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Received for review June 2, 1983
Accepted November 28, 1983

Slmulation of Catalytic Reactions in Shale Oil Refining

Tek Sutlkno’
Midwest Research Institute, Kansas City, Missouri 6 4 110

Stanely M. Walas
Department of Chemical and Petroleum Engineering, University of Kansas, Lawrence, Kansas 66044

Process yield data from advanced catalytic reaction of Paraho shale oil have been simulated. The properties and
the required refining severity of shale 011 are different from those of petroleum crudes. The simulation was made
to evaluate if mathematical models developed for hydrotreating, hydrocracking, and fluid catalytic cracking of
petroleum-based oils can be applied for simulation of these reaction processes used for shale oils. Preliminary
results indicate that refining of shale oil by these processes can be adequately simulated by the models derived
for petroleum-based oils. However, further process data at several reaction conditions of a variety of shale oils
are needed to confirm the applicabilities of these models.

Introduction though several research investigations of shale oil refining

The use of shale oil as an alternate feedstocks for the
production of transportation fuels has been the subject of
several investigations (Frost and Cottingham, 1974; Lovell
et al., 1981; Sullivan et al., 1978). It is generally concluded
that surface-retorted shale oil such as Paraho shale oil can
be refined to various specification-grade transportation
fuels-diesel fuel, gasoline, and jet fuel. The properties
of shale oil are, however, significantly different from pe-
troleum crudes, and the refining of shale oil is more com-
plex and severe than that of petroleum. Advanced cata-
lytic reaction processes are required to convert shale oil
to transportation fuels.
Most of the published models for simulations of ad-
vanced catalytic reaction processes in oil refining are de-
veloped from and verified with experimental data on pe-
troleum-based feedstocks. These models can be used for
the development of designs, operations, and refining
strategy development. Because of the specific properties
of shale oil and the refining severity required, this paper
evaluates the applicabilities of the readily developed
models for simulation of catalytic reaction processes in
shale oil refining. This applicability evaluation is necessary
if any of the petroleum refining reaction models is to be
used for designs, yield predictions, or optimization of the
respective reaction process in shale oil refining.
Process models for catalytic reactions in oil refining are
generally complex and involve several parameters. The
values of these parameters must be known if the model
is used for simulation or yield prediction purposes. Al-
0196-4305/84/1123-0827$01.50/0
have been conducted, these investigations are feasibility
studies in nature, and experimental yield data from cat-
alytic reaction processes of shale oil refining are very lim-
ited. A literature survey indicated that the pilot plant
refining data reported by Sullivan et al. (1978) are the most
comprehensive at present; three pilot refining schemes
shown in Figures 1to 3 were used in this pilot plant study
of shale oil refining. In light of their comprehensiveness,
those pilot plant data are used as the bases for present
simulation study.
As shown in Figures 1to 3, the major catalytic reaction
processes in shale oil refining are hydrotreating, hydro-
cracking, fluid catalytic cracking, and reforming. Only
hydrotreating, hydrocracking, and fluid catalytic cracking
data are simulated in this study; the reforming process is
not included because shale oil-derived naphtha is report-
edly identical with petroleum-based naphtha (Lovell et al.,
1981; Sullivan et al., 1978). Hydrotreating, hydrocracking,
and fluid catalytic cracking processes in shale oil refining
perform different functions, and simulation of each of these
processes requires specific mathematical framework. The
mathematical models for simulations of these processes
have been selected from the literature; these models and
the results of simulations are described next in the order
of hydrotreating, hydrocracking, and fluid catalytic
cracking.
A. Hydrotreating
In refining shale oil to transportation fuels, the main
purpose of hydrotreating is removal of nitrogen; therefore,
0 1984 American Chemical Society
828 Ind. Eng. Chem. Process Des. Dev., Vol. 23, No. 4, 1984

.C" Table I. Hydrotreating of Whole Shale Oil at Several

Product Nitrogen Levels
inlet nitrogen concentration 2.18% (wt)
Vrhoie catalyst: ICR 106, on stream time 1300-1800 h
reactor temperature, average 767 OF
total pressure 2200 psig
hydrogen partial pressure 1850 psia
total gas in 7000 SCF/bbl
recycle gas 5000 SCF/bbl
Outlet Nitrogen Concentrations at Various LHSV
outlet nitrogen concentration, ppm 640 30 1.3
LHSV, l / h 0.6 0.3 0.2
1 Battamr y Jet Fuei time on stream, h 24 48 48
Recycle

Gilbert, 19731, effective catalyst wetting model (Mears,

1 , C i i s butanes and iighter; Used for H2 plant feed, gasoline
blending, refinery f u e l . ond liquified petroleum gas (LPG).
2 . Some naphtha from hydrotreating units Qiso used for H2 plant feed.
3. Foul gor and water treoted t> recover NH3 ond ruifur.
Figure 1. Shale oil refining-hydrotreating
(Sullivan et al., 1978).
Whole
Dewatered
1 . C i i s butanes and lighter; Used for H2 piant f e e d , gosoline
b l e n d i n g , refinery fuel, and i i q u i f i e d petroleum gas ( L P G ) .
2 . Foul gos and water treoted to recover NH3 and sulfur.
Figure 2. Shale oil refining-hydrotreating
cracking (Sullivan et al., 1978).
Whole
Dewotered ;'4
Hydro-
treating
4 scale-up purposes
Refinery Fuel
1 . Ca i s butanes ond iighter; Used for hydrogen plant feed, gasoline
2.
b l e n d i n g , refinery f u e l , and l i q u i f i e d petroleum go' (LPG).
Foul go' and woter treated to recovery NH3 ond sulfur.
Figure 3. Shale oil refining-delayed coking and hydrotreating
(Sullivan et al., 1978).
a process model capable of predicting the reduction level
of nitrogen content is essential. In the pilot study of
Sullivan et al. (1978))surface-retorted Paraho shale oil was
hydrotreated in trickle bed reactors in which the liquid oil
and the gaseous hydrogen flow downward through a fiied
catalyst bed. For trickle-bed reactors used in the hydro-
processing of petroleum crudes, several process models
developed for performance prediction have been published.
Comprehensive reviews of these models are presented by
Satterfield (1975), Gianetto et al. (1978))and Shah (1979).
Included in this review are the hold-up model (Henry and
19741, and others. Recently, a phenomenological model
developed for trickle-bed reactors has been reported by
Crine et al. (1980). Because of the complexity of the
and hydrocracking trickle-bed reactor, some of the models are sophisticated
and involve several multiphase transport phenomena and
reaction mechanisms. Verifications of these models are
difficult and require clear identifications of all parameters
affecting the performance of the reactor. However, con-
fusion among authors still exists with respect to the the-
oretical interpretation of the experimental data [e.g.,
Marangozis (1980) and Shah (1980)l. In the present sim-
ulation of a commercial hydroprocessing trickle-bed re-
actor, simple correlating models were used rather than
sophisticated ones because experimental data obtained
from real reactors often are not accurate enough to dis-
criminate between the prediction of simple and more so-
phisticated models.
Among the models which have been evaluated with re-
spect to the predictive accuracy, the effective catalyst
wetting model developed by Mears (1974) has been re-
ported to correlate the experimental data well [Montagna
et al. (1977) and Gianetto (1978)l. It has been adopted
here for the simulation of shale oil hydrotreating. This
and fluid catalytic model is a semiempirical one, but no reliable theoretical
model is available. The model can be briefly described as
follows
dC - --k i W W
C' _ (1)
qGq dx LHSV
Goroi ine
where C = concentration, mol/cm3, x = dimensionless
distance, z / L , ki = first-order reaction rate constant, cm3
of liquid/(cm3 of reactor volume), h, 7 = catalyst effec-
tiveness, Aeff = A,/A,, dimensionless, where A , = wetted
area of catalyst and A, = total area of catalyst, and LHSV
= liquid hourly space velocity, cm3/h cm3 of catalyst. For
Aeff = 1 - exp(-1.36GaL0~05WeL0~2(~c/6L)0~75)
(2)
where GaL = d:gpL/pL2, dimensionless Galileo number,
d, = diameter of catalyst particle, cm, g = acceleration by
gravity, cm/s2, p L = liquid density, g/cm3, WL = liquid
viscosity, g/(cm)(s), WeL = GL2dp/BLpL, dimensionless,
Weber number, G L = liquid mass velocity, g/(cm2)(h),BL
= liquid surface tension, g/s2, and 6c = critical value of
surface tension for a given cracking, g/s2.
Combining eq 1 and 2 and integrating, one obtains
1 n Ci
-z- kill
[l - ~ X ~ ( - K L ~ ~ ~ ( L H S (3)
V)~~~J]
Co LHSV
where K = f(pL, BL, 6c, pL, d,) and L = reactor length, cm.
As shown in eq 3, three constants, (ki, 9,and K) must
be evaluated before the level of conversion can be com-
puted. Two sets of conversion data at different liquid
hourly space velocities are enough to evaluate these con-

0 Hydrotreating of Shale Oil
at 767' F
0 Hydrotreating of Petroleum-
Bared Charge Stock10/
10 100 i ,000
Calculated Unconverted N i t r o g e n , ppm
Figure 4. Parity plot of model predictions vs. experimentalresults.
stants since ki and 7 are lumped together.
In the hydrotreating of crude shale oil, Sullivan et al.
(1978) reported the nitrogen content reduction data at a
fixed reaction temperature for three values of LHSV.
These data are shown in Table I.
The two lumped constantrs, KL and kiq, were evaluated
analytically from the fmt two conversion data (0.6 and 0.3
LHSVs). The values of kill and KL0.4are solved to be 2.14
and 4.2, respectively, and eq 3 becomes
2.14
{I- e~p[-4.2(LHSV)~.~l}(4)
Note that the parameter K is lumped together with
since the length of the pilot reactor was proprietary and
K could not be evaluated separately. Equation 4 was used
to predict the nitrogen removal level at 0.2 LHSV; the
result is shown in Figure 4. It appears that the agreement
between the experimental and predicted values is fairly
good. Comparing the experimental and the predicted
values of nitrogen removal in hydrotreating of petroleum-
based charge stocks (Figure 4), it is clear that an effective
catalyst wetting model can simulate hydrotreating of shale
oil as well as it simulates hydrotreating of petroleum.
However, more experimental data with known values of
relevant parameters must be generated to evaluate the
individual values of the constants.
B. Hydrocracking
As shown in Figure 1, the heavy fraction (650 to 850 O F )
of the hydrotreated shale oil was refined further in an
extinction recycle hydrocracking unit. Hydrocracking
convertes heavy hydrocarbons into high grade jet fuels or
gasoline, reformer charge stock, and light gases. Pilot shale
oil refining studies of Sullivan et al. (1978) indicated that
hydrocracking is the only process scheme capable of ef-
ficiently maximizing jet fuel production; in the process of
Figure 1 the main purpose of the extinction recycle hy-
drocracker is to produce jet fuels from the heavy fraction
of the hydrotreated shale oil.
Hydrocracking of shale oil is conducted in a trickle-bed
reactor; thus, hydrocracking and hydrotreating processes
are hydrodynamically similar. However, the primary
function of hydrotreating is to remove impurities in the
feedstocks while that of hydrocracking is mainly to upgrade
the feedstocks by lowering the boiling range. The per-
formance of a hydrocracker is generally based on the true
boiling point (TBP) of the product; therefore, a mathe-
Ind. Eng. Chem. Process Des. Dev., Vol. 23, No. 4, 1984 829
matical model capable of predicting the boiling range of
the product is essential.
Several publications on the modeling of hydrocracking
have appeared. A comprehensive review has been made
by Choudhary and Saraf (1975). Qader and Hill (1969)
showed experimentally that hydrocracking of gas oil fol-
lows fit-order kinetics. Qader et d. (1970) have reported
first-order rate constants for light and heavy petroleum
oils in the hydrocracking process. Although it is reasonable
to expect that the hydrocracking of the 650 to 850 O F
fraction of the hydrotreated shale oil will follow first-order
kinetics, verification is desirable and could be checked with
adequate hydrocracking test data of shale oil, but such
experimental data are not available.
Zhorov et al. (1971) developed several chemical process
schemes to describe the hydrocracking conversion of pe-
troleum feedstock into gas, naphtha, diesel fuels, and
10,000 residue. These process schemes contain stoichiometric
coefficients describing the distribution of hydrocracking
products. At a given temperature, the stoichiometric
coefficients are relatively constant over a range of residence
times. However, for more severe hydrocracking, these
coefficients vary significantly and have not been properly
correlated.
Stangeland (1974) has developed a kinetic model capable
of predicting hydrocracker yields satisfactorily and is ac-
tually being used to simulate and optimize commercial
hydrocracker yields. This model is used here for simula-
tion of shale oil hydrocracking. Stangeland (1974) assumed
that the feed and product streams contain a continuum
of compounds that can be characterized solely by boiling
point. These compounds are then segregated into fixed
boiling ranges of 50 O F each. Each is characterized solely
by the true boiling point (TBP) of the end of the range.
The change in the amount of the ith compound is the
result of its cracking plus the contribution from the
cracking of all heavier compounds.
- - -k,f,(t) + i-1
-dfi(t) CPijkjfj(t) (5)
dt j=l
where f i = ith component with f i as the heaviest compo-
nent, ki = first-order rate constant, and Pij = fraction of
light component f i formed by cracking a heavier component
fr
Rewrite eq 5 in a single matrix differential equation
$0) = -(I - P)KF(t) (6)
where F ( t ) = vector containing the weight fractions of all
components I = identity matrix, P = lower triangular
product distribution matrix, and K = diagonal matrix
having the ki)s on the diagonal. If all cracking rate con-
stants are different, the solution to eq 6 is
F(t) = DE(t) (7)
or in the matrix form
The procedure to compute Dij, Pij, and ki is rather
lengthy and complicated, but it is described in detail by
Stangeland (1974). Primarily, the model has three ad-
justable coefficients: A, B, and C. Coefficient A relates
to reaction rate constants kj of each individual component;
830 Ind. Eng. Chem. Process Des. Dev., Vol. 23, No. 4, 1984

Table 11. Pilot Plant Hydrocracking of 650-850 OF Fraction 0.0, to 2.0 for C (Stangeland, 1974). The values of the
of Hydrotreated Shale Oil parameters used here for hydrocracking of hydrotreated
operating conditions shale oil are well within the ranges of those used suc-
catalyst ICR 106 cessfully to represent the hydrocracking yields of petro-
reactor temperature, average 785 O F leum-based feedstocks.
total pressure 2350 psig C. Fluid Catalytic Cracking
hydrogen mean pressure 2129 psia
total gas in 8700 SCF/bbl Catalytic cracking is a widely used process for converting
recycle gas, SCF/bbl 7300 SCF/bbl heavy oils into more valuable gasoline and lighter products.
liquid hourly space velocity 1.0/h Its role in the oil refining industry is described in a recent
per pass conversion 0.5351 review by Venuto and Habib (1979). In the pilot plant
C,+ products" accum wt, % study conducted by Sullivan et al. (1978), and 650 O F +
C4 group 2.26 fraction of the hydrotreated shale oil was catalytically
C5 - 175 O F 7.70 cracked to produce gasoline.
175 to 315 O F 19.90 Several process models for prediction of gasoline yield
315 to 560 O F 53.50 have appeared, for example by Reif et al. (1961), Schneider
a All temperatures shown are true boiling point temperature. et al. (1969), and others. A widely used model which is
capable of predicting the conversion level and the gasoline
0 Doto from Shale Gor Oil
A Data f r o m Petroleum Gar O i l %
yield was initially developed by Weekman (1968, 1969).
-Model Predictions This model was based on a three-lump cracking kinetic
scheme which includes a catalyst decay function. The
900
model has been shown to predict adequately the perform-
ances of various types of cracking reactors including fixed
bed, moving bed, and fluidized bed types. It has been used
as a mathematical framework to analyze many aspects of
the catalytic cracking process, for example, the effect of
molecular composition of feedstocks on cracking kinetics
(Nace et al., 1971), the effect of nitrogen poisoning and
recycle (Voltz et al., 1972),and the selectivity behavior of
catalytic cracking in various types of reactors (Weekman
and Nace, 1970). The model was also utilized by Paraskos
et al. (1976) and Shah et al. (1977) to describe the per-
formance of a transfer line catalytic cracking reactor with
0 IC 20 30 40 50 60 70 80 90 100
reasonable success. Elnashaie and Hennawi (1979) used
Y e d 3f Cq- V i r ic the same concepts to develop an integrated mathematical
Figure 5. Comparison of measured and predicted yields for ex-
model for parametric analysis of a steady state fluid cat-
tinction recycle hydrocracking of shale and petroleum gas oils. alytic cracking unit. Weekman (1979) has reported the use
of this model in the optimization ofcommercial catalytic
coefficient B relates to the product distribution function crackers.
( P J ;and coefficient C affects the product distribution and The three-lump model of Weekman has a key weakness,
determines the yield of butane. namely, that each time the charge stock is changed, a new
A computer program has been developed here to use set of rate constants and the catalyst decay function must
Stangeland's model for data simulation of shale oil hy- be determined from laboratory experimental data. This
drocracking. However, only one pilot run was made of is due to the fact that the model does not take detailed
hydrocracking of 650 to 850 O F fraction of hydrotreated account of the molecular compositions of the charge stocks.
shale oil, for which the operating conditions and product Since variation of compositions of charge stock is common
yields are given in Table 11. The data in this table were in refineries, the experimental efforts required to deter-
generated from a pilot hydrocracker operation in an ex- mine the constants in the model for each charge stock are
tinction recycle mode. In this mode, the fresh feed and quite expensive. In an effort to correct this drawback,
the recycle constitute the total feed to the reactor. Jacob et al. (1976) developed a ten-lump model which
The yield data in Table I1 were applied with the de- includes the cracking characteristic of the charge stocks.
veloped computer program to obtain the results shown in In the present simulation of shale oil catalytic cracking,
Figure 5. The TBP values were calculated from the the three-lump model is adopted since the avilable pilot
computer program with a specific set of values for A , B , plant data of shale oil catalytic cracking are not enough
and C. As shown in Figure 5, this specific set gives rea- to allow evaluation of the constants of the ten-lump model.
sonable agreement between the calculated and observed Details of the three-lump model are as follows. Week-
TBP values and was the best among several other sets man (1968) represented the cracking process by the simple
which had been tried. While the values of A , B , and C reactions
could have been determined by a nonlinear regression or
other optimization methods to best fit the experimental
data, these methods were not used because experimental
A, -
ko
a1A2+ azA3 (94
k2
data are too limited in number for statistically meaningful A2 ----* AS (9b)
evaluation of A , B, and C. As shown in Figure 5, the
agreements between the experimental and the predicted Al represents the gas oil charged, A2 represents the C5-410
values are fairly good for both shale and petroleum gas oils. O F gasoline product, and A, the butanes, dry gases, and
The values of the three parameters of the model are A = coke. For an isothermal, vapor phase, plug flow reactor
0.9, B = 0.75, and C = 0.01. For hydrocracking of feeds- with negligible intraparticle diffusion, the cracking reaction
tocks of petroleum source, the ranges of these parameters can be described in terms of two coupled continuity
are known to be -1.0 to 1.0 for A , -2.0 to 1.0 for B, and equations given below.
 lnd. Eng. Chem. Process Des. Dev., Vol. 23, No. 4, 1984 831

Table 111. Fluid Catalytic Cracking of 650 OF+ Fraction of

Hvdrotreated Shale Oil
operating conditionsa
run no. 1 2 3
reactor temperature, "F 930 930 975
weight hourly space velocity, h 7.85 7.86 7.71
y1 and y2 represent the instantaneous weight fractions of catalyst oil weight ratio 6.71 4.39 7.10
gas oil and gasoline, respectively. VI is the vapor velocity severity 0.855 0.558 0.921
in ft/s. The rate terms, R1 and R2, can be expressed as conversion, w t % 69.25 61.25 76.97
Product Yields, Weight Fraction
Ribi,t) = & ~ ( t ) ~ i ~ (12) coke, butane, and lighter 0.2038 0.1699 0.2717
gasoline (C5 - 430) 0.4887 0.4426 0.4981
R2b2,t) = k24WY2 (13) gas oil remaining 0.3075 0.3875 0.2303
4(t) is the catalyst decay function. Equations 12 and 13 a Catalyst Davison CBZ-1.
can be normalized into dimensionless equations.
At the exit of a fluid bed reactor (x = l), with y1 Ix=o =
1, eq 21 can be solved as

By dividing eq 17 by eq 18, one gets

where

dY1 KO

p v = the vapor density, lb/ft3 at reactor conditions, VI =

the reactor volume, ft3, Fo = the oil charge rate, lb/s, t,
= the vapor phase residence time, s, t, = the catalyst
residence time (s) under oil exposure condition, 0 = t 'It,
where t 'is the clock time, s, x = z / L , where z is the axial
distance (ft) in the reactor and L is the total reador length,
ft, p o = initial charge density at reactor conditions, lb/ft3
(vapor density if no reaction), ho= density of liquid charge
at room temperature, lb/ft3, s = Fo/pLoVr,and kl = alko.
p,,'s in eq 14 and 15 strictly should have been p:s; how-
ever, the model assumes the vapor density variation due
to cracking reaction is absorbed in the second-order
cracking reaction approximation. For steady-state oper-
ation the time derivatives of eq 14 and 15 are zero.
Moreover, 4 can be adequately expressed as
4(t) =
CYis the decay velocity constant. Equations 14 and 15 can
be written in eq 17 and 18 by transforming du = @/s dx
dyl/du = -K0I2
dy2/du = KlY12 - K2Y2
where KO= P & O / ~ L ~K1
, = P O Q . I ~ O / P L ' ,K2 = P O ~ ~ P L ~
The stretched time u is a function of the nature of the
catalyst decay function and the catalyst residence time.
With the assumptions of perfectly mixed catalyst flow and
plug gas flow in the fluidized bed reactor, the average
velocity constant (k)can be defined as
k = k o ~0 m I ( 0 ) ~ d
(BO )
The internal age distribution I(0) for a perfectly mixed
vessel is e"; 4(0) in eq 19 is e-x0with X = at,. k can be
solved as
With this expression for the average reaction velocity
constant, eq 14 can be solved as
With the boundary condition of no initial gasoline (yl
= 1, y2 = 0), the solution of eq 23 is
where
(16)
A combination of eq 22,24, and 25 can be used to predict
yield fractions from a fluid bed catalytic cracker. However,
the constants in eq 22 and 24 must be evaluated first if
(17) they are used for yield prediction. Two conversion data
points are necessary for evaluation of all constants in the
(18) models.
A total of five runs was reported by Sullivan et al. (1978).
. Three of these runs were conducted with a charge stock
of 1300 ppm nitrogen content. The other two runs were
made with two charge stocks with nitrogen contents of 385
ppm and 870 ppm. These last two runs were made at the
same conversion level and therefore could not be used for
the evaluation of constants in the model. Moreover, con-
version level in catalytic cracking process is dependent
(19) upon the inlet nitrogen content, and a different level of
nitrogen content may require a different set of values for
the kinetic constants.
The present data simulation of shale oil catalytic
cracking are based on the three runs with 1300 ppm ni-
trogen charge. Table I11 displays the operating data and
the product yield fractions.
The data from run no. 1and 2 were used to evaluate the
constants of the three-lump model. Because some of the
constants in the model cannot be solved explicitly and the
integration must be made numerically, a computer pro-
gram using a successive substitution method was developed
to evaluate the constants. The values of the various con-
832 Ind. Eng. Chem. Process Des. Dev., Vol. 23, No. 4, 1984
-
I , 2 . 3 Run Numberr in Catalytic
Crocking of Shale Bared Go5 O i l
0 Gar Oil
0.81 A Gasoline
Gasoline Y i e l d Doto from
E 0.71
0
Petroleum Eared Gar O i i w
u.
5 0.61
i
$$
2.00
/ d = diameter of catalyst particle, cm
f 0.3
i 0.2
00 0.1 0.2 0.3 0.4 0 5 0.6 0.7
Predicted Product Weight Fraction
Figure 6. Parity plot of model predictions vs. experimental resulta.
stants evaluated are shown in Figure 6. With the con-
stants evaluated from run no. 1and 2, the model was used
to predict the yield fractions from run no. 3. The exper-
imental and the calculated values are shown in Figure 6.
It can be seen that the calculated conversion is lower than
the experimental value. This is expected because the re-
actor temperature in run no. 3 is 45 O F higher than the
reactor temperatures of the first two runs from which the
constants were evaluated. The cracking reaction is en-
dothermic and high temperatures should increase the rate
constants. Compared to the calculated and experimental
value agreements obtained from the three-lump model for
petroleum-based charge stocks (Figure 6 ) )the agreement
for shale catalytic cracking seems reasonable. However,
more experimental data with better accuracy and con-
sistency are definitely required to confirm the applicability
of the three-lump model or even the ten-lump model for
yield predition of shale oil catalytic cracking.
D. Conclusion
While the selected models seem to simulate well the
hydrotreating, hydrocracking, and fluid catalytic cracking
process data of Paraho shale oil, the present applicability
assessment of these models for shale oil refining must be
at best regarded as preliminary in nature. Constants or
coefficients in the selected models have been evaluated
from the limited refining data of Paraho shale oil. New
values of these constants or coefficients may be necessary
to fit the refining data of other shale oils with chemical
composition significantly different from Paraho shale oil.
Moreover, the present simulation study has been limited
to a single temperature of each individual reaction process.
Thus, for simulation of similar reaction processes in re-
fining of shale o& from other sources or at other operating
conditions, further simulation studies with more well-de-
signed experimental data are needed to confirm the ap-
plicabilities of the selected models. Nevertheless, the
present work indicates that pilot data on hydrotreating,
hydrocracking, and fluid catalytic cracking of Paraho shale
oil can be closely simulated by available models.
Nomenclature
A = a parameter in Stangeland hydrocracking model; di-
mension1ess
A, = gas oil weight fraction
A2 = gasoline weight fraction
A3 = butane, coke and gases weight fraction
a1,.a2= coefficients of catalytic cracking reaction aa defined
In eq 9, lb of product/lb of feed
A& = ratio of wetted area to the actual surface area of catalyst,
dimensionless
dimensionless
E' = ( p , Vr)/(Fotc),
B = a parameter in Stangeland's hydrocracking model, di-
mensionless
C = a parameter in Stangeland's hydrocracking model, di-
mensionless, or concentration, mol/cm3
D = production distribution matrix defined in eq 7
D,, = coefficients of matrix D
8 = oil charge rate, lb/h
F ( t ) = vector containing the weight fractions of all compo-
nents, dimensionless
f , = weight fraction of ith component in hydrocracking feed
= 205.4/hi or hydrocrackage, dimensionless
= 77, l/hr
= 35.9/hr
Ga = dimensionless Galileo number
= 0,23/hr GL = liquid mass velocity, g/cm2 h
g = acceleration by gravity, cm/s2
0 8 0 9 1 00 Z = identity matrix
Z(8) = internal age distribution function of catalyst, dimen-
sionless
K = diagonal matrix having the ki's on the diagonal, or a
constant defined in eq 3
KO = (poko)/pLo,gas oil rate constant, l / h
K l = (Poalko)/PL
k, = mean average reaction velocity constant of ith reaction
ki = reaction rate constant of ith reaction in both hydro-
treating and hydrocracking models; k, is the reaction ve-
locity constant of ith reaction at 8 = 0 in the model for fluid
catalytic cracking
L = reactor length, cm
LHSV = liquid hourly space velocity, l / h
P,,= a distribution parameter of product from hydrocracking
RIP2= kinetic rate functions as defined in eq 14 and 15
r1 = Kl/KO
r2 = &/KO
s = F o / p L o V,, liquid hourly space velocity based on liquid
charge density and reactor volume, l / h
t ' = clock time, s
t, = catalyst residence time, s
t, = vapor phase residence time, s
U, = vapor velocity, ft/s
V, = reactor volume, ft3
W e L = dimensionless Weber number
x = dimensionless distance
y 1 = instantaneous gas oil weight fraction
y 2 = instantaneous gasoline weight fraction
y 3 = instantaneous weight fraction of light gases and coke
z = axial distance in the reactor, ft
Greek Letters
a = decay velocity constant, 1 h
6 = liquid surface tension, g/s I
6, = critical value of surface tension for a given packing, g/s2
e = instantaneous weight fraction converted
8 = t'/tc
X = extent of catalyst decay group, at,
9 = catalyst effectiveness, dimensionless
p L = liquid density, g/cm3
pLo =. liquid density at room temperature, lb/ft3
p o = initial charge density at reactor conditions, lb/ft3
p , = vapor density, lb/ft3
pL = liquid viscosity, g/cm s
$ ( t ) = catalyst decay function, dimensionless
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Received for review June 13, 1983
Accepted January 16, 1984

Thermophysical Properties of Complex Systems: Applications of

Multiproperty Analysis

Michael R. Brul6”

Kerr-McGee Corporation, Oklahoma City, Oklahoma 73 125

Kenneth E. Starllng

University of Oklahoma, Norman, Oklahoma 730 79

The “therm-trans” method is presented for predicting characterization parameters (e.g., critical properties) required
in multiparameter corresponding-states correlations. Multiproperty analysis of thermodynamic and transport data
is used to extract the characterization parameters through simultaneous calculation of the property data by an
equation of state and a viscosity correlation. The property data needed are similar to the inspection data obtained
for pseudocomponent fractions resolved from standard TBPdistillation analyses. This new approach for determining
correlation parameters altogether circumvents the need for critical properties per se. Application to complex
petroleum and coal-liquid fractions is demonstrated.

Prediction of Thermophysical Properties the presence of heteroatomic and attached functional

A modified Benedict-Webb-Rubin (BWR) equation of
state has been applied to predict the thermodynamic
properties of the simpler hydrocarbons found in petroleum
and coal-derived fluids (Brul6 et al., 1979, 1982). This
three-parameter corresponding-states correlation has been
used in conjunction with a conformal-solution model to
describe the vapor/liquid-equilibrium (VLE) bahavior of
model multicomponent mixtures representative of the
actual systems found in fossil-fuels processing (Watanasiri
et al., 1982; Brul6 et al., 1983; Brul6 and Corbett, 1984).
Equation-of-state characterization parameters and ideal-
gas thermodynamic properties have been estimated, by
using empirical correlations, as functions of the average
measurable properties of fractions such as normal boiling
point and specific gravity (Brul6 et al., 1982).
Many problems remain in predicting complex-system
thermophysical properties. Correlations must be capable
of predicting properties of high-molecular-weight, multi-
functional organic compounds at mild-to-severe operating
temperatures and pressures. Multipolar and associating
effects exhibited by some coal fluids are attributable to
0196-430518411123-0833$0 1.5010
groups such as -N-, -NH,and -OH. Such intermolecular
behavior cannot be described accurately by conventional
three-parameter corresponding-states correlations.
Characterization of Complex Fluids
The problem of characterization further compounds the
problem of correlation. A standard characterization pro-
cedure must be available for resolving a complex fossil
fluid, with hundreds of diverse distillable and nondistill-
able organic compounds, into a pseudocomponent mixture
with 20 or so fractions representing the overall properties
of the parent full-range fluid (Brul6 et al., 1981). Once a
full-range fossil fluid is resolved into effective pseudo-
component fractions, characterization parameters that
enable properties correlations to predict accurate ther-
mophysical properties must be determined for each of the
fractions.
As complex fluids increase in molecular weight, the
determination of characterization parameters at the normal
boiling point becomes less feasible. This presents an im-
passe, especially for many of the pure model compounds
used for correlation development, since only low-temper-
0 1984 American Chemical Society