Ind. Eng. Chem. Process Des. Dev.

1980, 79, 289-294

a firm should or should not enter into the manufacture of

an existing chemical.
To use the procedure, two pieces of information are
required: (1) the demand curve for the product; (2) estimates of the annual cost of manufacture. Using the
above information, eq 4a and 4b are solved simultaneously
and a search over process unit sizes can be performed to
find the size that maximizes profit under each market
assumption (Cournot's Implicit Collusion).
In this manner, a range of process unit sizes along with
estimates of market share, price, output, and profits can
be determined for the firms. Tables similar to Tables VI1
and VI11 can also be prepared which can serve the process
designer as quick, qualitative guides for the characterization of firms' behavior on any specific chemical market that
the firm may be considering entering.
By means of this procedure, more information is
available for the dec:ision-making process without the usual
assumptions to estimate market shares and production.
Furthermore, the rule-of-thumb procedures so common in
setting price are not needed.
We cannot conclude from our studies which of the two
assumptions, Implicit Collusion or Cournot's, describes
better the market behavior of the oligopolistic firms in the
chemical process industries. The only way to test the
validity of the two assumptions would be to compare their
predictions with actual performance for a particular duopoly. To do this, the total cost equation must be derivable
from the process technical information and enough price

28s

history must be available to estimate a demand curve at

the time of decision. The equilibrium price and industry
output plus each firm's market share could then be compared with the actual situation. Of course, such a comparison assumes that the firms behave in an optimal
fashion either by analysis or by experience.
Acknowledgment
The authors would like to acknowledge the financial
support provided by the Latin American Scholarship
Program of the American Universities (LASPAU), the
Chemical Engineering Department of the University of
Delaware, and the Universidad Catijlica Madre y Maestra,
Santiago, Dominican Republic. The authors are also most
grateful for many helpful discussions with Professor Eric
Brucker, Dean, College of Business and Economics of the
University of Delaware.
Literature Cited
Bogaert, R., M.ChE. Thesis, University of Delaware, Newark, DE, 1979.
Cohen, K. J.; Cyert, R. M. "Theory of the Firm: Resource Allocation in a Market
Economy", Prentice-Hall: Englewocd Cliffs, NJ, 1965; p 138.
Leftwich, R. H. "The Price System and Resource Allocation", 5th ed.; The
Dryden Press: Hinsdaie, IL, 1973; p 9.
Miller, R. L. "Intermediate Microeconomics", M&aw-Hill: New York, NY, 1978;
p 293.
Von Neumann, J.; Magenstern, 0. "Theory of Games and Economic Behavior",
Princeton University Press: Princeton, NJ, 1953; Chapter 1.
Wei, J.; Russell, T. W. F.; Swartzhnder, M. W. "The Structure of the Chemical
Processing Industries", McGraw-Hill: New York, NY, 1979; p 52.

Received f o r reuiew June 26, 1979

Accepted November 26, 1979

Prediction of the Composition of Petroleum Fractions

Mohiammad R. Riazi and Thomas E. Dauberl'
Department of Chemical Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802

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

The refractivity-intercept-density method of Kurtz et

al. (1958) is a triangular graphical relation between percentage carbon as aromatic, naphthenic, or paraffinic;
refractivity intercept ( R J ;and density. This method requires that the aromatic percentage must be known.
A number of other procedures have been discussed in
various sources (Boelhower et al., 1954; Kurtz et al., 1958,
1936,1937; Van Nes and Van Westen, 1951; Waterman et
al., 1958). However, all of the existing methods are useful
only for high-boiling virgin fractions and are accurate only
for data on which the method is based. The main purpose
of this work was to develop a general method to predict
mole fraction of paraffinic, naphthenic, or aromatic compounds for light and heavy fractions which is not based
on the composition of a certain group of petroleum fractions.
Development
If the mole fraction of paraffins, naphthenes, and aromatics for an olefin-free petroleum fraction are defined as
0 1980 American

Chemical Society

290

Ind. Eng. Chem. Process Des. Dev., Vol. 19, No. 2, 1980

Table I. Values of Characterization Factors in Figure 1

value range
hydrocarbon type

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

xp,x,, and x, respectively, three expressions for prediction

of these three unknowns can be developed. This requires
a set of three independent equations relating xp, x, and
x, to each other and some other known parameters. The
first equation is the obvious molar balance.
xp x, x, = 1
(1)

I Ob

A
1

I
oa

o a4

0 76

KI

2a

12

I
I

13

(3)

S - 0.24 - 0.022 log (V, - 35.5)

(4)
0.755
in which Vl and V, are Saybolt universal viscosities at 100
and 210 OF, respectively. Equations 3 and 4 give approximately the same value for VGC of a given hydrocarbon. Since in the above equations viscosity is defined
as Saybolt universal (SSV viscosity, therefore they cannot
be used for light hydrocarbons (approximately M 180).
Figure 1 and Table I show a comparison between Ri and
VGC with two other characterization factors: Watson K
and a factor I proposed by Huang (1977). Parameter I is
a function of only refractive index.
(5)

From Figure 1 it is obvious that R i and VGC separate

paraffins, naphthenes, and aromatics better than either
of the other two parameters. Also, Ri and VGC vary over
a small range when compared with K and I. This indicates
that a single value for Ri, for instance, can characterize Ri
values for all paraffins. Data on viscosity, refractive index,
and density of heavy hydrocarbons were taken from API
Research Project 42 (1962). For heavy ( M > 200) hydrocarbons, average values of Ri and VGC for each homologous hydrocarbon group were estimated. Values of 1.0482,

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

Figure 1. Comparison of different characterization factors (see

Table I).

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

The VGC is defined by Hill and Coats (1928) as

1 0 s - 1.0752 log (VI - 38)
VGC =
10 - log (V, - 38)

104

I02

+ +

Thus, two more equations are needed. In development of

these equations, it is necessary that properties of petroleum
fraction be related to the properties of each homologous
hydrocarbon group by a mixing rule, the simplest of which
is Kays rule. Therefore, at least two parameters are
needed to develop the two equations.
In order to predict the composition of petroleum fractions with reasonable accuracy, fractions are divided into
two molecular weight ranges-viscous fractions (200 < M
< 500) and light fractions ( M < 200). It should be noted
that these molecular weight range values are approximate
values.
1. Viscous Fractions. Among different characterization factors proposed in the literature, refractivity intercept
(Ri) and viscosity gravity constant (VGC) were chosen for
development of the two equations to use with eq 1. In
selection of these two parameters, it was attempted to
choose a parameter which can best separate different homologous hydrocarbon groups. Refractivity intercept
(Kurtz and Ward, 1936, 1937) is defined by
d
Ri=n- 2

c 3 2 N
I

R,

(7)

A regression of 33 defined hydrocarbon mixtures changes

the constants in these equations less than 2%. Various
compositions of these ternary systems were used-n-octadecane(P)-2-butyl-l-hexahydrindan(N)-2(ar),
6-dimethyl-3-octyltetralin(A); n-octadecane(P)-1-a-decalylpentadecane(N)-2(ar),6-dimethyl-3-octyltetralin(A); and
n-octadecane(P)-9(-as-perhydroindacenylheptadecane(N)-11-a-naphthyl-10-heneicosene(A)-whereP, N, and
A refer to paraffin, naphthene, and aromatic, respectively.
After regression, eq 6 and 7 become
Ri = 1 . 0 4 8 6 +
~ ~1 . 0 2 2 +
~ ~1 . 1 1 ~ ~
(8)
VGC = 0 . 7 4 2 6 ~+~0 . 9 +
~ ~1 . 1 1 2 ~ ~

(9)

Ri and VGC equations together with eq 1 can then be

solved simultaneously to obtain equations for xp, x,, and
x, which can then be used to predict the composition of
viscous fractions ( M > 200) if Ri and VGC are known. The
final results after simultaneous solution of eq 1, 8, and 9
may be summarized as follows
xP = - 9.00 + 12.53Ri - 4.228VGC
(10)

+ 2.973VGC

(11)

+ 7.37Ri + 1.255VGC

(12)

X,

= 18.66 - 19.90Ri

X,

= - 8.66

2. Light Fractions. As mentioned earlier for light

petroleum fractions the VGC cannot be calculated as defined by eq 3 and 4. It was attempted to define a new

Ind. Eng. Chem. Process Des. Dev., Vol. 19, No. 2, 1980

291

Table 11. Data o n t h e Composition of Light Petroleum Fractions'

composition
no.
1

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).

characterization factor for light hydrocarbons to be used

instead of VGC and then to develop a series of equations
similar to eq 10, 11, ,and 1 2 for prediction of the composition of light petroleum fractions.
Specific gravities of light paraffinic and naphthenic
hydrocarbons are plotted against the natural logarithm of
their kinematic viscosities at 100 O F in Figure 2. An
almost linear relationship exists between S and In uloO for
paraffins and naphthenes, each with the same slope. The
following equations represent the lines
for paraffins: S = 0.0332 In vloO + 0.7336 (13)
for naphthenes: S = 0.0332 In vloo

+ 0.7853

(14)

These equations can reproduce data within an average

deviation of less than 2 % . The new characterization factor
for light hydrocarbons may be defined as a function of S
and In ulW.
V G F = a bS + c In ulW
(15)
where V G F = viscosity gravity function, new characterization parameter, S == specific gravity a t 60160 O F , vloO =
kinematic viscosity at 100 OF,cSt, and a, b, c = numerical

constants. Arbitrary values of 0.74 and 0.92 have been

chosen for the average V G F of paraffins and naphthenes,
respectively. Thus by substituting eq 13 and 14 into eq
15 the constants a, b, and c can be determined and eq 15
becomes

V G F = - 1.816 + 3.4848 - 0.1156 In vloo

(16)

Equation 16 gives the value of V G F for any hydrocarbon

or fraction for which its specific gravity and kinematic
viscosity a t 100 O F are known.
By following the same procedure a correlation relating
V G F to specific gravity and kinematic viscosity at 210 O F
can be derived

V G F = - 1.948 + 3.5358 - 0.1613 In vzl0

(17)

in which vzlo is kinematic viscosity at 210 O F in centistokes.

Equations 16 and 17 which are similar to eq 3 and 4 give
almost the same value for V G F of a hydrocarbon or petroleum fraction.
Using eq 16 and 17, average values of V G F for light
paraffins, naphthenes, and aromatics are 0.74, 0.92, and

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

Figure 2. Viscosity-gravity relationship.

Table 111. Data o n t h e Composition of Viscous Petroleum Fractions"
composition

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

Table IV. Results of Prediction of t h e Composition of Light Petroleum Fractions

abs dev," mole fraction
no.
of
data source oils
Lenoirand
Hipkin
industrial
company
total

molwt
range

100-230

34

126-171

42

100-230

" Absolute deviation = Xpred

N = number of data points.

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 ;

1.12. Average values for Ri of paraffins, naphthenes, and

aromatics are 1.046, 1.04, and 1.066, respectively. Therefore, Ri and VGF for a petroleum fraction can be estimated
by
Ri = 1 . 0 4 6 +
~ ~1 . 0 4 +
~ ~1 . 0 6 6 ~ ~
(18)

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)

where M = molecular weight, T b = normal boiling point,

OR, d = density at 20 "C and 1 atm, g/cm3, and I =
characterization factor defined in eq 5 . By rearranging eq
23 and 5, the following correlations for prediction of refractive index of petroleum fractions were derived.

M S 200: I = 3.583 x 10-3Tb1.0147(M/d)-0.4787(24a)

1%

(-)+ 21
1
1-I

where n = refractive index at 20 " C , Tb = 50% boiling

point at 1 atm, O R , h4 = molecular weight, and d = liquid
density at 20 "C and 1 atm, g/cm3. Equation 24 can
predict refractive index of light ( M < 200) fractions within
an average deviation of about 0.5% while for heavy fractions the error is abfout4-5%.
For heavy fractions, a correlation similar to eq 24 can
be derived by use of data available on refractive indices
of heavy hydrocarbons in API Research Project 42 (1962).
After regression of data, the following equation was derived

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%.

Evaluation of the I?roposed Correlations

Tables I1 and I11 show experimental data on the composition of light and heavy petroleum fractions from
various sources. All physical properties necessary to use
the proposed correlations are also given.
Equations 20, 21, and 22 were used to predict the composition of the light ( M < 200) fractions listed in Table
11. A summary of results is given in Table IV, and
point-by-point evaluations are available. Average deviations of 0.03 and 0.04 mole fractions were obtained for xp
and x,, respectively. Similar results for heavy fractions
are shown in Table V using eq 10, 11,and 12 for prediction
of the composition of the fractions listed in Table 111.
Average deviations of 0.018 and 0.01 mole fractions for xp
and x,, respectively, were obtained. The results are generally better than those of existing methods such as the
n-d-M method.
Table VI shows a comparison of the use of experimental
vs. predicted compositions as input to enthalpy and viscosity prediction methods. As shown, predicted compo-

293

294

Ind. Eng. Chem. Process Des. Dev. 1980, 19, 294-300

Table VI. Comparison of t h e Use of Experimental vs.

Predicted Compositions for Enthalpy and
Viscosity Predictions

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.

API Research Project 44, Selected Values of Properties of Hydrocarbons and

h a t e a Compounds' , Taoles of Physical and Thermodynamic Properties of
Hydrocarbons. A and M Press, College Station, Texas (extant 1978).
A S M.E. Research Cornminee on Lubrication, 'Viscosity and Density of Over
40 Luoricating Fluids of Known Composition at Pressures to 150,000 psia
and Temperatures to 425 OF ', Report No. 1. 1953.
Boelhower. C.. Waterman, H. 1.. J . Inst. Pel., 40. 116 (1954).
Hili. J B.. Coats, H. B.. Ind. Eng. Chem.. 20, 641 (1928).
huang. P. K.. Ph.D Thesis, Department of Chemical Engineering, The Pennsylvanla State University, University Park, Pa., 1977.
hdang. P. K.. Daubert, T. E., Ind. Eng. Chern. Process Des. Dev , 13, 359
(1974).
Kurtz. S.S IJr.. King. R. W., Stout. W. J.. Peterkin, M. E., Anal. Chern , 30,
1225 (1958).
Kurtz. S. S , Jr., Ward, A. L.. J . Franklin Inst.. 222. 563 (1936).
K d z , S. S., Jr.. Ward. A. L., J . Franklin Inst.. 224, 583. 697 (1937).
Lenoir. ". M.. Hipkin. H. G., J . Chern. Eng. Data. 18, 195 (1973).
Private communications, Witco Chem. Co., 1973.
Private communications. Pennzoil Co., 1975.
Private communications, Indbstrial Co., 1977.
Riazi, M. R.. Ph.D. Thesis. Department of Chemical Engineering, The Pennsylvania State University, University Park, Pa.. 1979.
Van Nes, K , Van Westen, H. A.. "Aspects of the Constbtion of Mineral Oils".
Elsever PJOiiShing Co.. InC.. New Yorrc, 1951.
Waterman. H I , Boehower. C , Cornelissen, J.. Correht;on Between physical
Constants and Chemical StrLcture", Elsevier Publishing Co.. Inc.. New York,
1958.

Received f o r rerieu July 23, 19'79

. k e e p r e d December 7 , 1979

sitions do not materially affect the results.

Literature Cited
American Petroleum Institute (API) Research Project 42, "Properties of Hydrocarbons of High Molecular Weight", American Petroleum Institute (1962).

The Department of Refining of the American Petroleum Institute

provided major financial support of this research.

Kinetics of Oxydesulfurization of Upper Freeport Coal

D. Slagle, Y. T. Shah,' and J.

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

may also have to employ flue gas scrubbing in order to

meet environmental standards (Trindade et al., 1974). A
possible alternative to these processes is chemical coal
cleaning, i.e., removal of the sulfur by means of a chemical
reaction before burning the coal.
There are presently six major chemical coal cleaning
methods being developed (Oder et al., 1977). One of the
promising processes is the oxydesulfurization process
(Friedman and Warzinski, 1977; Friedman et al., 1977).
In this process, the sulfur is removed by oxidizing coal in
the presence of water. The process is operated at pressures
between 1.6 and 10 MPa and temperatures between 150
and 220 "C. Normally air is used as the gas phase.
The purpose of this paper is to report a kinetic study
for the D.O.E. oxydesulfurization process. Kinetic rate
expressions for the inorganic and organic sulfur removal
reactions and carbon oxidation reaction for Upper Freeport
coal are presented.

0 1980 American

Chemical Society