Académique Documents
Professionnel Documents
Culture Documents
28s
Based on the composition of defined hydrocarbon mixtures, an accurate, generalized method is proposed to predict
t h e firactional composition of paraffins, naphthenes, and aromatics contained in both light and heavy petroleum
fractions. Viscosity, specific gravity, and refractive index of the desired fraction are used as input parameters.
Introduction
In prediction of physical and thermodynamic properties
of petroleum fractions it is important to determine the
proportion of paraffinic, naphthenic, and aromatic hydrocarbons present in the fraction (Huang and Daubert,
1974; Riazi, 1979). Since the composition of petroleum
fractions is not usually experimentally determined, development of a reliable method to estimate molecular type
analysis is quite necessary.
Many methods have been developed to predict the
percentage of paraffins, naphthenes, and aromatics in an
olefin-free petroleum fraction. The most common procedures are the n-d-llf method and the refractivity-intercept-density method The n-d-M method of Van Nes and
Van Westen (1951) for estimating the percentage carbon
as aromatic, naphthenic, or paraffinic structure from
measured values of density, refractive index, sulfur content,
and molecular weight is a set of empirical equations at 20
or 70 "C.
0196-4305/80/1119-0289$01.00/0
Chemical Society
290
Ind. Eng. Chem. Process Des. Dev., Vol. 19, No. 2, 1980
Ri
VGC
Daraffin
Aapht hene
aromatic
331-535
2 4 8-4 29
180-395
1.048-1.05
1.03-1.046
1.07-1 . l o 5
0.74-0.75
0.89-0.94
0.95-1.13
13.1-13.5
10.5-13.2
9.5-12.53
0.267-0.27 3
0.278-0.308
0.29 8-0.362
I Ob
A
1
I
oa
o a4
0 76
KI
2a
12
I
I
13
(3)
I
I4
0 2b
11
lpl
I L
108
El
10
I O
N
A
A
0 92
1 1
0 30
I
0 32
0 34
1
0 36
1.038, and 1.081 were obtained for the average Ri of paraffins, naphthenes, aromatics, while values of 0.744,0.915,
and 1.04 were obtained for the average VGC of paraffins,
naphthenes, and aromatics, respectively. By using Kays
mixing rule, Ri and VGC of an olefin-free petroleum
fraction can be obtained by the following equations
Ri = 1 . 0 4 8 2 ~+~1 . 0 3 8 +
~ ~1 . 0 8 1 ~ ~
(6)
VGC = 0 . 7 4 4 ~+~0 . 9 1 5 ~+ ~1 . 0 4 ~ ~
VGC =
I = - n2 - 1
n2 + 2
- 1
VGC
104
I02
+ +
c 3 2 N
I
R,
(7)
(9)
+ 2.973VGC
(11)
+ 7.37Ri + 1.255VGC
(12)
X,
= 18.66 - 19.90Ri
X,
= - 8.66
Ind. Eng. Chem. Process Des. Dev., Vol. 19, No. 2, 1980
291
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
Tb
102
131
144
120
142
162
227
214
126
129
162
127
157
171
153
127
133
130
127
162
132
161
130
126
166
161
137
130
166
137
133
127
133
165
154
165
157
160
137
133
130
170
196
28 2
321
260
32 2
404
547
535
297
306
39 7
298
385
417
385
29 7
31 5
30 4
29 5
39 2
303
40 5
312
30 0
406
397
329
307
40 5
329
31 6
297
317
40 3
37 2
40 3
38 5
39 2
329
318
307
41 7
0.7322
0.77 33
0.8008
0.7358
0.7586
0.8045
0.8578
0.8433
0.7517
0.7701
0.799
0.769
0.801
0.810
0.786
0.7637
0.762
0.759
0.752
0.788
0.759
0.792
0.763
0.763
0.808
0.806
0.782
0.775
0.805
0.778
0.7740
0.77
0.767
0.786
0.779
0.797
0.7915
0.793
0.7756
0.7711
0.7671
0.799
1.4074
1.4335
1.4436
1.4188
1.4260
1.4444
1.4776
1.4694
1.428
1.434
1.4463
1.433
1.447
1.45
1.444
1.4301
1.435
1.4325
1.427
1.449
1.424
1.45
1.4345
1.4343
1.4485
1.45
1.437
1.4352
1.448
1.437
1.4354
1.4328
1.4365
1.443
1.4398
1.4457
1.444
1.4442
1.4382
1.4356
1.4378
1.4464
0.7365
0.7774
0.8046
0.7395
0.7624
0.8083
0.8616
0.847 5
0.7555
0.7740
0.803
0.7725
0.805
0.816
0.7899
0.7675
0.7658
0.7628
0.7558
0.792
0.7628
0.796
0.7668
0.7668
0.8121
0.8101
0.786
0.7789
0.809
0.7819
0.7779
0.77 39
0.7709
0.7899
0.7829
0.8
0.7955
0.797
0.7795
0.775
0.771
0.8025
v210
XP
Xn
Xa
0.364
0.444
0.525
0.414
0.503
0.739
1.239
1.179
0.464
0.520
0.7 1
0.555
0.75
0.83
0.78
0.535
0.51
0.47
0.458
0.700
0.52
0.74
0.508
0.50
0.79
0.76
0.60
0.55
0.74
0.557
0.530
0.516
0.515
0.753
0.665
(1.43)
(1.27)
(1.33)
(0.92)
(0.87)
(0.83)
(1.55)
0.362
0.397
0.186
0.619
0.593
0.309
0.298
0.388
0.605
0.490
0.375
0.420
0.300
0.260
0.538
0.500
0.665
0.650
0.655
0.580
0.510
0.563
0.656
0.637
0.285
0.295
0.390
0.420
0.365
0.455
0.475
0.510
0.600
0.590
0.600
0.420
0.435
0.425
0.460
0.490
0.500
0.420
0.582
0.396
0.698
0.306
0.308
0.643
0.456
0.415
0.135
0.31 5
0.440
0.390
0.495
0.525
0.181
0.270
0.170
0.170
0.170
0.225
0.395
0.187
0.171
0.174
0.505
0.495
0.415
0.400
0.455
0.350
0.320
0.310
0.150
0.200
0.190
0.405
0.385
0.395
0.320
0.295
0.290
0.410
0.056
0.205
0.106
0.076
0.099
0.048
0.233
0.172
0.260
0.195
0.185
0.190
0.205
0.215
0.281
0.230
0.165
0.180
0.175
0.195
0.095
0.250
0.173
0.189
0.210
0.210
0.195
0.180
0.180
0.195
0.205
0.180
0.250
0.210
0.210
0.175
0.180
0.180
0.220
0.215
0.210
0.170
M = molecular weight; Tb = 50% normal boiling point, F; d = liquid density a t 20 ' C and 1 a t m , g/cm3;n = refractive index at 20 " C and 1 a t m ; v z l O= kinematic viscosity at 210 ' F, cSt. Values in t h e parentheses are kinematic viscosities at 100
O F , cSt.
xprx,, x, = inole fraction of paraffin, naphthene, and aromatic. References: no. 1-8: Lenoir and Hipkin
( 1 9 7 3 ) ; no. 9-42: private communication (1977). Values of n for no. 9-42 are calculated using the method suggested in
this work (eq 24).
+ 0.7853
(14)
(16)
(17)
292
Ind. Eng. Chem. Process Des. Dev., Vol. 19, No. 2, 1980
ln(kinematic
V I S C O I I ~ ~ )0 1
100' F
M
233
248
267
281
305
245
28 2
325
403
265
297
523
250
394
253
364
no.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
0.9082
0.9360
0.9568
0.9 67 1
0.9742
0.8497
0.8709
0.8845
0.9001
0.8319
0.8425
0.8750
0.8912
0.8664
0.877
0.907
1.5016
1.5212
1.5366
1.5452
1.5492
1.4719
1.4842
1.4919
1.5002
1.4637
1.4694
1.4865
1.4896
1.477
1.4838
1.5142
0.9119
0.9397
0.9605
0.9708
0.9779
0.8535
0.8746
0.8883
0.9046
0.8357
0.8463
0.8760
0.8939
0.87
0.88
0.936
Tb
569.6
620.0
652.4
688.4
724.4
582.2
648.8
717.2
798.2
614.6
675.8
937.0
-------
----
----
VI,
48.2
66.7
111.1
203.1
516.5
43.2
58.7
108.8
336.0
45.5
59.4
463.0
60.6
155.4
54.6
680.5
XD
Xn
Xa
0.341
0.304
0.309
0.318
0.329
0.584
0.565
0.584
0.590
0.700
0.694
0.784
0.105
0.720
0.580
0.102
0.459
0.430
0.370
0.340
0.322
0.318
0.307
0.289
0.280
0.227
0.224
0.133
0.639
0.250
0.340
0.455
0.190
0.226
0.321
0.342
0.349
0.097
0.128
0.128
0.130
0.073
0.081
0.083
0.256
0.030
0.080
0.443
molecular weight; Tb = normal boiling point, O F ; d = liquid density a t 20 " C and 1 atm, g/cm3;n = refractive index
at 20 ' C and 1 atm; S = specific gravity at 6 0 / 6 0 F; V,, = Saybolt Universal Viscosity at 100 F, SSU. References: no.
1-11: Van Nesand Van Westen ( 1 9 5 1 ) ; no. 1 2 : Witco ( 1 9 7 3 ) ; no. 1 3 : P e n n z o i l ( l 9 7 5 ) ; no. 14-16: A.S.M.E. (1953).
a
molwt
range
100-230
34
126-171
42
100-230
Xn
XP
Rirange
VG F
range
xprange
range
av
bias
max
av
bias
max
1.0411.051
1.0441.055
0.7871.06
0.8270.950
0.190.62
0.260.66
0.300.65
0.130.53
0.039
-0.023
-0.125
0.043
-0.003
0.093
0.033
-0.010
-0.095
0.04
0.019
0.114
1.0411.055
0.7870.95
0.190.66
0.130.65
0.034
-0.012
-0.125
0.041
0.015
0.114
Xn
x e x p ~max
;
= maximum deviation; av = ( l / N ) z :Ideviationl; bias = ( l / N ) x d e v i a t i o n ;
V G F = 0 . 7 4 ~+ ~0 . 9 2 ~+ ~1 . 1 2 ~ ~
(l9)
Physical properties of 45 light defined hydrocarbon mixtures were estimated using the composition of the mixture,
properties of components from API Reseach Project 44
(1978), and Kay's mixing rule. After regression of eq 18
and 19 with the compositions of the 45 defined hydrocarbon mixtures and solution simultaneously with eq 1,
the following expressions were derived for xP, x,, and x,.
Ind. Eng. Chem. Process Des. Dev., Vol. 19, No. 2, 1980
xP = - 23.94
X,
X,
+ 24.21Ri - 1.092VGF
+ 0.627VGF
(21)
+ 15.22Ri + 0.465VGF
(22)
= 41.14 - 39.43Ri
= - 16.2
(20)
The above equations can be used to predict the composition of an olefin-free petroleum fraction if Ri and VGF
are known. Equations 20, 21, and 22 are similar to eq 10,
11,and 12 for composition prediction of viscous fractions.
Since refractive indices of petroleum fractions are not
always known, it is important to predict refractive index
with a good degree of accuracy in order to estimate the
refractivity intercept from eq 2. Huang (1977) correlated
molecular weight to boiling point, refractive index and
density as follows
M = 7.7776
X 10-67- 2.11971-2.089d
b
(23)
(-)+ 21
1
1-I
M 2 200: I = 1.4 X
r,i =
10-3Tb1.0u(M/d)-0.3984
(-)+ 21
1
1-I
The equations can predict refractive indices of heavy petroleum fractions within an average deviation of 0.2%.
293
294
pro pert y
liquid enthalpy
vapor enthalpy
viscosity at
100 " F (light)
viscosity at
2 10 F (light)
viscosity at
100 F (heavy)
viscosity at
210 " F (heavy)
av deva
no. of
fractions
exptl
compn
pred compn
435
292
38
2.4 Btuilb
3.7 Btullb
2.9%
2.7 Btu/lb
3.5 Btullb
2.8%
38
5.7%
5.2%
10
8.1%
8.5%
10
3.5%
3.5%
a Absolute deviation = predicted property - experimental property. Deviation, % = [(predicted property - experimental property)/experimental property] x 100. av =
(l/N)
z 1 deviation 1 . iv'' = number of data points.
B. Josh1
Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 1526 1
The kinetics of the oxidation of pyritic sulfur, organic sulfur, and carbon for the Upper Freeport coal are investigated.
Experiments were conducted in a semi-batch manner. The effects of batch time (0-2400 s),temperature (150-210
"C),partial pressure of oxygen (0.69-3.44 MPa), and total pressure (3.44-6.88 MPa) were studied. Two alternate
mechanisms have been proposed for the oxidation of pyritic sulfur. In one mechanism the fine pyrite particles
are assumed to be uniformly distributed in coal particles and the continuous reaction model was found to hoM where
the rate of reaction is second order with respect to pyritic sulfur. In the other mechanism, the pyrite particles
are assumed to exist free from coal and the shrinking core model was found to hold where the rate of reaction
is controlled by diffusion through ash. Both the carbon oxidation and organic sulfur reactions are zero order with
respect to carbon and organic sulfur, respectively. The activation energies for all three reactions agree closely
with those reported in the literature.
Introduction
The sulfur in coal occurs in three forms: pyritic, organic,
or sulfate. Pyrites, classified as compounds with the formula FeS, (where the standard value of x is 2), accounts
for the bulk of the sulfur in Eastern coals. Organic sulfur
is a broad classification containing any sulfur which is
chemically bound to the actual coal matrix. Organic sulfur
is the dominant sulfur form in Western coals. Sulfates
constitute less than a few percent of the total sulfur in most
coals.
The direct burning of coal causes the production of
noxious sulfur oxides (S0,'s). Presently, control of sulfur
oxide emissions is achieved mainly by either stack gas
scrubbing or physical coal cleaning techniques. The former
process is both expensive and energy intensive. The latter,
although relatively inexpensive and simple to operate, is
less effective. In fact, depending on the sulfur composition
of the feed coal, a plant burning physically pre-cleaned coal
0196-4305/80/1119-0294$01.00/0
0 1980 American
Chemical Society