I n d . Eng. Chem. Res.

1991,30, 2021-2058 2021

REVIEWS

Reactivities, Reaction Networks, and Kinetics in High-pressure

Catalytic Hydroprocessing
Michael J. Girgis*J**
and Bruce C. Gates*it
Center for Catalytic Science and Technology, Department of Chemical Engineering, University of Delaware,
Newark, Delaware 19716, and Central Research Laboratory, Mobil Research and Development Corporation,
Princeton, New Jersey 08543

This paper is a critical and thorough (but not exhaustive) review of the literature of catalytic
hydroprocessing reactions. It includes data characterizing thermodynamics, reactivities, reaction
networks, and kinetics of hydrogenation of aromatic hydrocarbons, hydrodesulfurization, hydro-
denitrogenation, and hydrodeoxygenation. The subject is organized by reaction type, and there are
separate sections on competitive reaction and inhibition effects. The results summarized are judged
to be the most reliable and useful available to guide process modeling for hydroprocessing of heavy
fossil fuels. The review is designed for use as a reference; most of the quantitative results are
summarized in tables and figures, and a table of contents and a chart with names and structures
of the organic compounds are also included.

I. Introduction 2021 VIA. Effects of Additives on Aromatic 2045

11. Hydrogenation of Aromatic Hydrocarbons 2022 Hydrogenation
IIA. Thermodynamics 2022 VIAL Sulfur Compounds 2045
IIB. Reactivities 2023 VIAS. Oxygen Compounds 2045
IIC. Reaction Networks and Kinetics 2024 VIA3. Nitrogen Compounds 2046
IIC1. Monoaromatics 2024 VIB. Effect of Additives on HDS 2046
IIC2. Aromatics with Two Fused Rings 2025 VIB1. Aromatic Hydrocarbons 2046
IIC3. Aromatics with Three Fused Rings 2025 VIB2. Sulfur Compounds 2048
IIC4. Aromatics with Four Fused Rings 2026 VIB3. Oxygen Compounds 2048
IIC5. Five-Carbon-Membered-Ring 2026 VIB4. Nitrogen Compounds 2048
Aromatics VIC. Effect of Additives on HDO 2050
111. Hydrodesulfurization (HDS) 2027 VIC1. Sulfur Compounds 2050
IIIA. Thermodynamics 2027 VICB. Oxygen Compounds 2050
IIIB. Reactivities 2027 VIC3. Nitrogen Compounds 2051
IIIC. Reaction Networks and Kinetics 2029 VID. Effect of Additives on HDN 2051
IIIC1. Thiophene 2029 VID1. Aromatic Hydrocarbons 2051
IIIC2. Benzothiophene 2030 VID2. Sulfur Compounds 2052
IIIC3. Dibenzothiophene 2031 VID3. Oxygen Compounds 2053
IIIC4. Benzonaphthothiophene 2032 VID4. Nitrogen Compounds 2054
IV. Hydrodenitrogenation (HDN) 2032 VII. Multicomponent Mixtures 2054
IVA. Thermodynamics 2032 VIII. Conclusions 2055
IVB. Reactivities 2033 IX. Literature Cited 2056
IVC. Reaction Networks and Kinetics 2034
IVC1. Pyridine 2034 1. Introduction
IVC2. Quinoline 2036 Catalytic hydroprocessing ranks in importance with
IVC3. Acridine and Benzoquinolines 2038 other large-scale petroleum refining processes (cracking
IVC4. Nonbasic Nitrogen Compounds 2039 and reforming), and its application is growing to meet
IVC5. Aniline Derivatives 2040 several needs, including the processing of heavier feeds,
V. Hydrodeoxygenation (HDO) 2041 the production of high-performance lubricants, and the
VA. Thermodynamics 2041 introduction of cleaner burning fuels. In the long term,
VB. Reactivities 2041 the anticipated processing of liquids from tar sands, coal,
VC. Reaction Networks and Kinetics 2042 and shale will lead to major new hydroprocessing appli-
VC1. Phenolic Oxygen Compounds 2042 cations.
VC2. Heterocyclic Oxygen Compounds 2043 The following review is meant to provide a summary of
VC3. Ethers 2044 quantitative results characterizing the thermodynamics,
VI. Binary Mixtures 2044 reactivities, reaction networks, and reaction kinetics of
catalytic hydroprocessing. The emphasis is on results of
University of Delaware. high-pressure (55-170 atm) experiments with compounds
* Mobil Research and Development Corp. representative of the least reactive constituents of heavy
0888-5885/91/2630-2021$02.50/0 0 1991 American Chemical Society
2022 Ind. Eng. Chem. Res., Vol. 30, No. 9, 1991

feeds, Le., the compounds most pertinent for process Chart I. Structures of Selected Organic Compounds
modeling and design. The reactant compounds considered 1, Aromatic Hydrocarbons
are aromatic, including polycyclics found in heavy fractions
derived from petroleum and other fossil fuels. Data 5 6
7
characterizing reactivities of industrial feedstocks (e.g., 8
2 7
overall conversions of compound classes, and product 7
6 3 6 3 2
physical properties) are omitted here because the relevant 5 4

quantitative information is lacking in the open literature. Naphthalene Anthracene Phenanthrene Pyrene
The premise of this review is that, because of the great
difficulty in fundamental interpretation of results obtained 3 4
2 5
with commercial feeds, pure compound data are the best 1 6
source available for developing a sound understanding of 3
4 5
6
the chemistry of hydroprocessing and provide the best 2 7
1 9 6
available quantitative foundation for process modeling and
catalyst development. Fluoranthew Fluorene

Several classes of reactions occur simultaneously in

hydroprocessing-hydrogenation, hydrodesulfurization 2. Organosulfur Compounds
(HDS), hydrodenitrogenation (HDN), and hydro-
deoxygenation (HD0)-and these must all be considered
if the reactivity patterns of commercial feedstocks are to
be understood. In addition, inhibition by some reactants
and products markedly affects the reactivity. Accordingly,
in this review we fist consider separately hydrogenation
of aromatic hydrocarbons, hydrodesulfurization, hydro-
denitrogenation, and hydrodeoxygenation. A discussion 10
9
of inhibition effects follows, with emphasis on the modeling 1 11 10
8
2 9 2
of reaction inhibition resulting from competitive adsorp- 3 8 3
tion. The few investigations carried out with mixtures
containing three or more compounds are considered next.
The consideration of all of the major reaction classes and
the inhibition effects is a distinguishing feature of this
review; previous reviews (Schuit and Gates, 1973; Katzer 3. Organonitrogen Compounds
and Sivasubramanian, 1979; Furimsky, 1983; Vrinat, 1983;
Ho, 1988) have focused on single reaction types. Hydro-
cracking (by dual-function catalysts) and hydro- 8 9 1

demetalation are beyond the scope of the review; the latter

has been reviewed recently (Quann et al., 1988).
:Q: 7
6
2
3

Almost all the available results have been obtained with Pyrdine hinoline Aciiine 5,6-Eenzoquinoline
undeactivated commercial hydroprocessing catalysts typ-
ified by sulfided Co0-Mo03/r-A1203 (Co-Mo/A1203),
commonly used for hydrodesulfurization, sulfided NiO-
Mo03/y-A1203(Ni-Mo/A1203),which is similar to the
former but has higher activity for hydrogenation and is
typically applied for HDN, and sulfided NiO-W03/y-
A1203 (Ni-W/AI2O3). The selections made from the vast 7.8-Eenrcqumoline Carbazole
literature represent the authors' judgement of which data
appear to be most thorough, reliable, and internally con-
sistent. The reactivities and inhibition parameters are all
4.Organo-oxygen Compounds
represented in the same units, insofar as possible; however,
some literature data are reported incompletely and do not
allow determination of rate constants. For example, results
are sometimes given as pseudohomogeneous rate constants,
e.g., in units of s-l rather than L/(g of cata1yst.s).
We stress that not all the results presented here are
mutually consistent. Typically, the catalyst used by one 1-Naphthol Eenzoluran Dibenzoluran

group of investigators is different from that used by an-
other. Nonetheless, the results are valuable in providing
a comprehensive summary of hydroprocessing chemistry
and they offer valuable insights for modeling the kinetics;
this is the first compilation of quantitative results of this
kind.
This review is organized for easy reference. Chart I
includes structures and names of the more complex organic
compounds, and the table of contents will help the reader
go back and forth in the document. For each class of
reaction, the results are presented in sequence in the
following categories: thermodynamics, reactivities, reaction
networks, and kinetics. These categories overlap, but it
seems useful to present comparisons of the reactions of
various compounds in a group before presenting the
quantitative models of reaction networks and kinetics; the
latter are available for only a small number of compounds.
Most of the quantitative results are presented in tables and
figures.
11. Hydrogenation of Aromatic Hydrocarbons
IIA. Thermodynamics. Hydrogenations of aromatic
hydrocarbons are reversible, with equilibrium conversions
of hydrocarbons often being less than 100% under prac-
tical processing conditions. These reactions are exother-
mic; the extent of reaction at equilibrium decreases with

Table I. Equilibrium Constants for Hydrogenation of
Aromatic Hydrocarbons (Frye, 1962; Frye and
Weitkamp, 1969)
mo,,0
kcal/mol
log K at of organic
naphthalene + 2H2 - 300 "C 350 "C 400 "C reactant
-1.13 -2.03 -2.80 -30
tetralin
phenanthrene + H2 - -1.57 -1.94 -2.25 -12
-
9,lO-dihydrophenanthrene
fluorene + 3H2
cis-hexahydrofluorene
-2.08 -4.17 -5.27 -42
OThe enthalpies are derived from the slopes of the van't Hoff
plots and are assumed to be standard enthalpies of reaction, al-
though they are not listed as such by the authors.
increasing temperature. Thus increasing the temperature
to give higher rates of other reactions results in lower
equilibrium conversions in aromatic hydrogenations
and-because the hydrogenations are often fast enough
to be nearly equilibrated-lower actual conversions as well.
In practice, the lower equilibrium conversions are espe-
cially significant at lower pressures.
There are few thermodynamics data for polyaromatic
hydrocarbons and the products of their hydrogenation that
are sufficiently accurate to allow useful calculations of
equilibrium concentrations of partially hydrogenated
products. Frye (1962)and Frye and Weitkamp (1969)
measured the compositions of several aromatic hydro-
carbon-hydrogen mixtures at several temperatures and
pressures after equilibrium was attained. All species were
in the vapor phase. The hydrocarbons included biphenyl,
indene, naphthalene, phenanthrene, acenaphthene, and
fluorene. Results for naphthalene, phenanthrene, and
fluorene (Table I) show that the hydrogenation equilibrium
constants are less than unity at typical hydroprocessing
temperatures (usually greater than 340 OC for heavy
feedstocks). Consequently, operation at high hydrogen
partial pressures is necessary to hydrogenate aromatic
hydrocarbons to an appreciable extent. For example, an
increase in the hydrogen partial pressure from 9.7 to 37
atm increases the equilibrium conversion of naphthalene
from 17 to 84% at 396 OC (Frye, 1962;Frye and Weitkamp,
1969). Although data for other multiring compounds are
also available (Reid et al., 19871,the corresponding data
for the hydrogenated products are lacking. The data
available for benzene, some alkylbenzenes, and the prod-
ucts of their hydrogenation are more extensive (Stull et
al., 1969).
Thermochemical data are needed; in their absence,
group contribution methods can be used to estimate the
equilibrium constants (Reid et al., 1987). Benson and
co-workers (Shaw et al., 1977;Stein et al., 1977)extended
their group contribution method (Benson et al., 1969)for
the estimation of standard enthalpies, entropies, and
ideal-gas heat capacities of selected aromatic compounds
and their hydrogenation products. The group contribution
methods provide only rough approximations. For example,
the uncertainty in the standard enthalpy of formation of
hydrogenated aromatic hydrocarbons is typically as high
as 3 kcal/mol, resulting in uncertainties of more than an
order of magnitude in the computed equilibrium constants.
Equilibrium constants for liquid-phase-hydrogenation
reactions are not readily available. The application of the
gas-phase equilibrium constants obtained from the sources
cited above to hydroprocessing reactions occurring in the
liquid phase in industrial tricklebed reactors is not strictly
correct. However, Shaw et al. (1977)pointed out that
gas-phase equilibrium constants provide good approxi-
Ind. Eng. Chem. Res., Vol. 30,No. 9,1991 2023
mations for reactions occurring in the liquid phase because
enthalpies and entropies of reaction, which affect the value
of the equilibrium constant most strongly, change only
slightly upon a change from the gas to the liquid phase.
Accurate computation of equilibrium concentrations in
liquid-phase reactions also requires knowledge of activity
coefficients for all species, including hydrogen. Such data
are generally unavailable for a given hydrocarbon and the
products of its hydrogenation. Activity coefficients for the
reactants may be estimated with group contribution
methods such as UNIFAC (Reid et al., 1987). A correlation
for hydrogen solubility and liquid-phase fugacity in several
hydrocarbons and coal liquid fractions has been proposed
(Sebastian et al., 19811,but its applicability requires fur-
ther examination.
IIB. Reactivities. Most of the quantitative reactivity
data characterize reactions of individual aromatic hydro-
carbons with hydrogen. A few investigations have been
reported with mixtures of hydrocarbons chosen so that
inhibition effects were negligible.
Pseudo-first-order rate constants for hydrogenation of
benzene, biphenyl, naphthalene, and 2-phenylnaphthalene
catalyzed by Co-Mo/A1203 were determined to be 2.81 X
lo*, 3.00 X lo4, 5.78 X lo-&,and 7.06 X lo-& L/(g of
catalystss), respectively (Sapre and Gates, 19811,under the
conditions shown in Table 11. These data suggest the
following generalization: naphthalene and substituted
naphthalenes are an order of magnitude more reactive than
benzene and substituted benzenes. The greater reactivity
of naphthalene and 2-phenylnaphthalene was speculated
to be a consequence of the greater resonance stabilization
of diaromatic surface species formed by a-bonding of the
naphthalene moieties to exposed Mo cations, which were
postulated to be the catalytic sites. The relatively high
reactivity of naphthalene moieties evidently extends to
monoaromatic and diaromatic moieties that are fused with
five-carbon-membered rings; for example, hydrogenation
of the naphthalene moiety in fluoranthene is an order of
magnitude faster than hydrogenation of the benzene
moiety in fluorene (Lapinas et al., 1991). Comparable
quantitative data for aromatic hydrocarbons with three
or more fused aromatic rings are lacking.
The results of Sapre and Gates also demonstrate that
the effect of the phenyl substituent on the reactivity is
weak. This weak effect of single hydrocarbon substituents
is consistent with results (Aubert et al., 1988)showing that
the relative rate constants for hydrogenation of benzene,
ethylbenzene, biphenyl, cyclohexylbenzene, diphenyl-
methane, and (cyclohexylmethy1)benzene(under the con-
ditions shown in Table 11) were 2, 2, 6, 2, 3, and 2, re-
spectively. The small effect of single Substituents suggests
that neither steric nor electronic factors are large. Com-
parable data characterizing reactivities of polysubstituted
monoaromatic hydrocarbons are lacking.
Using literature data, Nag (1984)observed a linear
correlation between the logarithm of the hydrogenation
rates of aromatic hydrocarbons under hydroprocessing
conditions and their ionization potentials. Assuming that
reaction intermediates in hydrogenations are a-complexes
on the catalyst surface formed by the transfer of electrons
from the highest occupied molecular orbital (HOMO) of
the hydrocarbon to an unoccupied d-orbital on the metal,
Nag reasoned that a higher HOMO energy should result
in a more facile electron transfer and hence a more stable
a-complex. On the basis of the inverse proportionality
between the HOMO energy and the ionization potential,
the correlation between the logarithm of the hydrogenation
rate and the ionization potential was developed. The
2024 Ind. Eng. Chem. Res., Vol. 30,No. 9,1991

Table 11. Reaction Conditione in Network Studies of Hydrogenation of Aromatic Hydrocarbons

reactant conditions reference
1. Monoaromatics
benzene, biphenyl batch reactor, 325 "C, 75 atm, n-hexadecane solvent, Sapre and Gates, 1981
Co-Mo/AlZOS catalyst
benzene, biphenyl, ethylbenzene, batch reactor, 340 "C, 70 atm, n-decane solvent, Aubert et al., 1988
cyclohexylbenzene, diphenylmethane, Ni-Mo/A1203 catalyst
(cyclohexylmethyl)benzene
2. Two-Fused-Ring Aromatics
naphthalene batch reactor, 325 "C, 75 atm, n-hexadecane solvent, Sapre and Gates, 1981
Co-Mo/AlZOs catalyst
batch reactor, 35 atm, 350 "C, white oil solvent, Bhinde, 1979
Ni-Mo/AlzOs catalyst
2-methylnaphthalene liquid-phase flow reactor, 280-360 "C, 40-128 atm, Ho et al., 1988
Ni-Mo/A120Bcatalyst
l-methylnaphthalene trickle-bed reactor, 310-350 "C, 50 atm, Patzer et al., 1979
Ni-Co-Mo/A1203 and proprietary catalysts
2-phenylnaphthalene batch reactor, 325 "C, 75 atm, n-hexadecane solvent, Sapre and Gates, 1981
Co-Mo/Alz03 catalyst
3. Three-Fused-Ring Aromatics
anthracene batch reactor, 220-435 "C, 102 atm, Ni-W catalyst Wiser et al., 1970
(unsupported)
phenanthrene batch reactor, 200-380 "C, 102 atm, 2 h reaction time, Shabtai et al., 1978a
Ni-W/Al2Oa catalyst
flow reactor, 402-543 "C, 136-204 atm, nonacidic Wu and Haynes, 1975
alumina chromia
flow reactor, 316-538 "C, 103-171 atm, 1-4 WHSV, Huang et al., 1977
Co-Mo/A1203 catalyst
batch reactor, 430 "C, 100 atm, Ni-Mo/A1203 catalyst Lemberton and Guisnet, 1984
4. Four-Fused-Ring Aromatics
batch reactor, 341 "C, 69-205 atm, 0.6 WHSV, Shabtai et al., 1978a
Ni-W/Al2O3 catalyst
batch microreactors, 375-425 "C, 18-72 atm, Johnston, 1984
Co-Mo/A1203 catalyst
batch reactor, 348-400 "C,35-137 atm, n-hexadecane Stephens and Chapman, 1983;
solvent, Ni-Mo/A1203 catalyst Stephens and Kottenstette, 1985
5. Five-Carbon-Membered-Ring-Containing Aromatics
fluorene batch reactor, 310-380 "C, 153 atm, n-hexadecane Lapinas et el., 1991
solvent, Ni-W/AI2O3 catalyst
fluoranthene batch reactor, 310-380 "C, 153 atm, n-hexadecane Lapinas et al., 1987

-0-
2.81

I
x lo4

x 10.'
1.0 x
solvent, Ni-W/A1203 catalyst
10.6
Hydrocarbon
Hydrocarbons
Figure 1. Reaction networke for benzene and biphenyl propoeed by
Sapre and Gates (1981) (Table 11). The numbers over the arrows are
pseudo-first-order rate constants in L/(g of catalystd at 325 "C.
correlation is evidently valid only for aromatics that have
collinear aromatic ring centers (e.g., anthracene) without
bulky substituents.
IIC. Reaction Networks and Kinetics. IIC1. Mo-
noaromatics. Reaction networks for hydrogenation of
benzene and biphenyl (Table 11, Figure 1) proposed by
Sapre and Gates (1981)account for the reversibility, which
was confirmed for biphenyl hydrogenation in experiments
with cyclohexylbenzene as a reactant. The unidentified
secondary products were thought to be formed by isom-
erization of saturated six-membered rings to give me-
thylcyclopentane rings. Products containing partially
hydrogenated rings (e.g., cyclohexadienes or cyclohexenes)
were not formed in measurable amounts. Aubert et al.
(1988)reported similar networks, but although their re-
action conditions were similar to those employed to de-
termine the results of Figure l, they did not detect isom-
erization products and reported only relative rate con-
stants.
Aubert et al. also reported reaction networks for
ethylbenzene, cyclohexylbenzene, diphenylmethane, and
(cyclohexylmethy1)benzene(Table 11). The networks all
involve hydrogenation of the benzene ring. In the case of
diphenylmethane, the two monoaromatic rings are hy-
drogenated sequentially, as in the biphenyl network.
Isomerization products were not reported, and no reverse
reactions were included.
Inferring that biphenyl is representative of the least
reactive class of aromatic hydrocarbons, Sapre and Gates
(1982)chose biphenyl hydrogenation for measurement of
kinetics. They used a flow reactor operated under dif-
ferential conversion conditions (biphenyl conversion less
than 16% ), without characterizing the reverse reaction
quantitatively. Experimenta were conducted at 300-375
"C and at several hydrogen, biphenyl, and hydrogen sulfide
concentrations (66-328,53-26, and 8.5-38 mmol/L, re-
spectively) with a Co-Mo/A120, catalyst. The sole reaction
product was cyclohexylbenzene. An empirical rate equa-
tion proposed for biphenyl hydrogenation is shown in
Table I11 with parameter values at two temperatures. The
rate increased with feed biphenyl concentrations and ap-
proached a saturation value. The rate increased more than
linearly with hydrogen concentration in the liquid. Hy-
drogen sulfide inhibited the reaction. The parameters that
indicate adsorption equilibrium constants according to the
 Ind. Eng. Chem. Res., Vol. 30, No. 9,1991 2025

Table 111. Rate Equation Proposed by Sapre and Gates

(1982) for Biphenyl Hydrogenation, Parameter Values at
Two Temperatures, and Corresponding Activation
EnergiedHeats of Adsorptiona
- BZCCB
BICBPCH,S
' I
r=
(1 &CBP + BdCHfis)2(1+ Bijc~J'

300
temp, "C
350
E, or AH,
kcal/mol
El,L4/(mo13.gof catalystd 0.015 0.024 34
Bo L/(g of catalyst-s) 3.3 X 10" 5.0 X lo4 not given
Ea, L/mol 23.0 4.6 -14
E,, L/mol 25.6 12.0 -16
E5,L/mol 32.2 27.2 -5
OThe subscripts BP and CB denote biphenyl and cyclohexyl-
benzene, respectively.
6.1 X 10
Hydrocarbons
Figure 2. Reaction networks for naphthalene and 2-phenyl-
naphthalene hydrogenation proposed by Sapre and Gates (1981)
(Table 11). The numbera over the arrows are pseudo-first-orderrate
constants in L/(g of catalyst4 at 325 OC.
Langmuir-Hinshelwood formalism are roughly equal for
biphenyl, hydrogen sulfide, and hydrogen at the lower
temperature.
IIC2. Aromatics with Two Fused Rings. Quanti-
tative reaction networks have been reported for naph-
thalene hydrogenation (Table 11, Figure 2). The hydro-
genation is sequential, with the rate of tetralin hydrogen-
ation being an order of magnitude less than that of
naphthalene hydrogenation and about the same as that
of benzene hydrogenation. The reversibility of naphtha-
lene hydrogenation was confirmed by using tetralin as
reactant. The dehydrogenation rates of the two decalins
are negligible. Because of differences in the conditions
used by the two groups of investigators listed in Table 11,
quantitative comparison of Co-Mo/A1203 and Ni-Mo/
A1203 catalysts for naphthalene hydrogenation activity is
not possible.
These results are generally consistent with those ob-
tained with methyl-substituted naphthalenes (Table 11).
Ho et al. (1984) investigated the hydrogenation of 2-
methylnaphthalene and proposed a network involving the
sequential hydrogenation of the reactant to give two me-
thyltetralins, which were subsequently hydrogenated to
give methyldecalins. However, in experiments with 1-
methylnaphthalene, Patzer and co-workers (1979) found
that l-methylnaphthalene was first hydrodealkylated to
give naphthalene, with the latter reacting further by the
I R
I
Figure 3. Reaction pathways for anthracene hydrogenation and
hydrocracking suggested by the results of Wiser et al. (1970) (Table
11).
sequence shown in Figure 2. Extensive dealkylation
leading to removal of small substituents in commercial
feedstocks would markedly increase light gas yields and
hydrogen consumption, and a better understanding of the
extent of dealkylation as a function of substituent type is
needed.
The reaction network determined for 2-phenyl-
naphthalene (Table 11, Figure 2) is analogous to that for
naphthalene. The secondary products consist mostly of
phenyl-substituted decalins. The absence of cyclohexyl-
naphthalenes in the products is consistent with the slow
hydrogenation of monoaromatics relative to diaromatics.
The hydrogenation of the ring in 2-phenylnaphthalene to
which the phenyl substituent is bonded proceeds more
rapidly, possibly because of electron-donationeffects from
the phenyl substituents.
IIC3. Aromatics with Three Fused Rings. Com-
pounds with three fused rings, anthracene and phenan-
threne, have been investigated (Table 11), but quantitative
reaction networks have not been reported. The proposed
reaction pathways for anthracene are shown in Figure 3.
Although the initial rate of formation of 1,2,3,4-tetra-
hydroanthracene appeared to be nonzero, it was not pos-
sible to establish whether it was a primary product. At
435 "C, alkyl-substituted naphthalenes were detected in
the reaction products, demonstrating the occurrence of
cracking of the outer ring, presumably following isomer-
ization. The formation of 9,lO-dihydroanthracene is sig-
nificant because of the potential for hydrocracking 1mol
of anthracene to give 2 mol of valuable gasoline-boiling-
range monoaromatic products.
Phenanthrene hydrogenation has been investigated by
several workers (Table 11), but the pathways proposed all
differ and generalizations are difficult.
Having measured product selectivities while varying the
temperature at constant reaction time and pressure,
Shabtai et al. (1978a) proposed that 9,lO-dihydro-
phenanthrene and 1,2,3,4-tetrahydrophenanthrenewere
primary products. 9,lO-Dihydrophenanthrenewas postu-
lated to be relatively unstable because of the strain in its
central hydrogenated ring and was assumed to undergo
dehydrogenation rapidly to give phenanthrene. Per-
hydrophenanthrene was formed only slowly, presumably
because of the sterically hindered central ring of ita pre-
cursor, sym-octahydrophenanthrene. The latter was pro-
posed to be formed from 1,2,3,4-tetrahydrophenanthrene.
Some edgewise adsorption of sym-octahydrophenanthrene
is inferred to have occurred, as producta were detected with
a partially hydrogenated central ring. The suggested
pathways, though not inconsistent with the data, would
be more convincing if the extrapolation of the selectivities
were performed using isothermal data. Moreover, the
reactant conversions were not specified; inference of the
2026 Ind. Eng. Chem. Res., Vol. 30, No. 9, 1991
pathways based on selectivity extrapolations is more
plausible at lower conversions.
Haynes and co-workers (1975) proposed reaction path-
ways similar to those suggested by Shabtai et al., but an
additional reaction was included whereby 9,lO-dihydro-
phenanthrene was hydrogenated reversibly to give
1,2,3,4-tetrahydrophenanthene; the reasons for including
this reaction are not clear. Another investigation (Wu and
Haynes, 1977) indicated the equilibrium limitation of the
hydrogenation. Cracking of the saturated outer ring oc-
curred at temperatures exceeding 427 O C , forming mostly
n-butyltetralins; cracking at the central ring did not occur
appreciably.
9,10-Dihydrophenanthrene, 1,2,3,4-tetrahydro-
phenanthrene, and sym-odahydrophenanthene were also
the predominant products at lower phenanthrene con-
versions, as observed by Lemberton and Guisnet (1984).
These authors postulated that the decreasing yields of
9,lO-dihydrophenanthreneat higher phenanthrene con-
versions were the result of conversion of the dihydro-
phenanthrene to give 1,2,3,4-tetrahydrophenantheneand
sym-octahydrophenanthrene; it is not evident why other
pathways (e.g., 9,10-dihydmphenanthrenedehydrogenation
to give phenanthrene) were ruled out. The higher yields
of cracking products (e.g., butylnaphthalenes) and isom-
erization products (having methylcyclopentane rings) as
well as the absence of perhydrophenanthrene isomers at
the higher conversions agree qualitatively with the results
of Haynes and co-workers.
In summary, the proposed pathways suggest that 9,lO-
dihydrophenanthreneand 1,2,3,4tetrahydrophenanthrene
are probably primary products. Interconversion of the
latter is possible but has not been established. The se-
lectivities to these products, the pathways to secondary
products, and the occurrence of central-ring opening all
require further investigation. Kinetics data are especially
needed.
IIC4. Aromatics with Four Fused Rings. Quanti-
tative networks have not been reported for hydrogenation
of four-ring aromatic hydrocarbons. The reported inves-
tigations have focused on the determination of product
distributions under various reaction conditions.
Several investigations of pyrene hydrogenation have
been conducted with thorough product analyses, but only
a few of these have been performed at high pressures with
typical hydroprocessing catalysts (Table 11). Johnston
(1984) demonstrated that equilibrium was attained be-
tween pyrene and 4,5-dihydropyrene, the predominant
hydrogenation product at longer reaction times at 375 OC
and 72.5 atm. At 425 OC, a constant concentration ratio
was attained but more rapidly and with a smaller value
than at the lower temperature. asym-Hexahydropyrene,
an unidentified hexahydropyrene isomer, and small
amounts of 4,5,9,10-tetrahydropyrenewere also detected.
The reversibility of the pyrene hydrogenation reaction was
c o n f i i e d by the formation of pyrene from its hydrogen-
ation products when the latter were allowed to react under
nitrogen.
Stephens and co-workers (Stephens and Chapman, 1983;
Stephens and Kottenstette, 1985)ale0 found that the yields
of pyrene and the major product, 4,5-dihydropyrene, ap-
proached constant values with increasing space time.
Other hydrogenation products included 4,5,9,10-tetra-
hydropyrene, sym-hexahydropyrene, and asym-hexa-
hydropyrene. Decahydropyrenes and perhydropyrenes
were also formed, but in trace amounts. The latter
products were not obeerved by Johnston, probably because
of the lower pressures employed in his work. Pseudo-
first-order rate constants were estimated for the hydro-
genation of pyrene to give 4,5-dihydropyrene and the re-
verse reaction only. The equilibrium constant for the
hydrogenation was determined, from which the standard
enthalpy of hydrogenation was estimated to be -10.6
kcal/mol, in good agreement with Johnston's determina-
tion (-10 kcal/mol).
From measurements of product selectivities at constant
temperature and space velocity and various hydrogen
partial pressures, Shabtai et al. (1978a) deduced that
4,5-dihydropyrene was a primary product that was con-
verted to asym-hexahydropyrene at higher pressure. The
small yield of 4,5,9,10-tetrahydropyrene,a presumed hy-
drogenation product of 4,5-dihydropyrene, is in agreement
with results of Johnston and Stephens et al. and was at-
tributed to its instability arising from its two strained
hydroaromatic rings. Perhydropyrene formation was
proposed to occur via hydrogenation of
1,2,3,3a,4,5,5a,6,7,8-decahydropyrene, the latter being
formed by the presumed hydrogenation of asym-hexa-
hydropyrene. Perhydropyrene was formed in appreciable
amounts only at pressures greater than 137 atm, presum-
ably because the proposed hydrogenation of the hindered
aromatic ring in decahydropyreneis slow. The proposed
pathways are open to some question for the same reasons
given earlier in reference to these workers' proposed
phenanthrene reaction pathways.
The results of these investigations all imply that equi-
librium considerations take on increasing importance with
an increasing number of rings in fused-ring aromatics.
Thus, higher hydrogen partial pressures are essential for
converting pyrene (and higher molecular weight poly-
aromatics) appreciably, especially to give fully hydrogen-
ated products. These high pressures imply a need for
developing more active catalysts so that the thermody-
namic advantage of lower temperatures can be realized.
Furthermore, the predominant formation of 4,5-dihydro-
pyrene implies that it is an appropriate model compound
for investigations of ring opening by dual-function cata-
lysts. Also, the rapid hydrogenation to give dihydro speciea
may also apply to more highly fused aromatics (e.g., co-
ronene), and the rapid hydrogenation of such bulky species
may be mass transfer controlled.
IIC5. Five-Carbon-Membered-RingAromatics.
Quantitative reaction networks for the hydrogenation of
fluoranthene and fluorene, each containing a five-carbon-
membered ring, have been reported (Lapinas et al., 1987,
1991) (Table 11). The fluoranthene network proposed by
these investigators is shown in Figure 4 with representative
values of the pseudo-first-order rate constants at 380 OC.
The dehydrogenations of 1,2,3,lObtetrahydrofluoranthene
and sym-decahydrofluorantheneto give fluoranthene and
1,2,3,1Ob-tetrahydrofluoranthene,respectively, were ki-
netically significant under these conditions. Hexahydro-
fluoranthene and asym-decahydrofluoranthene were
formed in appreciable amounts at the higher temperatures
only, as expected from the slow hydrogenation of mono-
aromatic moieties.
The network proposed for fluorene (Figure 4) involves
the sequential hydrogenation of the aromatic rings. The
dehydrogenation reactions were apparently insignificant
under these conditions, in contrast to the situation for
fluoranthene. The two isomerization products were formed
only in trace amounts, even at the highest temperature
(380 "0,and consequently rate constants were not esti-
mated for their formation. The slow hydrogenation of
fluorene relative to that of fluoranthene (to give
1,2,3,10b-tetrahydrofluoranthene)is consistent with the

-
1.4
7.2
x
x
10.~
10.6 2.3 X 10
1.01 x 10.'
Y 2-propanethiol + H2
1.3 x 10.41
15 x 10.41
053 V a
Figure 4. Reaction networks for fluoranthene and fluorene pro-
posed by Lapinas et al. (1987,1990) (Table 11). The numbers next
to the arrow8 are pseudo-firsborder rate constants in L/(g of cata-
1yst.s) at 380 O C .
slower hydrogenation of monoaromatic moieties than of
naphthalene moieties (because the methylene group in
fluorene effectively destroys the coplanarity of its two
aromatic rings). The relatively fast hydrogenation of the
biphenyl-like 1,2,3,1Ob-tetrahydrofluorantheneto give
sym-decahydrofluoranthene in comparison with the hy-
drogenation of fluorene was attributed to the relaxation
of ring strain upon hydrogenation of 1,2,3,10b-tetra-
hydrofluoranthene.
Quantitative comparisons of the reactivities of fluorene
and fluoranthene with those of fused-ring aromatics have
not been reported. Such comparisons would be especially
instructive for determining whether the five-carbon-mem-
bered ring hydrocarbons should be considered as a separate
reaction class for purposes of modeling hydrogenation
reactions of aromatic hydrocarbons.
111. Hydrodesulfurization (HDS)
HDS has long been a major refining process. One of its
purposes is the removal of sulfur from naphtha reformer
feedstocks; another is the removal of sulfur from heavier
fractions to minimize the emissions of sulfur oxides from
refineries and power plants. With continuing interest in
the hydroprocessing of high-boiling petroleum fractions
(e.g., residua) and with increasingly stringent air-quality
regulations demanding removal of even the least reactive
organosulfur compounds, recent research in HDS has been
directed at the chemistry of thiophenic compounds, be-
cause these are the least reactive organosulfur compounds
in petroleum and other fossil fuels (Gates et al., 1979).
IIIA. Thermodynamics. The HDS of organosulfur
compounds is exothermic and essentially irreversible under
the reaction conditions employed industrially (e.g., 340-425
"C and 66170 atm) (Gates et al., 1979; Speight, 1981;
Vrinat, 1983). Representative values of the gas-phase-
hydrodesulfurization equilibrium constants of several or-
ganosulfur compounds, including a mercaptan, a sulfide,
and a heterocyclic compound, are listed in Table IV with
the corresponding standard enthalpies of reaction. The
Ind. Eng. Chem. Res., Vol. 30, No. 9, 1991 2027
Table IV. Equilibrium Constants for the HDS of Selected
Organosulfur Compounds (Speight, 1981)
mom.'
kcal/m;i of
log K at organoeulfur
- 227 O C 427 O C
6.05 4.45
reactant
-13
propane + H a
thiacyclohexane + 2H2 - 9.22 5.92 -27
n-pentane + H2S
thiophene + 4H2
n-butane + H2S
- 12.07 3.85 -68
@Theenthalpies are assumed to be standard enthalpies of reac-
tion, although they are not listed as such by the author.
Table V. Reactivities of Several Heterocyclic Sulfur
Compoundso Determined by Nag et al. (1979)
pseudo-first-
order rate
const, L/
reactant structure (g of catdy8t.s)
thiophene 1.38 X lo-*
benzothiophene 8.11 X lo-'
dibenzothiophene 6.11 X lod
benzo[blnaphtho- 1.61 X lo-'
[2,3-d]thiophene
7,8,9,10-tetrahydro- 7.78 X lod
benzo[blnaphtho-
[2,3-d]thiophene
Reaction conditions: batch reactor using n-hexadecane solvent
(0.25 mol % reactant concentration), 300 O C , 71 atm, Co-Mo/
A1208 catalyst, each compound reacted individually.
equilibrium constants all decrease with increasing tem-
perature, consistent with the exothermicity of HDS, and
approach values much less than 1 only at temperatures
considerably higher than those required in practice.
Thermodynamics data for organosulfur compounds
present in higher boiling fractions (Le., multiring hetero-
cyclics) are unavailable, except for recent data for di-
benzothiophene HDS (Vrinat, 1983). The latter results
indicate that dibenzothiophene HDS to give biphenyl is
also favored at temperatures representative of industrial
practice and is exothermic (AHo = -11 kcal/mol). Ex-
trapolation of the latter results suggests that the HDS of
higher molecular weight organosulfur compounds (e.g.,
benzonaphthothiophenes) is also favored.
As will be discussed subsequently, sulfur removal occurs
either with or without hydrogenation of the heterocyclic
ring. The pathways involving prior hydrogenation of the
ring can be affected by thermodynamics because hydro-
genation of the sulfur-containing rings of organosulfur
compounds is equilibrium-limited at practical HDS tem-
peratures. For example, the equilibrium constant for
hydrogenation of thiophene to give tetrahydrothiophene
is less than unity at temperatures above 350 O C (Vrinat,
1983). Thus, sulfur-removal pathways via hydrogenated
organosulfur intermediates may be inhibited at low pres-
sures and high temperatures because of the low equilib-
rium concentrations of the latter species.
IIIB. Reactivities. The reactivities of a number of
organosulfur compounds, reported as the pseudo-first-
order rate constants for the disappearance of each at 300
OC and 71 atm, are given in Table V (Naget al., 1979);the
2028 Ind. Eng. Chem. Res., Vol. 30, No. 9,1991
experiments were conducted with a batch reactor and a
Co-Mo/A1203 catalyst, with the reactants dissolved in
n-hexadecane solvent. With the exception of benzo[b]-
naphtho[2,3-d]thiophene,the organosulfur reactants were
converted to give hydrocarbon products, implying that the
rates of disappearance are equal to the rates of sulfur
removal for these reactants. The three-ring compounds
are 1 order of magnitude less reactive than the two-ring
compounds, but the reactivity is similar for compounds
having three or more rings. However, other patterns of
reactivity have also been reported. Kilanowski et al. (1978)
found approximately equal HDS reactivities for thiophene,
benzothiophene, and dibenzothiophene in experiments
with a pulse reactor at 1 atm and 450 OC and with a Co-
Mo/A1203 catalyst. In experiments at 5-30 atm with
reactants in the vapor phase, Van Parijs et al. (1986)found
sulfur removal from thiophene to be substantially slower
than that from benzothiophene. Benzothiophene and
dibenzothiophene were found to have similar HDS re-
activities in experiments with a trickle-bed reactor at 59
atm with strong inhibitors such as quinoline present in the
feed (Rollmann, 1977).
The contrasting patterns of reactivities in HDS suggest
that they depend strongly on the reaction conditions. HDS
rates are functions of several variables (Tables X and XI),
including concentrations of organic reactants and products,
hydrogen, and hydrogen sullide. Comparison of reactivities
should thus be made when inhibition by other organic
compounds is weak and when concentrations of hydrogen
and hydrogen sulfide are similar to those used commer-
cially. The data in Table V, referring to the reactants in
a liquid phase, are probably most representative of in-
dustrial conditions.
The high-pressure reactivity data in Table V imply that
dibenzothiophene is one of the compounds most repre-
sentative of the unreactive organosulfur compounds in
higher boiling fractions of fossil fuels. Because it is readily
available commercially, it is a good model compound for
characterizing the HDS chemistry of heterocyclic sulfur
compounds.
The effect of methyl substituents on the reactivity of
dibenzothiophenehas been investigated by Houalla et al.
(1979)(Table VI). The HDS of the reactants listed in
Table VI is described by pseudo-first-order kinetics. To
a first approximation, the HDS pathways of the 2,8-and
3,7-dimethyldibenzothiophenesare as follows:
dimethyl-substituted dibenzothiophene
dimethyl-substituted biphenyl
--
dimethyl-substituted cyclohexylbenzene
The methyl substituents in these positions decrease the
reactivity only slightly.
In contrast, methyl substitution at the 4-position or at
the 4- and 6-positions results in an order of magnitude
decrease in reactivity (Table VI). In addition, the yield
of the respective substituted cyclohexylbenzene is higher
than that of the corresponding substituted biphenyl, in-
dicating that methyl substituents in the 4- or the 4- and
6-positions in dibenzothiophene cause hydrogenation to
occur to a larger extent than in the other substituted di-
benzothiophenes before the sulfur is removed. Because
hydrogenation of biphenyl is very slow under these con-
ditions, the higher yield of cyclohexylbenzene implies that
hydrogenation of the substituted dibenzothiophenes oc-
curs, with the cyclohexylbenzene produced predominantly
from the hydrogenolysis of the hydrogenated dibenzo-
thiophenes.
These methyl-substituted dibenzothiophenes are now
recognized as the organosulfur compounds that are most
Table VI. Reactivities of Selected Methyl-Substituted
Dibenrothiophener' As Determined by Houalla et al. (1980)
pseudo-first-
order rate
const, L/
reactant structure (g of catalystvs)
dibenzothiophene 7.38 x 106
. . ~-
l,&dimethyldibenzo- / 6.72 X loa
thiophene
3,7-dimethyldibenzo- 3.53 x 10-5
thiophene
4,6-dimethyldibenzo- 4.92 X 10"
thiophene
4-methyldibenzothio- 6.64 X 10"
phene
Reaction conditions: flow reactor, n-hexadecane carrier oil,
each reactant allowed to react individually at 300 "C at 102 atm in
the presence of a Co-Mo/A1203 catalyst.
slowly converted in the HDS of heavy fossil fuels. One of
the challenges for future technology is to find catalysts and
processes to desulfurize them. Compounds such as 4-
methyldibenzothiophene are evidently the most appro-
priate model compounds for characterization of new cat-
alysts and processes for heavy feeds.
The observation that the reactivity of the methyldi-
benzothiophenes substituted at positions a to the sulfur
atom is only 1 order of magnitude smaller than those of
the other substituted dibenzothiophenes (Table VI) in-
dicates that there is not a significant steric effect and
therefore suggests that adsorption of the sulfur compound
does not proceed in an end-on manner through the sulfur
atom (Lipsch and Schuit, 1969). If end-on adsorption
predominated, the rate constant for HDS of 4,6-di-
methyldibenzothiophene would be expected to be several
orders of magnitude less than that for 4-methyldibenzo-
thiophene. A multipoint adsorption model was therefore
proposed by Kwart et al. (1980)involving the adsorption
of the organosulfur compound through the sulfur atom and
also through the C1-Cp bond (i.e., the bond between the
carbon atoms that are in the a-and @-positionsrelative
to the sulfur atom). Consistent with this picture, Sauer
et al. (1989)proposed rekction mechanisms for thiophene
HDS on the basis of presumed analogies to molecular
organometallic chemistry.
A multipoint adsorption mechanism is also consistent
with the results of Singhal et al. (1981). The conversions
of the hindered compounds tetramethylthianthrene and
tetraphenylthiophene (Table VII) were found to be similar
to that of the unhindered thianthrene, which suggests that
adsorption of the organosulfur compounds cannot involve
just the coordination of the sulfur atom; adsorption of the
organosulfur reactants through their aromatic rings must
also occur. Moreover, the sulfur atom in tetraphenyl-
thiophene is especially electron deficient because of the
electron-withdrawing effect of the phenyl groups. Con-
sequently, tetraphenylthiophene adsorption on the catalyst
via the sulfur atom alone is even less likely. The higher
reactivity of the thianthrenes relative to dibenzothiophene
is attributed to the folded structure of the thianthrenes,
which have more localized lone-pair electrons on the sulfur
atoms, which are in turn more exposed. Thus,coordination
 Ind. Eng. Chem. Res., Vol. 30, No. 9, 1991 2029

Q
---
Table VII. Conversions of Heterocyclic Organosulfur
Commundso Invertiloted by Sinehal et al. (1981)
96 / \r

thianthrene
reactant structure
conver-
sion p
\
1
/"
p\/
1,4,6,9-tetramethylthianthrene Figure 5. Thiophene reaction pathways suggested by early low-
pressure studies (Gates et al., 1979).

benzene with the reactivities of benzenes having a variety

tetraphenylthiophene
dibenzothiophene 40-45
O Reaction conditions: vapor-phase flow reactor, 310 "C,41 atm,
space velocity of 6 g/(g of catalystah), Co-Mo/A1203catalyst with
large stoichiometric excess of hydrogen present.
Table VIII. Comparison of Reactivities of Compounds with
Folded Structums with that of Dibenzothiophene (Aubert
et al., 1986)O
re1
pseudo-first-order
reactant structure HDS rate const
thianthrene 12.6
phenothiazine H 11.7
phenoxathiin 10.8
thioxanthene 9.2
dibenzothiophene 1.0
O Reaction conditions: batch reactor, 340 O C , 70 atm, n-decane
solvent, Ni-Mo/A120s catalyst, each reactant investigated sepa-
rately.
of the sulfur atom is evidently important for the rapid
HDS of the thianthrenes.
The HDS reactivities of other folded thianthrene-like
compounds containing different heteroatoms are summa-
rized in Table VI11 (Aubert et al., 1986). The high re-
activities of these folded compounds (in comparison with
that of the planar dibenzothiophene) are attributed to the
relatively small energy difference between the transition
state and the adsorbed state of the folded molecules. The
higher reactivity of phenothiazine is inferred not to be a
consequence of a higher electron density on the benzenoid
rings [as had been suggested (Kwart et al., 1982; Geneste
et al., 1983)] as its reactivity is about the same as those
of compounds such as thioxanthene that have nondonor
substituents.
Some comparisons of the reactivities of organosulfur
compounds with thoae of aromatic hydrocarbons have been
reported. Moreau et al. (1987) compared the reactivity of
of heteroatom substituents, including thiophenol and di-
phenyl sulfide. Compounds having electron-withdrawing
substituents such as sulfur underwent hydrogenolysis re-
actions preferentially, i.e., scission of the bond between the
substituent and the aromatic carbon atom predominated
over the hydrogenation of the aromatic ring; the hydro-
genolyses of thiophenol and diphenyl sulfide were more
rapid than hydrogenation of benzene by more than 2 or-
ders of magnitude with a Ni-Mo catalyst at 340 O C and
70 atm. These results are in qualitative agreement with
those of Broderick et al. (1982), who found that dibenzo-
thiophene HDS was more rapid than benzene or biphenyl
hydrogenation with a Co-Mo catalyst. Broderick et al. ala0
reported that benzonaphthothiophene conversion was
more rapid than hydrogenation of 2-phenylnaphthalene.
However, benzonaphthothiophene conversion involved
both hydrogenation and hydrogenolysis occurring in par-
allel, and the rate of benzonaphthothiophene HDS was
comparable to that of 2-phenylnaphthalene hydrogenation.
Therefore, the results of Moreau et al. cannot be extended
to multiring aromatics.
IIIC. Reaction Networks and Kinetics. Experiments
leading to the proposal of reaction networks have been
carried out for thiophene, benzothiophene, dibenzo-
thiophene, and two isomers of benzonaphthothiophene. In
several investigations, the effects of the reactants and
products on the reaction rate were determined, leading to
the formulation of rate expressions.
IIIC1. Thiophene. Early thiophene HDS investiga-
tions, the great majority of which have been performed at
atmospheric pressure, have been reviewed (Gates et al.,
1979; Vrinat, 1983). Thiophene HDS evidently proceeds
by two parallel pathways (Figure 5), although the reaction
network is not completely understood, with results of
different investigators being in less than full agreement.
Rate equations from the low-pressure experiments indicate
that thiophene inhibits its own HDS; in some investiga-
tions, hydrogen sulfide has been found to inhibit HDS.
The possibility of inhibition by hydrogen is difficult to
assess because only small ranges of hydrogen partial
pressure have been used (Vrinat, 1983). Hydrogenation
and hydrogenolysis are inferred to occur on two different
kinds of sites since hydrogen sulfide affects rates of
thiophene hydrogenolysis and olefin hydrogenation dif-
ferently (Gates et al., 1979).
In a thorough set of experiments characterizing HDS of
thiophene in the vapor phase (Van Parijs and Froment,
1986),conditions were varied over a wide range (Table E).
A reaction network was proposed in which thiophene is
hydrodesulfurized to give 1-butene and cis- and tram-2-
butene, followed by hydrogenation of the butenes to give
butane. Neither tetrahydrothiophene nor butadiene
(which was proposed to be hydrogenated rapidly to give
the three butenes) was detected. Two different kinds of
catalytic sites were assumed, one for thiophene hydro-
genolysis and one for butene hydrogenation, in accordance
with results of low-pressure experiments (Vrinat, 1983).
2030 Ind. Eng. Chem. Res., Vol. 30,No. 9, 1991

Table IX. Reaction Conditions for HDS Network Studies

reactant conditions reference
thiophene vapor-phase flow reactor, 260-350 "C, 2-30 atm, molar H2/thiophene V& Parijs and Froment, 1986
ratio of 4-9, Co-Mo/A120t catalyst
benzothiophene batch reactor, liquid phase, 200-400 "C, 86 atm, Co-Mo/Al203 Daly, 1978
catalyst
batch reactor, liquid phase, 200-300 "C, 50 atm, Co-Mo/A1203 Geneste et al., 1980
catalyst
vapor-phase flow reactor, 240-300 "C, 2-30 atm, H2/benzothiophene Van Parijs et al., 1986
mole ratio of 4-9, n-heptane solvent, Co-Mo/A1208 catalyst
dibenzothiophene two reactor systems with Co-Mo/A1203catalyst: (a) flow reactor, 300 Houalla et al., 1978
"C, 102 atm, n-hexadecane solvent (0.15 mol % reactant); (b) batch
reactor, 300 "C, 71 atm, n-hexadecane solvent (0.37 mol % reactant)
flow reactor, 275-325 "C, 177 atm, n-hexadecane solvent, 0.2-4 mol % Broderick and Gates, 1981
reactant, Co-Mo/A1203 catalyst
batch reactor, 350 "C, 35 atm, n-hexadecane solvent, Ni-Mo/A1203 Bhinde, 1979
catalyst
benzo[b]naphtho[2,3-d]thiophene batch reactor, 300 "C, 71 atm, n-hexadecane solvent, Co-Mo/A1203
~~
Sapre et al., 1979
catalyst
benzo[b]naphtho[ 1,2-d]thiophene batch reactor, 250 "C, 40 atm, Ni-Mo/A1203 catalyst Vrinat, 1983

Table X. Rate Equations for Thiophene Hydrogenolysis

and Butene Bydragenation Assuming Dissociatively
Adsorbed Hydrogen (VanParijs and Froment, 1986)
1. Thiophene hydrogenolysis on u sites:

rT,. =
~T,DKT,$HJ'TPH~

[1 + (KHg,8HJ1'* + K T . p T + K H f i , p H & u / P H 2 1 s
2. Butene hydrogenation on T sites:
kB,$8,$H~P$H~
rA,r
[1 + (KH,?H2)"2 + KA,PA + K B , r h 1 2
where the subscripta T , A, and B denote thiophene, butane, and
butene, respectively.
Parameter values at 260 "C are as follows:
kT,, = 5.22 X 10' exp(-29.9/RT) 2.82 X lo4
K T ,=~ 6.60 X lo-' exp(lO.'l/RT) = 13.7
KH2,0 = 0.536
K ~ f i 91.2
ke,? = 2.21 x 10" exp(-38.1/RT) = 5.16 x lo4
Kkr = KB,, = 4.07 X lo-' erp(lO.6/RT) = 8.87
KH~,,= 8.88 X lo-'' e~p(-28.4/RT) = 6.02 X
where the rate parameters k and adsorption parameters K have
unita of mol/(g of catalysts) and atm-', respectively. The
adsorption parameter for hydrogen sulfide is dimeneionlees.
These resulta pertain to the temperature range 260-350 OC.
The data were correlated best by either of two sets of
Langmuir-Hinshelwood rate equations, one based on a
rate-determining surface reaction between adsorbed
thiophene and molecularly adsorbed hydrogen and the
other differing only in that hydrogen is assumed to be
diasociatively adsorbed, which is a more realistic postulate.
In each case, it was assumed that hydrogen sulfide was
formed by reaction of gas-phase hydrogen with adsorbed
sulfur by an Eley-Rideal mechanism. The rate equations
based on the assumption of dissociatively adsorbed hy-
drogen are given in Table X with the parameter values for
reaction at 260 OC. The existence of two different kinds
of sites was justified a posteriori by the large difference
between adsorption equilibrium constants for hydrogen
on the two sites (Table X). The adsorption parameters
of the organic compounds exceed those for hydrogen by
1-2 orders of magnitude. Hydrogen sulfide is a strong
inhibitor of hydrogenolysis but does not inhibit hydro-
genation. The data were also fitted to a model in which
the two kinds of sites are interconverted at a rate de-
pending on the hydrogen sulfide partial pressure, but the
fit was not substantially better with this more complicated
model.
IIIC2. Benzothiophene. There have been few quan-
titative investigations of benzothiophene HDS at high
1
W
Figure 6. Reaction network for benzothiophene proposed by Van
Parijs et al. (1986). Reaction conditions are given in Table IX.
pressures (Vrinat, 1983). The reported high-pressure ex-
periments with liquid-phase reactants (Table IX)lead to
contradictory conclusions regarding the network; whereas
Daly (1978) reported that benzothiophene HDS gives
ethylbenzene by either of two parallel pathways, Geneste
et al. (1980) reported that ethylbenzene is formed from a
dihydrobenzothiophene intermediate. The only rate con-
stants reported were for benzothiophene disappearance.
A quantitative network (Figure 6) has been reported for
conversion of vapor-phase benzothiophene (Van Parijs et
al., 1986) at higher pressures (Table E). Styrene was not
detected and was assumed to be hydrogenated rapidly to
give ethylbenzene after being formed from bemthiophene.
As in the thiophene study reported by the same authors
(Van Parijs and Froment, 1986), two different types of
catalytic sites were assumed: one for hydrogenolysis of
bemthiophene and of 1,2-dihydrobenzothiopheneand one
for hydrogenation of benzothiophene. A sequential design
of experiments was used to minimize the number of data
required for model discrimination and parameter estima-
tion. A best-fit rate equation (Table XI) was based on a
mechanism in which the surface reaction is the rate-lim-
iting step on both types of sites, with dissociative ad-
sorption of hydrogen and the rate-limiting step involving
simultaneous addition of two hydrogen atoms. The values
of the parameters in Table XI indicate strong inhibition
of benzothiophene hydrogenation by ethylbenzene. Hy-
drogenation of benzothiophene is reversible. Inhibition
by hydrogen on the hydrogenation sites is negligible.
Hydrogen sulfide inhibits hydrogenolysis, but not hydro-
genation, as for thiophene.
The functional forms of the rate equations based on the
assumption of dissociative adsorption of hydrogen are
identical for bemthiophene and thiophene (Tables X and
XI). This consistency suggests equivalent mechanisms.
Moreover, the adsorption parameters have similar values,
which suggests that the parameters have a physical

Table XI. Rate Equations and Parameter Values for
Benzothiophene Network (Figure6) Proposed by Van
P a d s et al. (1986)
~
1. Hydrogenolyeis of benzothiophene on u sites:
~ B , ~ B , J H ~ B B P H ~
[1 + ( K H s ~ H , ) " ' + ( K H f i , p H f i / P H d + KB,u(PB+ P D ) l 3
2. Hydrogenolyeis of 1,2-dihydrobenzothiopheneon u sites:
~D,~(B,JH~B#H~
rD,u =
[ l + ( K H ~ 8 H , ) ' / 2 + ( K H f i , p H f i / p H , ) + KB,u(PB+ P D ) l 3
3. Hydrogenation of benzothiophene on T sites:
rB,r =
~+E,&E,#'BPH, - p ~ / K i )
(1 + K E , , ( ~+ B PD)+ KE,PEI'
where B, D,E, and K1denote, respectively, benzothiophene,
lI2-dihydrobenzothiophene, ethylbenzene, and the equilibrium
constant for benzothiophene hydrogenation giving
1,2-dihydrobenzothiophene.
Parameter values at 260 "C are as follows:
k~,. 9.40 X l@exp(-17.6/RT) = 5.65 X lob
k ~ , ,= 2.01 X 108 exp(-31.3/RT) = 2.89 X lob
KB,, KD,, 19.3
KHfl.0 = 211
KH2,s = 0.358
k*~,, 8.84 X 10' exp(-24.1/RT) 1.14 X lob
KB,? 2.05
KR, 294
where the rate constants k have units of mol/(g of catalyst-s)and
the adsorption parameters K have units of atm-'. The rate
constant in the rate expression for benzothiophene
hydrogenation has units of mol/(g of catalyst-watm). These
results pertain to the temperature range 240-300 O C .
meaning in the context of Langmu+Hinshelwood models.
Methyl substituents on benzothiophene reduce its rate
of hydrogenation to give the dihydro species (Geneste et
al., 1980):
benzothiophene (1)> 2-methylbenzothiophene (0.4)>
3-methylbenzothiophene (0.2) >
2,3-dimethylbenzothiophene(0.1)
where the numbers in parentheses denote relative values
of pseudo-first-order disappearance rate constants. The
decrease in the rate is much less than expected from steric
hindrance; the authors attributed the results to electronic
effects, as a good correlation was obtained between the rate
constant for hydrogenation and the first ionization po-
tential.
IIIC3. Dibenzothiophene. Houalla et al. (1978)pro-
posed a detailed network for dibenzothiophene HDS
(Figure 7)on the basis of data from two laboratory reactor
types (Table IX). Experiments were performed with di-
benzothiophene and also with its products as reactants,
including lI2,3,4-tetrahydrodibenzothiophene, 1,2,3,4,5,6-
hexahydrodibenzothiophene,and biphenyl. Each of the
hydrogenated dibenzothiophenes was rapidly converted
to the other, and for purposes of a kinetics analysis, the
two hydrodibenzothiophenes were lumped. Figure 7 in-
dicates that dibenzothiophene conversion proceeds selec-
tively via the path of least hydrogen consumption and that
hydrogenation of biphenyl and cyclohexylbenzene is com-
paratively slow. However, the network shown is based on
data from a flow reactor in which the hydrogen sulfide
concentrations were low. The selectivity to the hydro-
genated dibenzothiophenes is higher when the hydrogen
sulfide concentration is higher. The latter selectivity also
depends on the catalyst composition, as Houalla et al.
found that the yield of cyclohexylbenzene at a given con-
version was about 3 times higher with Ni-Mo/A1203 cat-
Ind. Eng. Chem. Res., Vol. 30, No. 9,1991 2031
1 1 x 10.4 \ J4 7 x 10.6
0-0
I sbw
G-0
Figure 7. Reaction network for dibenzothiophene propod by
Houalla et al. (1980). Reaction oonditions are given in Table X The
numbers are the pseudo-first-order rate constants in L/(g of cata-
1yst.s) at 300 O C .
alyst than with Co-Mo/AlzO3 catalyst.
A similar network for dibenzothiophene hydro-
desulfurization and hydrogenation was also reported
(Bhinde, 1979) for a Ni-Mo/Alz03 catalyst (Table 1x1.
The hydrogenolysis of dibenzothiopheneto give biphenyl
was only 2.5 times more rapid than its hydrogenation. The
lower HDS selectivity (increased hydrogenation) in this
network relative to that shown in Figure 7 was attributed
to the greater hydrogenation activity of the Ni-Mo/A1203
catalyst in comparison with that of Co-Mo/Al2O9. How-
ever, a contribution of a higher hydrogen concentration
in Bhinde's experiments (it was approximately 50% greater
than that used by Houalla et al.) to the higher selectivity
to hydrogenated dibenzothiophenes cannot be ruled out.
The more rapid hydrogenation of dibenzothiophene sug-
gests that the contribution of this pathway contributes
more strongly at higher hydrogen concentrations, resulting
in higher hydrogen consumptions for HDS at high pres-
sures.
The kinetics of dibenzothiophene disappearance was
investigated by several authors (Vrinat, 1983;O'Brien et
al., 1986). Rate equations for dibenzothiophene disap-
pearance were given, some associated with Langmuir-
Hinshelwood mechanisms with hydrogen sulfide being an
inhibitor. However, as Figure 7 show, dibenzothiophene
disappearance includes parallel hydrogenolysis and hy-
drogenation. In the work of Broderick and Gates (1981),
rate equations were given for each pathway (Table XII).
Experiments were carried out with differential conversions
of liquid-phase reactants in a flow reactor at 275-326 OC.
The rates of hydrogenolysis and hydrogenation were taken
as the respective rates of formation of biphenyl and of the
lump consisting of cyclohexylbenzene and the two hy-
drogenated dibenzothiophenes. The rate equation for
hydrogenolysis (Table XII) corresponds to a Langmuir-
Hinshelwood mechanism whereby the rate-limiting step
is a surface reaction between molecularly adsorbed hy-
drogen on one type of site and dibenzothiophene on an-
other. Dibenzothiophene and hydrogen sulfide both in-
hibit hydrogenolysis, the latter more strongly, in agreement
with the kinetics of thiophene and benzothiophene HDS
(Tables X and XI). The adsorption parameter for hy-
drogen could not be estimated accurately as a function of
temperature (as evidenced by the positive enthalpy of
adsorption). Biphenyl is not an inhibitor. With the ex-
2032 Ind. Eng. Chem. Res., Vol. 30,No. 9, 1991
Table XII. Rate Equations for Dibenzothiophene
Hydrogenolyris and Hydrogenation Proposed by Broderick
and Gates (198l)O
1. Dibenzothiophene hydrogenolysis:
r=
~KDTKH,CDTCH,
(1 + K m C m + K H & H , s ) ~ (+~KH,CHJ
2. Dibenzothiophene hydrogenation:
k X'mKf~,CmCH2
r=
1 + K'mCm
where the subscript DT denotes dibenzothiophene.
Parameter values at 275 O C are as follows:
k = 7.87 X 105 exp(-30.1/R!?') = 7.67 x lo-'
KDT= 0.18 exp(4.5/RT) = 11
Ku. = 4 X 108 ex~(-8.4/RT)= 1.8
K Z = 0.70 exp(L5.3/RT) = 87
kf& = 4.22 X lo-' exp(-27.7/RT) = 2.78 X lo4
KtDT= 2.0 exp(l.l/RT) = 7.5
ONotes: (1) Reaction conditions are given in Table IX. (2) Rate
constants k are in mol/(g of catalystas); adsorption parameters K
are in L/mol. (3) The results pertain to the temperature range
275-325 "C.
ception of the dependence of the rate on hydrogen con-
centration, the equation is almost identical in form with
equations for hydrogenolysk of thiophene and benzo-
thiophene (Tables X and XI).
The difference in form between the dibenzothiophene
hydrogenolysis rate equation and that for its hydrogenation
(Table XII)is consistent with the notion that the two types
of reactions take place on separate kinds of catalytic sites.
Also, as stated above, hydrogen sulfide does not inhibit
hydrogenation, in agreement with resulta stated earlier for
thiophene and benzothiophene. The difference in form
between the dibenzothiophene hydrogenolysis equation
and the thiophene and benzothiophene hydrogenolysis
equations raises a question of the nature of the hydrogen
adsorption. It does not seem plausible that hydrogen is
molecularly adsorbed, as the equation for dibenzo-
thiophene hydrogenolysis would imply if it were inter-
preted according to the LangmubHinshelwood formalism.
The question of whether hydrogen and organic molecules
compete for the same adsorption sites remains open.
IIICI. Benzonaphthothiophene. Benzonaphtho-
thiophene is the heaviest organosulfur compound inves-
tigated, with reaction networks having been reported for
benzo[b]naphtho[2,3-d]thiophene (Sapre et al., 1980) and
benzo[b]naphtho[l,a-d]thiophene (Vrinat, 1983) (Table M,
Figure 8). In both networks, the rate of hydrogenation
of the sulfur-containing reactant is comparable to that of
its hydrogenolysis. For benzo[b]naphtho[2,3-d]thiophene,
the hydrogenolysis rate of the sulfur compound having a
saturated ring adjacent to the sulfur atom is only about
4 times greater than that of benzo[b]naphtho[2,3-d]-
thiophene. However, for benzo[b]naphtho[l,2-d]-
thiophene, the corresponding reactivity difference is more
than 2 orders of magnitude and thus comparable to that
observed in the dibenzothiophene network. The reasons
for this difference are not known, but may be related to
differing reaction conditions.
The substantial ring hydrogenation that accompanies
hydrogenolysis of dibenzothiophene and benzonaphtho-
thiophene explains in part why hydrogen consumptions
of heavy feedstocks exceed the stoichiometric amount
needed for sulfur removal in HDS (Gatea et al., 1979). The
relatively rapid hydrogenation of the benzonaphtho-
thiophenes also suggests that these compounds are ad-
sorbed flat on the catalyst to form r-bonded species to
which hydrogen may be added.
1 5.3 x 1 0 . ~
1 1.3 x 1 0 . ~
1 8.4 x 1 0 . ~
(A) The numbers next to the arrows denote pseudo iirst-order rale constants
in V(g of catalystas) at 308 C
1 260 11.9
(8) The numbers next to the arrows are relatlve values 01 the pseudo lirst.orde1
rate constants at 250' C
Figure 8. Reaction networks proposed for (A) benzo[b]naphtho-
[2,3-d]thiophene by Sapre et al. (1980) and (B)benzo[b]naphtho-
[1,2-d]thiophene (Vrinat, 1983). Reaction conditions are given in
Table IX.
Another difference between the two benzonaphtho-
thiophene networks concerns the relative rates of forma-
tion of the hydrogenation products of the corresponding
phenylnaphthalenes. In the benzo[ b]naphtho[ 2,3-d]-
thiophene network (Figure 8A), hydrogenation of 2-
phenylnaphthalene to give 2-phenyltetralin is faster than
that giving 6-phenyltetralin, whereas in the benzo[ b]-
naphtho[ 1,2-d]thiophene network, 5-phenyltetralin is
formed more rapidly than 1-phenyltetralin from 1-
phenylnaphthalene. No Langmuir-Hinshelwood rate ex-
pressions for reactions in any of the benzonaphtho-
thiophene networks have been reported.
IV. Hydrodenitrogenation (HDN)
The increasing interest in converting petroleum residua,
coal, and shale to liquid fuels has spurred research in the
chemistry of HDN. Nitrogen in these feedstocks is present
predominantly in heterocyclic aromatic compounds
(Katzer and Sivasubramanian, 1979). Nonheterocyclic
organonitrogen compounds such as aliphatic amines and
nitriles are also present, but in considerably smaller
amounts, and they are denitrogenated much more rapidly
than the heterocyclic compounds (Katzer and Sivasubra-
manian, 1979). Consequently, nonheterocyclic organo-
nitrogen compounds are less important for purposes of
elucidating the nitrogen-removal chemistry occurring in
the hydroprocessing of heavy feeds.
The nitrogen heterocyclic compounds in these feeds are
classed as basic and nonbasic. In the latter (e.g., indole
and carbazole), the lone-pair electrons on the nitrogen
atom are delocalized around the aromatic ring and are
unavailable for donation to a Lewis acid (Streitwieser and
Heathcock, 1976). The opposite is true for basic hetero-
cyclic compounds such as quinoline and acridine.
IVA. Thermodynamics. Nitrogen removal from
heterocyclic organonitrogen compounds requires hydro-
genation of the ring containing the nitrogen atom before
hydrogenolysis of the carbon-nitrogen bond occurs, at least
 Ind. Eng. Chem. Res., Vol. 30, No. 9, 1991 2033

Table XIII. Equilibrium Constantsa for Selected Table XIV. Reactivitieso for the HDN of Selected Basic
Hydrogenation, Hydrogenolysie, and Overall Nitrogen Heterocyclic Compounds (Mathur et al., 1982)
Nitrogen-Removal Reactions in the Quinoline and Indole pseudo-first-
Reaction Networks (Cocchetto and Satterfield, 1976; concn order rate
Cocchetto and Satterfield, 1981) in feed, const, L/
AHo,, compound structure wt % (g of catalystss)
kcal/iol
log K at of organic quin o1ine 1.0 9.39 x 10-4

- 300OC 4WoC reactant

quinoline + 2H2
-
1,2,3,4-tetrahydroquinoline
quinoline + 2H2
5,6,7&tetrahydroquinoline
1,2,3,4-tetrahydroquinoline+ 3H2 -
-1.4
4.7
-2.8
-3.2
-3.0
-5.4
-32
-41
-46
acridine

benz[clacridine
m 0.54 6.56

5.72
X

X
lo-'

lo-'
decahydroquinoline
5,6,7&tetrahydroquinoline + 3H2 - -3.5 -5.6 -37
Qc8
decahydroquinoline
1,2,3,4-tetrahydroquinoline+ H2 - 4.3 3.0 -23 0*47
o-propylaniline
decahydroquinoline + 2H2 - 6.3 7.9 -28
benz[a]acridine 0.42 4.03 X lo4

-
propylcyclohexane + NH8
o-propylaniline + H2 6.0 5.6 -7
quinoline + 4H2-
propylbenzene + NH3
propylbenzene + NH3
7.0 3.3 -65 dibenz[c,h]-
acridine
0.41 1.41 x 10-3

--
indole + H2 indoline -2.7 -3.3 -11

-
indoline + H2 o-ethylaniline
o-ethylaniline + H2
4.7
5.8
3.3
5.0
-25
-14 a Reactanta allowed to react separately in a batch reactor at 376

-
ethylbenzene + NH3
indole + 3H2 ethylbenzene + NH3 7.8 5.0 -49
a The values of the equilibrium constants in the table were read
OC and 136 atm using a Ni-Mo/A1203catalyst and paraffinic white
oil solvent.

from the van't Hoff plota given by the authors.

with the catalysts now used, typically Ni-Mo/A1203.
Hydrogenation of the heteroring is required to reduce the
relatively large energy of the carbon-nitrogen bonds in
such rings and thus permit more facile carbon-nitrogen
bond scission. The energies of carbon-nitrogen double
bonds and single bonds are 147 and 73 kcal/mol, respec-
tively (Streitwieser and Heathcock, 1976). If the carbon-
nitrogen bond energy in a typical heterocyclic compound
is close to that of a carbon-nitrogen double bond, a reac-
tion breaking the carbon-nitrogen bond is expected to have
a high activation energy.
The requirement that ring hydrogenation occur before
nitrogen removal also implies that the position of the
equilibrium of the hydrogenation reactions can affect ni-
trogen-removal rates if the rates of the hydrogenolysis
reactions are significantly lower than the rates of hydro-
genation. An unfavorable hydrogenation equilibrium
would result in low concentrations of hydrogenated ni-
trogen compounds undergoing hydrogenolysis; HDN rates,
at least at low surface coverages of organonitrogen com-
pounds, could thus be lowered. High hydrogen partial
pressures can be used to increase the equilibrium con-
centrations of saturated heteroring compounds to obtain
larger HDN rates.
Equilibrium constants for the gas-phase hydrogenation
and hydrogenolysis reactions of several heterocyclic orga-
nonitrogen compounds have been calculated (Cocchetto
and Satterfield, 1976,1981); the reactants included pyri-
dine, quinoline, isoquinoline, acridine, pyrrole, indole, and
carbazole. The equilibrium constanta were calculated from
the standard Gibbs free energies of formation at 1 atm.
Group contribution methods were used to estimate the
standard Gibbs free energies of formation of those com-
pounds for which free energies were unavailable. Because
the less accurate method of van Krevelen and Chermin
(1951) was used for estimating the standard Gibbs free
energies for the heterocyclics, errors in the equilibrium
constants for ring saturation reactions were estimated to
be 2-3 orders of magnitude, whereas those for C-N bond
hydrogenolysis reactions were about 1order of magnitude.
More accurate data are available for the hydrogenations
of heterocyclic compounds in the quinoline network; the
equilibrium constants were determined from experimental
results obtained from a network study of quinoline HDN
(Satterfield and Cocchetto, 1981).
Illustrative values are given in Table XI11 for selected
reactions occurring in the quinoline and indole reaction
networks. The data show that the equilibrium constants
are less than unity for ring saturations and become smaller
with increasing temperature, as the ring hydrogenations
are exothermic. The hydrogenolysis and overall HDN
equilibria are favorable, however, even at temperatures as
high as 500 "C. Although the hydrogenation equilibria are
unfavorable, the effect of higher hydrogen partial pres-
sures, such as those used in industrial hydroprocessing, is
to force the equilibria considerably toward the hydro-
processing products, and HDN is virtually irreversible
under typical reaction conditions.
In their thermodynamic analysis of the quinoline net-
work, Cocchetto and Satterfield also calculated the dis-
tribution of the heterocyclics at equilibrium. From these
results, 5,6,7,8-tetrahydroquinolinewas found to be more
favored thermodynamically than 1,2,3,4-tetrahydro-
quinoline. As shown below, the pathway for nitrogen re-
moval from 5,6,7,84etrahydroquinolineinvolves hydro-
genation to give decahydroquinoline (i.e., perhydro-
quinoline). The latter pathway involves a large hydrogen
consumption for nitrogen removal in the quinoline net-
work. Consequently, the thermodynamics favors a path-
way for HDN that requires more than the minimum hy-
drogen consumption.
IVB. Reactivities. Because nitrogen heterocyclic
compounds must first be hydrogenated before the nitrogen
is removed, there are numerous intermediate products that
contain nitrogen. Therefore, the conversion of a nitro-
gen-containing compound must be distinguished from ita
HDN conversion (Le., that giving hydrocarbon products
and ammonia).
The rates of HDN of several basic nitrogen heterocyclic
compounds were determined (Mathur et al., 1982) (Table
2034 Ind. Eng. Chem. Res., Vol. 30, No. 9,1991
Table XV. Reactivitiesaof Quinoline and
Dimethyl-Substituted Quinolines (Bhinde. 1979)
pseudo-first-
order rate
const, Lj
compound structure (g of catalysbs)
quinoline
m 3.81 X 10”
2,6-dimethylquinoline
ax 3 x 10-5
m
2,7-dimethylquinoline 2 x 10-6
2,8-dimethylquinoline
p 3 x 10-5
a Batch reactor, 350 O C , 34 atm, Ni-Mo/A120, catalyst, n-hexa-
decane solvent.
XIV) in experiments in which the concentrations of all the
organonitrogen species were measured. The rate of HDN
of each compound was pseudo-firsborder in the s u m of the
concentrations of the reactant and its organonitrogen
products. The comparison of the reactivities is rough
because of differences in initial reactant concentrations,
and these affect the HDN rate because of strong self-in-
hibition by nitrogen compounds (described below). The
data show that the reactivities are the same within an order
of magnitude; nitrogen-removal rates for three- and
four-ring compounds are not markedly different from each
other. The intrinsic quinoline reactivity is greater than
the value indicated in the table, as the initial quinoline
concentration was higher than those of the other organo-
nitrogen compounds.
Mathur et al. inferred that the rates of hydrogenation
were higher than those of C-N bond scission. The results
imply approximately equal HDN rates and suggest similar
rates of the C-N bond scission reactions. Hence, the steric
effects involved in the C-N scissions were inferred to be
nearly equivalent for all the nitrogen compounds listed in
Table XIV. Reactions of basic nitrogen compounds with
Lewis acids are strongly affected by steric hindrance (Ho,
1988),and the equivalence of the steric effects implies that
end-on adsorption through the nitrogen atom does not
occur since otherwise the HDN rates for the potentially
more hindered compounds, such as benz[c]acridine and
dibenz[c,h]acridine, would be expected to have been orders
of magnitude less than those for compounds such as
acridine.
The HDN of dimethylquinolines has been reported
(Table XV). Pseudo-fmt-order behavior was followed for
the HDN of all the methyl-substituted quinolines. The
nitrogen-removal rate is similar for each dimethylquinoline
and slightly less than that for quinoline. The similarity
of these HDN rates implies that the steric effects are
equivalent for all these compounds. The latter conclusion
in turn implies that end-on adsorption through the ni-
trogen atom is unlikely and suggests an adeorption through
the r-bonds of the aromatic rings, consistent with the
results of Table XIV.
Comparisons of reactivities of basic and nonbasic orga-
nonitrogen compounds are few. From investigations of
reaction networks of quinoline and indole conducted under
conditions similar to those shown in Table XV, Bhinde
(1979)found that the nitrogen-removal rates were similar,
with the pseudo-first-order rate constants for indole and
H t
I
-
+ NH3
Figure 9. Reaction pathways for pyridine HDN proposed by Han-
lon (1987). Reaction conditions are given in Table XVI.
quinoline HDN being 4.19 X lo4 and 3.81 X L/(g of
catalyst-s), respectively. (The initial molar concentration
of indole was 10% leas than that of quinoline.) The similar
reactivities could arise because nonbasic organonitrogen
compounds are converted to basic ones upon hydrogena-
tion (see discussion of indole network below). However,
additional data are needed to resolve these reactivity
differences between basic and nonbasic organonitrogen
compounds, especially for higher molecular weight com-
pounds such as carbazole.
The rates of conversion of three nonbasic nitrogen
compounds, pyrrole, indole, and carbazole, were deter-
mined with a batch reactor operated at 350 O C and 68 atm
with reactants in n-hexadecane solvent (Stern, 1979). The
reactanta were present in a mixture in equimolar amounts.
The relative first-order disappearance rate constants of
pyrrole, indole, and carbazole were 3.30, 1.16, and 0.12,
respectively, with a Ni-Mo catalyst. These rate constants
indicate hydrogenation and not nitrogen removal. The rate
decreases with the degree of substitution on the nitro-
gen-containing five-membered ring. No explanation was
offered for this effed; it is difficult to reconcile these results
with those of Mathur et al. because the latter reported
HDN reactivities.
IVC. Reaction Networks and Kinetics. Reaction
networks have been reported for pyridine, quinoline,
acridine, indole, and several anilines. The discussion be-
gins with pyridine and progresses to multiring Compounds.
IVC1. Pyridine. Investigations of the network of va-
por-phase pyridine reacting in the presence of catalysts
in the sulfided (McIlvried, 1971;Hanlon, 1987)and oxidic
(Sonnemans et al., 1973)forms have been reported. Re-
action conditions for the experiments with sulfided cata-
lysts are shown in Table XVI. The results indicate that
pyridine HDN occurs via the sequential pathway shown
in Figure 9. The side reaction involving alkyl transfer
occurs only to a minor extent (Sonnemans et al., 1973;
Hanlon, 1987). Pyridine hydrogenation is irreversible
under these conditions, as evidenced by its absence as a
product in experiments with piperidine as the reactant;
high hydrogen partial pressures are used to counter the
unfavorable hydrogenation equilibrium (Table XIII). The
HDN of n-pentylamine is an order of magnitude more
rapid than that of pyridine.
Quantitative generalizations about pyridine HDN are
not warranted because of the different assumptions made
to model the kinetics. Exact comparisons of the HDN
rates measured in the various experiments (Table XVI)
are not possible because the rates were expressed some-
times in terms of catalyst weight and sometimes catalyst
volume. The paragraphs below summarize the major
conclusions of the different investigations.
From experiments with piperidine as the reactant,
McIlvried (1971)found that its HDN followed pseudo-
first-order kinetics. The HDN rate decreased with in-
 Ind. Eng. Chem. Res., Vol. 30,No. 9,1991 2035

Table XVI. h a c t i o n s Conditions in HDN Network Investigations

reactant conditions reference
pyridine vapor-phase flow reactor, 316 "C, 51-102 atm, pyridine, McIlvried. 1973
piperidine partial pressure 0.01-0.6 atm, Ni-Mo/AlZO3
catalyst
vapor-phase flow reactor, 310 "C, 12-99 atm, pyridine, Hanlon, 1987
piperidine partial pressure 0.3-0.6 atm, hydrogen sulfide
partial pressure 0.05-0.3 atm, Ni-Mo/Alz03 catalyst
quinoline batch reactor, 0.1-1 wt % quinoline in paraffinic white oil, Shih et al., 1977; Bhinde, 1979
300-375 "C, 21-136 atm, Ni-Mo/Alz03 catalyst
vapor-phase reactants, 330-420 OC, 35 and 69 atm, Satterfield and Cocchetto, 1981;
Ni-Mo/Alz03 catalyst Satterfield and Giiltekin, 1981
trickle-bed reactor, 1-5 wt % quinoline in paraffinic white oil, Satterfield and Yang, 1984; Yang
350-390 OC, 69 atm, Ni-Mo/Alz03 catalyst and Satterfield, 1984
trickle-bed reactor, 2-13 wt % quinoline in white oil, 330 and Miller and Hineman, 1984
375 "C, 69 atm, Co-Mo/Alz03 and Co-Mo/USY-Al,03
catalysts
batch reactor, 0.47-0.57 wt % quinoline in n-hexadecane Gioia and Lee, 1986
solvent, 350 "C, 10-150 atm, Ni-Mo/Alz03 catalyst
acridine batch reactor, 317-365 "C, 54-172 atm, white oil solvent, Zawadski et al., 1982
0.5-1.0 wt % acridine in feed, Ni-Mo/Al2O3 catalyst
5,6-benzoquinoline batch reactor, 330 "C, 79-171 atm, n-dodecane solvent, 0.03 Shabtai et al., 1988
mol/L reactant concentration, Co-Mo/Alz03 (3 and 6 wt %
Co), Co-Mo on fluorided AlzO3, Ni-Mo/AlzOs catalysts
batch reactor, 340 "C, 70 atm, n-decane solvent, 0.1 mol/L Moreau et al., 1988
reactant concentration, Ni-Mo/AlZO3 catalyst
7,8-benzoquinoline same aa for 5,6-benzoquinoline above Moreau et al., 1988
batch reactor, 275 "C, 170 atm, n-decane solvent, Malakani et al., 1987
Ni-Mo/AlzOB catalyst
batch reactor, 200-380 "C, 198 atm, 2 h reaction time, Shabtai et al., 1978b
Ni-W/A1203 catalyst
indole batch reactor, 350 "C, 34 atm, n-hexadecane solvent, 0.5 wt % Bhinde, 1979
reactant concentration, Ni-Mo/Alz03 catalyst
batch reactor, 350 "C, 68 atm, n-hexadecane solvent, 0.06-0.12 Stern, 1979
mol/L reactant concentration, Ni-Mo/AlZO3 and
Co-Mo/AlzOS catalysts
batch reactor, 250-350 "C, 34-70 atm, n-decane or n-dodecane Olive et al., 1985
solvent, Ni-Mo/A1203, Co-Mo/AlZO3,and Ni-W/Al2O3
catalysta
trickle-bed reactor, 250-350 "C, 69 atm, 0.001-0.0075 mol/L Odebunmi and Ollis, 1983
reactant concentration, Co-Mo/Alz03 catalyst
aniline and o-ethylaniline batch reactor, 320 and 350 "C, 34 atm, n-hexadecane solvent, Mathur et al., 1982b
1wt % reactant concentration, Ni-Mo/Alz03 catalyst
N-ethylaniline, diphenylamine, batch reactor, 350 "C, 59 atm, n-decane solvent, Ni-W/Al2O3 Finiels et al., 1986
dicyclohexylamine, N-phenylcyclo- catalyst
hexylamine, 3-methyldiphenylamine
creasing feed piperidine concentration, implying similar tions of the network shown in Figure 9,with all nitrogen
degreea of inhibition by the organic reactant and ammonia. compounds assumed to adsorb. From experiments per-
(Inhibition by n-pentylamine was neglected, presumably formed with pyridine, piperidine, and n-pentylamine as
because of its low surface coverage owing to its high re- reactants, adsorption parameters were determined for
activity.) Piperidine HDN was modeled by the equation ammonia (5000 atm-l), n-pentylamine (105 atm-l), piper-
idine (6 X lo4atm-'), and pyridine (3 X lo4 atm-'); these
values are larger by 1-2 orders of magnitude than those
found by McIlvried, despite the fact that experimental
conditions in the two investigations were similar (Table
where the subscript 0 denotes initial piperidine partial XVI). It is difficult to determine which set of values is
pressure. The adsorption parameter K, inferred to be the more reliable since different forms of rate expressions were
same for piperidine and ammonia, was equal to 23 atm-' used by Hanlon and McIlvried.
at 316 "C. Hydrogen and hydrogen sulfide have different effects
The pyridine hydrogenation rate decreased with con- on pyridine hydrogenation and piperidine hydrogenolysis.
version, consistent with product inhibition. Ammonia was Hanlon (1987)found that the rate constant for pyridine
assumed to be the sole inhibitor, but it is not clear why hydrogenation increased linearly with hydrogen partial
inhibition by piperidine was neglected. The following rate pressure, but that hydrogen sulfide partial pressure had
expression was used: no effect on the pyridine hydrogenation rate constant (the
pattern is similar to that for hydrogenation of dibenzo-
thiophene and other organosulfur compounds, described
above). The piperidine hydrogenolysis rate constant de-
creased 2-fold as the hydrogen partial pressure increased
with K' = 150 atm-' at 316 "C. The differences in the from 1 to 10 atm at a constant hydrogen sulfide partial
ammonia adsorption parameters in these two equations pressure of 0.08 atm. However, at constant hydrogen
suggest that hydrogenation and hydrogenolysis occur on partial pressure, the piperidine hydrogenolysis rate con-
different types of sibs. stant doubled as the hydrogen sulfide partial pressure
In contrast to McIlvried, Hanlon (1987)used a one-site increased by a factor of 6. An equilibrium involving two
Langmuir-Hinshelwood rate expression for all the reac- catalyst sites, hydrogen, and hydrogen sulfide was propoeed
2036 Jnd. Eng. Chem. Res., Vol. 30, No. 9, 1991
3 75 x 10.~
50x10
1 2ox10.6
1 fast
Figure 10. Reaction network for quinoline HDN proposed by Sat-
twFeld acd Yang (1984). The numbers next to the arrows are
pseudorate constants at 375 "C with 5 wt 9i quinoline and 0.59 w t
% CS3 iq the feed in units of mol/(g of cata1yst.s).
to account for these effects, but quantitative evidence was
not given.
There is thus a need to resolve and quantify the effects
of hydrogen and hydrogen sulfide more precisely by using
Lmgmuir-Minshelwood rate expressions as was done for
hydrodesulfurization, although representing the inhibition
by hydrogen sulfide with such expressions may not be
strictly valid (section VIA1). The applicability of one-site
versus two-site expressions also needs to be addressed to
provide re!isb!e estimates of adsorption parameters.
Qumtlfying these effects for the pyridine network would
be much simpler than for the networks of more complex
polycyclic nitrogen compounds. The results for the simpler
compounds might then be used as guidelines for modeling
the kinetics of the more complex reactants.
IVC2. Quinoline. The complex reaction network of
quinoline is more representative of those of higher mo-
lecular weight organonitrogen compounds found in heavier
hydroprocessing feeds (Le., those boiling above 340 "C)
than that of pyridine. Most of the quantitative network
determinations with quinoline have been done for liquid-
phase reactants (Table XVI). The liquid-phase investi-
gatiom are emphasized below since the conditions are most
nearly comparable to those of hydroprocessing of com-
mercial feeds.
The networks proposed by most investigators (Table
XVI)can be represented by that shown in Figure 10 and
summarized as follows. Quinoline HDN requires the prior
hydrogenation of one or both rings. Quinoline hydrogen-
ation to give 1,2,3,4-tetrahydroquinolineis much more
rapid than that giving 5,6,7,8-tetrahydroquinolineand
approaches equilibrium at lower quinoline conversions.
The rapidity of 1,2,3,4-tetrahydroquinolineformation is
associated with the high ?r-electron density of the quinoline
heteroring. Hydrogenolysis of 1,2,3,4-tetrahydroquinoline
to give o-propylaniline is slower than ita hydrogenation to
give decahydroquinoline. The slow hydrogenolysis of
1,2,3,4-tetrahydroquinolinecould be due to the resonance
interaction between the benzenoid ring and the nitrogen-
It
- All Pressures
0" Light
Hydrocarbons
- Low Pressures
4
_ _ _ _ - High Pressures
--------------______________.
Figure 11. Reaction network for quinoline proposed by Gioia and
Lee (1986).
lone-pair electrons; this interaction "ties up" the lone-pair
electrons that may be involved in adsorption of 1,2,3,4-
tetrahydroquinoline (Shih et al., 1977). Most of the ni-
trogen removal therefore proceeds via decahydroquinoline,
with the pathway through 5,6,7,8-tetrahydroquinoline
dominating. The path of high hydrogen consumption is
thus favored kinetically.
The activation energies of the hydrogenation reactions
are lower than those of the hydrogenolysis reactions (Shih
et al., 1977; Satterfield and Yang, 1984; Yang and Sat-
terfield, 1984). Under severe conditions (high space times
and temperatures), high-molecular-weight products are
formed having structures that suggest the random linking
of fragments on the catalyst surface (e.g., 1,l'-bicyclohexyl).
At least some nitrogen removal from o-propylaniline ap-
pears to require its hydrogenation to give a reactive pro-
pylcyclohexylamine intermediate, as the propylcyclo-
hexenes detected among the reaction products (Figure 10)
are not formed from propylbenzene and propylcyclohexane
under the reaction conditions. Furthermore, the apparent
activation energy for o-propylaniline conversion is close
to the values for hydrogenation reactions; this result pro-
vides another basis for suggesting that o-propylaniline
HDN proceeds via a hydrogenated intermediate.
There is disagreement regarding the kinetic significance
of the dehydrogenations of the hydrogenated quinolines,
with some investigators (Shih et al., 1977; Bhinde, 1979)
having been able to correlate their data successfully by
neglecting the dehydrogenation reactions. Furthermore,
pathways for nitrogen removal in addition to those shown
in Figure 10 are claimed by Gioia and Lee (1986) (Figure
11). The additional reactions shown in Figure 11giving
light hydrocarbons (which could not be analyzed because
of their volatility) were assumed to occur because good
mass balances could not be obtained at lower pressures.
(High-molecular-weightproducts, too heavy to be
could also explain the lack of closure of the mass balances.)
Mechanistic evidence was not offered by Gioia and Lee
(1986) for the reactions in which 1,2,3,4-tetrahydro-
quinoline was converted to propylbenzene and propyl-
cyclohexane. However, good fits to the data were obtained
only when it was assumed that these two reactions oc-

Table XVII. Rate Equations Proposed in Quinoline
Reaction Network InvestiirationtP
1. Satterfield and Yang (1984);Yang and Satterfield (1984):
kj,KjCj
rij =
K M C M + KSACSA+ KACA
KdKM =
K A / K ~ 0.7
The subscripts A, SA, and AA denote ammonia,
decahydroquinoline, and aromatic amines, respectively;
quinoline, 1,2,3,4-tetrahydroquinoline,
5,6,7,8-tetrahydroquinoline, and o-propylaniline comprise the
aromatic amines, and are assumed to have the same adsorption
parameter KAA. CM denotes the s u m of the concentrations of
the aromatic amines. Adsorption parameter ratios are
assumed temperature independent.
2. Shih et al. (1977):
A. Hydrogenation
Adsorption parameter values at 342 "C are as follows:
K H ,= 0.05 atm-l
KN = 6.4 X 108 g of oil/mol
B. Hydrogenolysis
where n equals 1 and 0 for the respective hydrogenolyses of
1,2,3,4-tetrahydroquinolineand decahydroquinoline.
Adsorption parameter values at 342 OC are as follows:
KH, = 0.05 atm-l
KN = 6.4 X l@g of oil/mol
3. Gioia and Lee (1986):
ki jC j
1 I
rij =
1 + KlCl + K2Cz
where the subscripts 1 and 2 denote quinoline and
1,2,3,4-tetrahydroquinoline,respectively.
Adsorption parameter values at 350 O C are as follows:
K 1 = Kz = l@ g of solution/mol
Variation of the rate constants with the hydrogen partial
pressure is given by:
with m = 0 for dehydrogenation reactions and m = n = hydrogen
stoichiometric coefficient for hydrogenation reactions.
4. Miller and Hineman (1984):
kCN
= 1 + KNCN
'"
Respective adsorption parameter values at 330 and 375 O C are
KN = (7.S9.6)X l@ g of solution/mol
KN = (1.7-2.3) X 1@ g of solution/mol
OThe subscripts i j denote reaction of component i in reaction j .
curred. Although the postulate of these reactions appar-
ently contradicts earlier results (Figure lo), the issue is
open because previous workers did not provide quantita-
tive results pertaining to the rates of formation of the
individual hydrocarbons. Evidently not all the reactions
shown in Figure 11 occurred at each pressure. The net-
work reduces to one of two limiting forms at low (<31 atm)
and high (>78 atm) pressures (Figure 11).
The kinetics of the reactions in the quinoline network
and the overall HDN have been modeled with Lang-
muir-Hinshelwood rate expressions (Table XVII).
Peeudo-first-order kinetics are inadequate because of the
Ind. Eng. Chem. Res., Vol. 30, No. 9,1991 2037
strong inhibition by the nitrogen compounds, as evidenced
by data obtained with varied feed quinoline concentrations.
No generalizations can be made concerning the rate form
listed in Table XVII or the corresponding parameter
values. In almost all cases,alternate rate forms in any one
investigation were not considered. No single investigation
has been reported in which the effects of concentrations
of the organic reactants, hydrogen, and hydrogen sulfide
were quantified, as with organosulfur compounds. Instead,
each investigation typically focused on the effects of only
a few of the foregoing variables on the rate. A synopsis
of the various rate forms is given below.
Satterfield and Yang (1984) performed experiments with
each of the organonitrogen reactants shown in Figure 10
and were able to quantify the inhibition by each of the
organonitrogen intermediates in the network. A one-site
Langmuir-Hinshelwood rate equation was used for both
hydrogenation and hydrogenolysis reactions (Table XVII),
but the analysis was limited to reactions involving orga-
nonitrogen compounds. The term of unity in the denom-
inator was neglected, as quinoline HDN followed zero-
order kinetics, probably because of the high surface cov-
erage of the organonitrogen compounds under reaction
conditions. All nitrogen compounds were assumed to ad-
sorb and were divided into three groups (Table XVII).
Only relative values of the adsorption parameters (mumed
to be independent of temperature) were determined,
making extension of the results to mixtures impossible.
The secondary amine group (decahydroquinoline) was the
most strongly adsorbed, but the relative values for the
several compounds are not greatly different, being equal
within a factor of 3.
Satterfield and Yang also quantified the effect of hy-
drogen sulfide on hydrogenation and hydrogenolysis rate
constants. (Hydrogen sulfide was produced in situ from
carbon disulfide added to the feed.) Hydrogenation re-
actions were inhibited slightly by hydrogen sulfide, as the
rate constants decreased by about 10%. Hydrogenolysis
reactions, in contrast, were enhanced with increasing hy-
drogen sulfide concentration, as' the rate constants in-
creased as much as 6-fold. These results are similar to
Hanlon's (1987) for pyridine HDN. The different effect
of hydrogen sulfide on hydrogenation and hydrogenolysis
led the authors to propose that the two types of reactions
occurred on two different types of sites, but only one type
of catalytic site was assumed in their kinetics model.
Two kinds of sites were assumed by Shih et al. (1977),
one catalyzing hydrogenations and the other hydrogen-
olyses. Because the reactions of the quinoline network
followed pseudo-first-order kinetics at a given feed quin-
oline concentration, all nitrogen-containing species, in-
cluding ammonia, were assumed to have the same ad-
sorption parameter. The pseudo-first-order rate constants
were correlated with a Langmuir-Hinshelwood rate form
(Table XVII). The 100-fold differences in adsorption
parameters for the nitrogen compounds on each site are
consistent with the two-site assumption.
Gioia and Lee (1986) analyzed thoroughly the effect of
hydrogen concentration on the rates of the various reac-
tions. The rate expression shown in Table XVII was fitted
to each reaction of their proposed network. Including other
terms in the denominator did not improve the fit. Only
an order of magnitude estimate could be obtained for the
adsorption parameters. The effect of hydrogen partial
pressure on the rate of each reaction was estimated by
fitting to determine each of the pseudorate constants kjj
as shown in Table XVII. The pseudorate constants cor-
responding to hydrogenolysis reactions did not vary with
2038 Ind. Eng. Chem. Res., Vol. 30, No. 9, 1991
hydrogen partial pressure. In contrast, the pseudorate
constants corresponding to hydrogenation and dehydro-
genation reactions increased and decreased, respectively,
with hydrogen partial pressure. The latter results are in
qualitative agreement with those of Shih et al. for quinoline
and those of Hanlon for pyridine HDN. The quinoline
HDN rate increased with hydrogen partial pressure, but
the hydrogen consumption for a given HDN conversion
also increased with pressure because of the increasing
contribution to the overall HDN of the pathway through
decahydroquinoline (Figure 11).
The rate expression proposed by Miller and Hineman
(1984) applies only to the overall quinoline HDN. Quin-
oline, 1,2,3,4-tetrahydroquinoline,and decahydroquinoline
were assumed to have the same adsorption parameter, but
adsorption by ammonia was neglected. In contrast to the
results of Satterfield and Yang (1984),Miller and Hineman
retained the term of unity in the denominator, even though
the quinoline concentration was comparable in the two
investigations. Adsorption parameter values for a zeolitic
catalyst were within a factor of 1.3 of those for an
amorphous catalyst, and the values are within an order of
magnitude of those of Shih et al. and Gioia and Lee.
A comparison of quinoline HDN with reactants in the
vapor and in the liquid phase is provided by the results
of Satterfield and co-workers (references are cited in Table
XVI). Although the product distributions were similar in
the two cases, the adsorption parameters of the nitrogen
compounds were grouped differently, with 1,2,3,4-tetra-
hydroquinoline and decahydroquinolineclassified as sec-
ondary amines in the vapor phase. The ratios of KsA/KAA
and KA/KAA(terms are defined in Table X W )were found
to be 6 and 0.25,respectively, with the vapor-phase reac-
tants; for comparison, the values are 2 and 0.7 for the
liquid-phase reactants, respectively. This comparison led
to the proposal that the carrier solvent reduced the dif-
ferences in the adsorption parameters for liquid-phase
reactants.
IVC3. Acridine and Benzoquinolines. Reaction
networks have been reported for acridine, 5,6-benzo-
quinoline, and 7,&benz~quinoline.The networks are more
complex than those discussed above and include as many
as six organonitrogen compounds and more than 12 re-
actions in some cases. Analysis of the products is also
difficult because of their larger numbers. Quantitative
treatments have been limited to the assumption of pseu-
do-first-order kinetics in the organic reactant for a given
reaction, although the rates of individual reactions and
overall nitrogen removal are surely strong functions of
organonitrogen reactant concentration (see above).
The acridine network proposed by Zawadski et al. (1982)
(Table XVI, Figure 12) is the simplest one giving a good
fit to the data. Hydrocarbon HDN products were not
identified. Pseudo-fmt-orderkinetics in the corresponding
organic reactant was assumed for each reaction. Overall
nitrogen removal also followed first-order kinetics (in the
sum of the organonitrogen compound concentrations).
Both hydrogenations and hydrogenolyses were kinetically
important. The acridine HDN rate increased with hy-
drogen partial pressure at lower hydrogen partial pressures
(i.e., the HDN rate constant increased almost 6-fold as
hydrogen partial pressure increased from 60 to 100 atm)
but approached a limiting value at higher pressures (the
HDN rate constant being only a factor of 1.3 greater at 170
atm than at 100 atm). The authors attributed this be-
havior to two oppoaing effects: (a) an increasing reaction
rate with increasing hydrogen concentration at the lower
pressure and (b) an apparent saturation because of com-
-
0 13
I 0.13
[m-
-W-T H - H
I0.0190
i 0.0440
- Hydrocarbons
+ NY
Figure 12. Acridine reaction network proposed by Zawadski et al.
(1982). The numbers next to the arrows are pseudo-first-orderrate
constants in (g of carrier oil)/(g of catalyst4 at 367 "C,137 atm, and
0.5 w t 76 acridine in the feed.
petitive adsorption by hydrogen on hydrogenolysis sites
at the higher pressures. The HDN of acridine required
considerably higher pressures than that of quinoline; for
example, at 342 "C and at approximately the same initial
molar concentration of acridine and quinoline, a hydrogen
partial pressure of 136 atm was required to obtain a value
of the pseudo-first-order rate constant for acridine HDN
equal to that for quinoline HDN at a hydrogen partial
pressure of 34 atm.
The acridine network has several features in common
with the quinoline network. The primary hydrogenation
product formed by hydrogenation of the pyridine ring is
formed more rapidly than the primary product formed by
hydrogenation of another ring, presumably because of the ,
higher *-electron density on the heteroring. At short r e
action times, the ratio of the concentration of 9,lO-di-
hydroacridine to that of acridine was nearly constant,
which suggests that the latter compounds were in equi-
librium. The slower hydrogenolysis of asym-octahydro-
acridine relative to ita hydrogenation implies that the path
of low hydrogen consumption is not favored kinetically.
Steric effects may account for the relative rates of re-
actions in the acridine network. Such effects are probably
stronger in the acridine network than in the quinoline
network because of acridine's three-ring structure. For
example, the authors attributed the insignificantly slow
formation of asym-octahydroacridine from 1,2,3,4-tetra-
hydroacridine to the presence of the bulky fused cyclo-
hexane ring. The slow hydrogenation of sym-octahydro-
acridine was ascribed to the steric hindrance arising from
the two puckered cyclohexane rings fused to the central
ring.
Two networks have been proposed for 5,6-benzo-
quinoline (Table XVI). Shabtai et al. (1989) reported the
more detailed of these (Figure13). Product identification
was carried out by NMR, IR, and GC/MS. In contrast
to the HDN networks shown above, only one primary
hydrogenation product, 1,2,3,4-tetrahydro-5,6-benzo-
quinoline, was formed, that being the product of hydro-
genation of the nitrogen-containing ring. The slow hy-
drogenolysis of the latter was attributed to its strong
resonance-stabilized C-N bond (cf. the dow hydmgenolysis
of 1,2,3,4-tetrahydroquinoline).In contrast to the quino-
line case, however, no aniline derivative8 were detected.
The dominant nitrogen removal pathway occurs via the
1,2,3,4,7,8,9,10-octahydro-5,6-benzoquinoline and
1,2,3,4,11,12,13,14-octahydro-5,6-benzoquinoline to give

I7.2 X
I i3
9.3X10.6
4
I B x 10.~
Figun, 13. Reaction network for 5,6-benz.oquinoline proposed by
Shabtai et al. (1989). The numbers next to the arrows are the
pseudo-first-orderrate constants in L/(g of catalystd at 300 "C.
propyltetralins. This is not the path of minimal hydrogen
consumption; it is analogous to the dominant nitrogen-
removal path (via decahydroquinoline) in the quinoline
network at higher pressures. Apparent activation energies
were reported and, consistent with earlier results for
quinoline (Shih et al., 1977; Satterfield and Yang, 1984;
Yang and Satterfield, 19841, the values for hydrogenation
reactions (12-13 kcal/mol) were lower than those corre-
sponding to hydrogenolysis reactions (24-49 kcal/mol),
except for saturation of the terminal monoaromatic ring.
In agreement with results of Satterfield and Yang (1984),
pseudo-first-order rate constants for hydrogenation and
hydrogenolysis reactions decreased and increased, re-
spectively, with increasing hydrogen sulfide concentration.
The data given above allow some conclusions about the
effects of catalyst promoters (Table XVI). Increasing the
cobalt content from 3 to 6 w t % gave higher ring hydro-
genation activity but similar hydrogenolysis activity. At
the same 3 wt % loading, the nickel-promoted catalyst was
more active for hydrogenation but only slightly more active
for hydrogenolysis than cobalt-promoted catalysts. Sur-
prisingly, a fluoride-promoted Co-Mo catalyst did not
exhibit higher hydrogenolysis activity, but gave better
hydrogenation activity than the same catalyst without
fluorine.
The network reported by Moreau et al. (1988) differs
from that shown in Figure 13 in that two primary hydro-
genation products were observed, one formed by hydro-
genation of the pyridine ring and the other by hydrogen-
ation of the adjacent benzenoid ring. Hydrogenation of
the terminal benzenoid ring was not observed. Also in
contrast to the results of Shabtai et al., the dominant
nitrogen removal pathway occurred via hydrogenolysis of
the 1,2,3,4-tetrahydro-5,6-benzoquinoline to give propyl-
naphthalene without an aniline intermediate. This rapid
hydrogenolysis,which the authors found to be more rapid
than that of anilines, was attributed to the weaker reso-
nance interaction between the nitrogen atom's lone-pair
electrons and the aromatic ring arising from the puckered
configuration of the terminal saturated ring. The differ-
ences in the latter network and that shown in Figure 13
could be attributed to the different hydrogen partial
Ind. Eng. Chem. Res., Vol. 30, No. 9,1991 2039
t 7 t Y
t 3
Figure 14. Reaction network for 7,8-benzoquinolineproposed by
Moreau et al. (1988). The numbers next to the arrows are relative
values of the pseudo-first-order rate constants at 340 "C.
H
&
fast
@
H
3 4 2 X 10: x2
I
Hydrocarbons
Other + NH3
Products
Figure 15. Indole HDN network proposed by Bhinde (1979) (Table
XVI). The numbers next to the arrows are the pseudo-first-order
rate constants in L/(g of catalysbs) at 350 "C.
pressures, but a definitive assessment is not possible.
A partidy quantitative network for 7,&benzoquinoline
has also been reported by Moreau et al. (1988) (Figure 14).
Three primary hydrogenation products were observed, in
contrast to the observations for 5,6-benzoquinoline, but
the dominant hydrogenation product was found to result
from hydrogenation of the pyridine ring, in agreement with
earlier nonquantitative studies using 7,8-benzoquinoline
(Shabtai et al., 1978b; Malakani et al., 1987). The relative
amounts of hydrocarbons formed differ among the various
investigations. Whereas propylnaphthalene was reported
to be the hydrocarbon formed in greatest yield in two of
the investigations (Moreau et al., 1988; Shabtai et al.,
1978b), propyltetralin was reported to be the major hy-
drocarbon product in the other (Malakani et al., 1987).
This disagreement might again be attributed to the dif-
fering hydrogen partial pressures and suggests a need for
investigationsquantifjing hydrogen partial pressure effects
on product selectivities.
IVCI. Nonbasic Nitrogen Compounds. The only
nonbasic nitrogen compound for which quantitative re-
action networks have been reported is indole; several
networks have been reported (Table XVI). The most
detailed of these was proposed by Bhinde (1979) (Figure
15). Pseudo-first-order kinetics was followed for both the
overall indole HDN (in the s u m of the concentrations of
the organonitrogen compounds) and for each reaction of
the network (in the respective organic reactant). The
hydrogenation of indole to give indoline was rapid, and the
reaction attained virtual equilibrium; in the kinetics
analysis, the latter two compounds were lumped. No or-
ganonitrogen products were detected in which the ben-
zenoid ring was saturated, which implies the preferential
hydrogenation of the nitrogen-containing ring, as for the
other organonitrogen compounds. Two hydrocarbon
products were detected, ethylcyclohexane and ethyl-
2040 Ind. Eng. Chem. Res., Vol. 30, No. 9, 1991
benzene, and these were also lumped in the kinetics
analysis. Cycloolefins were not detected although their
formation is expected on the basis of the quinoline network
investigations carried out under similar conditions. The
initial rate of formation of ethylcyclohexane could not be
accounted for by the rate of disappearance of o-ethylaniline
alone. A second pathway was therefore assumed whereby
ethylcyclohexane was formed from the indole/indoline
pseudocomponent by way of a postulated perhydroindole
intermediate (which was not detected); such a pathway is
analogous to the formation of propylcyclohexane via de-
cahydroquinoline in the quinoline network (Figure 10). In
addition, a reaction of indole to high-molecular-weight
products was assumed, as the material balance closure with
the products detected was low.
Stern (1979) and Olive et al. (1985) proposed indole
reaction networks similar to that shown in Figure 15. In
contrast to Bhinde, the latter authors proposed that the
hydrocarbon products were formed exclusively through
o-ethylaniline. However, as in Bhinde's study, the rates
of formation of the hydrocarbons were not determined. In
both investigations, ethylbenzene was formed in consid-
erably lower yields than ethylcyclohexane, but because of
the slow hydrogenation of ethylbenzene under the con-
ditions employed, ethylcyclohexane was assumed to be
formed via 2-ethylcyclohexylamine and ethylcyclohexene,
a reaction analogous to the deamination of o-propylaniline
(Figure 10). Olive et al. detected neither ethylcyclohexene
nor 2-ethylcyclohexylamine, but ethylcyclohexenes were
detected in Stem's experiments. Stem also demonstrated
that 2-ethylcyclohexylaminewas converted rapidly under
reaction conditions to give ethylcyclohexene, ethylbenzene,
and ethylcyclohexane. The reversibility of the indole
hydrogenation to indoline was substantiated in both in-
vestigations by experiments in which indoline was the
reactant; by the time the batch reactor had been heated
to reaction temperature, at least some indoline was de-
hydrogenated to indole, even in the absence of catalyst.
The indole-indoline equilibrium was also observed in the
trickle-bed experiments of Odebunmi and Ollis (1983).
Quantitative network information for higher molecular
weight nonbasic nitrogen compounds is lacking. Some
information characterizing the HDN pathways of 3-
ethylcarbazole has been reported (Ho, 1988) on the basis
of experiments with a Ni-Mo/A1203 catalyst at 390 "C, 69
atm, and 1.4 LHSV. The nitrogen-containing compounds
formed in highest yields are hydrogenated 3-ethyl-
carbazoles, with tetrahydro-3-ethylcarbazolebeing the
dominant product, which suggests that hydrogenation of
the latter is slow. Neither amines nor anilines were formed
in appreciable yields, which implies that they underwent
relatively rapid hydrogenolysis.
IVC5. Aniline Derivatives. Aniline derivatives are
present in almost all the HDN networks of nitrogen het-
erocyclics. The reactions removing nitrogen from the an-
iline derivatives are among the most important in the
networks because the pathways involving these reactions
are the ones requiring the lowest hydrogen consumptions.
Furthermore, the direct hydrogenolysis of the C-N bond
in anilines is believed to require prior hydrogenation (Oliv6
et al., 1985; Satterfield and Yang, 1984; Stern, 1979), but
it is not clear whether full hydrogenation of the aromatic
ring bonded to the amine group is required. The hydrogen
required per mole of nitrogen removed (i.e., the total hy-
drogen consumption) depends strongly on whether full
hydrogenation of the aromatic ring occurs.
Investigations of the HDN of anilines indicate that both
direct hydrogenolysis and HDN via hydrogenated inter-
O N H *0S *-0 7.5 x 104
2.86 x 10-6
+ NH3
r 1
Figure 16. (A) Reaction network determined by Mathur et al.
(1982b) for aniline HDN (Table XVI). The numbers next to the
mows are pseudo-first-order rate constants in L/(g of catalystd at
350 "C. (B) Suggested mechanism for aniline HDN.
mediates may occur. The critical parameter appears to
be the hydrogen concentration. Mathur et al. (1982b)
examined the HDN of several anilines (Table XVI). The
proposed reaction network for the HDN of aniline (Figure
16A) shows that the primary product was an unsaturated
hydrocarbon. The primary hydrogenolysis products of
o-ethylaniline and diphenylamine were also unsaturated
products; o-ethylaniline gave ethylbenzene, whereas di-
phenylamine gave benzene and aniline. The results in-
dicate that full hydrogenation of the ring was not necessary
for nitrogen removal. However, the authors proposed that
the formation of the primary aromatic products did not
occur as a result of the hydrogenolysis of the C-N bond,
but instead that a dihydro intermediate was formed from
aniline. The formation of this intermediate presumably
destroyed the aromatic resonance interaction with the
lone-pair electrons of the nitrogen atoms, thereby weak-
ening the C-N bond. The scission of the C-N bond oc-
curred rapidly from the dihydro intermediate as a 6-elim-
ination (Figure 16B), driven by the regaining of the aro-
matic resonance energy upon formation of the aromatic.
Different conclusions were reached, however, by Finiels
et al. (1986), who examined the HDN of several aniline
derivatives and secondary amines (Table XVI). In their
experiments with diphenylamine, the following products
were formed: aniline, benzene, cyclohexene, N-phenyl-
cyclohexylamine, and cyclohexane, with the latter formed
in substantial amounts. The concentration of benzene was
considerably lower than that of aniline at shorter reaction
times, which implies that benzene and aniline were not
formed exclusively by the pathway involving the dihydro
intermediate proposed by Mathur et al. (If aniline and
benzene had been formed only via the dihydro interme-
diate, their concentrations would have been equal at the
short reaction times.) The high aniline concentration
relative to that of benzene further demonstrates that the
dihydro pathway was not the only one operative, since
aniline was hydrogenated more rapidly than benzene. The
authors therefore proposed that the predominant pathway
for nitrogen removal from aniline derivatives required f d
hydrogenation of one of the aromatic rings before breaking
of the C-N bond.
The greater importance of the pathway requiring full
hydrogenation observed by Finiels et al. is probably a
consequence of the higher hydrogen partial pressures a p
plied in their experiments (59 atm vs 34 atm for M a t h
et al.). Higher pressures would lead to faster hydrogena-
tion of the benzene ring and thus result in a smaller con-
tribution of the pathway involving the dihydro interme-
diate. Thus,in agreement with the conclusion of Gioia and

Table XVIII. Equilibrium Constants and Standard
Enthalpy of Reaction for the HDO of Organooxygen
Compounds (Edelman et el., 1988: Furimsky, 1983b)
AH0,?
kcal/mol of
log K at organic
350°C 400°C reactant
furan + 4Hz 7 11.4 9.2 -84
n-butane + HzO
tetrahydrofuran + 2Hz - 11.4 10.2 -20
n-butane + HzO
benzofuran + 3H2 -
ethylbenzene + H20
10 9.3 -25
OThe values of the standard enthalpies of reaction in the table
were read from the van't Hoff plots given by the authors.
Lee (1986) for the quinoline network, higher hydrogen
partial pressures result in higher hydrogen consumption
per mole of nitrogen removed.
V. Hydrodeoxygenation (HDO)
Relatively few investigations of HDO have been carried
out because the oxygen content of petroleum is consider-
ably less than the concentrations of sulfur and nitrogen
(Allen et al., 1985; Whitehurst, 1978). However, since
oxygen is the most abundant heteroatom in many coal
liquids, hydrodeoxygenation is expected to assume in-
creasing importance. Organooxygen compounds in com-
mercial hydroprocessing feedstocks fall predominantly into
two classes: (a) phenol and naphthol derivatives and (b)
heterocyclic oxygen compounds (Le., furan and its deriv-
atives) (Allen et al., 1985; Whitehurst, 1978). Alcohols,
carboxylic acids, and ketones are also present, but in
smaller amounts (Allen et al., 1985).
VA. Thermodynamics. Equilibrium constants for the
gas-phase HDO of furan and tetrahydrofuran (Furimsky,
1983b) and reactions in the benzofuran HDO network
(Edelman et al., 1988) have been calculated from ther-
mochemical data (Reid et al., 1987; Stull et al., 1969) and
group contribution methods (Benson et al., 1969). Rep-
resentative results (Table XVIII) indicate that, at typical
hydroprocessing temperatures, the exothermic HDO is
virtually irreversible. However, the hydrogenation of or-
ganooxygen compounds, which may precede oxygen re-
moval, is reversible; for example, the equilibrium constant
for the reaction
-
benzofuran + H2 2,3-dihydrobenzofuran
is 0.4 at 300 O C . Equilibrium constants for higher mo-
lecular weight organooxygen compounds have not been
reported. Group contribution methods can be used to
obtain rough estimates. The group contribution method
of Benson et al. (1969) has been adapted for pyrans (Shaw
et al., 1977).
VB. Reactivities. Reactivities of single organooxygen
compounds in the absence of other compounds have not
been reported. However, the reactivities of organooxygen
compounds present in mixtures with other types of com-
pounds have been determined. The results indicate that
benzofuran and dibenzofuran are much less reactive than
phenols and that substituent effects are important in the
HDO of the latter.
The reactivities of substituted phenols, cis-2-phenyl-l-
hexanol, benzofuran, and dibenzofuran in mixtures in-
cluding sulfur and nitrogen compounds and aromatic hy-
drocarbons have been determined (Rollmann, 1977) in
experiments with a trickle-bed reactor and Co-Mo/A120B
catalyst at 344 "C and 50 atm. cis-2-Phenyl-1-hexanolwas
by far the most reactive oxygen compound among these,
Ind. Eng. Chem. Res., Vol. 30, No. 9, 1991 2041
Table XIX. Pseudo-First-OrderRate Constants k i n L/(g
of catalyst s) for Disappearance of Components in Weak
Acid Fraction of SRC-I1 Coal Liquid (Li et al., 1988; Grandy
et al., 1986)O
k detd
by high-
k detd resoln
compound byGCb GC/MS'
5,6,7,8-tetrahydro-l-naphthol
2-phenylphenol
1.9 X lo-' 4.2 X lo-'
8.3 X lod 7.2 X lod
methylphenylphenol
4-cyclohexylpi~enol
dimethyldihydroxyindan
1.5 X lo-' 2.0 X lo-'
4.4 X lo-' 6.2 X lo-'
2.3 X lo-'
methyltetrahydronaphthol 4.5 x 104
methylphenyl or methylphenoxybenzene 1.4 X lo-'
1-naphthol 5.4 x 10-4
phenolic oxygen in weak acid fractiond 1.6 X lo4
"Experiments performed with a fixed-bed flow reactor at
300-350 "C and 120 atm with a Ni-Mo/Alz03 catalyst. The reac-
tants were dissolved in cyclohexane saturated with hydrogen a t
room temperature and ca. 100 atm. *Li et al., 1985. 'Grandy et
al., 1986. Determined by infrared spectroscopy.
Table XX. Pseudo-First-Order Rate Constants for
Disappearance of Methyl-Substituted Phenols in HDO
t", k, L/(g
reactant "C of catalyst-e) reference
2-methylphenol" 350 1.6 X lo-' Odebunmi and
Ollie, 1983a
3-methylphenol 350 3.1 X lo-'
4-methylphenol 350 9.4 X lo4
2-methylphenolb 300 2.4 X lob Gevert et al., 1987
4-methylphenol 300 4.9 x 10-6
2,4-dimethylphenol 300 2.8 X low6
2,6-dimethylphenol 300 6.3 X 10"
2,4,64rimethylphenol 300 8.3 X lo4
OTrickle-bed reactor, 350-400 OC, 68 atm, n-hexadecane solvent,
aged Co-Mo/A1203 catalyst. bBatch reactor, 300 "C, 50 atm, n-
hexadecane solvent, Ni-Mo/Alz03 catalyst.
having a pseudo-first-order rate constant for HDO of 10
relative to that for naphthalene hydrogenation. The rel-
ative rate constanta for 4-methylphenol,2-ethylphenol, and
2-phenylphenol were 5.2, 1.2, and 1.4, respectively, indi-
cating lower reactivities for the ortho-substituted phenols.
The benzofuran reactivity (1.0) was comparable to that of
the substituted phenols. Dibenzofuran was the least re-
active, with a relative rate constant of 0.4.
The rates of disappearance of several phenolic com-
pounds present in the "weak acid" and "very weak acid"
fractions of a SRC-I1 coal liquid, prepared by separating
the coal liquid by liquid chromatography (Petrakis et al.,
19831, have also been reported (Li et al., 1985b; Grandy
et al., 1986). The reactivities of a number of compounds
identified by GC/MS were determined by GC and high-
resolution GC/MS (Table XIX), and the rate of disap-
pearance of the phenolic hydroxyl groups was determined
by infrared spectroscopy. The results indicate that the
reactivities of the different phenolic compounds are the
same within one order of magnitude. The ortho-substi-
tuted 2-phenylphenol is less reactive than the para-sub-
stituted 4-cyclohexylphenolby a factor of 5-10; the latter
uncertainty shows the difficulty in quantifying relative
reactivities using even well-characterized commercial feeds.
The lower reactivity of ortho-substituted phenols relative
to para- and meta-substituted phenols has also been ob-
served in other investigations (Table XX). The presence
of an additional methyl substituent ortho to the hydroxyl
group reduced the reactivity further. The results of Table
XX also show that methyl substitution at an unhindered
position increased the reactivity somewhat. [The rate
constants reported by Odebunmi and Ollis (1983a) in
2042 Ind. Eng. Chem. Res., Vol. 30, No. 9, 1991

Table XXI. Reaction Conditions in HDO Network Investigations

reactant conditions reference
1-naDhthol batch reactor. 2W275 "C. 22-34-atm H, Dartial Dreesure. n-hexadecane Li et al.. 1985a
solvent, reactant concentration 0.016 gjL, Ni-M0/Alzd3 catalyst
4-methylphenol batch reactor, 300 "C, 50 atm, n-hexadecane solvent, Co-Mo/A&OS catalyst Gevert et al., 1987
2-hydroxydiphenylmethane batch reactor, 300-330 "C, 69 atm, n-hexadecane solvent, reactant Petrocelli and Klein, 1987
concentration 0.06 mol/L, Co-Mo/Al9O1 catalyst
benzofuran vapor-phase flow reactor,'3W400 "C, 3b k m , N&Mo/A120a catalyst Edelman et al., 1988
trickle-bed reactor, 220-340 "C, 69 atm, 0.15 mol/L reactant concentration, Lee and Ollis, 1984a
Co-Mo/AlZO3 catalyst
dibenzofuran batch reactor, 343-376 "C, 105 atm, n-dodecane solvent, Ni-Mo/A1203 Krishnamurthy et al., 1981
catalyst
vapor-phase flow reactor, 350-390 "C, 69 atm, n-hexadecane solvent, reactant LaVopa and Satterfield, 1987
partial pressure of 0.24 atm, Ni-Mo/AlZO3 catalyst
diphenyl ether batch reactor, 280-320 "C, 69 atm, n-hexadecane solvent, 0.05-0.7 mol/L Petrocelli and Klein, 1987
reactant concentration, Co-Mo/A1203 catalyst

Table XX are smaller by 2-3 orders of magnitude than

those reported by Gevert et al. (1987); such a large dis-
crepancy is surprising considering the similarity of the
reaction conditions and may be due to the aged catalyst
used by Odebunmi and Ollis.]
Tables XIX and XX indicate that the reactivity dif-
ferences between ortho- and para-substituted species are
within a factor of 3. [The differences are smaller than the
order of magnitude difference observed between the HDS
of dibemthiophene and 4methyldibemthiophene (Table
VI).] One might expect that if oxygen removal from or-
ganooxygen compounds occurred solely by coordination
of the oxygen atom with the catalyst surface, larger re-
activity differences should result (see section IIIB).
The electronic effect of the hydroxyl substituent on the
reactivity is substantial, however. Moreau et al. (1987)
compared the reactivities of phenol and diphenyl ether
with that of benzene (they used a Ni-Mo/A1203 catalyst
and a batch reactor at 340 O C and 70 atm) and found that
phenol was by far the most reactive compound. Whereas
benzene was hydrogenated to give cyclohexane with a
relative rate constant of 1,phenol reacted by two parallel
routes to give benzene (relative rate constant of 1) and
cyclohexanol (relative rate constant of 16), with the latter
hydrodeoxygenated rapidly to give cyclohexane. The rapid
hydrogenation of phenol to give cyclohexanol was attrib-
uted to the electron-donating hydroxyl substituent. Ox-
ygen removal from diphenyl ether also proceeded by
parallel pathways, but because the substituent was less
electron donating, hydrogenation and hydrogenolysis rates
were similar (relative rate constant of 3 for each).
VC. Reaction Networks and Kinetics. Reaction
networks have been reported for both phenolic and furanic
organooxygen compounds. The networks for the former
class are generally simpler and have a greater degree of
quantitative detail. The networks indicate that oxygen
removal can occur either with prior ring saturation (as in
HDN) or directly (HDO), suggesting the need for devel-
oping catalysts selective for the latter pathway to reduce
hydrogen consumption.
VC1. Phenolic Oxygen Compounds. Li et al. (1985a)
proposed a reaction network for the HDO of 1-naphthol
(Table XXI, Figure 17). Oxygen removal occurred via four
pathways, including direct oxygen removal and ring hy-
drogenation prior to oxygen removal. The fastest deoxy-
genation pathway at 200 O C occurred through a 1-tetralone
intermediate and required 3 mol of H2/mol of 0 removed,
implying high hydrogen consumptions for HDO. Deoxy-
genation of 1-tetralone to give tetralin was assumed. The
reversible formation of 1-tetralone was presumed to pro-
ceed by hydrogenation of 1-naphthol to give an undetected
dihydro intermediate followed by a rapid keto-enol in-
terconversion, giving 1-tetralone. Tetralin formation from
1.40 x 1 0 . ~ 1.16X10.7
t A 8 " //
Crackiryl
Products
W
Figure 17. Reaction network for 1-naphthol proposed by Li et al.
(1985a) (Table XXI). The numbers next to the arrows are pseudo-
first-order rate constants in L/(g of catalystes) at 200 "C.
5,6,7,8-tetrahydro-l-naphthol was demonstrated in ex-
periments with the latter as a reactant; these experiments
also showed that naphthalene was formed by tetralin
dehydrogenation. Decalin formation directly from
5,6,7,8-tetrahydro-l-naphthol (expected on the basis of the
rapid hydrogenation of phenols reported above) was not
considered. Unidentified products formed in small yields
were all assumed to be cracking products.
Apparent activation energies were estimated for some
of the reactions. The values for two hydrogenolysis re-
actions, 1-naphthol giving naphthalene and 5,6,7,&tetra-
hydro-1-naphthol giving naphthalene, were larger than
those corresponding to the hydrogenation of 1-naphthol
to give either 1-tetralone or 5,6,7,&tetrahydro-l-naphthol
(32-34 vs 11-24 kcal/mol); the trend is similar to that
observed for quinoline HDN. Thus, lower hydrogen con-
sumptions for HDO could occur at higher temperatures.
The apparent activation energy for the pathway leading
to the formation of the presumed cracking products was
uncharacteristically low (18 kcal/mol) for hydrogenolysis
reactions, suggesting that the assumed pathway may be
incorrect. The appreciable tetralin dehydrogenation rate,
the higher yield of trans-decalin than of cis-decalin, and
the much faster hydrogenation of naphthalene than of
tetralin are all consistent with reported naphthalene
networks (Bhinde, 1979; Sapre and Gates, 1981).
A reaction network for the HDO of 4-methylphenol
(Table XXI, Figure 18A) has been reported (Gevert et al.,
1987). As for 1-naphthol, the pathways include direct
oxygen removal as well as ring saturation before hydro-
genolysis. However, an additional pathway was proposed
leading to the direct formation of a nonaromatic hydro-
carbon (methylcyclohexane)via hydrogenated phenols.
The partially hydrogenated phenols (Le., methylcyclo-
hexenole) were not detected and were assumed to be highly

e3 \
OH ’ 1
- 9 d
A formed after cracking into two monoaromatic species.
PH /” Y HDO pathways of additional phenolic lignin model com-
\
1 (Petrocelli and Klein, 1987).
Q+O
Figure 18. (A) Reaction network for 4-methylphenol proposed by
Gevert et al. (1987) (Table XXI). (B) Simplified network used for
kinetics analysis,
reactive intermediates since the HDO of methylcyclo-
hexanol to give methylcyclohexenes in the presence of
y-Al,O, is fast. The postulated formation of the me-
thylcyclohexenes from partially hydrogenated phenols is
questionable since the former can be formed by the de-
hydration of methylcyclohexanol. Furthermore, no ketones
were detected, in contrast to the l-naphthol network
(Figure 17).
A simplified network was used for kinetics analysis
(Figure lSB), with the slow hydrogenation of toluene to
give methylcyclohexane and methylcyclohexenes being
neglected. 4-Methylphenol disappearance did not follow
pseudo-first-order kinetics, and the rate decreased with
increasing initial reactant concentrations, suggesting
weaker inhibition by water than by organooxygen com-
pounds. Two kinds of catalytic sites were assumed: hy-
drogenolysis sites on which 4methylphenol was converted
to toluene and hydrogenation sites on which 4-methyl-
cyclohexanol and the methylcyclohexenols were formed.
The same rate form was used for each site:
Inhibition by the products was assumed to be negligible.
The intrinsic rate constants kj for hydrogenolysis and
(3)
hydrogenation were 2 X lo-‘ and 2.3 X L/(g of cata-
lyst-s), respectively; the values of the adsorption equilib-
rium constants characterizing the hydrogenolysis and hy-
drogenation sites were 23 and 12 L/mol, respectively.
Thus,direct hydrogenolysis was the faster pathway under
the conditions employed. Since only two initial reactant
concentrations were used to estimate the parameters, the
estimates are imprecise.
A partial network has been reported for a higher mo-
lecular weight phenolic compound, 2-hydroxydiphenyl-
methane (Table XXI) (Petrocelli and Klein, 1987). The
products were not all identified. The HDO proceeded via
two major pathways: direct hydrogenolysis to give di-
phenylmethane and oxygen removal from phenolic species
Ind. Eng. Chem. Res., Vol. 30,No. 9, 1991 2043
o^ 0
Figure 19. Benzofuran reaction network proposed by Edelman et
al. (1988) (Table XXI).
pounds, including 4-methylguaiacol, 4-methylcatechol,
eugenol, vanillin, and o,o’-biphenol, have been reported
VC2. Heterocyclic Oxygen Compounds. Two groups
investigated the HDO of benzofuran (Edelman et al., 1988;
Lee and O b ,1984a) (Table XXI). In the network shown
in Figure 19, oxygen removal occurs only after partial
hydrogenation of benzofuran; direct hydrogenolysis of the
latter to give ethylbenzene was postulated not to occur,
in contrast to the situation with the sulfur analogue ben-
zothiophene (Figure 6). However, the data are incomplete
and the hydrocarbon formation sequence open to question.
Dealkylation reactions occurred, with phenol and toluene
being produced at 300 O C , the lowest temperature used.
Dealkylation reactions have also been observed in inves-
tigations of l-methylnaphthalene conversion (Patzer et al.,
1979) and HDO of acidic coal liquid fractions (Grandy et
al., 1986). Although benzofuran hydrogenation to give
2,3-dihydrobenzofuran followed pseudo-fmt-orderkinetics
(with an apparent activation energy of 11.8 kcal/mol), the
HDO did not. The poor fit to fmt-order kinetics for HDO
was attributed to the weaker inhibition by water. The
HDO data were fitted to a simplified Langmuir-Hin-
shelwood rate expression with an order of -1 in total or-
ganooxygen compounds (implying high coverage by the
latter). A similar network had been reported by Lee and
Ollis (1984a), except that dealkylation was not observed,
possibly because of the generally lower temperatures used
(Table XXI).
A quantitative reaction network for dibenzofuran has
been reported by Krishnamurthy et al. (1981). Dibenzo-
furan HDO was proposed to occur by the following four
pathways:
- - -
dibenzofuran 2-phenylphenol biphenyl
dibenzofuran 2-cyclohexylphenol-
dibenzofuran -
2-cyclohexylphenol-
cyclohexylbenzene
bicyclohexyl + single-ring products
-
dibenzofuran 1,2,3,4-tetrahydrodibenzofuran
6-phenyl-l-hexanol- (unspecified) hydrocarbons
-
The phenolic compounds listed in the above pathways were
not detected. The pathways involving 2-phenylphenol and
2-cyclohexylphenol were proposed on the basis of exper-
iments done with the latter as reactants. These pathways
evidently do not occur strictly in parallel. For example,
the authors did not rule out additional reactions involving
the intermediates such as hydrogenation of 2-phenylphenol
2044 Ind. Eng. Chem. Res., Vol. 30,No. 9, 1991
Products
2,049
a- 56x10.’
19.31X
Products Products
Figure 20. Simplified dibenzofuran network proposed by Krishna-
murthy et al. (1981) for kinetics analpis (Table XXI). The numbers
next to the arrows are pseudo-first-order rate constants in L/(g of
cata1yst.s) at 343 O C .
to give 2-cyclohexylphenol; such a hydrogenation is cer-
tainly expected on the basis of the rapid hydrogenation
of phenols (Section VB). The proposed network (Figure
20) is thus only approximate. Dibenzofuran conversion
occurs by direct oxygen removal as well as ring saturation.
The most rapid pathway, designated as “dibenzofuran
products”, represents the reaction sequence forming cy-
- valid; Broderick and Gates considered cyclohexylbenzene
clohexylcylcohexanol,phenol, and cyclohexane through the
formation of 2-cyclohexylphenol. The oxygen-removal
reaction sequence from phenols was not elucidated. Figure
20 indicates that all the dibenzofuran HDO reactions were
considerably slower than the hydrogenations of biphenyl
and cyclohexylbenzene. In the network for dibenzo-
thiophene HDS proposed by Houalla et al. (1978) (Figure
71, the rates of biphenyl and cyclohexylbenzene hydro-
genation were markedly lower than that of dibenzo-
thiophene hydrogenolysis. The comparison suggests that
dibenzofuran HDO is an order of magnitude slower than
dibenzothiophene HDS.
A dibenzofuran network was also reported by LaVopa
and Satterfield (1987) (Table XXI,Figure 21). Some
experiments were performed with organooxygen interme-
diates as the reactants, including 2-phenylphenol, 2-
cyclohexylphenol, 2-phenylcyclohexanol, 2-cyclohexyl-
cyclohexanol, and 1,2,3,4-tetrahydrodibenzofuran.Rate
constants for the individual reactions were not determined.
The product distribution was qualitatively similar to that
observed by Krishnamurthy et al. in that (a) yields of
single-ring HDO products were larger than yields of two-
ring compounds (with the former comprising about 75%
of the products), (b) cyclohexylbenzene was formed in the
highest yields among the two-ring compounds, and (c)
oxygen-containing products were not detected with di-
benzofuran feed.
In contrast to the results of Krishnamurthy et al., La-
Vopa and Satterfield did not detect 6-phenyl-l-hexanol.
The latter authors found a product having a GC retention
time similar to that of 6-phenyl-1-hexanol, namely, (cy-
clopentylmethyl)benzene,and they questioned Krishna-
murthy et al.’s claim of identifying 6-phenyl-l-hexanol.
Furthermore, LaVopa and Satterfield found no evidence
for the formation of the intermediate compounds 2-
phenylcyclohexanol and 2-cyclohexylcyclohexanol.
Addition of hexanethiol (which was rapidly converted
to give hydrogen sulfide at reaction conditions) to the feed
t
Single Ring Hydrocarbons
0-0
Figure 21. RBaction network for dibemfuran proposed by LaVopa
and Satterfield (1987) (Table XXI).
at a partial pressure at 0.137 atm gave a decrease in the
rate of dibenzofuran HDO. The selectivity to two-ring
compounds decreased with increasing feed hydrogen sul-
fide concentration. The authors interpreted the latter
finding to mean that hydrogen sulfide inhibited hydro-
genolysis more than hydrogenation, as observed in the
HDS of dibenzothiophene by Broderick and Gates (1981).
However, the analogy with the HDS results is not entirely
to be a hydrogenation product of dibenzothiophene (since
hydrogenolysis of the hydrogenated dibenzothiophenes was
much more rapid than their formation). The rate of cy-
clohexylbenzene formation from dibenzothiophene was
weakly affected by hydrogen sulfide; in contrast, the se-
lectivity to cyclohexylbenzene (a two-ring product) in
LaVopa and Satterfield‘s study evidently decreased with
increasing hydrogen sulfide concentration.
The inhibition by hydrogen suKde was reversible. The
disappearance of dibenzofuran followed pseudo-first-order
kinetica when hydrogen sulfide was present in the feed (at
0.14-atm partial pressure), with the rate constant at 350
“C being 1.2 X lo+ mol/(g of catalystvs).
VC3. Ethers. A proposed network for HDO of di-
phenyl ether (Petrocelli and Klein, 1987) indicates only
a direct hydrogenolysis pathway for oxygen removal, giving
phenol and benzene. Ring saturation prior to oxygen re-
moval did not occur, in contrast to the network for the
structurally similar dibenzofuran. At higher conversions,
phenol was converted to benzene and cyclohexane, but the
formation sequence was not given. There is a lack of
comparable quantitative networks for other ethers.
VI. Binary Mixtures
Most investigations of the hydroprocessing reactivities
of mixtures have been done with pairs of organic reactants,
whereby the concentration of at least one reactant was
varied to determine inhibition of the other’s reactivity. A
few investigations have been done with three or more
reactants, but because the quantitative analysis of the
products is more difficult, the results are limited to com-
parisons of either the rates of conversion of the reactants
or the conversions in the presence and absence of inhib-
itors, Binary mixture results are addressed first.
For purposes of the discussion, a compound added to
the feed to determine its effect on another’s reactivity is
termed an “additive“. The effects of additives consisting
of organic sulfur, oxygen, and nitrogen compounds on the
reactivities of aromatic hydrocarbons and organosulfur,
organooxygen, and organonitrogen compounds are con-
 Ind. Eng. Chem. Res., Vol. 30,No. 9, 1991 2046

Table XXII. Reaction Conditions for Investieations of Inhibition of Aromatic Hydrogenation

reactant additive conditions reference
1. Sulfur Additives
biphenyl, 5.8-26 mmol/L H2S, 8.5-38 mmol/L liquid-phase flow reactor, 300-375 "C, 70-200 atm, Sapre and Gates, 1982
n-hexadecane solvent, Co-Mo/A120s catalyst
propylbenzene, 0.13 atm H2S, 0 . 1 3 atm vapor-phase flow reactor, 375 "C, 68 atm, Gtiltekin et al., 1984
Ni-Mo/A120S catalyst
naphthalene, 4-6 w t % dibenzothiophene, batch reactor, 350 "C, 35 atm, n-hexadecane solvent, Lo, 1981
0-2.5 wt % Ni-Mo/A1203 catalyst
2. Oxygen Additives
biphenyl" H20,b0.1 wt % batch reactor, 350 "C,102 atm, n-dodecane solvent, Krishnamurthy and Shah, 1982
Ni-Mo/Al2O3 catalyst
3. Nitrogen Additives
naphthalene, 4.4 wt % quinoline, 0.2-2 w t % batch reactor, 350 "C, 35 atm, n-hexadecane solvent, Bhinde, 1979; Lo, 1981
Ni-Mo/A120S catalyst
2-methylnaphthalene, 2,4-lutidine, 0-1 wt % flow reactor, 280-360 "C, 39-128 atm, n-hexadecane Ho et al., 1984
20 wt % solvent, Ni-Mo/A1203 catalyst
naphthalene, 0.9 w t % indole, 0-4 wt % batch reactor, 350 "C, 35 atm, n-hexadecane solvent, Lo, 1981
Ni-Mo/A1203 catalyst
propylbenzene, 0.13 atm NH3, 0 . 1 3 atm vapor-phase flow reactor, 375 "C, 69 atm, Gtiltekin et al., 1984
Ni-Mo/A120s catalyst
"Produced from dibenzothiophene (1w t % ) HDS. bProduced from in situ HDO of o-cyclohexylphenol (1 wt %).

sidered. Effects of ammonia, water, and hydrogen sulfide
are also evaluated.
VIA. Effects of Additives on Aromatic Hydrogen-
ation. Reaction conditions for investigations of the effecta
of the various additives on reactivities of aromatic hy-
drocarbons are summarized in Table XXII.
VIAL. Sulfur Compounds. Modeling of the inhibition
by sulfur compounds, especially hydrogen sulfide, is com-
plicated by the fact that hydrogen sulfide can modify the
catalyst surface (e.g., by increasing the density of Bransted
acid sites), especially a t higher concentrations. Further-
more, hydrogen sulfide (with hydrogen) is evidently re-
quired to maintain the catalysts in the form of sulfides,
rather than oxides (Broderick et al., 1982). Thus, Lang-
muir-Hinshelwood rate expressions that do not account
for interconversion of catalytic sites may not be theoret-
ically valid over the whole range of hydrogen sulfide con-
centrations.
Sapre and Gates (1982)expressed hydrogen sulfide in-
hibition of biphenyl hydrogenation with a modified
Langmuir-Hinshelwood rate form (Table 111);the data
were collected in differential conversion experiments
(Table XXII). Hydrogen sulfide was always present in
their experiments, with its concentration varied by a factor
of 4. A t 350 OC, the adsorption equilibrium constant for
hydrogen sulfide (12L/mol) was slightly larger than that
for biphenyl (4.6L/mol), implying that inhibition by hy-
drogen sulfide was comparable to self-inhibition by bi-
phenyl. In the range of concentrations examined (Table
XXII), the inhibition was mild, with the product of the
adsorption parameter and the concentration being of order
1.
Comparable inhibition of propylbenzene hydrogenation
to give propylcyclohexane was observed by Gultekin et al.
(19841,who measured the effect of hydrogen sulfide con-
centration on the pseudo-first-order rate constant for hy-
drogenation (Table XXII). At 375 O C and 68.1atm, the
rate constant decreased by 56% from a value of 3.9 X lo-'
mol/(g of cata1yst.s) as feed hydrogen sulfide partial
pressure increased from zero to 0.13atm. In this work,
however, there was no hydrogen sulfide in the feed in the
base case, which means that the catalyst may have been
in a less active (nonsulfided) form a t the outset.
Inhibition of the two hydrogenation reactions in the
naphthalene network (Figure 2) by dibenzothiophene has
been reported by Lo (1981),who expressed the hydro-
genation rates of naphthalene and tetralin in terms of a
modified pseudo-first-order rate constant:
k: = ki
(4)
1 + KHCCHC
+ KDTCDT
where the subscripts HC and DT denote, respectively, the
aromatic hydrocarbons and dibenzothiophene. All the
aromatic hydrocarbons were assumed to be represented
by one value, KHc,and hydrogenated dibenzothiophenes
were assumed to be represented by K m Values of ki were
determined independently from experiments with uaph-
thalene in mixtures with quinoline. The results (Khc =
2.7 L/mol, KDT= 12 L/mol) show that inhibition by di-
benzothiophene is comparable (i.e., within 1 order of
magnitude) to that by the aromatic hydrocarbons, at least
when the molecular weights are similar. At the concen-
tration ranges employed, the KC products for both the HC
and DT groups were of order 1, which implies that in-
hibition by dibenzothiophene was not severe. Inhibition
by hydrogen sulfide produced from dibenzothiophene HDS
was not considered, although the ratio K&KHc (4.4) was
within a factor of 2 of the value for sulfi&,ipi,enyl
(2.6)reported by Sapre and Gates (1982)a t the same
temperature but with a different form of rate equation
(Table 111).
VIA%. Oxygen Compounds. Inhibition effects of or-
ganooxygen compounds and water on hydrogenations of
aromatic hydrocarbons have not been reported. However,
an investigation of the effects of water on the reactions of
the dibenzothiophene network (Table XXII) allowed es-
timation of the change in the pseudo-first-order rate con-
stant for biphenyl hydrogenation as water was added to
the feed (Krishnamurthy and Shah, 1982). With 1 w t %
dibenzothiophene in the feed, the pseudo-first-order rate
constant for biphenyl hydrogenation decreased from 0.0056
min-I to 0.0005 min-* upon addition of 1 wt % o-cyclo-
hexylphenol (which was rapidly hydrodeoxygenated to gh-e
water). However, this apparent strong inhibition of bi-
phenyl hydrogenation is inconsistent with the observation
that the pseudo-first-order rate constant for conversion of
dibenzothiophene to give cyclohexylbenzene increased by
about 20% upon addition of the same amount of water;
recall that conversion of dibenzothiophene to give cyclo-
hexylbenzene proceeds by slow hydrogenation of di-
benzothiophene (Houalla et al., 1978). Additional exper-
2046 Ind. Eng. Chem. Res., Vol. 30, No. 9, 1991
iments are needed to resolve the issue.
VIAS. Nitrogen Compounds. The role of organo-
nitrogen compounds as inhibitors of aromatic hydrogen-
ation reactions has been known for years (Desikan and
Amberg, 1963), but the effects have been quantified only
recently (Table XXII).
Strong inhibition of the hydrogenation reactions of the
naphthalene network by quinoline and its products has
been reported (Bhinde, 1979; Lo, 1981). Inhibition by
quinoline and the three products of its hydrogenation
(Figure 10) is apparently greater than that resulting from
the other nitrogen-containing species (o-propylaniline and
ammonia) formed at longer reaction times, as evidenced
by the lower rate of naphthalene disappearance at shorter
times. Two approaches were used to model the inhibition.
In the first, rate constants for each reaction in the naph-
thalene network were calculated separately for "early" and
"late" reaction times (determined somewhat arbitrarily)
and correlated with the feed quinoline concentration:
(5)
where the subscript denotes initial quinoline concen-
tration. The rate constants decreased as the amount of
quinoline in the feed increased, and the rate of decrease
was largest for the first increments of quinoline addition.
The values of KQ at the "emliern reaction times (1000-1300
L/mol) were somewhat larger than those at "later" times
(210-370 L/mmol), implying stronger inhibition by quin-
oline and ita hydrogenated derivatives since the latter are
mostly primary products (Figure 10).
A more rigorous kinetics analysis was also performed by
assuming a Langmuir-Hinshelwood rate expression of the
form
k;;C;
and estimating the parameters directly from the concen-
tration-time data. Quinoline, ita hydrogenated derivatives,
and o-propylaniline were grouped into the term designated
as KQ~Nand ammonia (A) was represented by Kk The
parameter estimation was complicated by statistical cor-
relation between the adsorption parameters (in the de-
nominator) and rate constants (in the numerator), re-
quiring a trial-and-error procedure whereby adsorption
parameters were estimated independently of the rate
constants. The values KQBN = lo00 L/mol and K A= 400
L/mol show that inhibition parameters characteristic of
the nitrogen compounds, including ammonia, are at least
2 orders of magnitude larger than that characteristic of
naphthalene and its products (KHC = 2.7 L/mol). Small
amounta of organonitrogen compounds in the feed there-
fore reduce hydrogenation rates markedly.
Strong inhibition of 2-methylnaphthalene hydrogenation
by 2,4-lutidine (2,4-dimethylpyridine) has also been re-
ported (Table XXII) (Ho et al., 1984). The proposed rate
expression for hydrogenation of the aromatic hydrocarbon
is the same in form as that used by Lo, except that the
ammonia adsorption was neglected:
~HCKHCCHC
rHC = (7)
1 + KNCN+ KHCCHC
The organonitrogen compounds formed, 2,4-lutidine and
2,4-dimethylpiperidine, were each assumed to be charac-
terized by KN.At 310 "C and 69 atm, the estimated values
of the parameters were K H C = 0.085 L/mol and KN = 0.9
L/mol. These values are smaller by 2 orders of magnitude
than those estimated by Lo on the basis of data obtained
at 350 O C . The data of Table XXII show that the higher
concentrations of inhibitors gave lower values of the in-
hibition parameters. Only one inhibitor concentration was
employed by Ho et al., and it is not clear how sound the
statistical basis of their estimates might be. It is also not
known how firm a basis there is for comparison of the data
from various investigators.
The effect of the nonbasic nitrogen compound indole on
the naphthalene reaction network has also been reported
(Lo, 1981). The rate constants ki were determined from
experiments with naphthalene and quinoline in the feed,
and an equation analogous to eq 4 was used to represent
kinetics of the naphthalene hydrogenation in the presence
of indole. Indole, being nonbasic, was assumed to have the
same adsorption parameter as naphthalene. Indoline and
o-ethylaniline, the basic reaction products, were charac-
terized by the parameter KBN. The ammonia parameter
was determined from experiments with naphthalene-
quinoline mixtures. KBN was estimated to be 710 L/mol,
which is close to the value of KeBNestimated for quinoline
and its hydrogenated analogues (lo00 L/mol). It appears,
then, that the best fmt approximation justified by the few
available data is to lump the basic organonitrogen com-
pounds into one group of strong inhibitors.
The inhibition of aromatics hydrogenation by ammonia
has been reported (Table XXII) (Giiltekin et al., 1984).
At 375 O C and 69 atm, the pseudo-fmborder rate constant
for propylbenzene hydrogenation decreased by a factor of
7 when the ammonia partial pressure increased from 0 to
0.13 atm, which was equal to the propylbenzene partial
pressure in the feed. Ammonia was thus a stronger in-
hibitor of hydrogenation than hydrogen sulfide, as the
latter reduced the pseudo-first-order rate constant by a
factor of only 2.3.
In summary, nitrogen compounds are the strongest in-
hibitors of aromatics hydrogenation. Inhibition by orga-
nonitrogen compounds is stronger than that by ammonia,
but quantitative agreement between different investiga-
tions is lacking. There are also inconsistencies concerning
the absolute values of the adsorption parameters charac-
terizing the inhibition by the organonitrogen compounds.
These results suggest that a more fruitful approach to
modeling the inhibition would be to conduct experiments
using organonitrogen compounds in the feed having sim-
pler networks (e.g., amines that form ammonia rapidly),
estimate the corresponding adsorption parameters, and
then repeat the process using organonitrogen reactants
having more complex networks (e.g., progress to anilines
and then quinolines).
VIB. Effect of Additives on HDS. HDS networks
include hydrogenation as well as hydrogenolysis reactions,
which evidently occur on different kinds of catalytic sites
(Desikanand Amberg, 1964; Satterfield and Roberts, 1968;
Broderick and Gates, 1981). The effecta of additives have
been determined for both types of reactions, with the re-
sults interpreted in terms of their competitive adsorption
on the two kinds of sites.
VIB1. Aromatic Hydrocarbons. Weak inhibition by
naphthalene of reactions in the dibemthiophene network
(Figure 7) has been reported by Lo (1981) (Table XXIII).
Naphthalene inhibits both the hydrogenation and hydro-
genolysis reactions of the dibenzothiophene network
mildly, with selectivities to the various products being
virtually unchanged with naphthalene in the feed. In the
kinetics analysis, hydrogenations of dibenzothiophene,
1,2,3,4-tetrahydrodibenzothiophene, and aromatic hydro-
carbons were all assumed to occur on the same kinds of
 Ind. Eng. Chem. Res., Vol. 30, No. 9,1991 2047

Table XXIII. Reaction Conditions for Investigations of Inhibition of HDS

reactant additive conditions reference
1. Hydrocarbon Additives
dibenzothiophene, naphthalene, 0-5.9 wt % batch reactor, 350 "C, 35 atm, n-hexadecane Lo, 1981
0.7-2.5 wt % solvent, Ni-Mo/A1203 catalyst
thiophene, 0.24 atm naphthalene, vapor-phase flow reactor, 360 "c,69 atm LaVopa and Satterfield, 1988
phenanthrene, 0 . 2 4
atm
dibenwthiophene, 5 phenanthrene, 0-2 w t % vapor-phase flow reactor, 300 "C, 100 atm, xylene Nagai and Kabe, 1983
wt% solvent, Mo/A1203 catalyst
2. Sulfur Additives
thiophene, H#, unspecified vapor-phase flow reactor, 260-350 "C, 2-30 atm, Van Parijs and Froment, 1986
unspecified concentration n-heptane solvent, Co-Mo/Alp03 catalyst
concentration
range, 0.4-6 atm
estimated
benzothiophene, 0.96 H@, unspecified vapor-phase flow reactor, 240-300 "C, 2-30 atm, Van Parijs et al., 1986
wt% concentration n-heptane solvent, Co-Mo/AlzOS catalyst
dibenzothiophene, H a , 0.001-0.068 mol/L flow reactor, 275-325 "C, 177 atm, n-hexadecane Broderick and Gates, 1981
0.008-0.13 mol/L solvent, Co-Mo/A120S catalyst
dibenzothiophene, 5 HZS, 0-2 wt % vapor-phase flow reactor, 300 "C, 100 atm, xylene Nagai and Kabe, 1983
wt% solvent, Mo/Al,03 catalyst
3. Oxygen Additives
benzothiophene, 0.15 m-cresol, 0 . 1 5 mol/L trickle-bed reactor, 375-400 OC, 69 atm, Odebunmi and Ollis, 1983b
mol/L n-hexadecane solvent, Co-Mo/Aln03, catalyst
dibenzothiophene, benzofuran, 0 . 1 5 mol/L trickle-bed reactor, 325 "C, 69 atm, n-hexadecane Lee and Ollis, 1984b
0.15 mol/L solvent, Co-Mo/Al,03 catalyst
dibenzothiophene, 5 phenol, dibenzofuran, vapor-phase flow reactor, 300 "C, 100 atm, xylene Nagai and Kabe, 1983
wt% xanthene, 0-2 w t % solvent, Mo/A1203 catalyst
dibenzothiophene, 1 dibenzofuran, H,O, 0-1 w t batch reactor, 350 "C,102 atm, n-dodecane solvent, Krishnamurthy and Shah, 1983
wt% % Ni-Mo/A1,03 catalyst
4. Nitrogen Additives
dibenzothiophene, 0.7 quinoline, 0-2 w t % batch reactor, 350 "C, 35 atm, n-hexadecane Bhinde, 1979;Lo, 1981
wt% solvent, Ni-Mo/A1203 catalyst
thiophene, 0.03-0.2 pyridine, 0 . 1 atm vapor-phase flow reactor, 200-500 "C, Satterfield et al., 1975
atm Co-Mo/Alz03, Ni-Mo/A1203, and Ni-W/A1203
catalysts
thiophene, 0.12 atm pyridine, 0.12 atm vapor-phase flow reactor, 200-400 "C, 11-69 atm, Satterfield et al., 1980
Ni-Mo/A1203 catalyst
dibenwthiophene, 5 acridine, carbazole, vapor-phase flow reactor, 300 "C, xylene solvent, Nagai and Kabe, 1983
wt% phenothiazine, Mo/A1303catalyst
dicyclohexylamine, 0-2
wtw
sulfur in petroleum see Table XXIII vapor-phase flow reactor, 292 "C, 11 atm, Gutberlet and Bertolacini, 1983
naphtha Co-Mo/Al2O3 catalyst
thiophene, 0.24 atm see Table XXIV, 0 . 2 4 vapor-phase flow reactor, 360 "C,69 atm, LaVopa and Satterfield, 1988
atm Ni-Mo/A1,03 catalyst
thiophene quinoline, pyridine, vapor-phase stirred balance microreactor 350 "C, 1 Miciukiewicz et al., 1984
aniline, piperidine, atm, Co-Mo/A1,03 catalyst
methyl-substituted
derivatives
dibenzothiophene, 5 see Table XII, 0 . 5 wt % flow reactor, 300 "C, 100 atm, xylene solvent, Nagai et al., 1986b
wt% Ni-Mo/Al,03 catalyst
sites. Hydrogenolysis reactions were assumed to occur on ation and hydrogenolysis. The inhibition was represented
these sites and an additional type of site. A two-site model by a rate expression with thiophene adsorption neglected
for hydrogenolysis reactions was selected because of the
good fit to the data, especially in modeling inhibition by
organonitrogen compounds (see below). To reduce the
number of parameters in the model, the inhibition pa-
rameters for the aromatic hydrocarbons and for dibenzo- At 360 "C, adsorption parameters for naphthalene and
thiophene and its hydrogenation products were assumed phenanthrene were 11 and 65 atm-', respectively. The
to be equal for both types of sites. Consequently, in the 6-fold increase in KHCas the number of rings increased to
absence of organonitrogen compounds, the rate expression three suggests that the adsorption parameters of com-
reduced to eq 4. The values of the adsorption parameters pounds having four fused rings could be as much as 1 order
were the same as those obtained in determining the effect of magnitude greater than that of naphthalene, but
of dibenzothiophene on the naphthalene network, namely, quantitative evidence for this suggestion is lacking.
KHC= 2.7 L/mol and K m = 12 L/mol. Inhibition by Other investigations, however, indicate that inhibition
naphthalene is thus quantitatively similar to self-inhibition of hydrogenation of organosulfur compounds by aromatic
by dibenzothiophene. hydrocarbons is stronger. In contrast to Lo's results, Nagai
Mild inhibition of thiophene conversion (equal to its and Kabe (1983)(Table XXIII) observed in differential
HDS in this case) by two aromatic hydrocarbons has also conversion experiments that addition of up to 2 wt %
been reported (LaVopa and Satterfield, 1988) (Table phenanthrene to a solution of 5 wt % dibenzothiophene
XXIII), but no distinction was made between hydrogen- decreased the yield of cyclohexylbenzene but not that of
2048 Ind. Eng. Chem. Res., Vol. 30, No. 9, 1991
biphenyl. Phenanthrene was therefore assumed to adsorb
solely on hydrogenation sites. Inhibition of the hydro-
genation reactions was represented by a rate expression
of the same form as eq 8 giving the rate of formation of
1,2,3,4-tetrahydrodibenzothiophenefrom dibenzo-
thiophene; the phenanthrene inhibition term was assumed
to be much larger than those of dibenzothiophene and its
hydrogenated derivatives. This assumption is consistent
with Van Parijs et al.’s finding that ethylbenzene is a
strong inhibitor of benzothiophene hydrogenation (Table
XI). The value of the phenanthrene adsorption parameter
estimated by Nagai and Kabe was equal to 10 atm-’ and
comparable to that obtained for thiophene HDS inhibition
by LaVopa and Satterfield.
In summary, inhibition of HDS by aromatic hydro-
carbons is not negligible. There is disagreement regarding
the degree to which aromatic hydrocarbons inhibit the
conversion of organosulfur compounds. Nevertheless, the
inhibition is much weaker than that by basic organo-
nitrogen compounds, as discussed below.
VIB2. Sulfur Compounds. The effects of hydrogen
sulfide on HDS networks were stated above. Briefly, hy-
drogen sulfide inhibits hydrogenolysis reactions but not
hydrogenations (Broderick and Gates, 1981; Van Parijs and
Froment, 1986; Van Parijs et al., 1986). Similar conclusions
were reached by Nagai and Kabe (1983) (Table XXIII),
who found that the yields of biphenyl and cyclohexyl-
benzene decreased with increasing amounts of hydrogen
sulfide (formed rapidly in situ from carbon disulfide)
added to the dibenzothiophene feed. Using the same rate
form as eq 8, a value of 12.3 atm-’ was calculated for the
hydrogen sulfide adsorption parameter. Inhibition by
hydrogen sulfide is thus similar to that by aromatic hy-
drocarbons.
VIB3. Oxygen Compounds. Oxygen compounds
mildly inhibit the reactions of organosulfur compounds.
Odebunmi and Ollis (1983b) investigated m-cresol inhib-
ition of benzothiophene HDS at nearly differential con-
versions (Table XXIII). The inhibition of the HDS re-
action was represented by
~KBTCBT
r= (9)
1 + KBTCBT~
+ KcrCcro
where the subscripts BT and Cr denote, respectively,
benzothiophene and cresol and the additional subscript
0 denotes a feed concentration. At 375 O C , the estimated
values of the adsorption parameters were Kcr = 8.4 L/mol
and KBT = 16.5 L/mol. Inhibition of HDS by water was
not considered because little water was formed at the low
conversions examined. Inhibition by hydrogen sulfide
formed from the benzothiophene was not considered either.
Inhibition of dibenzothiophene HDS by benzofuran has
been reported (Lee and Ollis, 1984b) (Table XXIII).
Determination of the inhibition of individual reactions in
the dibenzothiophene network was not possible because
experiments were performed a t differential dibenzo-
thiophene conversions. Dibenzothiophene disappearance
was represented by an expression of the same form as eq
9. At 325 “C,the values of the inhibition parameters were
comparable: K m = 11.9 L/mol and KBF = 61.7 L/mol.
The effects of single-ring and multiring oxygen com-
pounds on dibenzothiophene reactivity have been exam-
ined (Nagai and Kabe, 1983) (Table XXIII). Oxygen
compounds decreased yields of both biphenyl and cyclo-
hexylbenzene. Because the selectivities to biphenyl and
cyclohexylbenzene were independent of the amount and
type of oxygen compound added, poisoning of both hy-
drogenolysis and hydrogenation sites was inferred. In-
hibition of biphenyl and cyclohexylbenzene formation was
accounted for with expressions of the same form, with that
corresponding to biphenyl formation being
~KDTKHFDTPH~
rBP = (10)
1 + KOPO
where the subscript 0 denotes an oxygen compound.
Adsorption parameter values for dibenzofuran, xanthene,
and phenol in the biphenyl rate expression were 11.7,11.2,
and 9.2 atm-’, respectively, at 300 “C. The near equality
of values suggests that inhibition by one-ring and multirii
oxygen compounds is similar. These values were also
within a factor of 2 of those in the cyclohexylbenzene rate
equation. Data obtained at higher concentrations of the
oxygen compounds deviate from the predictions of eq 10,
presumably because of structural changes in the catalyst
surface induced by product water.
Weak inhibition of dibenzothiophene HDS by di-
benzofuran and water has also been reported (Krishna-
murthy and Shah, 1982) (Table XXIII). Addition of 0.75
wt % dibenzofuran to 1wt % dibenzothiophene reduced
the pseudo-first-order rate constant for dibenzothiophene
disappearance by only 25%. Addition of 1 wt % o-
cyclohexylphenol (which was rapidly hydrodeoxygenated
to form water) to 1 wt % dibenzothiophene reduced the
pseudo-first-order rate constant for the hydrogenolysis of
dibenzothiophene 2-fold.
VIB4. Nitrogen Compounds. Basic organonitrogen
compounds are among the strongest inhibitors of HDS and
therefore the most widely investigated, but only recently
have quantitative inhibition effects been reported.
A thorough analysis of the inhibition by quinoline of the
reactions in the dibenzothiophene network (Figure 7) was
carried out by Bhinde (1979) (Table XXIII). Quinoline
strongly inhibited all the reactions of the network. As for
inhibition of naphthalene hydrogenation, the inhibition
was stronger at earlier reaction times when quinoline and
its hydrogenated products were the predominant nitro-
gen-containing species. In the kinetics analysis, Bhinde
divided the reaction period into “early” and “late” segments
(the latter occurring when the only nitrogen-containing
compounds remaining were o-propylaniline and ammonia).
Pseudo-first-order rate constants for each reaction in the
dibenzothiophene network were calculated separately for
each region and correlated with the feed quinoline con-
centration. Hydrogenation reactions were inhibited more
than hydrogenolyses, and the approximate 2-fold difference
in the decrease of the rate constants was interpreted as
evidence of separate sites for hydrogenation and hydro-
genolysis.
Using Bhinde’s data, Lo (1981) developed a model based
on Langmuir-Hinshelwood rate expressions for each re-
action of the dibenzothiophene network; an advantage of
this approach was the simultaneous modeling of HDS and
HDN. It was found that a single-site model for the hy-
drogenolysis reactions in the dibenzothiophene network
(such as the one used to model naphthalene hydrogena-
tion) gave a poor fit to the data. A two-site model, with
more parameters, gave a better fit:
rij,tod = rij,I + rij,II (11)
kij,ICi
rij,r = (12)
1 + KHCCHC + KsCs + K Q B N J ~ Q+BKA,ICA
N
kij,&i
rij,II =
+ KsCs + K Q B N J I ~ Q
1 + KHCCHC +BKA,IICA
N
(13)
The form of the equations is suggestive of the two-site

Table XXIV. Adsorption Parameters for Nitrogen
Compounds at 292 "C Determined by Gutberlet and
Bertolacini (1983)
compound K, atm-l
4-ethylpyridine 0.23
3,5-dimethylpyridine 0.16
2,4-dimethylpyridine 0.012
2,6-dimethylpyridine 0 work of Gutberlet and Bertolacini, it is not clear whether
4-methylaniline 0.012
ammonia (produced from benzylamine) 0.099
model proposed years earlier by Desikan and Amberg
(1964), with the first term in eq 11corresponding to a more
active hydrogenolysis site that is more susceptible to
poisoning and the second term corresponding to a less
active site that is more resistant to poisoning. The values
of the adsorption parameters for the less active sites
(KBBN = KA,II= 20 L/mol) were found to be more than
an order of magnitude smaller than those for the more
active sites. The inhibition parameters for the hydro-
carbons and the sulfur compounds were assumed to be the
same for both kinds of sites to reduce the number of pa-
rameters to be estimated (note that the adsorption pa-
rameters corresponding to hydrocarbons and the sulfur
compounds are represented by KHCand Ks,respectively,
on both kinds of sites). This choice was defended only on
the basis of the goodness of fit, determined a posteriori.
The number ?f parameters in eqs 12 and 13 is still large,
however, and the representation of such a complex set of
phenomena is less well developed than would be desirable.
The assumption of two kinds of sites might be criticized
as being a computational expedient to give a better fit to
the data. However, earlier studies by Satterfield and co-
workers (Satterfield et al., 1975, 1980) (Table XXIII) of
inhibition of thiophene HDS by pyridine, among others
cited above, suggest that two kinds of sites are indeed
operative, although the data have been insufficient for
construction of a model.
Investigations of inhibition of the HDS of some sulfur
compounds by various nitrogen compounds have also been
reported. These results are useful for correlating molecular
structure with inhibition, and they provide insights into
inhibition mechanisms.
The degree of inhibition by organitrogen compounds as
a function of steric hindrance around the nitrogen atom
was investigated by Gutberlet and Bertolacini (1983)
(Table XXIII), who measured inhibition of the HDS of a
petroleum naphtha by various methyl- and ethyl-substi-
tuted pyridines (Table XXIV). In this work, distinction
between sulfur removal via direct hydrogenolysis of the
organosulfur species or by its prior hydrogenation was not
possible. Under the conditions employed (Table XXIII),
the organonitrogen compounds added to the naphtha un-
derwent little HDN. The naphtha HDS data were fitted
to the following equation:
kPa
, -
(1 + KHlSpHfi) (1 + KAPAO.' + KBpBO" + KCPcO.')
(14)
where S, A, B, and C denote, respectively, sulfur compo-
nents of the naphtha, ammonia, nitrogen components of
the naphtha, and nitrogen compounds added to the
naphtha. The data of Table XXIV show that the inhib-
ition parameters correlate well with the degree of steric
hindrance about the nitrogen atom; the hindered nitrogen
compounds were characterized by relatively low values of
the inhibition parameters. The weak inhibition by the
unhindered 4-methylaniline (Table XXIV) was attributed
to the partial delocalization of its lone-pair electrons as-
Ind. Eng. Chem. Res., Vol. 30, No. 9, 1991 2049
sociated with resonance interactions. Inhibition of HDS
by ammonia (produced by rapid HDN of benzylamine) was
comparable to that characterizing the unhindered heter-
ocyclics, in qualitative agreement with Lo's results.
The relatively weak inhibition by sterically hindered
species has also been reported for thiophene HDS by
LaVopa and Satterfield (1988) (Table XXIII). As with the
the HDS here involves hydrogenolysis of the thiophene
directly or desulfurization of a hydrogenated thiophene.
The pseudo-first-order rate constant k' for thiophene
disappearance in the presence of several inhibitors was
correlated by the following equation:
k' = k
(15)
1 + KIP1
where the subscript I denotes an inhibitor. At 360 "C,the
values of KI for pyridine, 1-methylpyridine, and 2,6-di-
methylpyridine were 430,263, and 110 atm-', respectively,
in qualitative agreement with the data of Gutberlet and
Bertolacini. There is apparently a lack of quantitative
agreement between the two sets of results, however.
A relatively weak inhibition by sterically hindered or-
ganonitrogen compounds has even been reported for low-
pressure experiments (Miciukiewicz et al., 1984) (Table
XXIII). The adsorption of nitrogen compounds on the
catalyst a t steady state was determined with feeds con-
taining a nitrogen compound and either thiophene or 1-
hexene. The inhibition was expressed in terms of ratios
of pseudo-first-order rate constants for the disappearance
of thiophene (or 1-hexene) with and without nitrogen
compounds. The hindered nitrogen compounds were more
weakly adsorbed than the others (as measured gravime-
trically) and inhibited the thiophene HDS less. Surpris-
ingly, the hindered nitrogen compounds inhibited 1-hexene
hydrogenation more than thiophene HDS.
The correlation of the degree of steric hindrance with
the inhibition parameter (identified with the adsorption
equilibrium constant of the inhibitor) for sulfur removal
suggests that the nitrogen compounds inhibit reaction by
adsorption through the sp2 lone-pair electrons of the ni-
trogen atom. This proposal at first might appear to con-
tradict the hypothesis of Mathur et al. (1982) that heter-
ocyclic nitrogen compounds are adsorbed flat through their
*-electrons (see above). However, in the inhibition ex-
periments just described, hydrogenation of the nitrogen
compounds did not occur to a significant extent, and the
adsorption leading to inhibition might well have been
different from that leading to catalytic hydrogenation of
the inhibitors. Moreover, as Kwart et al. (1982) have
pointed out, 2,6-dimethylpyridine is hydrogenated at
higher temperatures and pressures than those of the in-
hibition experiments, and the 2,6-dimethylpiperidine thus
formed is a strong inhibitor of HDS because its sp3 lone-
pair electrons are not hindered owing to the puckered
nature of the piperidine ring.
The foregoing results suggest relations between the
basicity of unhindered organonitrogen compounds and the
strength of their inhibition for conversion of organosulfur
compounds. Such relations were sought by LaVopa and
Satterfield (1988) for thiophene HDS and by Nagai et al.
(1986) for dibenzothiophene hydrogenation to give hexa-
hydrodibenzothiophene (Table XXIII). LaVopa and
Satterfield represented the inhibition with eq 15; param-
eters are listed in Table XXV. At the relatively low
temperature of 260 "C,Nagai et al. observed that nitrogen
compounds inhibited hydrogenation but not hydrogenol-
ysis of dibenzothiophene. The inhibition of the formation
of hexahydrodibenzothiophenewas accounted for with a
2050 Ind. Eng. Chem. Res., Vol. 30, No. 9, 1991

Table XXV. Adsorption Parameters at 360 OC of Nitrogen weaker inhibition of dibenzothiophene hydrogenation by
Compounds in Rate Equation for Thiophene HDS phenanthrene (adsorption parameter equal to 10 atm-')
Determined by LaVopa and Satterfield (1988) compared to nitrogen inhibitors and (b) the weaker in-
compound K,atm-' hibition by dicyclohexylamine consistent with steric hin-
ammonia 65 drance about its nitrogen atom.
aniline 95 LaVopa and Satterfield (1988) demonstrated that the
2-ethylaniline 100 approach of representing the inhibition by eq 15 has some
2,6-dimethylpyridine 110 generality. Using the inhibition terms for quinoline and
1-methylpyridine 260 its nitrogen-containing products determined in the HDS
pyridine 430
1,2,3,4-tetrahydroquinoline 465 experiments, they were able to generate concentration
carbazole 510 profiles for dibenzofuran conversion that matched well
piperidine 590 data from dibenzofuran conversion with quinoline in the
4-methylpyridine 690 feed.
quinoline 990 VIC. Effect of Additives on HDO. Investigations of
5,6,7,&tetrahydroquinoline 2000
decahydroquinoline 2000 the effects of aromatic hydrocarbons on HDO are lacking.
l,&bia(NJV-dimethy1amino)naphthalene 3000 The following discussion is therefore limited to additives
(proton sponge) containing sulfur, oxygen, or nitrogen.
VIC1. Sulfur Compounds. Organoaulfur compounds
Table XXVI. Adsorption Parameters at 260 "C inhibit HDO only weakly. From results of experimenta
Characterizing Nitrogen Compounds in Rate Equation for with mixtures composed of oxygen and sulfur compounds
Hexahydrodibenzothiophene Formation Determined by
Nag& et al. (1986) (Table XXIII), Ollis and co-workers (Lee and Ollis,1984b;
Odebunmi and Ollis, 1983b) found that the same form of
compound K,atm-' the Langmuir-Hinshelwood rate expression describes the
acridine 1.98 mutual inhibition of HDO by organosulfur compounds and
quinoline 1.31 of HDS by organooxygen compounds. Inhibition of m-
pyridine 1.07
piperidine 0.85 cresol conversion by benzothiophene was expressed by eq
cyclohexylamine 0.77 9, with Kcr = 8.4 L/mol and KBT= 16.5 L/mol at 375 O C ,
y -picoline 0.63 as stated earlier.
dicyclohexylamine 0.45 Under some conditions (with a deactivated and poorly
aniline 0.19 sulfided catalyst), sulfur compounds promote HDO, con-
rate expression identical with eq 8. (Tetrahydrodibenzo- sistent with the suggestion that a sulfided catalyst is more
thiophene was virtually in equilibrium with dibenzo- active than one in the oxidic form (Lee and Ollis, 1984b)
thiophene at 260 "C.)The parameters are shown in Table (Table XXVII). In experiments with varying amounts
XXVI. In both studies, the estimated adsorption pa- of dibenzothiophene in the feed, the rate of benzofuran
rameters correlated poorly with basicities of the nitrogen HDO increased at feed dibenzothiophene concentrations
compounds in aqueous solution (i.e., pK values). Instead, up to 0.075 mol/L, but decreased at higher concentrations.
these parameters generally correlated well with gas-phase The higher benzofuran HDO rate at lower dibenzo-
proton affinities, which evidently better represent the in- thiophene concentrations was attributed to promotion by
teraction between an organic base and a surface catalytic hydrogen sulfide produced from the dibenzothiophene. A t
site. Data characterizing hindered species did not follow higher feed dibenzothiophene concentrations, the domi-
the correlation, as expected. As the gas-phase proton nant effect was competitive adsorption of the organic
affinities are enthalpy changes for proton-transfer reac- species. No rate equation was given. The promotion by
tions, it was speculated that the hydrogenation sites poi- hydrogen sulfide was not mentioned by Odebunmi and
soned by the nitrogen compounds were Brernsted acid sitee. Ollis (198313) in the report concerning m-cresol and ben-
The inhibition effect of the nonbasic carbazole appears zothiophene, perhaps because only a fresh catalyst was
unexpectedly strong. Table XXV, for example, indicates used.
that the adsorption parameter characterizing carbazole is Weak inhibition of dibenzofuran conversion by di-
comparable to that characterizing much more basic species benzothiophene has also been reported (Krishnamurthy
(e.g., piperidine). Strong inhibition by carbazole has also and Shah, 1982) (Table XXVII). Addition of 0.24 wt %
been observed, but for dibenzothiophene hydrogenation, dibenzothiophene to a 1.0 wt % dibenzofuran feed de-
by Nagai and Kabe (1983) (Table XXIII). Inhibition of creased the pseudo-first-order rate constant for dibenzo-
dibenzothiophene hydrogenation to give tetrahydrodi- furan disappearance by only 5%.
benzothiophene was represented with a Langmuir-Hin- The effect of hydrogen sulfide on HDO has not been
shelwood rate expression of the form of eq 8. The inhib- established clearly. In their investigation of dibenzofuran
ition parameters were determined to be 690,650,62, and HDO, LaVopa and Satterfield (1988) observed that an
41 atm-l for acridine, carbazole, phenothiazine, and di- increase of hydrogen sulfide partial pressure from 0 to 0.05
cyclohexylamine, respectively. The high value of the ad- atm in the feed decreased the HDO conversion of di-
sorption characterizing carbazole was attributed to prod- benzofuran from 60 to 44%. Furthermore, the presence
ucts of a rapid hydrogenation converting it to basic com- of hydrogen sulfide in the feed reduced the selectivity to
pounds, although the identities of the basic compounds two-ring products. On the other hand, Krishnamurthy et
and the kinetics of their formation were not determined. al. (1982) found that the addition of 0.026 wt 70 carbon
This hypothesis appears reasonable in light of the networks disaide (which was rapidly converted to hydrogen sulfide
of nonbasic nitrogen compounds (section IVC4). Thus, the under reaction conditions) increased the rate of dibenzo-
distinction between nonbasic and basic organonitrogen furan HDO.
compounds, as far as inhibition is concerned, is lost after VIC2. Oxygen Compounds. Self-inhibition of HDO
hydrogenation of the nonbasic species to give basic ones. by organooxygen compounds is weak. Odebunmi and Ollis
Additional results of Nagai and Kabe's study are in (198310) fitted the HDO rate of m-cresol to an equation of
agreement with other investigations including (a) the much the form of eq 9; the mild inhibition is indicated by the
 Ind. Eng. Chem. Res., Vol. 30, No. 9, 1991 2061

Table XXVII. Reaction Conditions for Investigations of Inhibition of HDO

reactant additive conditions reference
1. Sulfur Compounds
benzofuran, 0.15 dibenzothiophene, trickle-bed reactor, 325 "C, 69 atm, n-hexadecane Lee and Ollis, 1984b
mol/L 0 . 1 5 mol/L solvent, Co-Mo/AlzO3 catalyst
dibenzofuran, 1 dibenzothiophene, carbon batch reactor, 350 O C , 102 atm, n-dodecane solvent, Krishnamurthy and Shah, 1982
wt% disulfide, 0 . 2 4 w t % Ni-Mo/AlzOS catalyst
dibenzofuran, hydrogen sulfide, 0 . 1 4 atm vapor-phase flow reactor, 360 "C, 69 atm, LaVopa and Satterfield, 1988
0.24 atm Ni-Mo/Alz03 catalyst
2. Oxygen Compounds
l-naphthol, 0.002 methanol, 0 . 0 0 3 mmol/g flow reactor, 225 "C, 120 atm, cyclohexane solvent, Vogelzang et al., 1983
mmol/g Ni-Mo/AlzOs catalyst
3. Nitrogen Compounds
m-ethylphenol, quinoline, o-ethylaniline, trickle-bed reactor, 375 "C, 69 atm, n-hexadecane Satterfield and Yang, 1983
o-ethylphenol, 0 . 4 mmol/g solvent, Ni-Mo/A1203 catalyst
benzofuran,
dibenzyl
ether,
benzodioxane,
0.4 mmol/g
dibenzofuran, 1 7,8-benzoquinoline, 0 . 2 5 w t % batch reactor, 350 "C, 102 atm, n-dodecane Kriahnamurthy and Shah, 1982
wt% solvent, Ni-Mo/AlzOS catalyst
m-cresol, 0.15 indole, 0 . 1 5 mol/L trickle-bed reactor, 250-350 "C, 69 atm, Odebunmi and Ollii,1983c
mol/L n-hexadecane solvent, C0-Mo/A120s catalyst

value of the m-cresol adsorption parameter, Kcr = 8.4
L/mol.
Investigating dibenzofuran HDO, LaVopa and Satter-
field (1988) (Table XVII) found that a partial pressure of
0.24 atm of water in the feed (with hydrogen sulfide also
present) did not affect the dibenzofuran HDO rate at 69
atm; the temperature and space time were not given, but
may correspond to the authors' standard reaction condi-
tions: 360 O C and 160 (hag of catalyst)/(mol of dibenzo-
furan). Vogelzang et al. (1983) (Table XVII) also observed
that water weakly inhibits l-naphthol HDO. The HDO
conversion was stabilized after approximately 20 h on
stream in the flow reactor without water in the feed. On
addition of 0.00312 mmol of methanol/g of feed (methanol
was rapidly deoxygenated to form water under reaction
conditions), both the steady-state HDO conversion and the
product distribution became similar to those obtained
without water in the feed. However, the catalyst attained
its steady-state activity faster with water present in the
feed.
VIC3. Nitrogen Compounds. Inhibition of the HDO
of several compounds by two basic nitrogen compounds
was examined by Satterfield and Yang (1983) (Table
XXVII). The effects of quinoline and o-ethylaniline were
determined with equimolar binary mixtures containing one
oxygen compound and one nitrogen compound. Quinoline
and o-ethylaniline strongly inhibited the HDO of m-
ethylphenol, o-ethylphenol, benzofuran, and dibenzyl
ether, but the inhibition was leas severe with o-ethylaniline.
A kinetics analysis was not presented; representative re-
sults are as follows: at a space time of 50 (g of catalyst.
h)/(mol of m-ethylphenol), the HDO conversion of m-
ethylphenol was 98%. Addition of quinoline to the feed
decreased the HDO conversion to about 60%,and addition
of o-ethylaniline decreased the conversion to approximately
79%.
The strong inhibition of HDO by basic organonitrogen
compounds is also evident from the resulta of Krishna-
murthy and Shah (1982) (Table XXVII). Addition of 0.25
wt % 7,&benzoquinoline to 1wt % dibenzofuran reduced
the pseudo-first-order rate constant for disappearance of
the latter by a factor of 3.7.
Inhibition of the HDO of m-cresol by the nonbasic ni-
trogen compound indole was investigated by Odebunmi
and Ollis (1983~)at nearly differential conversions. Indole
Table XXVIII. Inhibition Parameters Calculated by
Odebunmi and Ollis (1983~)from Binary m-Cresol and
Indole Experimentso
temp, KC,, KN, k m o , mol/(g ~HDN.mol/(g
"C L/mmol L/mmol of catalystnh) of catalyst-h)
250 0.0211 0.0037 1.34 X lod 1.1 X lo-'
300 0.0017 0.0037 2.55 X 5.3 X lo-'
"Reaction conditions are given in Table XVII.
inhibited m-cresol HDO, the inhibition being greater at
lower temperatures because of the larger ratio of indoline
to indole concentration at lower temperatures arising from
the equilibrium between the latter. A rate expression of
the form of eq 9 was proposed. Inhibition terms corre-
sponding to (a) m-cresol and (b) indole and its nitrogen-
containing producta were included. The indole adsorption
parameter was assumed to be equal to that of the other
nitrogen-containing products (Le., indoline and o-ethyl-
aniline). In light of the discussion of HDS inhibition by
carbazole (section VIB4), lumping indole with ita basic
products is an oversimplification since the inhibition is
likely to be dominated by the latter; the approach em-
ployed by Lo (1981) to model naphthalene hydrogenation
with indole in the feed is probably more appropriate
(section VIA3). As shown in Table XXVIII, the inhibition
parameter representing indole and its products is com-
parable to that for m-cresol at 300 O C , but much larger at
the lower temperatures, a result attributed to the higher
concentration of the basic compound indoline in the re-
actor at the lower temperatures.
VID. Effect of Additives on HDN. VIDl. Aromatic
Hydrocarbons. The inhibition of both the hydrogenation
and the hydrogenolysis reactions of the quinoline network
by aromatic-hydrocarbons is minimal. Bhinde (1979) and
Lo (1981) reached this conclusion in investigations of the
influence of quinoline on the naphthalene network dis-
cussed earlier (Tables XXII and XXIX). For example,
Bhinde found that the pseudo-first-order rate constants
for his proposed quinoline network (similar to that shown
in Figure 10) were lower by 10-15% when 5.9 wt %
naphthalene was added to a feed containing 0.2 wt %
quinoline in hexadecane. This result is consistent with the
conclusion that the inhibition parameters for naphthalene
and ita hydrogenation products are 2 orders of magnitude
smaller than those for ammonia and the organonitrogen
2052 Ind. Eng. Chem. Res., Vol. 30,No. 9, 1991

Table XXIX. Reaction Conditions for Investigations of Inhibition of HDN

reactant additive conditions reference
1. Aromatic Hydrocarbons
quinoline, 0.2 wt % naphthalene, 0-5.9 wt % batch reactor, 350 "C, 35 atm, Bhinde, 1979 Lo, 1981
n-hexadecane solvent, Ni-Mo/A1203
catalyst
2,4-lutidine, 1wt % 2-methylnaphthalene, 20 wt % flow reactor, 280-360 OC, 39-128 atm, Ho et al., 1984
n-hexadecane solvent
2. Sulfur Compounds
quinoline, 0.5 wt % dibenzothiophene, 0 . 7 wt % batch reactor, 350 "C, 35 atm, Bhinde, 1979; Lo, 1981
n-hexadecane solvent, Ni-Mo/A1203
catalyst
acridine, 0.25 wt % thiophene, benzothiophene, flow reactor, 280-360 "C, 99 atm, Nagai et al., 1986a
dibenzothiophene, dimethyl xylene solvent, Mo/A1203(sulfided
sulfide, ethanethiol, 0-1 wt and unsulfided forms)
%
pyridine, 0.1 atm thiophene, 0.034.2 atm vapor-phase flow reactor, 200-500 "C, Satterfield et al., 1975
Co-Mo/Alz03, Ni-Mo/A1203, and
Ni-W/A1203 catalysts
pyridine, 0.12 atm thiophene, 0.12 atm vapor-phase flow reactor, 200-400 OC, Satterfield et al., 1980
11-69 atm, Ni-Mo/A1203 catalyst
3. Oxygen Compounds
quinoline, o-ethylaniline, m-ethylphenol, o-ethylphenol, trickle-bed reactor, 375 "C, 69 atm, Satterfield and Yang, 1983
0.4 mmol/g benzofuran, dibenzyl ether, n-hexadecane solvent, Ni-Mo/Alz03
0.4 mmol/g catalyst
quinoline, 5 wt % H20, H2S, 0 . 1 2 atm trickle-bed reactor, 375 "C,69 atm, Satterfield et al., 1985; Satterfield
n-hexadecane solvent, Ni-Mo/A1203 and Smith, 1986
catalyst
7,8-benzoquinoline, 1 wt % dibenzofuran, o-cyclohexyl- batch reactor, 350 "C, 102 atm, Krishnamurthy and Shah, 1982
phenol, 0-1 wt % n-dodecane solvent, Ni-Mo/A1203
catalyst
indole, 0.15 mol/L m-cresol, 0 . 1 5 mol/L trickle-bed reactor, 250-350 "C, 69 atm, Odebunmi and Ollis, 1983c
n-hexadecane solvent, Co-Mo/A1203
catalyst
acridine, 0.25 wt % xanthene, 0-1 wt % flow reactor, 280-360 "C, 99 atm, Nagai et al., 1986a
xylene solvent, Mo/Al2O3 (sulfided
and unsulfided forms)
4. Nitrogen Compounds
quinoline, 0.5 wt % indole, quinoline, 0.2-2 wt % batch reactor, 350 OC, 35 atm, Bhinde, 1979
n-hexadecane solvent, Ni-Mo/A1203
catalyst

compounds in the quinoline network (Lo, 1981). Ho et al. Table XXX. Inhibition Parameters Determined by Nagai et
(1984) reached similar conclusions. al. (1986a) for Perhydroacridine and Selected Sulfur
VID2. Sulfur Compounds. Sulfur compounds are Compoundsa
also weak inhibitors of HDN. Bhinde (1979) (Table additive K A , atm-' KpA, atm-'
XXIX) determined pseudo-first-order rate constants for dibenzothiophene 16.9 1350
the quinoline network from data for feeds containing either benzothiophene 6.9 720
0.5 wt % quinoline or 0.5 w t % quinoline and 0.7 wt 90 thiophene 5.2 560
dibenzothiophene. The rate constants for the overall ni- dimethyl sulfide 3.2 910
trogen removal and for the individual reactions in the ethanethiol 1.0 830
quinoline network were almost unchanged by the addition See Table XXIX for reaction conditions. The subscripts A and
of dibenzothiophene. The only discernible effect of the PA denoted "additive" and 'perhydroacridine", respectively.
dibenzothiophene was a 25% enhancement in the pseu-
do-first-order rate constant for the hydrogenolysis of de- data were represented with the following equation, which
cahydroquinoline. In a more rigorous analysis of Bhinde's reflects the additional assumption that perhydroacridine
data, Lo (1981) estimated the inhibition parameter for was the sole nitrogen compound adsorbed on the hydro-
quinoline to be 2 orders of magnitude greater than that genolysis sites:
for dibenzothiophene.
Nagai et al. (1986a) investigated the effect of several
sulfur compounds (Table XXIX) on the HDN of acridine
at HDN conversions less than 20% (assumed to be dif- where the subscripts DCM, PA, and S denote dicyclo-
ferential). The addition of the sulfur compounds inhibited hexylmethane, perhydroacridine, and the sulfur additive,
acridine HDN, with the yield of dicyclohexylmethane respectively. The inhibition parameters at 360 OC were
decreasing with increasing concentration of the sulfur determined separately for each binary mixture. This
compound. In the kinetics analysis, the slow reaction in procedure unfortunately gave different estimates for KPA,
nitrogen removal was assumed to be the hydrogenolysis one value for each sulfur additive investigated (Table
of perhydroacridine to give dicyclohexylmethane. This XXX). KpA was 2 orders of magnitude larger than KS for
assumption may be criticized since the acridine network any of the sulfur compounds, in qualitative agreement wlth
investigation discussed earlier (Zawadski et al., 1982) Bhinde's and Lo's results. Sulfur compounds having two
showed that rates of hydrogenation and hydrogenolysis or more rings were considerably stronger inhibitors than
reactions in the network were comparable. The kinetics mercaptans or sulfides. The inhibition parameter for

hydrogen was also found to be 3 orders of magnitude
smaller than any value of Ks.
The effect of thiophene on the HDN of pyridine was
characterized in the investigations by Satterfield and co-
workers (Satterfield et al., 1975, 1980) with feeds con-
taining thiophene, pyridine, or mixtures of the two. In
both low- and high-pressure experiments at temperatures
below 325 OC, the HDN of pyridine was less when
thiophene was added to the feed. The authors postulated
competitive adsorption of thiophene and pyridine on the
hydrogenation sites. At temperatures exceeding 325 "C,
however, pyridine HDN was greater when thiophene was
added to the feed. The effect was attributed to the pro-
motion of piperidine hydrogenolysis by hydrogen sulfide
formed from thiophene. It was speculated that hydrogen
sulfide kept the catalyst in a sulfded state (no other source
of sulfur was present in the feed), or perhaps the hydrogen
sulfide aided in removing basic nitrogen compounds from
the surface. The data were insufficient for construction
of a kinetics model.
The effect of hydrogen sulfide on HDN was addressed
in the discussion of HDN (see above). The studies by
Satterfield and co-workers (Table XVI) of quinoline HDN
demonstrated that hydrogen sulfide enhanced the hydro-
genolysis of C-N bonds and inhibited hydrogenation
slightly (but see below). The overall effect was to enhance
the HDN. The effect of hydrogen sulfide has not been
presented in terms of a Langmuir-Hinshelwood rate ex-
pression, but if the effect of hydrogen sulfide is to modify
the catalytic surface in some way, then such a simple rate
expression would not be appropriate.
VID3. Oxygen Compounds. The effects of m-ethyl-
phenol, o-ethylphenol, benzofuran, and dibenzyl ether on
the HDN of quinoline and o-ethylaniline were investigated
by Satterfield and Yang (1983)(Table XXIX). In ex-
periments with quinoline or a mixture of quinoline and
equimolar amounts of an oxygen compound, the quinoline
HDN conversion increased when the oxygen compound
was added, and the enhancement was the same for each
compound. (hydrogen sulfide was also present.) For ex-
ample, a t a space time of 300 (g of catalyst.h)/(mol of
quinoline), the HDN conversion increased from 33% with
no oxygen compound present to 60% when an oxygen
compound was present. The yield of decahydroquinoline
was less without oxygen compounds, suggesting that hy-
drogenolysis was enhanced by the oxygen compounds. All
the oxygen compounds had nearly the same effect on the
HDN. This result and the observation that the HDO was
rapid led the authors to propose that the water formed was
the cause of the HDN promotion. This hypothesis was
confirmed by addition of 0.01 wt % water to the feed,
which had the same effect.
The effect of the oxygen compounds on the HDN of
o-ethylaniline was different. The ethylphenols increased
the HDN conversion, but benzofuran inhibited it slightly;
addition of 0.01 wt % water did not change the HDN
conversion. The authors therefore concluded that since
the HDN conversion of o-ethylanilinewas strongly affected
by its rate of hydrogenation, water did not enhance hy-
drogenation. It was suggested that oxygen compounds
exerted opposing effects, a form of promotion in addition
to adsorption in competition with o-ethylaniline.
More thorough experiments addressing the effects of
water on quinoline HDN have been reported (Satterfield
et al., 1985;Satterfield and Smith, 1986)(Table XXIX).
The effects of the addition of hydrogen sulfide, water, and
both of these on the HDN were investigated; representative
results are given in Table XXXI. The addition of water
Ind. Eng. Chem. Res., Vol. 30,No. 9,1991 2053
Table XXXI. Effect of Hydrogen Sulfide and Water on
Quinoline HDNO (Satterfield et al., 1985; Satterfield and
Smith, 1986)
P H ~atm , atm ?& quinoline HDN
0 0 42
0.063 0 54
0 0.12 78
0.063 0.12 94
"Conditions: 375 "C, 69 atm, space time = 365 (g of catalyst.
h)/(mol of quinoline). See Table XXIX for additional details.
without hydrogen sulfide in the feed caused a small en-
hancement in the HDN rate. The enhancement was less
than that obtained with hydrogen sulfide in the absence
of water. The addition of water with hydrogen sulfide in
the feed increased the HDN rate markedly. Removal of
hydrogen sulfide from the feed resulted in a rapid decrease
in HDN, whereas removal of water from the feed (with
hydrogen sulfide present) resulted in a more gradual de-
cline in the HDN rate.
Satterfield and Smith also determined the effects of
hydrogen sulfide and water addition on the HDN kinetics,
assuming rate expressions identical with those used earlier
(Table XVII). Each additive was absent or present a t a
partial pressure of 0.13 atm. The only effect of water
addition was to increase the hydrogenolysis rate constant
for decahydrequinolineby 20%. The addition of hydrogen
sulfide enhanced the rates of some of the hydrogenation
reactions as well as those of the hydrogenolysis reactions.
With both water and hydrogen sulfide in the feed, the rate
constants for all the reactions were larger than when either
water or hydrogen sulfide alone was present. The rate of
the hydrogenolysis of decahydroquinoline was most sen-
sitive to the presence of the additives; the addition of
water, hydrogen sulfide, and both caused the following
percentage increases in the hydrogenolysis rate constant:
20,167,and 197,respectively. The enhancement of the
hydrogenation and hydrogenolysis rates was suggested to
be related to increased acidity of the catalyst surface.
Somewhat different results were reported for the effect
of dibenzofuran and water, as measured by the rate of
disappearance of 7,8-benzoquinoline(Krishnamurthy and
Shah, 1982) (Table XXIX). Addition of 1 wt % di-
benzofuran to 1 wt % 7,8-benzoquinoline reduced the
pseudo-first-order rate constant by only 5%. However, the
addition of 1 wt % o-cyclohexylphenol (which was rapidly
converted to give water) reduced the rate constant by 15%.
In either case, the inhibition was very mild. The differ-
ences in the effect of water observed by the two groups of
investigators may be associated with differences in catalyst
pretreatment conditions. The effect of water might be
especially difficult to determine because precautions must
also be taken to ensure the exclusion of moisture in
base-case experiments.
The inhibition effects of m-cresol on the HDN of indole
were determined from experiments by Odebunmi and Ollis
(1983~) (Table XXIX). Their rate equation for both HDO
and HDN was of the form of eq 9;the values of the pa-
rameters given in Table XXVIII show that m-cresol in-
hibited the HDN slightly. This inhibition of HDN by an
oxygen compound does not agree with the results of Sat-
terfield and co-workers mentioned above, possibly because
the conversions were differential and any promotional
effect of water was minimized.
Nagai et al. (1986a),in an investigation of various ad-
ditives on acridine HDN (Table XXIX), also examined the
effect of xanthene, which was found to inhibit the acridine
reactions in the same manner as the organosulfur com-
pounds, Le., by retarding the hydrogenolysis of per-
2054 Ind. Eng. Chem. Res., Vol. 30,No. 9,1991
Table XXXII. Variation of Selected Pseudo-First-Order
Rata Constants in L/(g of catalyst 0s) for the Quinoline
HDN Network for Various Feed Quinoline Concentrations'
(Bhinde. 1979) ~ ~~
quinoline feed concn, wt %
quinoline + 2H2 -.
reaction 0.2
3.2 X
0.5 2.0
1.8 X 10-97.8y10-'
decahydroquinoline
hydrocarbons + NH3
-
5,6,7,&tetrahydroquinoline
Ha
7.5 x 10-3 3.1 x 10-3 1.5 x 10-3
quinoline
carbons
-Ha
+ NHS
hydro- 6.7 X lo-' 2.8 X lo-' 9.7 X loa
a Reaction conditions are given in Table XXIX.
hydroacridine. Using eq 16, they calculated an adsorption
parameter of 0.18 atm-', which is more than 2 orders of
magnitude smaller than the corresponding parameter for
acridine.
In summary, competitive adsorption involving oxygen
and nitrogen compounds leads to mild inhibition of HDN
at low conversions. At higher HDO conversions, when
substantial amounts of water are formed, the HDN is en-
hanced slightly.
VID4. Nitrogen Compounds. The effect of quinoline
on indole HDN was investigated by Bhinde (1979) (Table
XXIX). The pseudo-first-order rate constants were cal-
culated for the indole network shown in Figure 15. The
addition of 0.5 wt % quinoline to 0.5 wt % indole de-
pressed the pseudo-first-order rate constants by one-third,
which indicates a substantial inhibition by quinoline and
its nitrogen-containing products. However, Bhinde ob-
served that the inhibition by quinoline of the reactions in
the indole network was less severe than the inhibition of
the reactions of the naphthalene network; in the latter case,
the same amount of quinoline reduced the pseudo-first-
order rate constants by an order of magnitude. Bhinde
inferred that indole and its nitrogen-containing products
were more strongly adsorbed than the aromatic hydro-
carbons. It was not possible to determine from the
analysis, however, whether indole itself was more strongly
adsorbed than the hydrocarbons.
Bhinde also examined the effect of indole on quinoline
conversion by comparing the pseudo-first-order rate con-
stants in the quinoline network determined in experiments
with 0.5 wt % quinoline and the indole-quinoline mixture
mentioned above. The indole affected the pseudo-first-
order rate constants by less than 10%. This weak inhib-
ition was attributed to the weaker adsorption by indole,
which is nonbasic. However, one expects that if sufficiently
large amounts of indole were present, the concentrations
of the basic products formed from it (e.g., indoline) would
have been large enough to inhibit the quinoline reactions.
The inhibition of quinoline conversion by its own re-
action products was addressed by Bhinde (1979) in ex-
periments with mixtures of quinoline and naphthalene (or
dibenzothiophene). The quinoline concentration was
varied from 0.2 to 2.0 wt % with the concentrations of the
other reactants held constant (Table XXIX). Pseudo-
first-order rate constants were estimated for the quinoline
reaction network; each decreased significantly with in-
creasing feed quinoline concentration (Table XXXII).
In analyzing Bhinde's data, Lo (1981) found that if the
rate constant k and absorption parameter were estimated
simultaneously in a rate expression such as
kC
r=
(1 + Kc)m
and the adsorption parameter was large, the estimated
Table XXXIII. Relative Pseudo-First-OrderRate
Constants for Disappearance of Reactants or Heteroatom
Removal in Mixturea" (Rollmann, 1977)
compound re1 rata const
hydrocarbons
2-methylnaphthalene
2,3-dimethylnaphthalene
1.0
1.4
organosulfur compounds
dibenzothiophene HDS
benzothiophene HDS
3.6
3.4
thiophenol HDS
organonitrogen compounds
indole HDN
o-ethylaniline HDN
210
0.9
1.1
quinoline HDN 1.3
organooxygen compounds
benzofuran HDO 1.0
dibenzofuran HDO 0.4
2-phenylphenol HDO 1.4
cis-2-phenyl-1-cyclohexanolHDO 210
p-cresol HDO 5.2
Reaction conditions: trickle-bed reactor, 344 O C , 48.6 atm, Co-
Mo/A1203 catalyst stabilized by operation for 4 days.
value of K was close to zero while the estimated value of
the rate constant was close to the actual value of k / ( K C P .
This result implies that the rate constant in the numerator
and the adsorption parameter in the denominator are
statistically correlated and should be estimated separately.
VII. Multicomponent Mixtures
There are only a few quantitative results characterizing
the individual hydroprocessing reactions of mixtures with
more than two organic reactants. Rollmann (1977) de-
termined the relative rates of disappearance of compounds
in various mixtures containing 10 organic compounds.
Experiments were conducted with a trickle-bed reactor at
several space velocities with two Co-Mo/A1203 catalysts.
Standard reaction conditions were 344 OC, 48.6 atm, and
a hydrogen to organic reactant molar ratio of 8; no solvent
was used. The feed included combinations of aromatic
hydrocarbons as well as sulfur, nitrogen, and oxygen com-
pounds. The major products formed from each reactant
were identified, being consistent with those found in the
pure-component experiments discussed above. Neither
quantitative reaction networks nor inhibition effects were
considered. The disappearance of the sulfur and oxygen
heterocyclics and nitrogen removal from the organo-
nitrogen compounds followed pseudo-first-order kinetics;
the hydrogenations of napthalene and 2-methyl-
naphthalene were reversible, but only the hydrogenation
rate constants were determined.
The reactivity of each compound was expressed in terms
of a pseudo-first-order rate constant for disappearance
relative to that for naphthalene. Data are given in Table
XXXIII. The most reactive compounds were mercaptans
and alcohols. In contrast to the results of Nag et al. (1979),
the HDS reactivities of benzothiophene and dibenzo-
thiophene were approximately the same. Dibenzofuran
had a low reactivity; only mesitylene was less reactive (but
quantitative results were not given). In agreement with
the results of Odebunmi and Ollis (1983a), o-cresol was
found to be less reactive than m-cresol.
Similar experiments were reported by Badilla-Ohlbaum
et al. (1979a,b),who used a trickle-bed reactor at 68 atm
with several Ni-Mo catalysts on different supports at 400
and 480 "C. The space velocity was approximately0.2 (g
of feed)/(g of cataIyst*h),calculated on a solvent-free Mi.
(17) The feed consisted of dibenzothiophene (10 wt %), quin-
oline (20 wt %), dibenzofuran (7 wt %), and phenanthrene
(10 wt %) dissolved in n-heptane. The product distribu-

tion was consistent with that obtained from the individual
compound experiments discussed earlier. Dibenzo-
thiophene was completely desulfurized at both tempera-
tures. Pseudo-first-order rate constants for disappearance
or heteroatom removal were estimated from data at one
space time for the other reactants at 400 "C; reaction in
the presence of a commercial Ni-Mo/A120s catalyst was
characterized by the following relative values of the
pseudo-first-order rate constants: 5.0, 3.1, and 0.68 for
phenanthrene hydrogenation, quinoline HDN, and di-
benzofuran HDO, respectively. The resulta are similar to
Rollmann's, although the conditions were different.
Chu and Wang (1982) measured the reactivities of di-
benzothiophene, aniline, and naphthalene in mixtures; the
solvent was a toluenemesitylene mixture. Five com-
mercial catalysts were used. Cumene and pyridine were
present in the feed, but their reactivities were not reported.
The experiments were conducted with vapor-phase reac-
tants at 220-375 "C and 15-55 atm. Dibenzothiophene
HDS, aniline HDN, and naphthalene hydrogenation fol-
lowed pseudo-first-order kinetics. Dibenzothiophene HDS
was more rapid than the other reactions. The pseudo-
first-order rate constants were 17.3, 1.4, and 1.2 h-' for
dibenzothiophene HDS, naphthalene hydrogenation, and
aniline HDN, respectively, catalyzed by Co-Mo/A1203. As
observed by Rollmann (1977) and Badilla-Ohlbaum et al.
(1979a,b), HDS was faster than HDN.
The rates of disappearance of several compounds
present (with many others) in the neutral oils fraction of
a coal liquid from the SRC-II process were determined by
Katti et al. (1983). Experiments were performed with a
batch reactor operated at 355 "C and 36 atm with a Ni-
M0/A1203catalyst. The neutral oils fraction was composed
primarily of polynuclear aromatic hydrocarbons and sulfur
and oxygen heterocyclic compounds (e.g., thiophenes and
furans) (Petrakis et al., 1983); inhibition effects were in-
ferred to be less severe than for reactants containing ni-
trogen.
The rate constants for disappearance of fluorene,
phenanthrene, a methyl-substituted phenanthrene, and
pyrene were estimated to be 4.4 X lo4, 2.2 X 1.7 X
and 6.1 X lo-' L/(g of catalyst-s), respectively. Ev-
idently, the reactivity of pyrene, which has four fused rings,
was similar to that of phenanthrene, which has three. The
reactivity of pyrene was only slightly greater than that of
fluorene, which has a benzene moiety; this small difference
in reactivities is in contrast with the trend observed by
Sapre and Gates (1981) and Lapinas et al. (1987, 1991),
who observed a large difference in reactivity between
compounds with a monoaromatic moiety and those with
two fused rings.
The work of Katti et al. is one of several publications
reporting the conversion of chemically similar fractions of
a heavy coal liquid (Grandy et al., 1986; Li et al., 1985b).
In a more recent study (Gray, 19901, the reactivity of a
coker gas oil has been expressed in terms of the rates of
selected functional groups measured by Nh4R spectroscopy
and elemental analysis. Such investigations are among the
first to characterize reactivities of hydroprocessing
feedstocks in terms of the chemistry of their components.
Development of a systematic basis for connecting pure
compound results to whole feedstock resulta in hydro-
processing remains a topic of current research. Such a
methodology has been proposed recently for the catalytic
cracking of gas oils (Liguras and Allen, 1989a,b).
VIII. Conclusions
The data presented here are believed to represent the
best pure-compound results available to provide a better
Ind. Eng. Chem. Res., Vol. 30,No. 9, 1991 2055
understanding of hydroprocessing chemistry of heavy
feedstocks and to guide modeling efforts. However, the
available data are not all consistent with each other, and
the conditions of some of the reported experiments are not
close to those of commercial practice. The limitations in
the data indicate many research opportunities.
There is a strong need for good thermodynamics data
to determine reaction equilibria aecurately in the liquid
phase, especially for the equilibrium-limited hydrogenation
reactions. It would be of great value to obtain correlations
indicating equilibrium concentrations of species at dif-
ferent temperatures and hydrogen partial pressures for
representative one-, two-, three-, and four-ring aromatic
hydrocarbons and selected sulfur, nitrogen, and oxygen
compounds. Such correlations could be used to determine
accurately hydrogen partial pressure effects on the equi-
librium position at conditions representative of industrial
practice. The estimates that can now be obtained with
group contribution methods are too crude for design or
modeling purposes.
Many of the available kinetics data are represented in
an oversimplified manner, usually with pseudo-first-order
rate equations assumed. More thorough kinetics inves-
tigations are needed. Effects of temperature need to be
investigated further, especially to characterize inhibition
effects. Because of the potentially large number of ex-
periments required, statistical model discrimination pro-
cedure and optimal experimental design procedures could
play an important role here. Results of such work, in
conjunction with reliable thermodynamics data, would be
especially useful for modeling commercial adiabatic reac-
tors operating with significant temperature gradients.
Additional problems also need to be addressed. The
complex effects of hydrogen sulfide (an inhibitor of some
reactions, an apparent promoter of others, and unimpor-
tant in others) need to be explained. Mawtransfer effecta
on the rates of hydroprocessing reactions also need to be
explained; whereas most fundamental investigations are
performed using small catalyst particles, the catalysts in
commercial hydroprocessing reactors consist of extrudatea,
meaning that mass-transfer effects can be significant, es-
pecially for high-molecular-weight compounds. Quanti-
tative characterization of catalyst deactivation is also
needed.
Even with their limitations, the results presented here
are of practical value. For example, a small fraction of the
organosulfur compounds (exemplified by 4-methyl- and
4,6-dimethyldibenzothiophene)are identified as the key
reactants in heavy fossil fuels, Le., those that are desul-
furized most slowly. One could envision processing cor-
relations based on the reactivities of these compounds-
and modern analytical methods now allow their quanti-
tative measurement even in heavy fractions. Additionally,
the results indicate that organonitrogen compounds are
the dominant inhibitors, with their adsorption parameters
exceeding those of other species by 2 orders of magnitude.
Estimates can be made as to which reactions are so slow
as to be kinetically insignificant and which are so fast as
to attain virtual equilibrium; approximate reaction net-
works and kinetics, including inhibition effects, can then
be formulated.
Models such as those envisioned for hydroprocessing
have proved their worth in other refining processes, in-
cluding cracking (Jacob et al., 1976) and reforming (Ram-
age et al., 1980). The complexity of the industrial feeds
and reactions suggests that progress toward process models
may be slow, but the rapid advances in the analytical
chemistry of heavy, complex mixtures resulting from
2056 Ind. Eng. Chem. Res., Vol. 30,No. 9,1991
progress in capillary column gas chromatography, liquid
chromatography, mass spectrometry, and NMR spec-
troscopy indicate that the opportunities are excellent.
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