) (Kw < 11.8).

Calculate as above, only for the 790 F+ residue
The TBP curve for resid is first reconstructed as follows;
IBP is the final T reached by vac. distill. = 790 F
10 % T is 0.1(100-79) + 79 = 81.1%, T = 800 F
30 % T is 0.3(100-79) + 79 = 85.3%, T = 820 F
50 % T is 0.5(100-79) + 79 = 89.5%, T = 890 F
70 % T is 0.7(100-79) + 79 = 93.7%, T = 930 F
90 % T is 0.9(100-79) + 79 = 97.9%, T = 1030 F
FBP remains the same as before at about 1100 F
as an alternative, using computer program
(petrochem toolkit) API = 19 MeABP = 860 F
Kw = 11.67
1200
90
80
1000
800
60
50
600
40
400
30
20
200
10
0
0
0
20
40
60
80
Percent Distilled
4-24
100
API Gravity
Temperature (F)
70
Ok
Characterization of Well Defined Hydrocarbon Mixtures

For hydrocarbon mixtures for which the composition is
known, the pure component physical properties and acentric
factors adequately characterize the system.
For more complex mixtures such as petroleum fractions, it
neither practical nor possible to analyze the entire mixture to
define the concentration of all components.
These undefined mixtures are usually characterized by
parameters that are derived from the normal inspection tests,
an ASTM D86 or D1160 distillation, and the specific gravity
of the mixture.
Many characterizing parameters have been proposed but very
few are generally useful.
Among the useful parameters are five different boiling points
and the Watson characterization factor
Boiling points
Each boiling point reduces to the normal BP for pure
hydrocarbons and is significant for a different group of
correlations.
Volumetric average boiling point
n
VABP = x viT bi
(4.7)
i=1
xvi = volume fraction of component i.

Tbi = normal boiling point of component i (F or R).
4-25
Molal average boiling point

n
MABP = x iT bi
(4.8)
i=1
xi = mole fraction of component i.

Weight average boiling point
n
WABP = x wiT bi
(4.9)
i=1
xwi = weight fraction of component i.

Cubic average boiling point [R]
CABP =
n
1/3
x viT bi
i=1
(4.10)
Tbi = normal boiling point of component i (R only).

Mean average Boiling point
MeABP =
MABP + CABP
2
(4.11)
Watson characterization factor
(MeABP)1/3
Kw =
(sp.gr.)@60F
4-26
(4.12)
- The Watson K is an approximate index of paraffinicity,

with high values corresponding to high degrees of
saturation.
For multicomponent mixtures for which the composition is
known.
n
K w = x wiK i
(4.13)
i=1
Example 4.5:
Calculate the Watson characterization factor and the correlation index for
the following LPG mixture.
C3
n-C4
n-C5
Vol %
45
50
5
Solution:
LPG is at high pressure, but the laboratory analysis for gas composition
are done at atmospheric pressure. This is close to ideal conditions and the
volume % is equal to the mole %.
C3
n-C4
n-C5
mole %
45
50
5
MW
44
58
72
sp.gr.
0.507
0.584
0.63
Boiling Point, F (R)

- 43.75 (416)
31 (491)
97 (557)
Average Sp.gr. = (0.45)(0.507)+(0.5)(0.584)+(0.05)(0.63) = 0.552

VABP = (0.45)(416)+(0.5)(491)+(0.05)(557) = 460.7 R
MABP = VABP (for ideal gas)
4-27
C3 wt% = (0.45*44)/[(0.45*44)+(0.5*58)+(0.05*72)] = 37.8 wt%

C4 wt% = (0.5*58)/[(0.45*44)+(0.5*58)+(0.05*72)] = 55.3 wt%
C5 wt% = (0.05*72)/[(0.45*44)+(0.5*58)+(0.05*72)] = 6.9 wt%
WABP = (0.378)(416)+(0.553)(491)+(0.069)(557) = 467.3 R
3
CABP = 0.45(416)1/3 0.5(491)1/3 0.05(557)1/3 459.4 R
MeABP = (MABP+CABP)/2 = (460.7+459.4)/2 = 460 R

Into equation (3) above
1
(460)
K w = (0.552) = 13.9
3
or
n
K w = x wiK i = 0.378(14.7) + 0.553(13.5) + 0.069(13.03) = 13.92

i=1
Into equation (4) above
87,552
CI = (460) + 473.7 (0.552) 456.8 5
Example 4.6: Watson K for petroleum fractions
For the following SR Naphtha,
69.1 API & ASTM D86 distillation3
Vol %
T (F)
IBP
92
5%
118
10%
128
30%
164
50%
198
70%
230
90%
262
95%
272
3
D1160 cant be used

4-28
FBP
300
Recovery = 98.8 vol.%
Calculate,
(1)
(2)
(3)
(4)
(5)
(6)
(7)
The volumetric average boiling point, VABP

The weight average boiling point, WABP
The molal average boiling point, MABP
The cubic average boiling point, CABP
The mean average boiling point, MeABP
The Watson characterization factor, Kw
The US bureau of mines correlation index, CI.
Solution:
No correction for temperature is required (since T < 475 F).
The volumetric average boiling point, VABP
90
Ti
VABP i 10
5
VABP = T10% T 30% T 50% T 70% T 90%

5
= 128+164+198+230+262 = 196.4 F
5
Assuming ASTM curve is linear between 10 & 90%
ASTM slope = T 90% T10% 262 128 1.675
90 10
80
From Figure 2B1.1 API data book
For MABP T = -17 F
For CABP T = -3 F
For WABP T = +4 F
For MeABP T = -10 F
4-29
Using the corrections

MABP = 196.4 17 = 179.4 F
CABP = 196.4 3 = 193.4 F
WABP = 196.4 + 4 = 200.4 F
MeABP = 196.4 10 = 186.4 F
or
= (179.4+193.4)/2 = 186.4 F
The Watson characterization factor, Kw
Sp.gr. = 141.5/(69.1+131.5) = 0.705
(MeABP)1/3 (186.4+460)1/3
Kw =
12.3 (mainly saturated)

(sp.gr.)@60F
(0.705)
The US bureau of mines correlation index, CI.
87,552
CI = (186.4+460) + 473.7 (0.705) 456.8 0.7 (paraffinic)
4-30
4-31
Coordination Number (Hydrogen Deficiency) or Z Number

Cn H 2n+Z
As Z-number decreases, density increases.
Group
Paraffins
Olefins
Naphthenes
Aromatics
2
0
0
-6
Examples of Z-values for Aromatic compounds
C6H6
C10H8
C14H10
Z = -6
Z = -12
Z = -18
C10H12
C10H10
C24H12
Z = -8
Z = -10
Z = - 36
4-32
Properties Estimation of Petroleum Fractions
1. Graphical Methods.
2. Correlations.
Example 4.7: Graphical Method
For the following SR Naphtha; 69.1 API & ASTM D86 distillation
Vol %
T (F)
IBP
92
5%
118
10%
128
30%
164
50%
198
70%
230
90%
262
95%
272
FBP
300
Recovery = 98.8 vol.%
Calculate the MW, aniline point, H/C ratio, the true and pseudocritical
temperatures and pressures.
Solution:
Previously calculated, the mean average boiling point,
MeABP = 186.4 F
Using Figure 2B2.1 from the API technical data book
The molecular weight, MW = 96
and the Watson characterization factor KW = 12.2
(Compare to 12.3 calculated previously).
4-33
The aniline point = 125 F.

H/C ratio = 5.5
MABP = 179.4 F Figure 4A1.2 Tpc = 490 F.
WABP = 200.4 F Figure 4A1.2 Tc = 510 F.
MeABP = 186.4 F Figure 4B1.2 Ppc = 440 psia.
Tc/Tpc = (510+460)/(490+460) = 970/950 = 1.02
Ppc = 440 & Tc/Tpc = 1.02 Figure 4B1.1 Pc = 520 psia.
4-34
4-35
4-36
4-37
4-38
Liquid Viscosity
1. The absolute (or dynamic) viscosity.

Defined as the ratio of shear resistance to the shear velocity
gradient.
This ratio is constant for Newtonian fluids.
Expressed in Pa.s (poise)
Commonly used unit is mPa.s (centipoise, cP)
2. The kinematic viscosity.

Defined as the ratio between the absolute viscosity and the
density.
Expressed in mm2/s (centistokes, cSt)
The liquid dynamic viscosities at 100 F and 210 F are used

to characterize (heavy) petroleum fractions.
Viscosities can be estimated by the relation of Abbott et al.
log 100 4.39371 1.94733K W 0.12769K W2
3.2629.104 A 2 1.18246.102 K W A
4-39
(8.0325.102 K W 1.24899A 0.19768A 2 )
(A 26.786 2.6296K W )
(4.14)
log 210 0.463634 0.166532A

5.13447.104 A 2 8.48995.103 K W A
(8.0325.102 K W 1.24899A 0.19768A 2 )
(A 26.786 2.6296K W )
where
Kw = Watson characterization factor
A = API gravity
v100 = viscosity at 100 F [mm2/s]
v210 = viscosity at 210 F [mm2/s]
log = common logarithm (base 10)
notes:
Should not be used if Kw < 10 and A < 0.
Recommended for the following range;
0.5 < v100 < 20 mm2/s
0.3 < v210 < 40 mm2/s
Average error about 20%.
Molecular Weight
Can be estimated with two different means (5% ave error)

4-40
(4.15)
1. From the normal BP and standard specific gravity.

Riazi method: for light fractions
(sp.gr. < 0.97 & Tb < 840 K).
M = 42.965 (Tb1.26007 S4.98308)

[exp(2.097.10-4 Tb 7.78712 S + 2.08476.10-3 Tb S)]
Lee-Kesler: for heavy petroleum fractions
(Tb > 600 K & 60 < MW < 650).
M 12272.6 9486.4 S T b (8.3741 5.9917 S )
107
222.466
(1 0.77084 S 0.02058 S 2 ) 0.7465
Tb
Tb
1012
17.3354
3 (1 0.80882 S 0.02226 S 2 ) 0.32284
Tb
T
Where
M = Molecular weight [kg/kmol].
Tb = Normal boiling point [K].
S = Standard specific gravity.
4-41
2. From the viscosities at 210 F and 100 F and the standard

specific gravity (ave. error is 10%).
(1.1228 S 1.2435) (3.47583.038 S )
0.6665
M 223.56 100
210
S
where
M = Molecular weight [kg/kmol].
v100 = viscosity at 100 F [mm2/s].
v210 = viscosity at 210 F [mm2/s].
Pseudo-Critical Constants for Petroleum Fractions.

To make use of the principle of corresponding states.
Use the method of Lee-Kesler (ave. error 10%)
1. Pseudo-Critical Temperature.
T C 189.8 450.6 S T b (0.4244 0.1174 S )
(14, 410 100,688 S )

Tb
where,
4-42
Tc = Pseudo-critical temperature [K].

2. Pseudo-Critical Pressure
ln PC 5.68925
0.0566
S
4.12164 0.213426
103T b 0.436392
S
S2
11.819 1.53015
107T b 2 4.75794
S
S2
9.901
1010T b 3 2.45055
S2
where,
Pc = Pseudo-critical pressure [bar].
ln = Napierian logarithm
4-43
Acentric Factor for Petroleum Fractions.

For Tr < 0.8
7.904 0.1352K W 0.007465K W2

8.359T br
T br
1.408 0.1063K
W
T br
Tb
Tc
where
= acentric factor.
Tbr = reduced boiling point temperature.
Kw = Watson characterization factor.
For Tr > 0.8 (use Edmister's equation)
3 x

(log Pc 1.0057)
7 1 x
where x
Tb
Tc
and
Pc = Pseudo-critical pressure [bar].
Tc = Pseudo-critical temperature [K].
4-44
log = common logarithm (base 10)

Specific Heat of Petroleum Fraction in the Ideal Gas State
H gp 2.325A BT CT 2 DT 3 ET 4 FT 5
C pgp 4.185B 2CT 3DT 2 4ET 3 5FT 4
T 1.8T
'
0.2846
B 0.35644 0.02972KW 0.29502
104
2.9247 1.5524KW 0.05543KW2 C '
C
2
5.0694
C ' 6.0283
10 7
1.6946 0.0844
D
3
12.8
10

11
K
KW
W
S 0.885S 0.7 .10 4
Kw = Watson characterization factor

4-45
S = standard specific gravity
Flash Point
The API method (error 5C)
Tf
1
2.84947
0.02421
0.0034254
T 10
ln T 10
T10 = temperature at the 10% volume distilled point from ASTM

D86 [k].
Liquid Enthalpy
HL = A1 T 259.7 A2 T
A3 T
259.7 2
259.73
A1= 10 -3
1149.8246535KW
1171.26 (23.722 24.907 ) KW
A2= 10 -6
13.817
(1.0 0.82463KW ) 56.086
A3= -10 -9
2.3653
(1.0 0.82463KW ) 9.6757

Temperature (T)
Specific Gravity (SG)
Characterization Factor (Kw)
4-46
Vapor enthalpy
H V H L B 1 T 0.8T C
B3 T
B 1 10
B 2 10
B 3 10
B4
0.512T C
B2 T
RT C
MW
0.64T C
H H
4.507 5.266
RT
356.44 29.72KW B 295.02 248S.46

4
146.24 (77.62 2.772K )K B 301.42 253.46

W
W
56.487 2.95B
4
12.8
10.0
4

K 1.0 1.0 K S 0.885S 0.7 10
W
W
HL Liquid Enthalpy of Petroleum Fractions

T Temperature
Tc Critical Temperature
R Gas Constant
MW Molecular Weight
Acentric Factor
S Specific Gravity
KW Watson Characterization Factor
(Ho- H)/RTC Pressure Effect on Enthalpy
4-47
Hv Vapor Enthalpy of Petroleum Fractions

Calculation of Density by the Lee and Kesler Method
Z Z 1 2.5138' 'w ' ( Z 2 Z 1 )

w w 1
Z Z 1 (Z 2 Z 1 )
w 2 w 1
b
b
b
B i b1i 2i 32i 43i
Tr Tr Tr
c 2 i c 3i
C i c1i
T r T r3
D i d 1i
d 2i
Tr
c 4i ( i2 i ) exp( 2i )
PrVri
Bi
Ci
Di
V ri
V ri
zi
1
Tr
Vri Vri 2 Vri 5
T r3V ri2
l
PM
z l RT
Pressure for Saturation

Ps Pcm exp[f (T rm , m )]
f (T rm , m ) ln Pr0 m ln Pr0
ln Pr 0 5.92714
6.09648
1.28862lnT rm 0.169347T rm6
T rm
4-48
ln Pr 1 15.2518
15.6875
13.4721lnT rm 0.43577T rm6
T rm
Pressure Correction for Density

1
B P
B Ps
1 C ln
C 0.0861488 0.0344483m
B Pcm a k k 1
4
k 1
1 T r
1/ 3
Estimation of the pour point (page 172):
T EC 130.47S 2.971M
( 0.6120.474S )
v 100
( 0.310.333S )
Estimation of the Interfacial Tension of Petroleum fractions:

(page 167)
293.15 1.232
]
Tcf
Kw
673.7[1
Thermal Conductivities of Liquids: (page 132)
0.17 1.418 E 4T
Influence of Pressure on the Viscosity of Liquids (Kouzel's

method):
4-49
log
M
(P Ps )(5.829E 4Ms 0.181 1.479E 4)
Ms
Specific Heats for liquid Petroleum Fractions (Lee Kessler

1975) Page 121:
Cp 4.185(0.35 0.055Kw )(0.3065 0.16734S T (1.467 *10 3 5.508 *10 4 S ))
l
4-50
Exercises
4.1. Repeat example 4.5 using another method by calculating Kw for
pure components to find the same for the mixture.
4.2. Classify the crude oil handed out to you using the US bureau of
mines classification.
4.3. Is your crude oil suitable for asphalt or lube oil manufacture?
4.4. Draw the TBP and API curves for the crude oil assay handed out to
you. Use the probability density function to construct the heavier
portion of your TBP curve.
4.5. Estimate the MW, aniline point, and H/C ratio for the crude oil
handed out to you.
4-51

Crude Oil Characterization

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Crude Oil Characterization

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Petroleum Refining Chapter 4: Characterization

API Gravity (API)

API = 141.5 131.5

Light crude have lower density (sp.gr.) API is higher.

Distillation Range (Curve)

Petroleum Refining Chapter 4: Characterization

Types of distillation curves

Petroleum Refining Chapter 4: Characterization

TBP is the most useful.

Petroleum Refining Chapter 4: Characterization

(2) Find the atmospheric TBP mid (50%) temperature using

Note: it is possible to convert TBP temperatures to ASTM

Petroleum Refining Chapter 4: Characterization

Crude oil analysis are reported in 2 parts,

Petroleum Refining Chapter 4: Characterization

Figure 4.1: Boiling point distribution curve

Figure 4.2: Crude oil TBP Distillation Curve Probability Chart.

Petroleum Refining Chapter 4: Characterization

Example 4.2: construction of the TBP & API Curves

Petroleum Refining Chapter 4: Characterization

2. Better results are obtained when using the probability density

Where x is the volume fraction distilled, T is the distillation

TBP Temperature (F).

Petroleum Refining Chapter 4: Characterization

Characterization & Classification

More commonly used.

For crude oil 10.5 < Kw < 12.9

2. US Bureau of Mines Correlation Index

87,552 + 473.7 (sp.gr.)

- TB & sp.gr. as above.

Petroleum Refining Chapter 4: Characterization

Higher CI values high conc. of naphthenes &

Example 4.3: Watson K for pure components

Using equation (5.4) above

Table 5.4: Comparison of Kw and CI for pure components

Classification of crude oil

Both from TBP curve

Petroleum Refining Chapter 4: Characterization

Crude Suitable for Asphalt Manufacture:

Figure. TBP and gravity-mid percent curves

Fraction (1) from 482-527 F atm. distillation (760 mmHg).

Equivalent to 740-790 F atm. distillation (760 mmHg).

Petroleum Refining Chapter 4: Characterization

From the table above, this crude would be classified as Naphthene,

(specified in the data sheet for crude oil)

(2) (KW)550F (KW)750F < 0.15

at 550 F API = 32 SG = 0.865

Kw = 11.79 11.6 = 0.19 (> 0.15)

(3) Residue (MeABP = 750 F) (Kw < 11.8).

Petroleum Refining Chapter 4: Characterization

Characterization of Well Defined Hydrocarbon Mixtures

xvi = volume fraction of component i.

Molal average boiling point

xi = mole fraction of component i.

xwi = weight fraction of component i.

Tbi = normal boiling point of component i (R only).

Watson characterization factor

Petroleum Refining Chapter 4: Characterization

- The Watson K is an approximate index of paraffinicity,

Boiling Point, F (R)

Average Sp.gr. = (0.45)(0.507)+(0.5)(0.584)+(0.05)(0.63) = 0.552

C3 wt% = (0.45*44)/[(0.45*44)+(0.5*58)+(0.05*72)] = 37.8 wt%

CABP = 0.45(416)1/3 0.5(491)1/3 0.05(557)1/3 459.4 R

MeABP = (MABP+CABP)/2 = (460.7+459.4)/2 = 460 R

C3 wt% = (0.4544)/[(0.4544)+(0.558)+(0.0572)] = 37.8 wt%