Znd. Eng. Chem. Res.

1995,34, 101-117 101

Polynuclear Aromatic Hydrocarbons Hydrogenation. 1.

Experimental Reaction Pathways and Kinetics
Styliani C. Korret and Michael T. Klein
Department of Chemical Engineering, University of Delaware, Newark, Delaware 19716

Richard J. Quann
Mobil Research and Development Corporation, Paulsboro Research Laboratory, Paulsboro, New Jersey 08011

The relationship between molecular structure and hydrogenation reactivity in heavy oil
hydroprocessing was sought via the elucidation of the controlling reaction pathways and kinetics
of one-, two-, three-, and four-fused ring compounds. Hydrogenation reactions of o-xylene,
tetralin, naphthalene, phenanthrene, anthracene, pyrene, and chrysene and their multicompo-
nent mixtures were studied in cyclohexane solvent using a presulfided CoMo/AlzOs catalyst in
an l-L batch autoclave a t PH,= 68.1 atm and T = 350 C.Quantitative network analysis allowed
estimation of 45 hydrogenation rate parameters and a n equal number of equilibrium ratios for
36 aromatic and hydroaromatic compounds. These values were then used in the evaluation of
five adsorption parameters for aromatic ring number-based lumps from the multicomponent
mixture experiments. Three classes of hydrogenation were discerned, based on the magnitude
of numerator rate parameters. The adsorption parameters clearly increased with increasing
aromatic ring number.

Introduction 1972; Qader, 1973; Qader and McOmber, 1975; Salim

The increased attention paid to catalytic hydropro-
cessing in recent years is due in part to stricter
environmental legislation and the public demand for
cleaner fuels. Hydroprocessing technology is unique in
that it can handle the sulfur and nitrogen heteroatoms
in heavy feeds while increasing the hydrogen to carbon
ratio and thus the fuel value of the oil. Hydroprocessing
chemistry involves bifunctional catalysts, where a metal
function promotes hydrogenation and an acidic function
promotes isomerization, ring opening, and dealkylation.
The hydrogenation function is important from the point
of view of product hydrogen to carbon ratio and in the
establishment of the balance of olefin (aromatic) and
alkane (naphthenic) characters of the molecule.
Heavy oils can contain an appreciable amount of
polynuclear aromatic hydrocarbons (PNAs). This has
motivated keen interest in the discernment of hydro-
genation pathways, kinetics, and mechanisms through
the use of model or pure component experiments. quently unclear. For example, there appears to be
Moreover, since hydrogenations are exothermic, higher
temperatures applied to enhance acid center transfor-
mations, for example, benefit dehydrogenations more
than hydrogenations. It is therefore of interest to
examine not only rate but also saturation equilibrium
issues in heavy oil catalytic hydroprocessing.
The field has been recently reviewed (Moreau and
Geneste, 1990; Girgis and Gates, 1991). A large body
of information for single-ring aromatics hydrogenation
exists (Aubert et al., 1988; Moreau et al., 1990). Naph-
thalene (Qader and Hill, 1972; Qader, 1973; Salim and
Bell, 1982; Zeuthen et al., 1987), phenanthrene (Qader
et al., 1973; Qader and McOmber, 1975; Wu and
Haynes, 1975; Huang et al., 1977; Shabtai et al., 1978;
Haynes et al., 1983; Lemberton and Guisnet, 1984;
Salim and Bell, 19841, and anthracene (Qader and Hill,
* Author to whom correspondence should be addressed
(klein@he.udel.edu).
+ Present address: E x o n Research and Engineering Com-
pany, P.O.Box 101,Florham Park, NJ 07932.
0888-5885/95/2634-0101$09.00/0 0 1995 American Chemical Society
and Bell, 1984) hydrogenation have been examined in
considerable detail as well. Pyrene hydrogenation has
been analyzed in the context of its hydrogen-donating
ability for coal liquefaction (Qader and Hill, 1972;
Shabtai et al., 1978; Haynes et al., 1983; Stephens and
Chapman, 1983; Johnston, 1984; Stephens and Kotten-
stette, 1985). Polynuclear aromatic hydrocarbons con-
taining five-membered rings (fluoranthene, fluorene)
were examined more recently under hydrocracking
conditions by Lapinas and co-workers (Lapinas et al.,
1987; Lapinas, 1989). Finally, the equilibrium-related
thermochemistry of these molecules has also been
examined (Frye, 1962; Frye and Weitcamp, 1969; Shaw
et al., 1977; Stein et al., 1977).
In spite of this impressive literature base, the avail-
able data are often fragmented and catalyst dependent.
Few generalizations with respect to reactivity can be
made, since the impact of different conditions is fre-
agreement that hydrogenation reactivity increases with
the number of aromatic rings (Girgis and Gates, 1991;
Neurock and Klein, 1993), but the effect of alkyl
substituents and/or naphthenic rings is not clear. Op-
posing suggestions have been offered (Shabtai et al.,
1978; Moreau and Geneste, 1990). The effect of com-
petitive adsorption and subsequent inhibition (Bhinde,
1979; LaVopa and Satterfield, 1988) has not been
pursued at length. There is often controversy sur-
rounding the pathways of even the most extensively
studied molecules, such as the direct conversion of di-
to tetrahydrophenanthrene. Finally, the results re-
ported often do not contain detailed quantitative kinet-
ics.
Thus, the field is far from settled in terms of reactivity
information. Quantitative networks are needed under
consistent reaction conditions for a wide array of
aromatics and hydroaromatics. This motivated the
current study of hydrogenation of compounds bearing
from one to four aromatic rings, such as o-xylene,
tetralin, naphthalene, phenanthrene, anthracene, pyrene,
102 Ind. Eng. Chem. Res., Vol. 34, No. 1, 1995
and chrysene. Hydrogenation yields the respective
hydroaromatics, and carefhl product identification has
enabled estimation of their rate and equilibrium pa-
rameters from experiments with the aromatics as
reactants. Finally, multicomponent mixture experi-
ments enabled the evaluation of adsorption constants
for aromatic ring number-based lumps.
Experimental Procedure
Materials and Equipment. Hydrogenation experi-
ments were performed in a l-Lbatch autoclave, equipped
with a spinning catalyst basket, reactant loader for good
zero time determination, on-line data acquisition, and
continuous sampling capabilities. A detailed description
is available elsewhere (Landau, 1991). Reactions took
place in the presence of 420 g of cyclohexane as a solvent
and 68.1 atm of Hz at 350 "C. The total pressure,
including cyclohexane vapor pressure at 350 "C, was
191.6 atm. Hydrogen back-pressure was kept constant
throughout the reaction. The selected conditions were
intended to emphasize hydrogenation rate measure-
ments. Thus, sampling concentrated on the early
hydrogenation stages. Nevertheless, long-time experi-
ments were also scheduled to provide hydrogenation
equilibrium information.
The reacting mixture was in a one-phase supercritical
state in all cases, as verified both by calculations
employing the Virial equation of state (Reid et al., 1987)
and also from the actual experimental vapor pressure
data. The excellent material balance closures further
attest to the absence of crystallization. Cyclohexane
was subject to limited isomerization (x .e 2 x to
methylcyclopentane during heatup, which continued
during the typical reaction time of 3 h without any
apparent effect of the presence of the aromatic reactant.
An average additional conversion of x = 8 x was
observed over the course of the reaction.
The catalyst was 10 g of CoMo/AlzOs (1.7% Co, 7.0%
Mo) in particles of 0.3 cm and was presulfided in the
autoclave for 135 min at 400 "C in a stream of 10%HzS
in Hz. CSz (1mL) was added with each experiment to
keep the catalyst in a sulfided state. The catalyst was
equilibrated for 10 h at 350 "C and 68.1 atm of Hz
during three naphthalene hydrogenation experiments
in cyclohexane (Landau, 1991). All experiments were
performed using the same catalyst charge, and the
steady-state catalytic activity was periodically verified
by naphthalene hydrogenation kinetics (Korre, 1994).
Routine sample analysis was performed immediately
after sampling on a Hewlett-Packard 5880A flame
ionization gas chromatograph employing a J&W Scien-
tific DB-5 fused silica capillary column. A Hewlett-
Packard 5970 mass selective detector connected t o the
outlet stream of a Hewlett-Packard 5890 gas chromato-
graph was also used for product identification. Yields
less than 0.1% could be safely detected at all cases.
Response factors were established for the commercially
available reactants and several of the products. For the
bulk of the hydroaromatics, response factors were set
equal to that of the aromatic with the same number of
rings.
Parameter Estimation. Nonlinear parameter es-
timation was performed using a Simplex optimization
algorithm (Press et al., 1986) and the LINPAC DASSL
predictor/corrector method ODE solver. The objective
function F was the sum of the squares of the differences
between experimental and calculated yields:
nmes
i=l
The Langmuir-Hinshelwood-Hougen-Watson
(LHHW)kinetics formalism was used to account for the
competitive adsorption of all aromatic hydrocarbons
(Froment and Bischoff, 1990). The rate law reflected
the model of a reversible bimolecular surface reaction
as the rate-determining step (Qader, 1973; Landau,
1991). Nevertheless, since there was no statistical
difference between models for a unimolecular and a
bimolecular surface reaction, the simpler case of uni-
molecular reaction was adopted. The reaction order in
hydrogen was not considered explicitly, since its pres-
sure was the same for all experiments and was kept
constant throughout a run (Bhinde, 1979).
Individual estimation of adsorption parameters for
each compound examined was statistically uncertain
because of the relatively low initial concentration of
reactants combined with the multitude of products.
Thus the adsorption parameters, Km, were lumped
according t o the number 0 I1 I 4 of aromatic rings
(Neurock and Klein, 1993). This required estimation
of only five adsorption parameters, KL, for the whole
series of experiments. Implicit is the approximation
that the adsorption parameter is weakly dependent on
the alkyl substituents, at least for the narrow range
examined. This approximation leads to the inevitable
loss of detail during the estimation of numerator rate
parameters, k ~ .They thus implicitly contain an adsorp-
tion constant dependence. The validity of this
approximation is assessed in detail in a following
publication (Korre et al., 1995).
Equation 2 summarizes the foregoing discussion in
terms of the operative LHHW rate law used to reduce
the experimental data to rate and adsorption param-
eters:
In eq 2, r~ (mol kg,,t-l s-l) is the rate of conversion of
compound i to compoundj, Ci (mol L-l) is the con-
centration, k~ (L kg,,-l s-l) is the numerator rate
parameter, including surface reaction and adsorption
contributions, KU (molj/mol i) is the equilibrium ratio,
Km (L mol-l) is the adsorption parameter of individual
compounds, and KL(L mol-l) is the adsorption param-
eter of aromatic ring-number based lumps. It follows
that the overall equilibrium constant is K,$ = K~~/(PHJ~,
where a is the reaction stoichiometry w t h respect t o
hydrogen. This is because the forward rate parameters
contain a hydrogen partial pressure dependence. The
overall rate of production of a given compound Ci was
obtained as the summation of all the conversion rates
involving species i.
The rate parameters and equilibrium ratios were
regressed individually for each compound, with the
constraint of non-negativity. Equilibrium ratios were
further constrained during parameter estimation by
application of the Denbigh rule concerning equivalent
pathways in a network.
The parameter estimation strategy examined both
relative and absolute rates, in turn. For a given
compound, pure component and mixture experimental
 Ind. Eng. Chem. Res., Vol. 34, No. 1, 1995 103
Table 1. Experimental Plan for Pure Compound those structures yielded the respective hydroaromatics.
Hydrogenation Specifically, the hydrogenation reactions of o-xylene
NA' reactant loading (g) (h)
tmax (Aldrich, 99%), tetralin (Aldrich, 99%), naphthalene
1 o-xylene 34.18 5.993 (Aldrich, 99+%), phenanthrene (Aldrich, 98+%), an-
1 tetralin 29.75 3.000 thracene (Aldrich, 97%), pyrene (Aldrich, 99+%), and
2 naphthalene 23.90 3.147 chrysene (Aldrich, 98%) were studied.
3 phenanthrene 15.18 3.000 The mixture experiments summarized in Table 2
3 anthracene 2.06 3.000 allowed quantitative assessment of competitive adsorp-
4 PPene 5.75 3.000 tion and inhibition interference. Single-ring aromatics
4 chrysene 2.0 4.733
were represented by o-xylene, two-ring aromatics by
a N A = number of aromatic rings. naphthalene, three-ring aromatics by phenanthrene,
Table 2. Initial Aromatics Distribution (wt %) for
and four-ring aromatics by pyrene and chrysene. The
Mixture Experiment@ initial distributions for the PNA mixture experiments
summarized in Table 2 were selected so as to mimic
NA* reactant GAUS LCO SR TCFD EQUIL aspects of the aromatic distributions in both straight-
1 o-xylene 13.00 13.01 20.00 24.00 0.00 run and processed oil fractions (van der Eijk et al.,
2 naphthalene 20.04 61.51 14.01 19.00 27.80 1990). The LCO distribution is triangular, centered at
3 phenanthrene 33.96 22.02 14.00 26.00 27.56 two-ring aromatics (i.e., naphthalene). The SR distribu-
4 pyrene 20.11 3.50 32.00 19.01 27.92
4 chrysene 12.99 0.00 20.01 12.00 16.72 tion was approximated by an inverted triangular dis-
tribution. The TCFD and EQUIL distributions had
loading(g) 20.02 20.01 20.00 20.00 17.94 approximately equal amount of PNA's with two to four
tmax (h) 6.939 7.000 7.638 6.295 9.574
rings, but EQUIL did not include single-ring aromatics.
a GAUS = Gaussian, LCO = light cycle oil, SR = straight run. The gaussian (GAUS) distribution was centered at
TCFD = thermally cracked flashed distillate, EQUIL = equilib- three-ring aromatics (Korre, 1994).
rium run. NA = number of aromatic rings.
The cumulative wt % distribution is also of interest.
data (where available) were used simultaneously. As The SR distribution had the highest content of four-ring
a first step, parameter estimation was performed using aromatics, with 52.01 wt %, and the EQUIL distribution
the product yield vs reactant conversion data involving had the highest combined content in three- and four-
a particular compound (ri VS.XI). These relative rates ring aromatics, with 72.20 wt % (Table 2). The LCO
eliminated the LHHW denominators and provided rate distribution had the lowest content in both cases (3.50
and equilibrium parameters that were independent of wt % four-ring aromatics, 25.52 wt % three- and four-
the mixture composition (eq 3): ring aromatics combined).
These experiments are considered below on a com-
pound by compound basis. Product identification issues
are addressed first. Then the product rank in the
network, as provided mainly by the yield and selectivity
vs conversion information (Delplots), is considered
(Bhore et al., 1990). Subsequent parameter estimation
using the kinetics data with the proposed network
affords rate, equilibrium, and adsorption parameters,
In eq 3, CO(mom) is the initial reactant concentration. as discussed above.
The rate parameters k~ and equilibrium ratios KG
regressed by eq 3 were then held constant, and eq 2 was Kinetics and Thermodynamics Results
used for the estimation of adsorption parameters, Kl,
using the yield vs time data, simultaneously for all o-Xylene. Reaction of o-xylene in 420. g of cyclohex-
experiments involving a particular compound and for ane solvent was a t 68.1 atm of H2 and 350 "C. The
all compounds in the mixture. This assured maximum conditions for the experiments involving o-xylene are
agreement and between experiments with varying presented in Tables 1-3. Reaction duration was 4.637
initial compositions (Korre, 1994). tf < 7.638 h, and the ultimate conversion was 0.138
Experimental Design. The hydrogenation experi- < XM < 0.183. The major products were truns-1,2-
mental plan is outlined in Tables 1 and 2. Pure- dimethylcyclohexane, cis-1,2-dimethylcyclohexane, m-
compound experiments were complemented by polynu- xylene, and p-xylene. Traces of cis- and truns-1,3-
clear aromatics mixture experiments at different initial dimethyl- and -1,4-dimethylcyclohexaneswere also
loadings. detected. All products were identified by co-injections
The model compounds of Table 1were selected so as and mass spectral information.
to represent fundamental structural characteristics The kinetics of conversion corresponding t o the mix-
encountered in heavy oils. The structural parameter ture experiments in Table 2 are presented in Figure 1.
varied for the reactant selection was the aromatic ring The highest conversion for a particular time was
number (one to four aromatic rings). Hydrogenation of observed for experiments with the LCO distribution
Table 3. Mass Balances and Maximum Conversions for Compounds in the Mixture Experiments
o-xylene naphthalene phenanthrene PFene chrvsene
MB closure (%) xmax MB closure (%) xmax MB closure (%) xmax MB closure (%) xmax MB closure (%) xmax
Pure 0.984f 2.07 0.183 0.981 f 3.101 0.952 0.990 f 2.564 0.977 0.945f 1.900 0.858 0.969f 2.826 0.999
Gauss 0.997 f 2.01 0.151 0.976f 3.447 0.984 0.973f 1.381 0.959 0.966 f 4.585 0.832 0.950 f 7.035 0.992
LCO
SR
*
0.989 0.79
0.994f 1.34
0.156
0.155
0.958f 3.987 0.976 0.988f 3.676 0.959 0.993f 6.536
0.978f 4.007 0.982 0.970f 3.517 0.953 0.944f 4.707
0.851
0.855
-
0.962 f 3.834
-
0.984
TCFD 1.005 f 1.67 0.145 0.985 f 7.062 0.989 0.994f 7.297 0.959 0.973f 5.546 0.887 0.956f 10.68 0.992
EQUIL - - 0.972f 4.763 0.998 0.978f 7.923 0.996 0.952f 8.866 0.915 0.976i 7.067 1.000
104 Ind. Eng. Chem. Res., Vol. 34, No. 1, 1995

the selectivity vs conversion Delplots (Bhore et al., 1990)

e 0.14
of Figure 2(ii).
0 A replicate experiment produced identical results, as
'E
El
0.12 is depicted in Figure 2(ii). Thus the apparent zero
:: 0.1 initial selectivity to hydrogenation, relative to isomer-
u" 0.08 ization, is telling. Perhaps subtleties in the differences
in adsorption of the xylene isomers are manifested as
=,Ic 0.06 apparent autocatalytic kinetics. This would have caused
8 0.04 the dimethylcyclohexaneproduction rate to increase as
the o-xylene concentration decreased. However, the
8 0.02 maximum conversion is not likely enough to account for
0 the observed production acceleration. This is reflected
0 120 240 360 480 in a small regressed value of adsorption parameter
Time (min) (maximum 1.364 m3 kmol-I, with eq 21, which cannot
Figure 1. Effect of reacting mixture composition on o-xylene account for the observed kinetics.
SR; (A)TCFD; (-1
conversion kinetics. ((0)GAUS; (+) LCO; (0) The apparent secondary rank of the dimethylcyclo-
Est.) hexanes could also result from the autocatalytic action
of hydrogen transfer from the hydrogenated product,
0.16
1i1 I according to the combined unimolecular and bimolecular
0.14 rate expression of eq 4. The plausibility of this scheme
0.12 derives from the several conjugated structures possible
0. I
after abstraction of a tertiary hydrogen. This somewhat
0 empirical scheme fit the experimental data extremely
.I0.08
+ well. This is demonstrated by the continuous lines of
0.06 Figure 2(i).
0.04
0.02
n
0 60 120 180 240 300 360
Time (min)

1 (4)

0.8
2!
*
-
.- 0.6
.-*
-g
m
Y
0.4
0.2
0 critical slopes in Figure 2(i) that led to the hydrogen-
0 0.02 0.04 0.06 0.08 0.1
ortho-xylene conversion x
Figure 2. Kinetics of o-xylene hydrogenation. (i) Yield vs time
and (ii) selectivity vs conversion plots. (i) Solid curves represent
the network correlation with eq 4.Dotted curves represent the
network correlation of Figure 4.F = 1.636 x estimated
deviation = 5.720 x ((+) o-xylend7; (0)cis- and truns-l,2-
dimethylcyclohexane; (W) metu- and para-xylene; (A) 1,3-dimethyl-
and 1,4-dimethylcyclohexane.)(ii) Open symbols represent repli-
cate experiment; (0,0) truns-l,2-dimethyl- plus cis-1,2-dimeth-
ylcyclohexane; (W, 0 ) m-plus p-xylene; (A,A) 1,3-dimethyl- plus
1,4-dimethylcyclohexane.
because of the lower loading in aromatics with higher
ring numbers. Equivalently, the lowest conversions
were observed for the SR hydrogenation, with the GAUS
and TCFD distributions inhibiting in similar degree.
The evolution of products with time for the reaction
of pure o-xylene is presented in Figure 2(i). Clearly,
m- and p-xylene were primary products, and their
concentrations reached constant values after 30 min.
cis- and truns-l,2-dimethylcyclohexanes were the major
hydrogenation products observed, in very similar yields.
Relative to the behavior of the xylene products, the
dimethylcyclohexanes, including both cis- and truns-1,2-
dimethyl, formed with what appeared to be zero slope
at t = 0 in Figure 2(i). This is exposed more clearly by
However, the quantitative aspects of eq 4 undermined
the hydrogen-transfer scenario. Note that the best fit
equilibrium ratio is less than 1 (0.175). This implied
that o-xylene would be more abundant than 1,2-di-
methylcyclohexane at equilibrium, contradicting previ-
ous studies that reported equilibrium ratios for single-
ring hydrogenations well over 10 at 350 "C(Frye, 1962;
Frye and Weitcamp, 1969). This suggested that the
0.12 0.14 0.16 transfer hypothesis were overemphasized a t the low
conversions.
This suspicion motivated a set of experiments aimed
a t broadening the range of conversions to probe the
hydrogen-transfer hypothesis further. A series of ex-
periments at conditions identical to those for o-xylene
were thus performed where o-xylene was reacted in a
mixture with 1,2-dimethylcyclohexanes. Figure 3a,b
presents results from 0 wt %, 50 wt %, and 80 wt %
1,2-dimethylcyclohexanesin o-xylene. The net 1,2-
dimethylcyclohexaneyields (Figure 3a) exhibited similar
behavior at t = 0 for all three experiments. Their
subsequent evolution with time, however, was much
different than the equilibrium predicted based on the
autocatalytic rate law (eq 4) and its parameters.
Parameter estimation on eq 2 was thus performed for
all three experiments simultaneously. The results are
summarized in the numerical values of the combined
unimolecular and bimolecular rate expression of eq 5
and the fair fit of Figure 3a,b.
dy1,2 - r3.16 x
-- - y1,2/5.61 x
10-*(Yortho lo4) + 2.69 x
dt

.,
0.14
0.12
0 60 120 180 240 300 360 0 0.2 0.4 0.6
Time (min) Yield
0.12 . Interconversion between 1,2- and 1,3/1,4-dimethyl cy-
0.1 / clohexanes is also included. p-Xylene yields were less
0
* 0 0.06
2 . O 8 i m n ,
0.04
0.02
0
0
I30
60
m n
,
120
~ ~
180 240 300
., 360
Time (min)
Figure 3. Initial composition dependence of xylene hydrogenation
product distributions. (a) Net 1,2-dimethylcyclohexaneyield vs
time for different initial compositions. (Curves represent param-
eter estimation results with eq 5. F = 2.439 x estimated
deviation = 1.030 x low2.(0,0 ) 100 w t % o-xylene;(A) 50 w t %
o-xylene, 50 wt % 1,2-dimethylcyclohexanes; (H) 20 w t % o-xylene,
80 wt % 1,2-dimethylcyclohexanes).(b)Reaction time as calculated
from o-xylene hydrogenation yields for different initial composi-
tions. (Curves represent parameter estimation results using eq 5:
(W) o-xylene; (A) 1,2-dimethylcyclohexanes.)(c) 1,3-Dimethylcy-
clohexane yield from m-xylene for different initial compositions
((HI Reactant, pure m-xylene;(0) reactant, 50 w t % m-xylene, 50
w t % 1,2-dimethylcyclohexanes.)
Note that the bimolecular rate parameter is two orders
of magnitude lower than in eq 4, and the equilibrium
ratio is much larger than 1. These results essentially
nullified the hydrogen-transfer hypothesis. The best-
fit total yield profiles are presented in Figure 3b as the
curves, along with the experimental data. The time for
a desired conversion was calculated from eq 5, and was
28.0 h for 0.470 conversion and 67.2 h for 0.818
conversion. Note that, on the scale of Figure 3b, the
autocatalytic behavior at very low conversions is at
most a boundary layer phenomenon.
The absence of hydrogen-transfer reactions was also
demonstrated by two additional experiments involving
m-xylene as the reactant, with and without the candi-
date hydrogen transfer additive 1,2-dimethylcyclohex-
ane. Figure 3c demonstrates that the yields of 1,3-
dimethylcyclohexane were almost identical in both
cases. Thus, the hydrogen-transfer hypothesis as an
explanation of the apparent secondary rank of the
dimethylcyclohexanes was abandoned.
The bifunctional catalyst thus promoted both isomer-
ization and hydrogenation reaction pathways. The
isomerizations to m- and p-xylene were substantially
faster than hydrogenation; recall that the products of
the latter reaction appeared with a low initial rate.
Although the xylene isomers yields were low-the
maximum yield to m- and p-xylene was 0.0131-they
were achieved within the first 30 min of reaction. This
suggested that the rates were high. Indeed, Figure 2b
indicated that the initial selectivity to m- and p-xylene
was close to unity.
This motivated construction of the network of o-xylene
reactions presented in Figure 4. o-Xylene hydrogenates
to 1,2-dimethylcyclohexanesin parallel with its isomer-
ization to m- and p-xylene. The latter in turn hydro-
genate to 1,3-dimethyl- and 1,4-dimethylcyclohexanes.
Ind. Eng. Chem. Res., Vol. 34, No. 1, 1995 106
Figure 4. Proposed network for xylenes hydrogenation. (k in
0.8 1 L/(kg,t s). Numerator rate parameters underlined).
1
than 10% of m-xylene yields and thus not always
quantitatively detectable. Consequently, m- and p -
xylene were lumped into one component. The same was
true for 1,Cdimethyl- and 1,3-dimethylcyclohexanes.
Parameter estimation to this network exploited the
420
range of available experimental compositions. Thus, the
pure o-xylene data, the 50 w t % data, the 80 w t % 1,2-
dimethylcyclohexane in o-xylene data, as well as the
m-xylene hydrogenation experimental data combined to
give the parameter set of Figure 4. Isomerization of o-
to m-xylene was approximately 1 order of magnitude
slower than hydrogenation of o-xylene to 1,a-dimethyl-
cyclohexanes. Hydrogenation of o-xylene proceeded
with a higher rate parameter than hydrogenation of the
m- and p-xylene lump; both reactions were virtually
irreversible. Finally, the rate parameter for isomeriza-
tion of 1,2-dimethyl- to 1,3-and 1,4-dimethylcyclohex-
anes was negligible. This parameter set provided the
calculated yield profiles corresponding to conversion
interval 0-0.181 presented as the dotted curves in
Figure 2(i).
The reaction patterns discovered above were repeated
for o-xylene hydrogenation in the PNA mixture (Table
2). No shifts in selectivity were observed, although
o-xylene conversion was inhibited in the presence of
higher aromatics. This allowed for evaluation of ad-
sorption parameters for the aromatic ring number-based
lumps, as discussed below.
Tetralin. Reaction of 29.75 g of tetralin took place
in 420. g of cyclohexane solvent at 68.1 atm of Hz and
350 C. Conversion after 3 h was 0.137. The major
products were trans-decalin, cis-decalin, and naphtha-
lene, which accounted for 0.991 f 0.011 material
balance closure. The balance consisted of traces of
decalin isomers, 1-and 2-methylindans and ring-open-
ing products (total max. 1.1%).Including those prod-
ucts, the material balance closure was 1,000 f 0.009.
All products were identified by coinjection and mass
spectral information.
Figure 5 summarizes the evolution of product yields
and selectivities with tetralin conversion. Naphthalene
was the product with the highest initial selectivity,
followed by trans- and cis-decalin. Notice the similari-
ties between the Delplots for tetralin in Figure 5 and
those for o-xylene in Figure 2. Decalins appeared to
be fairly unreactive under these conditions, while
naphthalene hydrogenated back into tetralin. All three
major products were thus considered primary in the
network of Figure 6. The interconversion between cis-
and trans-decalin was also included for completeness.
Parameter estimation to the network of Figure 6
using the tetralin yield vs conversion data and eq 3 is
summarized as the smooth curves in Figure 5. The
equilibrium ratio for isomerization of trans- t o cis-
decalin was obtained as the ratio of the two hydrogena-
tion equilibrium ratios, according to Denbighs rule, and
is denoted in italics.
106 Ind. Eng. Chem. Res., Vol. 34,No. 1, 1995

0.08 .
0.07 -
0.06 .
0.05 -
0.04 .

0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14

x Tetralin og I
0 120 240 360 480
Time (min)
Figure 7. Effect of reacting mixture composition on naphthalene
GAUS; (+) LCO; (0)SR (A)TCFD; (A)
conversion kinetics. ((0)
EQ; (-1 Est.)

0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14

x Tetralin
Figure 5. Kinetics of tetralin hydrogenation. Yield (i) and 0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
selectivity (ii) vs conversion plots. (Curves represent the parameter x Naphthalene x Naphthalene
estimation results of Figure 6 ((0)trans-decalin; ( 0 )cis-decalin;
(W naphthalene).) 0.25
trans
-
e
.-
0.2

-x. c3
1
1u 0.361
?
.m

h
0.15

0.1

0.05

m
Figure 6. Proposed network for tetralin hydrogenation. (k in
L/(kg,,t 9). Numerator rate parameters underlined. F = 1.75 x
estimated deviation = 0.009 35.)
Figure 6 also summarizes the kinetics. The overall
rate parameter for hydrogenation of tetralin was slightly
higher than that for hydrogenation of o-xylene. Con-
sidering the similar position of the alkyl substituents
with respect to the aromatic ring, this enhancement
may be attributed to the presence of the saturated ring,
either by additional inductive effect or by improved
adsorption properties. These results also show that the
naphthalenic moiety hydrogenated 2 orders of magni-
tude faster than the benzenic moiety. To quantify this
effect further, naphthalene was employed as a reactant.
Naphthalene. Reaction of naphthalene in 420.g of
cyclohexane solvent was at 68.1 atm of H2 and 350 "C.
The conditions for the experiments involving naphtha-
lene are presented in Tables 1-3. Reaction duration
was 3.147 < tf < 9.574 h, and maximum conversion
varied between 0.952 < XM 0.998. The major hydro-
genation products were tetralin, trans-decalin, and cis-
decalin, accounting for more than 95% of the initial
weight of naphthalene. Traces of methylindans, alkyl-
benzenes, and alkylcyclohexaneswere detected as well.
Figure 7 summarizes the kinetics of conversion for
the mixture experiments of Table 2. The highest
conversion for a particular time was observed for
experiments with the LCO composition distribution; the
0
0 0.2 0.4 0.6 0.8 1 o 0.2 oi 0.i 0.i i
x Naphthalene x Naphthalene
Figure 8. Kinetics of naphthalene hydrogenation. Yield (i) and
selectivity (ii) vs conversion plots for tetralin (a) and cis-decalin
(b). (Curves represent the parameter estimation results of Figure
9. (W Pure; (0) GAUS; (+I LCO; ( 0 )SR (A)TCFD; (A) EQ; (-)
Est.)
lowest conversions were observed for the SR and EQUIL
hydrogenation experiments. This may be attributed to
the fact that although EQUIL distribution had a lower
content in four-ring aromatics than SR, it had a higher
combined content of three- and four-ring aromatics.
These inhibition effects imply a higher adsorption
parameter for the three-ring than for the two-ring
aromatics lump.
The reaction network was revealed by the selectivity
vs conversion Delplots of Figure 8(ii). The initial
selectivities show that tetralin was the sole primary
product, whereas cis- and trans-decalins were clearly
secondary. Note that the data of Figure 8 coincide for
all experiments. This shows that the numerator rate
and equilibrium parameters are concentration-indepen-
dent and attests t o the validity of eq 3 and the
parameter estimation approach.
Parameter estimation to the implied network of
Figure 9 was performed using the rate expression of eq
3. The equilibrium ratio for isomerization of trans- to
cis-decalin was constrained as above. Figure 8 shows
that the resulting best-fit numerator parameters of
Figure 9 provide good agreement between model and
data. Note that the kinetic parameters are quite close

hWlS
M
cis
Figure 9. Proposed network for naphthalene hydrogenation. (k
in I.4kg-t s). Numerator rate parameters underlined. F = 0.123; concerning the hydrogenation pathway and reactivity
estimated deviation = 0.0428.)
0%
0 120 240 360 480
Time (min)
Figure 10. Effect of reacting mixture composition on phenan-
GAUS;(+) LCO; (0)
threne conversion kinetics. ((0) S R (A)TCFD
(A) EQ;(-1 Est.)
to those estimated from the experiment with tetralin
as a reactant (Figure 6).
Phenanthrene. Reaction of phenanthrene in 420.
g of cyclohexane solvent was a t 68.1 atm of H2 and 350
"C. The conditions for the experiments involving phenan-
threne are presented in Tables 1-3. Reaction duration
varied between 3.147 tf < 9.574 h, and ultimate
conversions of 0.953 < X M < 0.996 were observed. The
identified products were dihydrophenanthrene, tetrahy-
drophenanthrene, symmetric and asymmetric octahy-
drophenanthrene, and perhydrophenanthrene. These
accounted for more than 97% of the initial weight of
phenanthrene at all cases. Traces of methylbiphenyls
and biphenyl were also detected (total max. 3.5%).
The kinetics of phenanthrene conversion at the mix-
ture compositions of Table 2 are presented in Figure
10. The inhibition due to the presence of higher
aromatics is revealed in the lowest conversion for the
SR and EQUIL hydrogenation mixtures and the highest
conversion for the LCO mixture.
Resolution of the reaction pathways required careful
analysis of the product spectra. Identification of 9,lO-
di-, 1,2,3,4-tetra-, and perhydrophenanthrene was
straightforward, as they were the only GC peaks cor-
responding to molecular weight 180, 182, and 192,
respectively. Five GC peaks of molecular weight 186
were detected, correspondingto octahydrophenanthrene
isomers. The three earlier-eluting GC peaks exhibited
identical MS fragmentation patterns, including frag-
ments of molecular weight 43 and 57-signifying two
fused saturated rings-and were associated with 1,2,3,4,-
4a,9,10,10a-octahydrophenanthrene (as-octahydro-
phenanthrene) conformational isomers. The two later-
eluting GC peaks exhibited a distinct MS fragmentation
pattern with fragments of molecular weight 28-signify-
ing a saturated ring fused with an aromatic ring-and
were attributed to 1,2,3,4,5,6,7,8-octahydrophenan- (Moreau and Geneste, 1990). Notice that the equilib-
threne (s-octahydrophenanthrene)conformational iso-
mers (McLafTerty, 1980).
Ind. Eng. Chem. Res., Vol. 34, No. 1, 1995 107
The selectivity vs conversion plots of Figure ll(ii)
provided information about the reaction network. Di-
and tetrahydrophenanthrenes were clearly primary
products, the former appearing with higher initial
selectivity (projected 0.7 vs 0.3). On the other hand,
both octahydrophenanthrenes exhibited secondary be-
havior. Perhydrophenanthrene appeared very late in
the reaction network, and only with low yields.
The phenanthrene network contains an ambiguity
of dihydrophenanthrene. This is still an open question
in the literature. Lemberton et al. (Lemberton and
Guisnet, 1984) and Wu et al. (Wu and Haynes, 1975)
suggest interconversion of di- to tetrahydrophenan-
threne. The driving force behind this reaction may be
energetic, i.e., the recovery of the two fused aromatic
ring system, in place of the two isolated aromatic rings.
Additionally, the dihydrophenanthrene molecule is ster-
ically strained, as the hydrogenation of the middle ring
forces the aromatic rings out of coplanarity (Shabtai et
al., 1978). In contrast, more recent studies (Girgis and
Gates, 1991), employing dihydrophenanthrene as the
reactant a t comparatively milder conditions than the
present study, suggest that its main reaction was
dehydrogenation to phenanthrene.
The foregoing motivated the present studies of the
catalytic reaction of dihydrophenanthrene with CoMol
A1203 and the standard conditions of 350 "C and 68.1
atm of H2. As shown in Figure 12a(ii), the initial
selectivity to phenanthrene approached unity at zero
conversion (0.58 conversion at the first 15 min), while
the initial selectivity to tetra- and octahydrophenan-
threnes approached zero. The underlying driving force
appeared to be thermodynamic, as demonstrated in
Figure 12b, where the evolution of the dihydrophenan-
threndphenanthrene ratio with time was plotted for the
two experiments. In both cases, the ratio approached
a constant value of approximately 0.6, which was very
close to the equilibrium concentration ratio. Thus these
results suggest that a reasonable phenanthrene network
would include a fast reversible reaction of phenanthrene
to dihydrophenanthrene with no further reaction of
dihydrophenanthrene to deeper hydrogenation products.
These observations led to the construction of the
network of Figure 13. Hydrogenation proceeded in a
ring-by-ring manner, phenanthrene t o tetra- to octa-
and perhydrophenanthrene. Secondary hydrogenation
of dihydrophenanthrene does not occur in Figure 13.
Figure lla-c contains the results of parameter
estimation as the smooth curves. The rate expression
of eq 3 and the phenanthrene network of Figure 13 were
used with all experimental data involving phenanthrene
and dihydrophenanthrene simultaneously. The as-
octahydrophenanthrene to perhydrophenanthrene equi-
librium ratio was constrained by the three other equi-
librium ratios in the network to account for the reaction
path degeneracy and is denoted in italics in Figure 13,
along with the best-fit parameters. There is very good
agreement between experimental and calculated yield
profiles, as shown in Figures 11 and 12.
The parameter estimation results invite scrutiny of
qualitative structureheactivity relationships. Phenan-
threne hydrogenation at the middle ring was kinetically
favored over that at the terminal ring. This may be
attributed to the increased reactivity of the 9,lO-bridge
rium ratio for this reaction was less than one (0.5821,
which indicates that more phenanthrene than dihydro-
108 Ind. Eng. Chem. Res., Vol. 34, No. 1, 1995

0.7
E
0.6
e5 0.5
0.4
0.3
oh
0.2
0.1
c
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
x Phenanthrene x Phenanthrene

P 0.35 >
0.14
I
8 0.12
I 0.1
9 0.08
8e 0.06
p" 0.04
2
E 0.02
h O
0 0.2 0.4 0.6 0.8 I 0 0.2 0.4 0.6 0.8 1
x Phenanthrene x Phenanthrene
$ 0.25
C
9P 0.2
e
oh 0.15
-
2

6 0.1

0.05

$ 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 I
x Phenanthrene x Phenanthrene
Figure 11. Kinetics of phenanthrene hydrogenation. Yield (i) and selectivity (ii) vs conversion plots for dihydrophenanthrene (a),
tetrahydrophenanthrene (b), and as-octahydrophenanthrene(c). (Curves represent the parameter estimation results of Figure 13. (W)
Pure; (0)GAUS; (+) LCO; (0) SR; (A)TCFD; (A) EQ; (-1 Est.)

::;Ji.
I * 1,
(a,)

0.7 '

0 50 100 150 200 0 0.5 1

T h e (min) x Dihydrophenanthrene Figure.13. Proposed network for phenanthrene hydrogenation.
(k in L4kg-t s). Numerator rate parameters underlined. F =
1, 0.0648; estimated deviation = 0.0334.)
g 0.8
5C 0.7 for the hydrogenation of a single aromatic ring. The
g . 0.6 0
* * * * e *o o* presence of saturated rings also had an effect on
0.5 -
o o
2 *O o o o o o reactivity. For example, the hydrogenation of octahy-
$ 0.4 . drophyanthrenes was much faster than that of either
0.3 .
2 0.2 . * tetralin or o-xylene. These results are in qualitative
0.1 - agreement with those of Aubert et al. (19881, who
04 1 suggested an anchoring effect of the naphthenic sub-
0 50 100 I50 200 stituents on the catalyst surface. This is contrary to
Time (min) the results reported by Shabtai et al. (19781, who
Figure 12. Kinetics of dihydrophenanthrene hydrogenation. (a) suggested that the bulkiness of the naphthenic rings
Yield (i)and selectivity (ii) vs conversion plots. (Curves represent would result in lower hydrogenation rates than less
the parameter estimation results of Figure 13. ( 0 )Phenanthrene; substituted molecules.
(A) dihydro-, (W) Tetrahydro-, (0)s-octahydro-, (0)as-octahydro-,
(A) perhydrophenanthrene.) (b) Equilibrium between phenan- Another revelation of the parameters in Figure 13 is
threne and dihydrophenanthrene. ((0)Dihydrophenanthrene re- the difference in hydrogenation rates between terminal
actant; ( 0 )phenanthrene reactant.) and middle rings for the "ring-substituted" benzenic and
naphthalenic moieties. The terminal ring in tetrahy-
phenanthrene is present at equilibrium. Rate param- drophenanthrene (naphthalenic moiety) hydrogenated
eters for hydrogenation of both two- and three-fused faster than the middle ring. This may be attributed to
aromatic rings were 1 order of magnitude higher than inaccessibility of the internal ring t o hydrogenation due

0.6 -,
c1
0.4 1I 0 .e-
0.5 0.6 0.7 0.8 0.9
x Anthracene
0.6
.
X
0.5
0.4
.-"
h
2 parameters for the initial part of the anthracene net-
* 0.3
V work are larger than for phenanthrene, possibly due to
0.2
0. I
0 larger than in the phenanthrene network, but still less
0.5 0.6 0.7 0.8 0.9
x Anthracene
Figure 14. Kinetics of anthracene hydrogenation. Yield (i) and
selectivity (ii) vs conversion plots. (Curves represent the parameter
estimation results of Figure 15. (A) Dihydro-, (H) tetrahydro-, (0)
s-octahydro-, (0)as-octahydro-, (A)perhydroanthracene.)
m Figure 14 shows that the results of parameter estima-
Figure 15. Proposed network for anthracene hydrogenation. (k
in L/(kg,,t s). Numerator rate parameters underlined. F = 0.0164;
estimated deviation = 0.0158.)
to sterics. The same observations hold for as- vs
s-octahydrophenanthrene hydrogenation.
Anthracene. Reaction of 2.06 g of anthracene took
place in 420. g of cyclohexane solvent at 68.1 atm of Hz
and 350 "C. The major products were dihydroan-
thracene, tetrahydroanthracene, symmetric and asym-
metric octahydroanthracene, and perhydroanthracene.
These accounted for 0.968 f 0.043 of the material
balance closure. The balance consisted of traces of
hydrophenanthrene isomers, whose yields brought the
material balance closure to 1.000 & 0.048. Product
identification followed the reasoning detailed above for
phenanthrene; the retention times and order were very
similar.
The kinetics of anthracene hydrogenation are sum-
marized in Figure 14. Di- and tetrahydroanthracenes
were clearly primary products, the former apparently
appearing in higher initial selectivity, while octahy-
droanthracenes exhibited secondary behavior. This
suggested the anthracene hydrogenation network to be
as shown in Figure 15.
Parameter estimation using eq 3 in the network of
Figure 15 and the yield vs conversion data of Figure 14
provided a quantitative summary of the kinetics. As
was the case for phenanthrene, the equilibrium ratio
for as-octahydroanthracene hydrogenation was con-
strained, according to Denbigh rule. The resulting rate
Ind. Eng. Chem. Res., Vol. 34,No. 1, 1995 109
1
- 1 I
0.9
0.8
I
-5E 0.7
$ 0.6
C
8 0.5
1
0 120 240 360 480
Time (min)
Figure 16. Effect of reacting mixture composition on pyrene
GAUS (e)LCO; (0)
conversion kinetics. ((0)
EQ; (-1 Est.)
S R (A)TCFD; (A)
anthracene's decreased resonance stabilization energy
(Moreau and Geneste, 1990). The equilibrium ratio for
the hydrogenation of the middle of the three rings is
1 than unity. Deeper in the network, tetrahydroan-
thracene hydrogenation is overall slower than tetrahy-
drophenanthrene hydrogenation. The single-aromatic-
ring hydrogenation rate parameters observed from
octahydroanthracenes' hydrogenation are also lower
than those regressed from phenanthrene network. The
preferential hydrogenation of a terminal vs an internal
ring in one- and two-aromatic ring systems was also
seen in both tetra- and octahydroanthracenes. Overall,
tion to the anthracene hydrogenation network proposed
above are quite good.
Pyrene. Reactions of pyrene took place in 420. g of
cyclohexane solvent at 68.1 atm of Hz and 350 "C. The
conditions for experiments involving pyrene are pre-
sented in Tables 1-3. Reaction duration was 3.147 <
tf < 9.574 h, which afforded maximum conversions
between 0.831 < XM < 0.915. The major identified
products were dihydropyrene, tetrahydropyrene, sym-
metric and asymmetric hexahydropyrene, decahydro-
pyrenes A and B, and perhydropyrene. Traces of
alkylphenanthrenes and alkylbiphenyls were also de-
tected.
Figure 16 summarizes the kinetics of pyrene conver-
sion for the mixture experiments of Table 2. A time-
invariant plateau was established in all cases after
approximately 4 h. Pyrene conversion rates also de-
creased with increasing heaviness of the feed. The rate
was highest for the lightest feed (LCO) and lowest for
the heaviest feeds (SR and EQUIL). Pyrene conversion
was more inhibited in the EQUIL composition distribu-
tion than in the SR distribution.
Resolution of the reaction pathways required careful
analysis of the product spectra. The identification of
pyrene, 4,5-dihydropyrene, and perhydropyrene was
straightforward from the mass spectra, as they were the
only possible products with molecular weights 202,204,
and 218, respectively. The two hexahydropyrene iso-
mers were identified by co-injection of available s-
hexahydropyrene (1,2,3,6,7,8-hexahydropyrene, Aldrich
94%). The presence of 4,5,9,10-tetrahydropyrenewas
deduced as it was the only stable tetrahydropyrene, and
in addition it eluted earlier than both hexahydropy-
renes, signifying the presence of single aromatic rings.
Three GC peaks corresponding to molecular weight 212
110 Ind. Eng. Chem. Res., Vol. 34, No. 1, 1995
0.8 ,
0.6 -
0.3 -
. 0.2 -
0.1 -
0,
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
x Pyrene x Pyrene

0.06 0.14 -
e
t
0.05 -
$ 0.04 -
b
R 0.03 - $, 0.08 -
P
2 0.06-
2F 0.02 -

h 0.01 - $ 0.02 -
0 1
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
x Pyrene x Pyrene

0.18 0.25
I 5
2 0.16
h
P 0.14 ;0.2
*
g 0.12
I.

2a 0.1s
P 0.1
8 0.08
q 0.1
9 0.06 E
g 0.04 0.05
0.02
h O
ch O
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
x Pyrene x Pyrene

Figure 17. Kinetics of pyrene hydrogenation. Yield (i) and selectivity (ii) vs conversion plots for dihydropyrene (a),tetrahydropyrene (b),
and as-hexahydropyrene (c). (Curves represent the parameter estimation results of Figure 18. (H)Pure; (0) GAUS; (e)LCO; (0) SR (A)
TCFD; (A) EQ; (-1 Est.)

were detected and attributed to decahydropyrene iso-

mers. The earlier eluting isomer exhibited an MS
fragmentation pattern distinctly different from the later
two, and was identified with 1,2,3,3a,4,5,9,10,10a,lOb-
decahydropyrene by the NBS-REVE mass spectral
library (decahydropyrene A), leaving the latter two GC
peaks for 1,2,3,3a,4,5,5a,6,7,8-decahydropyrene (decahy-
dropyrene B) conformational isomers.
Selectivity data for hydrogenation of pyrene and
hydropyrenes are presented in Figure 17a-c. The
selectivity vs conversion plots show clearly that dihy-
dropyrene appeared as a primary product. Tetra-, and
s- and as-hexahydropyrenes exhibited mixed primary
and secondary behavior. Finally, deca- and perhydro-
pyrenes were clearly of tertiary or higher rank.
These observations led t o the construction of the
network of Figure 18. The interconnectivity of the
network rendered four equilibrium ratios redundant,
and they were calculated in terms of the other equilib-
rium ratios in the network. They are presented in
italics in Figure 18.
Subsequent parameter estimation provided an indica-
tion of structurelreactivity trends. Pyrene hydrogena-
tion at the middle ring was faster than hydrogenation
a t the terminal ring. Further hydrogenation of the
phenanthrenic moiety in dihydropyrene at the middle
ring proceeded with a rate parameter very close to that
for phenanthrene itself. The equilibrium ratio for both
middle-ring hydrogenations was less than unity. As
was the case for phenanthrene, this indicates that
Figure 18. Proposed network for pyrene hydrogenation. (k in
L/(kg,, 9). Numerator rate parameters underlined. F = 0.153;
estimated deviation = 0.0513.)
middle-ring hydrogenations were influenced by the
equilibrium limitation, with the parent aromatic more
abundant than the hydroaromatic at equilibrium.
Hydrogenation of dihydropyrene at the terminal ring
to as-hexahydropyrene was faster than the formation
of tetrahydrophenanthrene from phenanthrene. as-
Hexahydropyrene production directly from pyrene was
negligible. s-hexahydropyrene was a minor primary
hydrogenation product of pyrene, as well as an isomer-
ization product of as-hexahydropyrene. This is in
agreement with the pathways involving consecutive
rearrangements proposed in previous works (Johnston,
1984; Girgis, 1988).
The secondary reactions of s-hexahydropyrene were
notably slow. The rate constant for its further hydro-

1 The identification of di-, tetra-, and perhydrochrysene
0.9
= 0.8
.-E 0.7
al
2 0.6
8 0.5
f 0.4
5 0.3
8 0.2
0.1
,~
0 120 240 360 480
Time (min)
Figure 19. Effect of reacting mixture composition on chrysene
GAUS; (0)S R (A)TCFD; (A) EQ; (-)
conversion kinetics. ((0)
Est.)
genation to B-decahydropyrene was small compared to
values for similar moieties in other host molecules. The
location of the aromatic rings in internal parts of the
molecule could adversely affect hydrogenation reactiv-
ity. Indeed, in the as-hexahydropyrene isomer, hydro-
genation of the equivalent internal ring also proceeds
much more slowly than hydrogenation of the terminal
ring.
A possible explanation for these trends could involve
steric as well as thermodynamic arguments. Assuming
that s- and as-hexahydropyrene need to adsorb flatly
on the catalyst for the addition of all four hydrogen
atoms to proceed to the innermost loa- and 10b-
positions, the availability of sites would be reduced
(compared to tetrahydrophenanthrene or naphthalene)
due to the size and bulkiness of naphthenic substitu-
ents. In that respect, the sterics of their saturation
would approximate single-ring saturations and should
therefore proceed with equivalent rate constants. The
equilibrium ratios in both unfavored hydrogenations are
also less than unity. This indicates a strong dehydro-
genation trend of the resulting single-ring hydroaro-
matic. This is distinctly different from all other naph-
thalenic moieties and can be used to explain the
equilibrium limitations in pyrene hydrogenation sug-
gested in the kinetics data of Figure 16.
Rate constants for the hydrogenations of the benzenic
moieties in the decahydropyrenes were slightly higher
than for the benzenic moieties in phenanthrene. It can
be speculated that the presence of two more methylene
groups further enhanced hydrogenation reactivity. Ter-
minal ring hydrogenations were again preferred to
internal ring hydrogenations.
Figure 17a-c shows the goodness of fit of the optimal
rate and equilibrium parameters to the network of
Figure 18. Overall, the parameter estimation results,
represented by the smooth curves of Figures 16 and 17,
represent the observed pyrene conversion kinetics well.
Chrysene. Reactions of chrysene in 420. g of cyclo-
hexane solvent were at 68.1 atm of Hz and 350 "C. The
conditions for these experiments are presented in Tables
1-3. Reaction duration was 3.147 < tf < 9.574 h, and
this produced maximum conversions of 0.962 < X M
1.000. The major identified products were dihydrochry-
sene, tetrahydrochrysene, hexahydrochrysene, symmet-
ric and asymmetric octahydrochrysene, dodecahydro-
chrysenes A and B, and perhydrochrysene. These major
products accounted for more than 95% of the initial
weight of chrysene in all cases. Traces of perhydro-
chrysene isomers, alkylphenanthrenes, and alkylbiphe-
nyls were also detected.
Ind. Eng. Chem. Res., Vol. 34, No. 1, 1995 111
was straightforward from the mass spectra, as they
were the only possible products with molecular weights
230, 232, and 246, respectively. The abundance of a
single peak a t mle 234, which could be either a hexahy-
drochrysene or a butylphenanthrene, was too low to
allow decisive discrimination. However, the formation
of butylphenanthrene was considered unlikely, because
of the low acidity of the catalyst and the lack of further
cracking products such as phenanthrene. Moreover, the
mle 234 peak appeared early in the network. This
suggested a hexahydrochrysene product and, on the
basis of the pattern of selective terminal vs internal ring
hydrogenation established so far, 1,2,3,4,5,6-hexahy-
drochrysene was selected against 5,6,11712,14,17-hexahy-
drochrysene. The latter would have lower stability, as
a product of two consecutive internal ring hydrogena-
tions. The two octahydrochrysene isomers were differ-
entiated by their fragmentation patterns: as-octahy-
drochrysene was characterized by a prominent propyl-
enic fragment (236/193). The dodecahydrochrysene
isomers also exhibited two distinct fragmentation
patterns: one contained a propylenic fragment (240/197)
in addition to the pronounced presence of an ethylenic
fragment (240/212),and the other an M - 82 (2401158)
peak in the absence of an ethylenic fragment. The first
pattern implicated dodecahydrochrysene B, because of
the presence of one saturated ring attached t o an
aromatic. This left the other pattern for dodecahydro-
chrysene A.
The kinetics of chrysene conversion for the conditions
of Table 2 are presented in Figure 19. Chrysene
conversion rates appeared t o be the fastest and most
insensitive to the reactant mixture composition of all
previously examined PNAs. This may imply that chry-
sene is the most strongly adsorbed of all model com-
pounds examined.
The conversion dependence of the yields and selectivi-
ties of the initial chrysene hydrogenation products are
summarized in Figure 20a-c. Di- and tetrahydrochry-
senes were primary products, with approximately equal
projected initial selectivity (0.45),while hexahydrochry-
sene exhibited mixed primary and secondary behavior.
Octa-, dodeca-, and perhydrochrysenes were clearly of
rank 2 or higher.
The richness of the product spectrum and the pos-
sibilities opened by the secondary hydrogenation of
hexahydrochrysene complicated the chrysene network.
Thus, using the phenanthrene and naphthalene net-
works as guides, all possible reaction pathways were
included in the chrysene reaction network. Parameter
estimation t o the resulting network of Figure 21 using
the relative rate expression of eq 3 reduced some of the
complexity caused by the phenanthrene-like reaction
path degeneracy. Six of the equilibrium ratios were
redundant due to the high degree of interconnectivity
in the network and were constrained by the other
equilibrium ratios. They are denoted in italics in Figure
21.
Scrutiny of the rate law parameters of the chrysene
hydrogenation network led to reactivity trends analo-
gous to those drawn from the preceding experiments.
Middle-of-threeand middle-of-fourring hydrogenations
in tetrahydrochrysene and chrysene proceeded with
equilibrium ratios less than 1, as was the case for the
corresponding moieties in phenanthrene and pyrene
(i.e., chrysene t o dihydrochrysene and tetrahydrochry-
sene to hexahydrochrysene). Hydrogenation at the
112 Ind. Eng. Chem. Res., Vol. 34,No. 1,1995
0.2 0.45
0.18 A
A
2 0.16 m
0.14
; 0.12
; 0.25
e 0.1
R 0.08
g 0.06
0.04 0.1
0.02 'h 0.05
0I
0 0.2 0.4 0.6 0.8 I 0 0.2 0.4 0.6 0.8 1

x Chrysene x Chrysene

$ 0.3
-
0.4
(b,) &*-;a%,
5 0.25
; 0.2
a
0.3 - b
R
-
'0
0.2 -
c
Eb 0.15
0.1
f k2 0.1 -
0.05 E
h
0 0,
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 I
x Chrysene x Chrysene

0.2 , I 025, I

'ok 0.1
c 0.1
x / x
0.05
h
.x
0.05
+
0 0.2 0.4 0.6 0.8 I 0 0.2 0.4 0.6 0.8 1
x Chrysene x Chrysene
Figure 20. Kinetics of chrysene hydrogenation. Yield (i) and selectivity (ii) vs conversion plots for dihydrochrysene (a),tetrahydrochrysene
(b), and hexahydrochrysene (4.(Curves represent the parameter estimation results of Figure 21.(m) Pure; (0) GAUS; (0) SR (A)TCFD;
(A) EQ; (-1 Est.)

to B-dodecahydro

OLW 1111.82

29.0 11 0.0362
to asym-octahydro
Figure 21. Proposed network for chrysene hydrogenation. ( K in L/(kg,t s). Numerator rate parameters underlined. F = 0.40912; estimated
deviation = 0.1013.)
middle ring was faster than hydrogenation at the parameters and equilibrium ratios larger than unity,
terminal ring for tetrahydrochrysene and of the same which is typical of the benzenic moieties. Hydrogena-
order of magnitude as that for chrysene. Based on these tion of the terminal ring in hexahydrochrysene was
values, chrysene was the most reactive of all molecules preferred to hydrogenation of the internal ring.
examined. The similar reactivities of the s- and as-octahydro-
The reactivity of dihydrochrysene was essentially chrysenes was also similar to or higher than the
limited to hydrogenation of its naphthalenic moiety to reactivity of other naphthalenic moieties. The A- and
hexahydrochrysene. Hydrogenation of the benzenic B-dodecahydrochryseneswere fairly reactive for single-
moiety in dihydrochrysene and further reactions of aromatic-ring hydrogenation, with A-dodecahydrochry-
hexahydrochrysene proceeded with very small rate sene the most reactive molecule in the benzenic class.

Table 4. Aromatic Ring Number-Based L u m p
Adsorption Constants from Parameter Estimation to Eq
2 for the Emeriments in Table 2
K (Umol)
four ringdpyene 38.5
four ringdchrysene 38.5
three-ring lump 17.5
two-ring lump 7.7
one-ring lump 7.4
saturates lump 3.9
The general pattern appears to confirm the conclusion
that reactivity increases with the addition of naphthenic
rings.
Figure 20a-c shows, as the curves, the results of rate
and equilibrium parameter estimation to the network
of Figure 21. The parameter estimation results, rep-
resented by the smooth curves of Figures 19 and 20,
represent the observed chrysene conversion kinetics
well.
Adsorption Results
The compound-by-compound kinetic information pre-
sented thus far allowed the exploration of detailed
hydrogenation reaction pathways. The application of
eq 3 resulted in the evaluation of 45 LHHW numerator
rate parameters and 45 numerator equilibrium ratios,
14 of which were constrained. This parameter set
satisfactorily represented the yields of products with
respect to reactant conversion. The effect of the reacting
mixture composition on reactant conversion provides the
remaining piece of the quantitative rate law that will
in turn allow predictions with respect to time or space
velocity.
To this end, parameter estimation to eq 2 was
performed using all available data simultaneously for
the time dependence of component yields. This utiliza-
tion of all the experiments of Table 2 represented
Ind. Eng. Chem. Res., Vol. 34,No. 1, 1995 113
regression to approximately 1700 experimental data
points. Anthracene and tetralin data were not used, as
these components were not present in the mixture
experiments. cis- and trans-decalins were considered
as one lump in the naphthalene network, as were all
dimethylcyclohexanes and all xylenes in the o-xylene
network. These approximations reduced the number of
numerator rate and equilibrium parameters to 68.
These were held constant, as the five adsorption pa-
rameters of the aromatic ring number-based lumps were
optimized t o the 1700 data points.
No statistical difference was observed between LHHW
models with denominator exponents n = 1 and n = 2
(eq 2). Therefore, the simpler case of n = 1was adopted.
The results are presented in Table 4 and their
implications are illustrated in Figure 22a-b. Table 4
shows that the value of the adsorption parameters
increased with the number of aromatic rings, i.e., it was
lowest for the saturates lump and highest for the four-
ring compounds lump. A manifestation of this is
demonstrated in Figure 22a, where the four-, three-, and
two-aromaticring number-based lump yields are plotted
with respect to time for all the initial compositions.
Although the absolute value of the yield for a particular
time depends on the initial composition, it is clear that
the rates are essentially independent of the initial
composition of the mixture for the four-aromatic ring
lump. The rates for the three-aromatic ring lump
decreased with increases in the heaviness of the com-
position. This effect is even more pronounced for the
two-aromatic ring lump.
The parameter estimation results are shown as the
smooth curves in Figure 1 for xylene, Figure 7 for
naphthalene, Figure 10 for phenanthrene, Figure 16 for
pyrene, and Figure 19 for chrysene. In Figure 22b a
typical example of the results for the reactants of the
straight run composition experiment is presented (SR,

1.2 1.6 1.2

0 1 0 1.4 % 1
'j; 0.8
'j; 1.2

z 1 E 0.8
5
4
P
0.6 5 0.8
-1
0.6
g 0.4 0.6
M
t 0.4
3 0.2
0.4
4 0.2 a 0.2
-l

0 0 0
0 120 240 360 480 0 120 240 360 480 0 120 240 360 480
Time (min) Time (min) Time (min)

1
0.9
0.8
0.7
'j; 0.6
*
5 0.5
*
g 0.4
2 0.3
0.2
0.1
0
0 60 120 180 240 300 360 420 480
Time (min)
Figure 22. Adsorption parameter estimation results. (a) Aromatic ring number-based lump yields with respect to time for the four-
aromatic ring lump (i), three-aromatic ring lump (ii), and two-aromatic ring lump (iii).(Curves represent results with the adsorption
parameters of Table 4. (0)GAUS; (e) LCO; (0) SR (A)TCFD; (A) EQ; (-) Est.) (b) Reactant yields vs time for the straight run distribution
(SR).(Curves represent results with the adsorption parameters of Table 4. (W) o-Xylene; (0)
naphthalene; ( 0 )phenanthrene; (A) pyrene;
(A)chrysene; (--) Est.)
114 Ind. Eng. Chem. Res., Vol. 34, No. 1, 1995
I I
0.00947 10.0269 a I 0.394 @@ I
0.00356 b.00733 [r0.0992@@0
0.0743 @ 10.0937
I
0.0925 @ 0.403 @
o.Oo0 &Io.OOo
Benzenic
Figure 23. Rate parameters for hydrogenation of polynuclear aromatics. (Shade indicates the ring being saturated. k in L/(kgCts).)
Table 3). The parameter set thus represents the yield
vs time experimental data very well.
Discussion
Qualitative Hydrogenation Reactivity Trends.
This experimental plan yielded reactivity information
for a wide range of aromatic and hydroaromatic mol-
ecules under the same set of reaction conditions. Over-
all, 45 ring saturation reactions were probed. The
regressed numerator rate parameters suggest the fol-
lowing qualitative trends: (1) PNA hydrogenation pro-
ceeded in a ring-by-ring manner; (2) hydrogenation
reactivity increased with the number of aromatic rings;
(3) for groups with the same number of fused aromatic
rings, hydrogenation reactivity increased with the pres-
ence of alkyl substituents and naphthenic rings; (4) for
moieties with one and two aromatic rings, hydrogena-
tion of a ring located at the end of the molecule was
faster than hydrogenation of an internal ring.
These trends suggest that three broad categories of
saturation, differentiated by numerator rate parameter
magnitude and driving force, are operative. These
categories are illustrated in Figure 23. The first cat-
egory, single aromatic ring hydrogenation, was termed
benzenic hydrogenation (six hydrogen atoms added).
Hydrogenation of one out of two fused aromatic rings
was the naphthazenic hydrogenation class, where four
hydrogen atoms were added. Saturation of the terminal
of three- or four-hsed aromatic ring compounds has also
been included in this group. The unique hydrogenation
of an aromatic ring fused between aromatic rings
defines the phenanthrenic hydrogenation category, where
two hydrogen atoms are added.
There are several possible causes for separation into
distinct hydrogenation classes based on the number of
fused aromatic rings. As the number of fused aromatic
rings increases, the resonance stabilization energy per
aromatic ring decreases (Dewar, 1969) and the highest
electronic density increases (Neurock and Klein, 1993).
Both these factors can account for the observed increase
in numerator rate parameter magnitude (Korre et al.,
1995).
I
1 0.160 I 0.686 e 0.708 @@@
0.336 &
I 0.393 @ 0.379 @
0.0288 @ 0.200@ 0.599
89
0 . 1 3 0 8 !0.0362@ 0.608
I 0.0253&@ 0.480 8 0.428 &@
I I
Naphthalenic 'henanthrenic
The numerator rate parameters of Figure 23 implic-
itly contain a hydrogen pressure dependence, which, if
extracted, would further enhance the separation of the
three hydrogenation classes. That is, division of the rate
parameters by the hydrogen pressure raised to the
hydrogen stoichiometric coefficient, a,would decrease
the rate constant most for the benzenic class (a= 3)
and least for the phenanthrenic hydrogenation class (a
= 1).
The numerator rate parameters also encompass the
kinetically possible symmetries. For example, hydro-
genation of phenanthrene at the terminal ring can occur
a t two possible positions, while hydrogenation of tet-
rahydrophenanthrene at the terminal ring can occur at
only one position. Other examples of such symmetries
include hydrogenations of pyrene and chrysene a t the
middle ring and hydrogenations of s-hexahydropyrene
and s-octahydrochrysene. All these factors need to be
taken into account for the quantitative interpretation
of numerator rate parameter information (Korre, 1994;
Korre et al., 1995).
HydrogenatiodDehydrogenationEquilibria Al-
though the selected conditions and most measurements
were intended to emphasize the hydrogenation rate, the
longer-time mixture experiments allowed regression of
reliable dehydrogenation rate parameters for each step
in each network. This was revealed in the form of
equilibrium ratios, as shown in eqs 6 and 7. For
hydrogenation of an aromatic, (A), to a hydroaromatic
(HA),with n mol of H2, the equilibrium parameter, Kes,
can be obtained by dividing the equilibrium ratio, K,
by the hydrogen pressure to the nth power:
(7)
The equilibrium ratio may be viewed as the equilibrium
constant for 1 atm of hydrogen pressure. It also
possessed intuitive bounds. For example, an equilibri-
 Ind. Eng. Chem. Res., Vol. 34,No. 1, 1995 115

I I I
1OOOOO I 151. a I 55.3 @@ I
78.9 I 242. 4.11 I 12.6 I 7.84 @@@ 0.934 @@@
64.7 & II 170. e 2.34 & II 6.16 I
I 8.33 0.582 &
10.5 8I 14.9 @ 0.645 @ I 6.67 &) I 2.74 @ 0.238 @

188. 6.48 @ 3.76 & 0.681 @ 91.2 &@ 0.708 @

6.16 5.12 @@ 14.2 8 11.8 &@ I 29.0 0.511 @
809. 818 6.72 I 3.31 &@ 2.29 &@ 0.353 &@
- &I- g?jQ@ I I
I Benzenic Naphthalenic Phenanthrenic
Figure 24. Equilibrium concentration ratios for hydrogenation of polynuclear aromatics. (Shade indicates the ring being saturated. K
= KePHzn-I

1000

100

6
e-
m
10

A;
1 I I
I I
I I
I I
I I
I I

0.1 I
I
I
I
I
I

0.1 1 10 100 1000

Frye et al.
Figure 25. Comparison between literature and experimentally determined equilibrium ratios. (Hydrogenations in naphthalene and
phenanthrene network a t 350 "C and 68.1 atm of Hz.)

um ratio K < 1implies more aromatic than hydroaro-
matic at equilibrium, and thus indicates a compara-
tively unfavorable reaction at the given conditions. In
the present work the equilibrium ratio was of order
unity or higher.
The best-fit equilibrium ratios K are listed in Figure
24. Several qualitative trends are apparent. For
hydrogenation of an isolated aromatic ring, such as in
benzenic hydrogenation, where three hydrogen mol-
ecules are added, the equilibrium ratios are usually
much larger than unity. This implies that the fully
saturated (perhydrogenated) molecule is much more
abundant than the parent single-ring aromatic a t equi-
librium. The best-fit equilibrium ratio is very large for
xylene (K > 1000) and gradually decreases as more
naphthenic rings are added. Thus it appears that the
more complex the hydroaromatic structure, the lower
the equilibrium ratio.
Equilibrium ratios larger than unity were also found
for hydrogenation of a terminal aromatic ring fused to
only one additional aromatic ring, such as in the series
naphthalene, tetrahydrophenanthrene, octahydrochry-
sene, etc. Note that 2 mol of H2 are added in these
instances. These equilibrium ratios also dropped as
more naphthenic (and aromatic)rings were added to the
unit sheet. Indeed, the value for s- and as-hexahydro-
pyrene hydrogenation a t an internal ring was less than
unity. This implies that the hexahydropyrenes are more
abundant than the decahydropyrenes a t equilibrium
and explains the equilibrium limitations observed in the
overall pyrene network.
Comparatively small equilibrium ratios K < 1were
also observed for the hydrogenation of the middle-of-
three or -four aromatic rings, such as in the addition of
1 mol of H2 to phenanthrene, pyrene, dihydropyrene,
chrysene, and tetrahydrochrysene.
Figure 25 compares calculations of the equilibrium
ratios K based on experimental work by Frye and co-
workers (Frye, 1962; Frye and Weitcamp, 1969) against
those found in the present experimental work for
116 Ind. Eng. Chem. Res., Vol. 34, No. 1, 1995
reactions in the naphthalene and phenanthrene net-
work at 350 "C and 68.1 atm of Ha. An excellent
agreement persists over about 4 orders of magnitude,
lending credibility to the values reported here and
summarized in Figure 24.
Adsorption. The adsorption constant trends based
on aromatic ring number are consistent with an as-
sumption of acidhase interactions between the catalyst
and the adsorbed molecule. Indeed, the observed in-
crease in adsorption constants with increasing aromatic
ring number may be attributed to the concurrent
increasing basicity of the PNAs. This has been revealed
by both experimental measurements of gas-phase ba-
sicity (LaVopa and Satterfield, 1988)) as well as com-
putational chemistry calculations of proton affinity
(Neurock and Klein, 1993).
The adsorption equilibrium constants for the aromatic
ring number-based lumps listed in Table 4 are es-
sentially an average of the molecules present in mix-
tures of different compositions that contained the same
number of aromatic rings. This renders them a very
good estimate of the competitive inhibition in a mixture;
nonetheless, they must yet be considered as devoid of
rigorous microscopic structural significance (i.e., adsorp-
tion energetics or other adsorption fundamentals).
It is thus reasonable to suspect that significant
differences could be observed on a microscopic scale
within a lump. They would depend on the number of
saturated rings, their position with respect to the
aromatic ring(s), and the nature of their adsorption on
a given catalytic site. A bulky hydroaromatic molecule,
such as B-decahydropyrene, could adsorb flatly on the
catalytic surface, and thus reduce the number of sites
available to other molecules. Even with the same
energetics of its one aromatic ring adsorption lump, it
could thus appear in kinetics experiments to have a
higher adsorption constant than o-xylene, for example.
Such differences could be observed even between iso-
mers, such as A- and B-decahydropyrenes. Further
elaboration of these ideas could reveal more information
and will be pursued in a following publication (Korre
et al., 1995; Korre, 1994).
Conclusions
An extensive experimental plan provided a consistent
data base of quantitative reactivity information for 36
aromatic and hydroaromatic compounds containing up
to four aromatic rings subject to 45 reactions at 350 "C
and 68.1 atm of Hz.
o-Xylene hydrogenation proceeded with relatively
slow rates, inhibited by the presence of other aromatics.
Tetralin hydrogenation to cis- and tram-decalin was
equally slow, while dehydrogenation to naphthalene
occurred until equilibrium concentrations were reached.
Phenanthrene hydrogenation proceeded through tet-
rahydro- and octahydrophenanthrenes to complete satu-
ration, while experiments with dihydrophenanthrene
established it as a "dead end" in the network, its only
reaction being dehydrogenation t o phenanthrene. An-
thracene pathways were similar to those for phen-
anthrene. Pyrene hydrogenation pathways were equi-
librium limited, probably due to the high dehydro-
genation reactivity of the intermediate tetra- and hexahy-
dropyrenes; perhydrogenated products were detected,
though. Finally, chrysene hydrogenation was the fast-
est and the least affected by equilibrium or inhibition
considerations.
Three classes of hydrogenation were discerned, based
on the magnitude of saturation numerator rate par-
ameters: 1,benzenic (single isolated aromatic ring); 2,
naphthalenic (two isolated aromatic rings or terminal
of three- and four-aromatic ring systems); 3, phenan-
threnic (middle-of-three or four fused-aromatic rings).
Hydrogenation equilibrium ratios were much larger
than unity for the benzenic hydrogenation class, gener-
ally larger than unity for the naphthalenic hydrogena-
tion class, and smaller than unity for the phenanthrenic
hydrogenation class. There was excellent agreement
between the values reported here and those published
by Frye and co-workers (Frye, 1962) for the same
conditions.
Adsorption parameters were evaluated for aromatic
ring number-based lumps. They clearly increased with
increasing aromatic ring number, which is consistent
with an acid-base interaction between catalyst and
adsorbed molecule.
Acknowledgment
The authors acknowledge the financial support of
Mobil Research and Development Corp. (Paulsboro
Research Laboratory) and the State of Delaware, as
authorized by the State Budget Act of Fiscal Years
1990-1992. Mr. Dennis Kalaygian's help with the
laboratory experiments is greatly appreciated.
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Received for review March 17,1994
Revised manuscript received August 10,1994
Accepted August 26,1994*
@ Abstract published in Advance A C S Abstracts, November
1, 1994.