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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
(4.1)
(60F )
sp.gr. = oil
water(60F )
(4.2)
4-3
Copyrights 2001 2012, Dr. Tareq Albahri, Chem. Eng. Dept., Kuwait University
4-4
4-5
Copyrights 2001 2012, Dr. Tareq Albahri, Chem. Eng. Dept., Kuwait University
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
(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
4-7
Copyright 2001-2014 Dr. Tareq Albahri, Chemical Engineering Dept., Kuwait University, All rights reserved
4-8
4-9
Copyright 2001-2014 Dr. Tareq Albahri, Chemical Engineering Dept., Kuwait University, All rights reserved
4-10
4-11
Copyright 2001-2014 Dr. Tareq Albahri, Chemical Engineering Dept., Kuwait University, All rights reserved
4-13
Copyright 2001-2014 Dr. Tareq Albahri, Chemical Engineering Dept., Kuwait University, All rights reserved
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.
T-T o = A ln 1
B 1-x
To
1/B
(4.3)
B
1-x
To
4-15
1/B
(4.4)
Copyright 2001-2014 Dr. Tareq Albahri, Chemical Engineering Dept., Kuwait University, All rights reserved
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
1400
1200
1000
800
600
400
200
0
0
60
Vol. %
4-16
80
100
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)
contain
highly
aromatic
compounds
4-17
< 15
contain
highly
paraffinic
compounds
Copyright 2001-2014 Dr. Tareq Albahri, Chemical Engineering Dept., Kuwait University, All rights reserved
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.
@60 F
456.8
(4.6)
(97+460)
K w = (0.63) = 13.06
3
87,552
CI = (97+460) + 473.7 (0.63) 456.8 0
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
Copyright 2001-2014 Dr. Tareq Albahri, Chemical Engineering Dept., Kuwait University, All rights reserved
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
Fraction (2)
30
20 30
30
20 30
20
20 30
< 20
4-21
Copyright 2001-2014 Dr. Tareq Albahri, Chemical Engineering Dept., Kuwait University, All rights reserved
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
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
Copyright 2001-2014 Dr. Tareq Albahri, Chemical Engineering Dept., Kuwait University, All rights reserved
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
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
Copyright 2001-2014 Dr. Tareq Albahri, Chemical Engineering Dept., Kuwait University, All rights reserved
MABP = x iT bi
(4.8)
i=1
WABP = x wiT bi
(4.9)
i=1
CABP =
n
1/3
x viT bi
i=1
(4.10)
MeABP =
MABP + CABP
2
(4.11)
(MeABP)1/3
Kw =
(sp.gr.)@60F
4-26
(4.12)
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
Copyright 2001-2014 Dr. Tareq Albahri, Chemical Engineering Dept., Kuwait University, All rights reserved
(460)
K w = (0.552) = 13.9
3
or
n
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
FBP
300
Recovery = 98.8 vol.%
Calculate,
(1)
(2)
(3)
(4)
(5)
(6)
(7)
Solution:
No correction for temperature is required (since T < 475 F).
The volumetric average boiling point, VABP
90
Ti
VABP i 10
5
Copyright 2001-2014 Dr. Tareq Albahri, Chemical Engineering Dept., Kuwait University, All rights reserved
(MeABP)1/3 (186.4+460)1/3
Kw =
87,552
CI = (186.4+460) + 473.7 (0.705) 456.8 0.7 (paraffinic)
4-30
4-31
Copyright 2001-2014 Dr. Tareq Albahri, Chemical Engineering Dept., Kuwait University, All rights reserved
Paraffins
Olefins
Naphthenes
Aromatics
2
0
0
-6
C6H6
C10H8
C14H10
Z = -6
Z = -12
Z = -18
C10H12
C10H10
C24H12
Z = -8
Z = -10
Z = - 36
4-32
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
Copyright 2001-2014 Dr. Tareq Albahri, Chemical Engineering Dept., Kuwait University, All rights reserved
4-34
4-35
Copyright 2001-2014 Dr. Tareq Albahri, Chemical Engineering Dept., Kuwait University, All rights reserved
4-36
4-37
Copyright 2001-2014 Dr. Tareq Albahri, Chemical Engineering Dept., Kuwait University, All rights reserved
4-38
Liquid Viscosity
3.2629.104 A 2 1.18246.102 K W A
4-39
Copyright 2001-2014 Dr. Tareq Albahri, Chemical Engineering Dept., Kuwait University, All rights reserved
(A 26.786 2.6296K W )
(4.14)
(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
(4.15)
107
222.466
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
Copyright 2001-2014 Dr. Tareq Albahri, Chemical Engineering Dept., Kuwait University, All rights reserved
where
M = Molecular weight [kg/kmol].
v100 = viscosity at 100 F [mm2/s].
v210 = viscosity at 210 F [mm2/s].
S = Standard specific gravity.
1. Pseudo-Critical Temperature.
T C 189.8 450.6 S T b (0.4244 0.1174 S )
where,
4-42
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
Tb = Normal boiling point [K].
S = Standard specific gravity.
4-43
Copyright 2001-2014 Dr. Tareq Albahri, Chemical Engineering Dept., Kuwait University, All rights reserved
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
H gp 2.325A BT CT 2 DT 3 ET 4 FT 5
T 1.8T
'
0.2846
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
Copyright 2001-2014 Dr. Tareq Albahri, Chemical Engineering Dept., Kuwait University, All rights reserved
Flash Point
The API method (error 5C)
Tf
1
2.84947
0.02421
0.0034254
T 10
ln T 10
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
A3= -10 -9
2.3653
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
56.487 2.95B
4
12.8
10.0
4
K 1.0 1.0 K S 0.885S 0.7 10
W
W
Copyright 2001-2014 Dr. Tareq Albahri, Chemical Engineering Dept., Kuwait University, All rights reserved
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
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
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
T EC 130.47S 2.971M
( 0.6120.474S )
v 100
( 0.310.333S )
293.15 1.232
]
Tcf
Kw
673.7[1
0.17 1.418 E 4T
Copyright 2001-2014 Dr. Tareq Albahri, Chemical Engineering Dept., Kuwait University, All rights reserved
log
M
(P Ps )(5.829E 4Ms 0.181 1.479E 4)
Ms
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