1

Catalytic Hydrodearomatization
BY MEHRI SANATI, BJORN HARRYSSON, MOSTAFA FAGHIHI,
BORJE GEVERT, AND SVEN JARAS

1 Introduction

Hydroprocessing of various feeds for the production of fuels is extensively

practised in the petroleum industry, and to some extent in coal liquefaction
and in the upgrading of synthetic fuels and lubricant oils. Another promising
area where hydroprocessing can be applied is the development of renewable
non-fossil fuels (pyrolitic bio-oil) for the elimination of the oxygen-containing
molecules and the improvement of the H/C ratio.
Hydroprocessing reactions occur on the active sites of the catalysts. Also, a
suitable pore size distribution of the catalysts is required to ensure the access of
reactant molecules to the active sites. The catalysts used in hydroprocessing
consist of a molybdenum catalyst that is supported on a high surface area
carrier in the 100-300 m2/g range, most commonly alumina, and is promoted by
either cobalt or nickel. The concentration by weight of the metal is usually 1-4%
for Co and Ni, and 8-16% for Mo.' The catalysts are active in the sulfided
state, being either presulfided or sulfided on stream with a sulfur containing
feed. Monometallic (Pt or Pd) and bimetallic (Pt-Pd) catalysts of noble metal
supported on y-A1203are known to be highly active in the hydrogenation of
aromatics under mild conditions. However, noble metal catalysts are easily
poisoned by a small amount of sulfur; severe pre-treatment of the feedstock is
needed to reduce sulfur to a few ppm. Recent studies have dealt with how to
improve the activity of these catalysts and their sulfur tolerance, e.g. by adding
a second transition metal or using different support
The typical feedstock for laboratory tests is usually either a mixture of
model mono-compounds and/or a mixture of different aromatic hydro-
carbons. 12-13 In industrial feeds, however, several types of aromatics are
present, whose hydrogenation activities differ considerably. The composition
and concentration of various nitrogen and sulfur compounds also significantly
influence the activity.
The process is normally carried out in a trickle-bed reactor at an elevated
temperature and hydrogen pressure. In the case of severe deactivation, an
ebullating bed reactor might be used but this type of reactor is not suitable due
to back-mixing when a high conversion is needed. The specific characteristic of
a trickle bed reactor is that a part of the catalytic surface is covered by a liquid

Catalysis, Volume 16
0The Royal Society of Chemistry, 2002
1
2 Catalysis

and the other part by a gas. In the common set up, the liquid phase flows
downwards through the reactor concurrently with a gas phase that partly
consists of vaporized compounds. The temperature and pressure ranges for the
hydrogenation of aromatic hydrocarbons in a liquid phase batch reactor were
reported to be 450-700 K and 3.5-17 MPa, re~pectively.'~-~~~*~-'~
Hydroprocessing catalysts are quite versatile, exhibiting activity for a
number of important reactions. Those of major interest in hydroprocessing
that might be referred to as hydrorefining correspond to removal of heteroa-
toms; hydrodesulfurization (HDS), hydrometallization (HDM), hydrodenitro-
genation (HDN) and hydrodeoxygenation (HDO). These reactions involve
hydrogenolysis of C-heteroatom bonds. The removal of sulfur and nitrogen is
necessary to meet environmental limits. Sulfur may also cause problems with
catalyst poisoning and corrosion. HDN is needed to avoid catalyst poisoning
of acid sites and improving stability in lube oils.
An important reaction in petrochemical industry and refineries is hydro-
conversion, which enables a change in the molecular weight and structure of
organic molecules. Examples are hydrogenation (HYD) and hydrodearo-
matization (HDA). When oil is hydrotreated, the reduction of aromatic
compounds competes with the removal of sulfur and nitrogen. The purpose of
hydrotreating (in the latter sense) is to improve the stability and quality of the
product. The reduction of aromatic compounds, especially polyaromatics,
gives a higher stability to the product, as well as affecting the solubility and
colour of the product. Aromatics in fuels not only lower the quality and
produce undesired exhaust emissions, they also have potential hazardous
and carcinogenic effects.26 Thus polyaromatic compounds are removed to
meet health and environmental regulations. The growing understanding of
health hazard associated with these emissions is leading to limitation in the use
of aromatics in both Europe and the United States.27
The process to make cleaner fuels that are more environmentally friendly is
often accompanied by desulfurization and hydrodearomatization. Decreasing
the aromatic content increases the cetane number in diesel fuel.
Two approaches, a single-stage process and a two-stage process, have been
proposed for distillate fuels (particularly diesel fuels) to meet these strict
standards for diesel fuels. The single-stage process combines severe hydrode-
sulfurization and hydrogenation using a single conventional sulfided CoMo,
NiMo or NiW catalyst. In order to reach the necessary aromatic saturation the
H2 pressure needs to be substantially higher than the H2 pressure at which
current hydrodesulfurization units operate.28
The two-stage system uses a conventional hydrotreating catalyst in the first
reactor and a noble metal catalyst in the second; this yields a low aromatic
diesel stream at moderate hydrogen p r e s s ~ r e . ~ ~ ~ ~ ~
This latter system is highly active for the reduction of aromatics but is very
susceptible to sulfur poisoning; the sulfur concentration at the inlet of the
second reactor must be reduced to a few parts per million.31
Thus, the use of these catalysts depends strongly on severe pre-treatment
conditions, unless the sulfur tolerance can be greatly improved for the noble
1: Catalytic Hydrodearomatization 3

metal catalyst. A number of recent studies have attempted to address this

problem by developing catalysts with a high resistance to the sulfur poisoning
and at the same time retaining a high hydrogenation activity.
In spite of the large number of articles published in recent years, the subject
has been widely reviewed. The catalytic aspects of the hydrogenation were
discussed by Krylov and N a ~ a l i k h i n a Special
.~~ attention to the preparation
methods was discussed in more detail by P. Grange and X. Vanhaeren.27 A
comprehensive review of the hydrodeoxygenation, with particular focus on
upgrading of bio-oils, was published by F u r i m ~ k y .Catalyst
~~ deactivation
during hydroprocessing, including the adverse effects of the 0-compounds,
was reviewed by Furimsky and M a s ~ o t h . ~ ~
In this review, the primary focus is on the most recently reported work in the
literature for both basic and industrial aspects of hydrodearomatization
reactions. It is an extension and update of recent studies dealing with the
aromatic reduction in different petrochemical feedstocks. These reviews, which
have recently appeared in literature, provide comprehensive information
regarding hydrodear~matization.~~. 35-37
A comprehensive review of the reactions during hydroprocessing has been
published by Topsoe et al.

2 Hydrogenation of Mono-, Di-, Tri-, Multiring and Mixtures of Aromatic

Compounds

In recent years an increasing awareness of the use of aromatics contained in

different feedstocks, especially distillate fuel (in particular diesel and gas oils),
with respect to the adverse effects of undesired emissions and potential health
risks, has received considerable attention. In addition, a high aromatic content
is associated with poor fuel quality, giving low cetane number in diesel fuel and
a high smoke point in jet fuel.
To date, a number of the model compounds that are representative of
components in industrial feeds, have been extensively studied on several
catalysts. These include both unsupported and y-A1203 supported hydro-
genation catalysts, using the conventional CoMo, NiMo, NiW, and platinium
group metals (including ruthenium, rhodium, palladium and platinum). On all
catalysts, the rate of hydrogenation generally increases with the number of
aromatic rings present, i.e. a low rate of hydrogenation is observed for mono-
aromatic rings such as benzene.' The greater reactivity for hydrogenation with
higher fused ring systems, such as naphthalene and anthracene, is due to the
fact that the resonance energy of the second ring of these multiple compounds
is less than for benzene.35
Table 1 of this review shows the recent related publications on hydrodear-
omatization and the catalytic systems, reaction conditions and product selec-
tivities for these studies. The choice of model compounds were often the
mono-aromatics compounds or a mixture of the aromatics in order to simulate
a composition similar to the industrial feedstock in refinery.
 P
Table 1 Hydrogenation of polyarornatics

Year Catalyst Reaction conditions I remarks Substrate Products I remarks RefW

2000 Ni-MolAlZO3, support T = 290 to 330 "C,150 t/d pilot
- plant,
- Recycle solvent in coal The tetra-aromatic, for example 38
y-alumina cylindrical solvent dimethyl disulfide continuously liquefaction, tetrahydronaphthalene, formed much
grain added at a conc. 0.5% wt. naphthalenes: 15.8, more than decahydronaphthalenes
The hydrogenation rate increases in phenanthrenes 3.25
the order naphthalenes > phenanthrenes anthracene 2.3, pyrene
> anthracenes > pyrenes 3.9 (wt %)
2000 y-alumina-supported T = 260 and 280 "C,P = 5 MPa, Phenanthrene + 1 wt Radioacti~e~~S-labeled DBT was used to 2
Pt-Pd HYD activities over the bimetallic YOdibenzothiophene measure of catalytic HDY activity of
catalyst (Pt-Pd) were higher than that (DBT) phenanthrene, which was monitored by a
of the mono-metalliccatalysts together change in unreacted [3sS]DBTto form
[3sS]H2S
2000 Pt-Pd/Si02-Al2O3 T = 300 "C,P = 4.9 MPa and LHSV 1.5 Oil fraction Enhancement of catalytic activity, which 3
h-l, the long-term stability test under containing 32-40 vol depended on the Pd/(Pt+Pd) weight ratio
industrial operating conditions YOaromatics (20.5 and reached a maximum of aromatic
demonstrated the excellent stability of Mono, 17.3 Di, 2.2 hydrogenation of about 0.7 Pd/(Pt+Pd)
the catalyst Tri) and 172-474 ppm weight ratio.
sulfur Hydrated mono, di, tri was about 30,4
and 3 vol YO,respectively
2000 PtPd/Si02-A1203, T = 195-250 "C,P = 5 MPa, WHSV Toluene and PtPd/Si02-A1203catalyst shows the 4
Pt/Si02-A1203 and 4.5 h-l, aromatic reactivity follows: naphthalene mixture highest activity for the hydrogenation of
Pd/Si02-A1203 naphthalene >> toluene > tetralin. (20% Mono and 2% mono- and di- in the presence of S, Pt/
This order was related to a decrease in Di) and the amount of Si02-A1203has the lowest activity.
the resonance energy per atomic ring, sulfur was varied from The excellent activity of PtPd catalyst
difference in the .n-electron cloud 0.065 to 0.070 (DBT). was attributed to the electron - deficient
density in the aromatic ring, as well as platinum species (site isolation) of
inductive effect of the methyl group isolated Pt cluster on the Pd surface
 b
2000 Mo-Ni supported on Alumina support provides a higher Black oil The dependency of the catalytic activity 39 * *

y-A1203,or hydrated catalytic activity than the
titanium dioxide hydrogenation of aromatics, under
(HTD), or reaction conditions as used in industry
palygorskite-
montmorillonite clay
(PMC)
2000 Pt/WO,-ZrO2, (12.7 T = 200-300 "C, P = 3.0 MPa, Pt/Beta
wt YOW) and Pt/Beta has a higher sulfur resistance than Pt/
(Si/Al= 12) WOx-ZrO2. The lower sulfur resistance
of P W Z r could be explained by a
strong interaction of part of the Pt
with surface W6+
1999 Ru/A1203and Pt/ T = 120 "C, P = 6 MPa, ratio substrate : Mono-aromatic
A1203 solvent = 3 g : (6-0.75 g), reaction time compounds, toluene,
was 2 h
1999 PtPd/Si02-A1203, Fixed bed reactor, 200-300 "C, total
Pt/Si02-A1203 and pressure 4.9 MPa, LHSV 1.5 h- and
Pd/Si02-A1203 hydrogen to feed oil ratio 500 NYl.
EXAFS characterization of the
catalysts
hydrotreatment on thesupport has been considered s3
z8'
L
=L
Benzene, n-heptane / Cyclohexane and methylcyclopentane 5
B3
benzene mixture (25 isomer, a total selectivity to CH+MCP 3
wt YObenzene), in the above go%, the concentration of MCP
presence (200 ppm) increased withreaction temperature for i;.
se
and absence of sulfur both catalysts 6'
3
Dependency of solvent effect on the 6
hydrogenation activity.
phenol, etc. Toluene conversion in MeOH, EtOH,
1-PrOH (alcohol as a solvent), Ru/A1203
was 95, 100 and 100, respectively.
Toluene conversion in MeOH, EtOH,
1-PrOH (alcohol as a solvent), Pt/A1203
was nil
LCO (middle distillate EXAFS (X-ray absorptionfine structure) 7
refinery product) / for characterisation of the catalysts,
SRLGO feed obtained structure, interaction between Pt and Pd
from refinery in the Pt-Pd/Si02-Al,03 catalyst. The
amount of Pt (0.5 wtY0)-Pd/SiO~-A1~0~
was sufficient for obtaining optimum
catalytic performance.
Regarding the activities of aromatic
hydrogenation, it was assumed that the
Pd sites dispersed on Pt particle were
responsible for the high hydrogenation ul
activity

Table 1 (contd.)
Year Catalyst Reaction conditions / remarks
1999 Pt (or Pd)/ y-A1203 T = 220 "C, P = 6 MPa, WHSV 2 h-l,
Pt (or Pd)/ PLC, PLC H2 / hydrocarbon volume ratio 800,
is pillared clay which catalyst with particle size 40-60 mesh,
are known as cross- the feed was a mixture containing 20
linked smectites, a wt% hydrocarbon with 80 wt%
new class of molecular n-hexane
sieve-like materials
with a large pore size
1999 Ru-B/Si02 Autoclave with a magnetic stirrer and
amorphous 1000 rpm stirring, T = 150 "C, P = 4
and Ru / Si02 MPa
1999 Ni/SiO;? Fixed bed glass reactor (i.d. = 15 mm), Benzene, toluene,
atmospheric pressure, temperature
range 120 "C 5 T 5 250 "C, space
velocity 2 x lo3 h-l, hydrogen
pressure was varied from 1.9. to
9.6. MPa at constant aromatic
pressure 0.004 MPa using dry nitrogen
as the diluent; when aromatic pressure
was varied 0.001-0.006 MPa, the
hydrogen pressure was constant, 0.094
MPa and again nitrogen as the
make-up gas
o\
Substrate Products / remarks Ref (s)
Benzene, xylene, Both catalysts, Pt (or Pd)/y-A1203and Pt 8
mesitylene (or Pd)/PLC showed the same saturation
activity for benzene, although the
selectivityfor cyclohexane Pd/Al-PLC is
lower than Pt/Al-PLC.
Generally, Pt (or Pd)/ PLC show much
higher catalytic activity for the
hydrogenation of large aromatic
molecules, large pore structure and weak
acidity
Selective Improve selectivity of benzene 9
hydrogenation of hydrogenation to cyclehexene.
benzene Ru-B/Si02 (amorphous) exhibited better
selectivitytowards cyclohexene than the
corresponding RdSiO2
The role of hydrogen partial pressure in 40
o-xylene, rn-xylene the hydrogenation of benzene, toluene
and p-xylene and three isomeric forms of xylene over
Ni/Si02; TOF decreases in the order
benzene>toluene>p-xylene>m-xylene>
o-xylene, representing the order of
increasing stability and decreasing
reactivity, of the adsorbed x complex
1999 Two stage, new design Low temperature catalytic Distillatefuels Multiple catalyst bed to achieve deep
catalyst concept in the hydrogenation processes over noble hydrosulfurization and hydrogenation,
hypothetical stage, metal catalyst without addition of first stage ‘HDS’ Ni-Mo or Co-Mo
First Ni-Mo or dibenzothiophene catalyst, second stage ‘HDY’ over
Co-Mo. Second noble-metal catalyst supported on
noble-metal, which dealuminated mordenite
will be supported as
bimodal on zeolite
with two pore
openings, < 5 A and
in laqge pore opening
<6A
1999 Alumina-supported Pt T = 200-400 “C,P = 5 MPa, a dual Phenanthrene Dihydrophenanthrene,
and Pd, Pt (or Pd)/ noble metal catalyst Pt(2)-Pd( 10) tetrahydrophenanthrene,
A1203,presulfided showed similar hydrosulfurization octahydrophenanthrene
(mixture of 5% H2S in results and better hydrogenaton perhydrophenanthrene
H2) Co-Mo catalyst compared with a Co-Mo catalyst Pt-Pd catalyst showed better
performance in hydrogenation of
phenanthrene in presence of 1 wt% DBT
than the conventional Mo-based catalyst
1998 Modified catalysts Micro-catalytic stainless steel reactor, Benzene, toluene Benzene to cyclohexane, toluene to 43
containing 0.35% L = 10 cm, d = 6 mm, T = 50-250 “C, methylcyclohexane, respectively.Toluene
Pt-Al203, introducing flow rate H2 20 cm3/ min
- possesses higher activity than benzene on
a second metal Ir, Rh, the monometallic catalysts, the benzene
Re and U and hydrogenation activity of the bimetallic
fluorination and catalysts follows the order PtRh > PtIr >
chlorination with PtRe > Pt > PtU, the corresponding
different halogen order for toluene hydrogenation follows
contents of 1.3 and PtRh > PtRe > PtIr > Pt > PtU
6 wtYo
 00
Table 1 (contd,)

Year Catalyst Reaction conditions I remarks Substrate Products I remarks RefW

1998 Ni on different Industrial conditions, a-A1203 Benzene Hydrogenated cyclic compounds 44
supports supported nickel showed the best
activity, with 40% nickel concentration
and optimum metal area of 10.8 m2/g
1998 Conventional NiMoI Batch autoclave reactor, pressure 6.9 n-Propylbenzene The reaction is moderately reduced by 45
yAlzO3,3.2 wt% NiO MPa, T = 330,350 and 375 "C alone; sulfide and severely inhibited by
and 15.4 wt% Moo3, n-propylbenzene and ammonia, addition of water did not
presulfiding with a 1: 9 hydrogen sulfide; further affect the aromatic
H2S-H2 mixture at n-propylbenzene, hydrogenation
325 "C, 8 h hydrogen sulfide and
ammonia;
n-propylbenzene,
hydrogen sulfide,
ammonia and water
1998 Pt/yA1203 Continuous down flow fixed-bed Tetralin with The material balance is about 98% for 46
reaction system, WHSV ranging from benzothiophene as a the catalytic performance tests.
2.0 to 12 (g of feed/h:g of catalyst), model compounds for CO chemisorption and extended X-ray
investigation of the relation between sulfur poisoning absorption h e structure (EXAFS)
sulfur-poisoningand catalytic (0- 1000 ppm sulfur spectroscopy revealed that the decline of
properties of Ptly-A1203catalysts for content) the reaction rate is caused by the form-
aromatic hydrogenation. ation of PtS and the reduction of PtS was
T = 270 "C,total pressure 3.2 MPa achieved by hydrogen reactivation
1998 (P)NiMo/Ti-HMS T = 325 "C, total pressure 4.4 MPa, Naphthalene Tetralin, trans- and cis- decalins.
and (P)NiW/Ti-HMS, 7 h, naphthalene dissolved in n- All samples demonstrate high
phosphorus hexadecane hydrogenation activity in the first step
concentation was 0.2 when tetralin is formed. In the second
wt% P205,NiMo/ step, trans- and cis- decalins are formed,
Ti-HMS, NiW/ the tungsten catalysts are two times more
Ti-HMS, sulfidation active than the molybdenum catalysts.
mixture (H2 15 vol YO Mo for mild hydrogenation, while
H2S) tungsten is superior for deep
hydrogenation
1998 Phosphoric acid- Autoclave, P = 10 MPa HZ, T = 430 "C 1. Naphthalene 1. Dimethylcyclohexane, ethylbenzene,
promoted The addition of phosphoric acid to the 2. Anthracene decalins, tetralin
Mn203-Ni0 catalyst was an attempt to change the 3. Carbazole 2. Perhydroanthracene
chemical properties of the catalyst, in 4. Dibenzothiophene 3. Benzene, cyclohexane, hexylbenzene,
order to increase activity of 5. Coal-derived oil hexylcyclohexane, cyclohexylbenzene,
heteroatom removal bicyclohexyl, dodecahydro-,
octahydro-, hexahydro-,
tetrahydrocarbazole
4. Benzene, cyclohexane, hexylbenzene,
hexylcyclohexane, cyclohexylbenzene,
bicyclohexyl, biphenyl, tetrahydro-,
hexahydrodibenzothiophene
5 . Different hydrocarbons etc.
1998 Pt and Pd, zeolite- Characterization of the catalysts by For the proupose of The results showed that the higher sulfur 10
supported catalysts, different technique, i. e. EXAFS the hydrogenation of tolerance of the bimetallic Pd-Pt was
(Pd : Pt mole ratio of measurement aromatics achieved when Pd-Pt was supported on
4 : 1). The sulfidation the highest acidity zeolite, the sulfur
of the catalysts was tolerance decreasing when the acidity of
done in a 1000 ppm support decreases
H2S/N2stream

Table 1 (contd.)
Year Catalyst Reaction conditions I remarks
Simultaneous hydrogenation,
hydrosulfurization and
hydrooxygenation were observed with the absence of sulfur
minimal deactivation of Mo2C up to
30 ppm for sulfur, 2000 ppm oxygen
and 5 wt % cumene, Ptly-A1203
deactivated immediately upon addition
of sulfur.
P=5.1 MPa, T=250"C, 5.3 pmol s-l
(5 cm3h-l)
1998 Ni-Mo/alumina First-order reaction with respect to
aromatic and partial pressure of
hydrogen.
P=4-12MPa, T=400"C
1998 Rdalumina catalysts Catalytic test were performed in a
(0.21-5.1 1 wt% Ru) continuous flow fixed bed
microreactor, atmospheric (0.10 MPa)
pressure, T = 250 "C, H2 flow = 60 cm3/
min, weight of catalyst = 20-40 mg,
the conversion level was kept below
10%
w
0
Substrate Products I remarks Ref($1
5 wt% cumene and 95 Cumene hydrogenation yielded 49
wt% tetradecane, in isopropylcyclohexane is the only
product, Hydrogenation of cumene, in
the absence of sulfur.
5 wt% cumene and 95 wt% tetradecane
Mo2C possesses higher activity than
noble metal catalyst, the
thermodynamic equilibrium conversion
was 99.99%, indicating neither Mo2C nor
Ptly-Al203 achieve equilibrium
conversion. MoS2 is not an active
catalyst for hydrogenation
1-Methylnaphthalene, Examination of the hydrogenation of 50
coal-derived middle 1-methylnaphthalene was used to
distillate quantify the conversion rate of the
hydrogenation of the aromatics contents
in the coal-derived middle distillate
Benzene At low Ru content (Ru 0.2) cyclohexane 51
is the hydrogenation product.
As the Ru content increases cyclohexane
formation decreases and hydrogenolysis
product (methane) will be formed
1998 Ni-Moly-AlzO3, Trickle bed reactor
catalyst was P = 9.8 MPa, T = 350 "C, hydrogen anthracene oil
presulfided by a flow 4.0 x dm3 s - l , the main dissolved in toluene
mixture of 10% of H2S purpose of the experiment was to
in H2 obtain information on the effectiveness
factor for both the wetted and dry
zones of the catalyst
1997 Ruthenium supported T = 303 "C, atmospheric pressure (0.10
on silica and silica- MPa), a semi-batch magnetically
active charcoal stirred reactor with a coolingjacket
contained 5 wt YOof
the metal by sol-gel
method
1997 Pt/MCM-41, Pt/A1203 T = 180"C, P = 4.2 MPa, concurrent
down-flow trickle bed reactor, the
metal dispersion on MCM-4lwas
higher than that on A1203
1997 Pt/Y-zeolite Reaction conditions were close to
realistic industrial conditions,
temperature dependency with a max.
in the reaction rate at 325 "C, the
pressure dependency of the rate with
respect to the ratio of the toluene/H2
was sensitive to the level of the sulfur
in feed
A light fraction of Main components of the hydrogenation 13
product, Naphthalene to decalins and
tetralin; acenaphthene to
tetrahydroacenaphthene; phenanthrene
to dihyrophenanthrene,
tetrahydrophenanthrene,
octahydrophenanthrene; anthracene to
dihydroanthracene, terahydroanthracene
and octahydroanthracene; fluoranthene
to tetrahydrofluoranthene; and pyrene to
dihydropyrene
Toluene, solvent was Methylcyclohexenesand 11
either in mixture of methylcyclohexane
water (33.4 mol%) and
methanol (66.6 mol%)
or methanol
Naphthalene in Higher acidity of Pt/MCM-41 has been 52
n-hexadecane was favoured over the higher activity of
used to simulate the Pt/A1203,for aromatics hydrogenation
aromatic in diesel
fuels
Toluene Methylcyclohexenes and 53
methylcyclohexane
 c
N
Table 1 (contd.)
Year Catalyst Reactionconditions I remarks Substrate ProductsI remarks Ref(s)

1997 Pt and Pd supported T = 200 "C, in a microautoclave Naphthalene in the Decahydronaphthalene 54

on mordenite reactor, mordenite-supported Pt and absence and present of Tetrahydronaphthalene
(HM38), a Y zeolite Pd catalysts are more active than Y sulfur
(HY), A1203 and Ti02 zeolite supported Pt and Pd, (Benzothiophene),
respectively. Y zeolite supported n-tridecane was used
catalysts afford higher yield of cis- as a solvent
decalin. Mordenite-supported catalysts
give higher yield of trans-decalin.The
addition of sulfur decreases the activity
of all catalysts tested
1997 Sulfided Ru on T = 300 "C, the activity for RuKYd Tetralin, in presence 55
dealuminated Y was higher than for NiMoIalumina. of H2S, or dimethyl
zeolite (RuKYd), The activity of the RuKYd was disulfide in solution in
NiMo/alumina dependent on the sulfidation method, n-heptane
the catalyst sulfided by dimethyl
disulfide was less active than when
sulfided by H2S/H2mixture
1997 Pt supported on Competitive hydrogenation of Cyclohexene, 1-hexene Cyclohexane, hexane 56
carbon fibers; small cyclohexene and \-hexene pore, with a
constriction (5 A), constriction of 5 A yielded higher rate
large constriction of hydrogenation for 1-hexene. Other
(7 A) catFlysts supported on a constriction
(7 A) and activated coal display
comparable rates for both reactants.
Gas-phase fixed-bed reactor,
T = 100 "C, WHSV = 25-50 h-'
1997 Wy-A1203 Normal sulfur poisoning, tetralin with To develop high sulfur tolerant Pt
1000 ppm sulfur, T = 270 "C, P = 3.2 catalysts for hydrogenation of aromatics,
MPa. With more severe conditions, 19 the choice of catalyst support and/or the
atm and 2000 pprn sulfur, finding of the second metal (for the
WHSV 4.8 (g of feed/h:g of catalyst). formation of bimetallic interactions, so
Continuous fixed bed reactor the sulfur adsorption decreases) is
necessary
1997 Pt/ (two MCM-41 Batch reactor, (reaction conditions for 1. Hydrotreatment of Tetralin, cis- and trans-decalin, both
supports, differing in naphthalene hydrogenation) naphthalene + 200 MCM-41 and USY supports showed the
their chemical T = 225-275 "C, total P = 5.0 MPa, PPm (DBT) greatest sulfur resistance. Ptf (A1)MCM-
composition) solvent was n-decane; dibenzothiophen 41 presented the highest activity for
Wamorphous LCO hydrogenation, T = 300-350 "C, 2. light cycle oil hydrogenation of aromatics in LCO
mesoporous silica- total P = 5.0 MPa, WHSV = 4 h- (LCO) (400 ppm feedstock, especially at low temperature
alumina (MSA sulfur, 70 wt 'YO (300 "C)
Si/Al= 100) aromatic)
Pt supported on a
commercially
amorphous silica-
alumina (ASA)
WUSY zeolite
Ptfy-AlzO3
PtfSiOZ
The nominal
Pt = 0.5- 1 wt%

c,
w
 b-
P
Table 1 (contd.)
Year Catalyst Reaction conditions / remarks Substrate ProductsI remarks Ref(s)
1997 Ru dispersed in a Microreactor system, for toluene Tetralin and toluene From HDY of toluene the major product 59
series of zeolites with HYD, T = 280-390 "C and P 4.5 - in the presence of was methylcyclohexanewith a 50%
various acidic MPa; for tetralin HDY, T=250-300 "C, 1.9% H2S selectivity, the others were
properties; HY, KY P 4.5 Mpa. For tetralin HDY, the
- ethylcyclopentane,methylcyclopentane
(prepared from Nay), specific activities were found to and dimethylcyclopent anes;
KHYd (prepared decrease in the order: From HDY of tetralin the major product
from commercial RuHYd > RuHY > RuKHYd >> was cis- and trans-decalin with a 90%
dealuminated HYd NiMo/ A1203> RuKY selectivity, small quantities of
zeolite) and For toluene HYD, the specific methylindanes and methylcyclopentanes
subsequent sulfidation activities were decreased in the order: were observed
RuHYd > RuKHYd > RuHY >>
RuKY NiMo/A1203
-
1997 Ruthenium sulfide The hydrogenation activity was very Tetralin in presence of From HDY of tetralin the major product 60
supported in a Y zeolite, high in the presence of H2S and large amounts of H2S was cis- and trans-decalin
HYd (commercial roughly 300 times the activity (1.85%)
dealuminated) and (expressed per metal atom) of an
KYd (prepared from industrial NiMo/ A1203 catalyst. The
commercial active phase, which consists of cluster
dealuminated HYd of ca. 50 Ru-S, is located in the zeolite
zeolite) and framework
subsequent sulfidation
1997 Pt/A1203,Pt/MCM-41 Concurrent down flow trickle bed Naphthalene dissolved cis-Decalin, trans-decalin 61
reactor, T = 180 "C, P = 4.2 MPa, in n-hexadecane The selectivity of cis-decalin was studied
LHSV = 2.8 h- l , H2/liquidfeed 800 for HYD purpose
mVml, the hydrogenation activity of
PdMCM-41 is higher than that of
PdA1203, but cis-decalin selectivity
was lower than with Pt/A1203
1997 Powdered, cylindrical Batch reactor, T = 310-350 "C, 1-Methylnaphthalene Methyltetralins and methyldecalins 62 '
and trilobed P = 5.0-8.0 Mpa. This study focused diluted in a C14-C16 i2
commercial on the difference in kinetics, between normal paraffin is
Co-Moly-Al203 powdered and pellet catalysts in liquid- mixture 5
phase HDY reactions of the aromatic k
ring. The inhibitory effect of k
1-methylnaphthalene was clearly 2
observed for the powdered catalyst 8
1997 Ruthenium supported Autoclave, initial P = 10 MPa (H2), I. Naphthalene I. Etthylcyclohexane, decalin, tetralin, 63
others
on mixed oxides T = 430 "C 11. Anthracene
'i$
(Mn203-Zn0, 111. Coal-derived oil I I. Per-, octa-,tetr ahydr o-anthracene,
Mn203-Ni0, others
g
5'
3
Mn203-La203) with 111. Different aromates
different molar
compositions.
The supports were
loaded with 0.1,0.2,
0.5 and 1.0 wt
ruthenium
1997 Ni/SiOz Gas-phase hydrogenation, 0-,m-and p-xylene Stereoisomeric product mixtures of the 64
T = 120-250 "C, the hydrogen pressure saturated dimethylcyclohexane
was constant, 0.095 MPa; where the
pressure of each aromatic was varied
in the range 0.001-0.006 MPa, the
TOF of the three xylenes increased in
the order o-xylene < rn-xylene <
p-xylene, over the entire temperature
range studied

c
#
 c
Table 1 (contd) m
~ ~~~ ~

Year Catalyst Reaction conditions I remarks Substrate Products I remarks Ref(s)

1997 NilAl2O3 Gas-phase hydrogenation, from the
kinetic investigation suggested a non-
competitive adsorption of hydrogen
and aromatic compounds on the
catalyst surface. Thermodynamics
suggested the stepwise hydrogen
addition to the aromatic molecule
1996 Pt-PdlrAl203 The bimetallic catalysts possess a
relatively high selectivity for aromatic
reduction and other hydrotreating
processes, T = 340 "C,P 2 4 MPa
1996 Pt on pillared T = 310 "C, P = 7.0 MPa, for kinetic
interlayered clay investigation the temperature was 320,
(P1LC)-alumina and 340 and 360 "C. The enhanced activity
Y-zeolite-alumina of Pt/Y-zeolite-alumina catalyst is
attributed to unique structure of the
support, producing well-dispersed Pt
metal clusters
0-,
p-xylene cis- and trans-dimethylcyclohexane;the 65
distribution of stereoisomerswas
dependent on the reactant pressure as
well as on temperature. The
stereoisomers were governed by the
adsorptioddesorption kinetics of an
intermediate cyclic olefin; the
configuration of the final product
depended on the orientation of the olefin
double bond upon adsorption
Commercial diesel The analysis of product samples from 66
long-term stability tests (25 days),
collected periodically, found that
aromatic conversion ranges from 3- 10
wt%, depending on precursors and pre-
treatment conditions
Synthetic crude The aromatics conversion was 29% for Pt 67
distillates from on pillared interlayered clay (PILCj
Canadian oil sands of alumina and 44% for Pt/Y-zeolite
varying sulfur content,
high > 100 ppm and
low < 10 ppm,
monoaromatics
content 31 mass%;
diaromatics 8
- -
mass% and
triaromatics 0.8
-
mass%
1996 Commercial T = 95-125 "C, P = 2-4 MPa. The Di- and tri-substituted The main reaction product was the 68
preactivated catalyst, activity of different substituent aromatics, such as o- completely hydrogenated cycloalkane
nickel-alumina positions decreased in the order para > m-and p-xylenes,p-
meta > ortho, the trisubstituted cymene and
benzene (mesitylene) had a lower mesitylene
reaction rate than the disubstituted
compounds (xylenes)
1996 Pd/Si02-A1203 T = 80 "C, P = 0.007 MPa (total Benzene and toluene The relative rate of toluene and benzene 69
(0.22-1.64 wt0/0Pd), aromatic partial pressure) and 0.095 HDY with an equimolar gas mixture
Pdq-Al203 (1.67 wt MPa (hydrogen partial pressure) showed that toluene was less reactive
YOPd), Ptlq-Al203 than benzene on Pd catalysts, whereas
(0.78 wt% Pt) and the value for toluene HDY indicates that
commercial P d C is favoured on Pt catalysts
(3.61wtYo Pd)
1996 Pt supported on The reaction parameters such as metal Methyl benzoate The catalysts showed activity and 70
inorganic polymer, loading, temperature and solvents selectivity to HDY reaction of aromatics
silica- effect have been studied
polysulfoalumoxane,
with different metal
loading
1996 Sulfied ruthenium on Flow reactor, T = 300 "C, P = 7 MPa Tetralin Naphthalene, decalin and several 71
KY zeolite (total). products with the same formula C10H18
DMDS and H2S were used to study
the effects of the sulfidation method
and its dependencies on hydrogenation
activity.
It was found that the H2S method was
the most suitable
Table 1 (contd.)

Year Catalyst Reaction conditions / remarks Substrate Products/ remarks Ref w

1996 Ammonium T = 350,400 and 450 "C, P = 7.2 MPa, 1. Naphthalene 1. Tetralin the only hydrogenation 72
tetrathiomolybdate as hydrogedreactant molar ratio (5: l), 2. Phenanthrene product
a catalyst precursor microautoclave reactor, the rate of the 3. Pyrene 2. Primary product is
reaction is most important for bicyclic dihydrophenanthrene and
compounds, as ring size increases, tetrahydrophenanthrene.
kinetic play a less important role and Octahyrophenanthrene is a
thermodynamics become the driving hydrogenated product of the primary
force for the outcome of the reaction products
3. The major product at all temperatures
for pyrene hydrogenation is
dihydropyene. Secondary
hydrogenation products are
tetrahydropyrene and
hexahydropyrene
1996 Platina on A 30 ml stainless-steel tubing bomb I Naphthalene I Decalin tetralin 73
mesoporous batch reactor was used. The reactor I1 Phenanthrene I1 Tetra-, di-, octa-,
aluminosilicate was heated in a fluidized sand batch tetradecahydrophenanthrene
(Al-MCM-4 1) under vertical shaking (240 cycles/
support with varying min), P=7-10.5 MPa H2,
WA1 ratios using T = 200-300 "C. The catalyst was
different aluminum active for hydrogenation of large
sources (aluminum aromatics, the activity was significantly
isopropoxide, pseudo different depending on the synthesis
boehmite and conditions, especially with respect to
aluminum sulfate) the source of aluminium
1996 Pt, Ru and Ir Tubing bomb microreactor, Naphthalene in Tetralin cis- trans-decalins
promotion on three T = 310 "C, P = 6.90 MPa cold hexadecane (as a
commercial A1203- hydrogen pressure. The Pt-promoted solvent) was used.
supported catalysts catalysts were more active than the In the reaction with
(NiMo, CoMo and original catalysts in the oxide forms, sulfided catalysts, an
NiW) whereas the activities of the sulfide additional 1.5 wt.%
catalysts both in promoted and non- Dimethyl disulfide
promoted were similar was added as a sulfur
source
1996 Pf/A1203,PdA1203, Tubing bombs, Naphthalene, the Tetralin, cis- and trans-decalins and
Pd/Ti02 and NiMo/ T = 200 and 280 "C, solvent used was others. The equilibrium conversion
A1203(commercial) P = 6.99 MPa H2. tridecane. The decreases with increasing temperature.
The Pd/TiOZ showed higher sulfur hydrogenation Tetralin becomes the dominant product
resistance in comparison with the other reaction was started at higher temperatures
catalysts when bezothiophene
was added to the
solvent
1996 Silica-supported T=30°C P=O.lOMPa Benzene, toluene Cyclohexane and methylcyclohexane 76
carboxymethyl-
cellulose platinum
complex (Si02-CMC-
Pt>
1996 Zeolite-supported Low temperature 77
noble metal catalysts hydrogenation of
aromatics in the
absence and presence
of DBT
1996 Mo, Ni, Ni-Mo and T = 350°C P = 6 MPa. The Toluene in the Methylcyclohexane 78
Ni-Mo-P/alumina hydrogenation was performed over a presence of H2S
large range of H2S partial pressures.
The Nualumina is nearly inactive
 h,
0
Table 1 (contd.)

Year Catalyst Reaction conditions I remarks Substrate ProductsI remarks Ref0)

1996 Commercial nickel- The hydrogenation has been carried
molybdenum (3 wt% out under pressure of different coke
NiO, 15 wt?h Moo3 oven gases = 55 vol.% H2 instead of
on alumina) and Pd (5 pure hydrogen, influence of reaction
wt% on alumina) time and temperature were studied
T = 300-450 "C, P = 11-25 MPa, 16 h
1996 Mathematical calculation of
hydrogenation
1996 Ni/A1203 Kinetic investigation of gas-phase
hydrogenation, T = 130-220 "C,
differential fixed bed reactor, hydrogen
pressure was varied over 0.04-0.09
MPa and xylene pressure over
0.01-0.035 MPa, helium was a make-
up to adjust the flow to 10 mmollmin
1996 17 wt .Yo Ni/A1203 Gas-phase hydrogenation,
T = 145-220 "C,m-xylene partial
pressure was varied over 0.01-0.035
MPa and hydrogen partial pressure
was in the range 0.4-0.9 bar
Phenanthrene Dihydrophenanthrene, 79
tetra hy drophenanthrene,
octahydrophenanthrene; the maximum
yield was at 370 "C
Benzene, naphthalene Cyclohexane, decalin 80
and pyrene
0-,
p-Xylene Main product, cis- and trans- 81
dimethylcyclohexaneswas formed in
non-equilibrium ratios; the kinetic results
showed that the reaction proceeds
through consecutive hydrogen addition
steps on the catalyst surface and cyclic
olefin was intermediate product
m-Xylene The distribution of stereoisomers 82
depended only on temperature, mixtures
of stereoisomeric products of the
saturated dimeth y lcyclohexane. Rate
maximum for saturated product was at
about 405 K
1996 Ni-Mo/yAlzO3 Batch reactor at 350 "C and 17 MPa, Naphthalene Tetralin and two isomers of decalin, 83
enriched with various kinetic investigation. Vanadium sulfide tetralin is identified as a primary product,
amounts of nickel and deposits led to decrease hydrogenation decalins are identified as non-primary
vanadium by contact rate in the naphthalene network; the products
with solutions of the results showed a sequential
respective meta1 hydrogenation of naphthalene to form
naphthenates. CS2 tetralin which was hydrogenated to
was added to the give decalin
mixture so that the
catalysts was
presulfided
1996 0.15-0.33 wt % Rhl The anionic exchange on a low and Benzene Cyclohexane, the data obtained from 84
CeOz catalysts high specific surface area ceria, exhibits benzene hydrogenation were found to be
the same amount of exposed metallic in very good agreement with the
Rh atoms, hence the high surface area percentages of metal exposed
ceria contain 50% more Rh
1996 Commercial pre- T =95-125 "C, P = 2-4 MPa. A Benzene, toluene, Completely hydrogenated cycloalkane 85
activated catalyst of model on competitive adsorption of ethylbenzene, cumene and trace amounts of cycloalkenes,
nickel-alumina (Ni hydrogen and the aromatic compound hydrogenation rate decreased with
16.6 wt%) fitted the experimental data. The increasing length of the substituent in the
hydrogenation rate was based on a benzene ring
sequential addition mechanism of
adsorbed hydrogen to the aromatic
nucleus
 h)
t
4
Table 1 (contd.)
~

Year Catalyst Reaction conditions I remarks Substrate Products I remarks Ref (s)
1996 Lithium Autoclave, T = 250 "C, 4- 18 h, P = 7 1. Naphthalene + 1. Tetralin 86
diisopropylamide MPa hexane 2. 9,lO dihydroanthracene
Potassium 2. Anthracene with 3. 1,2,3,4,5,6,7,8,-octahydroanthracene
bistrimethylsilylamide lithium 4. Octahydrophenanthrene
diisopropylamide 5. Dodecahydrochrysene
3. Anthracene with 6. Dodecahydro-l,2-benzanthracene
potassium
bistrimethyl-
silylamide
4. Phenanthrene with
the lithium
diisopropylamide
5. Chrysene
6. 1,Zbenzanthracene
1996 Pt-aluminium borate P=5.17 MPa, LHSV=2.8 h-' Naphthalene dissolved The catalytic activity of Pt-aluminium 87
in n-hexadecane borate was higher than that of Ptly-
A1203,but its cis, trans decalin selectivity
is lower than that of Ptly-Al203 catalyst
owing to the higher acidity; too much
boron (A1:B = 8) degrades the
hydrogenation activity
1995 Pt/y-A1203 Continuous fixed-bed reactor, Tetraline A Langmuir-Hinshelwoodreaction 88
T = 270 "C, P = 1.2-3.3 MPa, kinetic model, which was based on a
investigation of sulfur on the chemisorption scheme with irreversible
deactivation of catalysts surface reaction control for tetralin and
reversible surface reaction for sulfur
poisoning was proposed to describe the
deactivation model of the catalysts
1995 Pt/y-A1203,modified Hydrogenation feed contain 1000 ppm Tetralin + 1000 ppm Pt-Pd combination catalyst showed the 89
by adding a second sulfur, H2/hydrocarbon = 2.7, sulfur and highest sulfur resistance. The
metal, Co, Mo, Ni, T =280 "C,P = 2.62 MPa straight run distillate interpretation of the spectroscopic
Re, Ag and Pd diesel investigation was that the role of Pd in
enhancing sulfur resistance was due to
decreasing the electron density of Pt and
thereby inhibiting the adsorption of H2S
1995 Pt/A1203-aluminium Trickle bed reactor, P = 5.17 MPa, A solution of Tetralin, decalin, Walumina-aluminium 15
phosphate T =240 "C naphthalene in n- phosphate had a better hydrogenation
hexadecane was used activity and lower cis-decalin selectivity
to simulate the than Wy-A1203, due to the higher acidity
aromatic in diesel of the support
fuels
1995 Ptlalumina-aluminum P = 6.8 MPa, T = 350 "C,trickle bed Naphthalene dissolved The result showed that the catalyst had a 16
phosphate reactor, LHSV = 2.8 h- in n-hexadecane better hydrogenation activity and lower
cis-decalin selectivity than Pt/y-A1203
catalyst due to the higher acidity of the
support
1995 Rh and Ni Mild reaction conditions, 80 "C and Benzene, toluene, Total conversion of benzene, toluene and 90
organometallic 0.6 MPa of HzO, the strong co- a-methylstyrene a-methylstyrene using zeolite containing
complexes anchored operative effect between the zeolite the Rh complex was achieved after
on USY zeolites surface and the transition metal reaction times of 6, 18 and 24 h
surface was thought to be responsible respectively. The Ni complex was less
for the enhancement of hydrogenation active than the corresponding Rh
reaction complex. The positive influence of the
zeolite was attributed to an increase in
the concentration of reactants inside the
pores

h,
w
Table 1 (contd.)
Year Catalyst Reaction conditions I remarks
1995 Presulfided CoMoI Batch autoclave, T = 350 "C,P = 6.9
A1203 MPa H2, presulfiding at 400 "Cfor 135
min. in 10% H2S in H2.
Cyclohexane was used as a solvent.
Focus on the relationship between
molecular structure and hydrogenation
reactivity in heavy oil processing.
Equilibrium ratios were much larger
than unity for benzenic, larger than
unity for the naphthenic and smaller
than unity for the PHE
1995 PtlA1203 T = 200-260 "C, P = 1.7-8.7 MPa and
LHSV 1.5-8.0 liquid hourly space
velocity, trickle bed reactor
Substrate Products I remarks Ref0)
1. o-xylene 1. cis-trans-l,2-dimethylcyclohexane, m- 91
2. Naphthalene xylene, p-xylene, cis- and trans- 1,3-
3. Phenanthrene dimethyl- and -1,4-
4. Pyrene dimethylcyclohexanes
5. Anthracene 2. Tetralin and cis-trans-decalins
6. Chrysene 3. Di-, tetra-, octa- and
perhydrophenanthrene
4. Di-, tetra-, hexa-, deca- and
perhydropyrene
5 . Di-, tetra-, octa- and
perhydroanthracene
6. Di-, tetra-, hexa-, octa-, dodeca- and
perhydrochrysene
Naphthalene in inert Tetralin and cis- and trans-decalin. The 92
solvent n-hexadecane reaction was sequential, i. e. naphthalene
hydrogenated to tetralin, followed by
sequence hydrogenation to cis- and trans-
decalin. The apparent activation energies
for hydrogenation of tetralin to cis- and
trans-decalin were found to be 9.88 and
7.25 kcallmol, respectively
 r,
1995 Catalyst comprising a Stirred autoclave having a Parr 4561 Selective The combination of both catalysts was 93 ..
mixture of catalytically- assembly system, T = 150-250 "C, P up hydrogenation of found to produce conversion in excess of 2
active mixture of to about 6.90 MPa. The hydrogenation benzene in gasoline 40% which was much more than either of s
water-soluble, was carried out in a biphasic system of the catalysts separately
organometallic water and gasoline. The benzene was
compounds. Catalyst selectively solubilized in the water for %
k
(l), M[L],[X], wherein further hydrogenation in the presence ?
Q.
M is a metal selected of the water-soluble catalyst mixture
from Cr, Fe, Co, Ni,
B
Mo, Ru, Rh, Pd, Ta, $5
W, Re, Os, Ir, Pt, La G-
and Ce; L is an aro- 5
matic hydrocarbon; X 6'
3
is halogen; x and y are
integers from 1 to 10.
Catalyst (2),
tris(tripheny1-
phosphine)-
rhodium(1)halide or
tris(tripheny1-
phosphine)-
ruthenium(1)halide
1995 Molybdenum nitride Formation of surface sulfide on the Vacuum gas oil 94
catalyst
1995 Ni-Mo sulfide The synergistic effects between Ni(Co) Benzene Cyclohexane, Ni-Mo sulfide in the 95
catalysts supported on and Mo and between metal loading zeolite is highly dispersed and responsible
zeolites (HY), and acidity of zeolite was investigated. for the high hydrogenation activity,
conventional Ni-Mo/ The synergistic effect occurs at a Ni/ which was comparable to the
A1203 (Ni+Mo) ratio of about 0.4-05 and conventional Ni-Mo/A1203
was related to the formation of
Ni-Mo-S phases within the structure
of zeolite

Table 1 (contd.)
Year Catalyst Reaction conditions I remarks Substrate
1995 PdIC The carbon atoms on the surface and Benzene
in the bulk of Pd particles of the
catalyst showed a capacity for
chemisorption and hydride formation
1995 NiMo on Y zeolite T = 380 "C , P = 6 MPa, various
amount of o-xylene (5, 10 and 20 mol%
was added to n-heptane)
1995 Mordenite-supported The isomers of trans- and cis-decalin
Pt catalysts takes place on acid sites
1995 17 wt.% Ni/A1203 Differential microreactor, atmospheric Ethylbenzene
pressure, T = 130- 190 "C, ethylbenzene
partial pressure was varied from 0.01
MPa to 0.035 MPa, hydrogen partial
pressure was kept in the range of
0.04-0.09 MPa
1995 Molybdenum Total P = 5 MPa (hydrogen at 4.14
oxynitride MPa, cyclohexane at 0.85 bar and
propylbenzene at 0.06 MPa),
T=267-397 "C
h,
a
ProductsI remarks Ref(s)
The main product was cyclohexane, the 96
turnover frequency in benzene
hydrogenation was a structure-insensitive
reaction
o-Xylene The rate of formation of m- and p - 97
isomers allow an estimation of the acid
activity of a bifunctional catalyst. The
hydrogenation activity was defined as the
rate of formation of all Cg naphthenic
compounds, which is proportional to the
content of Ni and Mo of the catalyst and
independent of the zeolite content
Naphthalene Tetralin, trans- and cis-decalin 98,99
Kinetic investigation of ethylbenzene 100
hydrogenation. Rate maximum was
obseved at 160- 175"C, depending on the
concentration ratio of the reactant, main
hydrogenation product was
ethylcyclohexane
Propylbenzene Propylcyclohexane,characterization 101
through, chemical analysis. TPD of
propylbenzene and preadsorbed benzene
at room temperature and successive
catalytic runs indicated that, during
catalytic runs, the surface of the catalyst
will be chemically modified; an
oxycarbonitride is formed without
decrease of the specific surface area
I : Catalytic Hydrodearomatization 27

2.1 Reactivity in Hydrogenation Reactions. - The recent reactivity studies

have been reviewed by Moreau and G e n e ~ t e ,Girgis
~ ~ and Gates36 and
Stanislaus and Cooper.37 In these reviews, the reactivity of aromatic com-
pounds was defined as the overall conversion of aromatic compounds to fully
and/or partially hydrogenated products.
The hydrogenation reactivity of aromatic hydrocarbon was affected by the
following factors:

0 aromaticity; the aromatic character of a molecule is a measure of its degree

of unsaturation and on its thermodynamic stability
0 the total aromaticity; generally given by total resonance energy which is
defined as the value obtained by subtracting the actual energy of the
molecule from that of the most stable contributing structure102-10s
0 partial resonance energy; as the number of fused aromatic rings was
increased, the resonance stabilisation energy per aromatic ring was decreased
0 hydrogenation reactivity related to geometric modification of model
compounds
0 the contribution of the structural and geometrical effects of organic mole-
cules to the reactivity; this is taken into account where interaction between
the molecule and the catalyst surface was an important parameter
0 differences in the n- electron cloud density in alkylated aromatics
0 electronic effects; when the model compounds was substituted by alkyl or
aryl groups, the slight differences observed in reactivity was accounted for in
terms of electronic effect
0 the presence of bulkier substituents; a significant effect on reactivity was
assumed to be due to the steric effects. These effects have been most
important when fused multiring aromatics were hydrogenated
0 relationship to the reaction rate constant

Unlike olefin hydrogenation, high hydrogen pressures are required to effect

ring saturation in aromatics hydrogenation. This is partly due to the low
reactivity of the aromatic structure as a result of resonance stabilization of the
conjugated system and partly due to limitations determined by the thermo-
dynamic equilibrium at the pressures and temperatures employed. Therefore,
most studies on the reactivity of aromatics have been conducted at pressures
and temperatures that favour low equilibrium concentrations of aromatics.
Relative hydrogenation reactivates of one ring in the multi-aromatic model
compounds over a sulfided NiMo/A1203 were correlated to the rate constant
by Moreau et al.,35 the correlation showed the following order:
benzene (1) < phenanthrene (4) < naphthalene (20) < anthracene (40)
where the numbers are relative rate constants.
The reactivity of the aromatic compounds was correlated to the aromaticity
of the rings.35-106
The total aromaticity is generally given by resonance energy
(RE);lo5 resonance energy increases with the number of aromatic rings,
independently of the presence or the absence of heteroatoms in the rings.35
28 Catalysis

Table 2 Hydrogenation of mono- di- and tri-aromatic hydrocarbons, positions

for addition reaction in di- and tri-aromatic
Hydrogenat ion reaction Total resonance Resonance energy1
energy ring
(kcal mol-') (kcal mol-')

36-40 40

59-75 28

+H2=Q 71-105
10

10

The magnitude of resonance energy per ring was less for naphthalene
compared with benzene, and consequently the hydrogenation rate was low for
benzene.lo6The low aromatic character of one of the rings in the naphthalene
molecule is experimentally shown by its ability to undergo addition reactions
across 1,2-positions, and the corresponding positions are 9,10 for phenan-
threne and anthracene,lo7the behaviour is shown in Table 2.
The increase in resonance energy with the angularity of the system,105e.g.
anthracene and phenanthrene which are isomeric hydrocarbons (containing
the same total number of aromatic rings) resulted in lower reactivity for
phenanthrene.
It is commonly argued that the presence of methyl substituents on the
benzene ring stabilizes the adsorbed n complex with the resultant introduction
of a higher energy barrier to aromatic ring hydrogenation. The hydrogenation
rate in the presence of the noble metal catalysts decreased in order benzene >
toluene > p-xylene > m-xylene > o-xylene under moderate reaction conditions,
confirming this hypothesis.
The bonding of a molecule on the surface of solid catalysts depends on the
local electron density of states on the adsorbing metal atoms. Aromatic
compounds are bonded to the solid surface of the catalysts via n-bonds
involving an electron transfer from the aromatic ring to the unoccupied
d-metal orbitals.lo8 Since the n-electron cloud density in toluene is higher than
that of benzene, it would be expected that toluene is more strongly adsorbed
on the metal surface. Consequently, a strong interaction between aromatic
1: Catalytic Hydrodearomatization 29

compounds and the metal atoms will lead to a reduction in the hydrogenation
rate of the former. An increase in electron density cloud with the addition of
another methyl groups can account for the lower reactivity of xylene.
For metal sulfide catalysts, such as Ni-W-S/A1203 and Ni--Mo-S/A1203, the
reactivity pattern of aromatic and alkylated aromatic compounds is the
opposite.37In other words, addition of methyl groups to aromatic compounds
gives rise to an enhancement of the reactivity of these molecules for hydro-
genation; the corresponding hydrogenation rate for the same homologous
series (as stated above) will decrease in the order benzene < toluene < p-xylene
< rn-xylene < o-xylene over moderate reaction conditions.
Both the number and position of the substituted groups in benzene ring
affected the hydrogenation activity.68The observed reaction rate of a trisub-
stituted benzene (mesitylene) over a commercial pre-activated catalyst particles
of nickel-alumina was lower than the reaction rate of the disubstituted
(xylene) benzene? The activity of the different substituent positions decreased
in the order para > meta > ortho.68The lowest reactivity of ortho-isomers has
been attributed to steric effects.37
Steric hindrance of neighbouring methyl groups in ortho-positions had a
more significant effect on the formation of n-bonded complexes.
Pondi and V a n n i ~ observed
e~~ that the relative rate of toulene and benzene
hydrogenation with an equimolar gas mixture for the Pd supported catalysts in
A1203and Si02-A1203 was less than unity. A value less than unity indicated
that toluene was less reactive than benzene on Pd catalyst^.^^ In the same
experiment a threefold higher value for relative rate was reported for Pt
catalysts; the authors interpretation was that toluene hydrogenation was
favoured on Pt.69
For the three catalytic systems, Pt/Si02-A1203, Pd/Si02--A1203, and PtPdl
Si02-A1203, under moderate operating conditions and in the presence of 113
ppm sulfur, the order of aromatic reactivity was as the following sequence:
naphthalene >> toluene > tetralin.4 This reactivity sequence was related to a
decrease in the resonance energy per aromatic ring as well as to differences in
the n-electron cloud density in the aromatic ring because of the inductive effect
of the methyl group in t01uene.~The bimetallic catalyst exhibited higher
hydrogenation activity for those three aromatic compounds. This enhancement
in the aromatic hydrogenation activity in presence of sulfur was attributed to
the synergetic effect between Pt and Pd.4 Of course, there are a variety of
interpretations concerning the noble bimetallic effect on catalytic activity, but
obviously the greater reactivity is a result of the presence of an addition effect,
as opposed to a synergetic effect.
In agreement with the literature data, in addition to the influence of
resonance energy and stereochemistry, additional factors such as choice of the
catalyst metal and reaction conditions have a significant effect on the reactivity
of the aromatic molecules.
Hydrogenation activity on a commercial Ni-alumina catalyst decreased with
increasing length of the substituent in the benzene ring, thus benzene appeared
to be the most reactive.85
30 Catalysis

100

iE
W
80

60
I,
0

40

20 " Pt (3)-Pd (10)

0
150 200 250 300 350 400 450
Temperature ('C)
Figure 1 Conversion of PHE hydrogenation as a function of temperature on several
catalysts (fromref 42)

The rate of hydrogenation of derivatives of benzene varies with the nature,

number and position of the substituents. The ratio KTIB (toluene to benzene) of
the adsorption coefficients is very large on ruthenium, about 9-10 on rhodium
and about 1 on palladium. This behaviour was interpreted as an effect of a
considerable electron transfer from methyl groups of the aromatics to the
metal. Large KTIBratios are associated with the electron-deficient character of
the metal.log
Pyrene, fluoranthene, anthracene and fluorene were hydrogenated over a Pt,
Pd, Rh and Ru catalyst in a study by Sakanishi et al. 110Also here the results
showed a change in reactivity order depending on the catalyst used. However,
the difference in reactivity can not be explained only by the structural proper-
ties of aromatic compounds. The reactivity will be influenced by the properties
of the catalysts.
The appearance of differences in reactivity depended on varying the type of
catalyst and diversities recorded from the different reported works confirmed
that more research is needed with a special focus on the reactivity aspects.

2.2 Thermodynamics of Hydrogenation. - One important property of the

hydrodearomatization reaction is that the maximum equilibrium conversion
occurs at temperatures close to or even below the temperatures needed for the
hydrodearomatization rate to be of industrial interest and this is clearly seen in
Figure 1. To the right of the maximum of the curves the equilibrium rate is
limiting the hydrogenation process and to the left, the hydrogenation rate is
limited by the temperature.2
This is why catalysts from the platinum group with a high activity are
preferred rather than less active sulfided catalysts. Keane and Patterson40
included equilibrium curves for benzene, toluene and o-xylene at 0.1 MPa.
1 :Catalytic Hydrodearornat iza tion 31

Djega-Mariadassou et al. lol present equilibrium data for ethylbenzene at 5.0

MPa total pressure and a hydrogen pressure of 4.1 MPa.

2.3 Reaction Pathways and Kinetics of Hydrogenation. - The reaction

network for hydro-dearomatization has been studied by several groups and
will be presented below. Reaction order, activation energies and thermody-
namic values will be presented.

2.3.1 Reaction Network. The hydrogenation of a one-ring system can be

influenced by the presence of other functional groups. The reaction in this case
will start with either hydrogenation of the functional group or hydrogenation
of the aromatic ring. Takagi et aZ.6 have studied the effect of solvent for the
hydrogenation of benzyl alcohol. This makes it possible to control the
selectivity in the reaction. When hydrogenating monoaromatics the major
product will be the hydrogenated ring, but also some cyclic mono alkenes are
also formed.'" It is this alkene that according to Salmi et aZ.65981385undergoes
'roll-over' in the adsorbed state and two different cis and trans isomers are
formed. In the same way naphthalene is hydrogenated first to tetralin and
finally to decalin in both the cis and trans f0rms.83992Huang et al.92present a
figure, originating from Weitcamp, l2 claiming that several other intermediates
exist. They present indications of the existence of octalin, as this compound is
a necessary intermediate for the formation of the isomerized products.
Qian et al.42 presented phenanthrene (an aromatic with three rings) dear-
omatization using both PdPt catalysts and sulfided CoMo catalysts. Total
pressure was kept at 5 MPa with decalin as solvent and 1% aromatic, at
various temperatures. Hydrogenation of phenanthrene proceeds through a
network of reversible reactions. The middle ring was the most likely to be
hydrogenated first.

2.3.2 Reaction Order. Keana hydrogenated xylenes over a nickel catalyst on

silica. The turnover frequency (TOF) followed the following general expression.
TOF = kPxmPnH2
where the reaction order for the xylenes varied from 0.1 at 393 to about 0.44 at
530°C. The value of n for the hydrogen pressure increased with temperature
from 0.7 to 2.3.

2.3.3 Activation Energies. Huang and Kang92 and Corma et aZ.58 provide a
table of older results on apparent activation energies for hydrogenation of
aromatic hydrocarbons, mainly benzene. Discussion of activation energies is
given by Keane and P a t t e r s s ~ n . ~ ~ * ~
The true activation energy can be calculated from the observed apparent
activation energy by subtracting the sum of adsorption energies of the
aromatic and the hydrogen. The adsorption energies provide the major
contribution to the true activation energy. Adsorption energies for an aromatic
are in the range 100-140 kJ mol-'.
32 Catalysis

2.4 Catalysts and Nature of Catalytic Sites. - Because of more stringent

environmental regulations, greater attention has been focused on the reduction
of aromatics in distillate fractions. Also important is the use of deep catalytic
hydrogenation of the aromatic compounds to produce petrochemicals, e.g.
conversion of benzene into cyclohexane in the synthesis of caprolactam.
The choice of catalyst type varies according to the application, nature of the
feedstocks and desired activity/selectivity of the reactions. Conventional
hydrotreating catalysts containing sulfided mixed oxides (NiMo, NiW, CoMo)
can only accomplish moderate levels of aromatic saturation under typical
hydrotreating conditions. Because of the thermodynamic limitations in hydro-
dearomatization, a deep level of aromatic saturation has not been achieved by
increasing operation severity (high temperature and high Hz pressure).
Among the conventional catalysts, NiMo and NiW are preferred for
aromatic saturation. NiW catalysts have the highest activity for aromatic
hydrogenation at low hydrogen sulfide partial pressures,37but their use has
been limited due to the higher cost. Models of the active phases and structural
aspects of these mixed oxides (NiMo, NiW, CoMo) have been recently
reviewed by Topsoe and co-workers.
Transition metals, as well as platinium-group metals, have been used as the
catalyst for this type of hydrogenation. Platinum-group metals have the
advantage of high hydrogenation activity at low temperature. The catalyst
activity for the hydrogenation of benzene was reported to be in order Rh > Ru
>> Pt >> Pd >> Ni > C0.113
Three categories of catalysts have been studied for hydrodearomatization in
literature. The first category is a mono-metallic noble-metal catalyst. Ob-
viously, these catalysts will be used in the hydrogenation processes in the
absence of sulfur in the feedstocks. The second category of catalysts consists of
two noble metals and is known as a bimetallic noble-metal catalyst. Several
combinations of Pt, Pd, Rh and Re have been proposed. The third is a
combination of the conventional hydrotreating catalysts promoted by a noble
metal; these catalysts consist of three metals.
An attribute of the noble-metal based catalysts is that they are active at
lower temperatures; thereby they are the preferred catalysts for deep aromatic
saturation. The main drawback of noble-metal hydrogenation catalysts is that
they are poisoned by small amounts of sulfur and nitrogen organic compounds
present in the feed. However, because in the industrial feeds several heteroaro-
matic compounds are present, considerable attention has been paid recently to
developing catalysts with the high hydrogenation activity while maintaining
strong resistance to poisoning by the small amounts of sulfur- and nitrogen-
containing compounds in the feed stream. Several attempts have been made to
minimize the poisoning effects of heteroatoms. The resistance to poisoning by
heteroatoms is improved by adding a second noble metal to Pt, changing the
particle size, or changing the acid-base properties of the carrier. With respect
to the latter, it is reported that the sulfur tolerance of the noble metal catalysts
can be greatly enhanced by using acidic supports such as zeolites, whereas less
I : Catalytic Hy drodearomat iza tion 33
acid supports such as Si02-Al203 can generate moderate sulfur resis-
tance.28.3 1,37,41,114- 115
The studies performed by Vannice et al.69J16-117found that the activity of
the Pt or Pd catalyst for benzene and toluene hydrogenation was much higher
when loaded on Si02-Al203 compared with an A1203-supported catalyse. The
enhancement of the activity was explained by the more acidic nature of the
Si02-Al2O3 as a support.
The exceptional performance of the PtPd catalyst in aromatic hydrogenation
was interpreted in terms of the electron-deficient platinum species (isolated Pt
cluster on Pd surface) in the resultant PtPd particle^.^
It has been reported in literature118y119 that the high sulfur tolerance and
higher activity of zeolite-supported Pt or Pd catalysts arises from the formation
of an electron-deficient cluster of metal particles, Pt6+ or Pds+ upon the
hydrogenation of the aromatic compounds. The close contact between the
strong acidic support and the small cluster of Pt or Pd atoms makes it possible
for the electron to be withdrawn from the noble metal thereby creating an
electron-deficient metal particle. 120~121In the case of zeolite-supported bime-
tallic PtPd catalysts, it seems that the molar ratio of the PtRd is seldom greater
than unity.
Also the role of the acidic support is to modify the active site, which is the
noble metal. The catalytic cracking reaction of the acidic support, under
hydrogenation conditions, is undesired as this lowers the selectivity towards
the desired hydrodearomatization reaction.
The hypotheses that the deactivation effect is related to acidic support has
been proven by using a less acidic carrier. In these studies, the Si02-Al203
carrier was replaced by the more acidic support such as zeolites in order to
minimise the effect of the cracking activity, which accelerate the catalytic
deactivation by coke and results in enhanced yields of naphtha and g a ~ . ~ . ~
The sulfur resistance and saturation activity of the aromatic catalysts was
improved by using MCM-41 materials as a support for noble metal catalyst^.^^
The higher saturation activity of naphthalene on Pt/MCM-41, in comparison
with the Pt/A1203,was attributed to the medium-strong acidity of the MCM-
41 support and its higher metal d i s p e r s i ~ n . ~ ~
Different s t u d i e have
~ ~ ~been
~ ~devoted
~ to the nature of the active phase on
the supported mono-noble metals such as ruthenium or rhodium in hydrodear-
omatization. The ruthenium or rhodium sulfide phase was identified as the
active phase for aromatic hydrogenation.
Aromatics hydrogenation in the presence of H2S shows that a weak Pt (or
Pd)-S sulfide bond is formed.2 It was further found that the synergetic effect
observed on the bimetallic PtPd was not as significant as those achieved with
typical CoMo catalysts.2 The observed activity in Figure 1 indicates clearly the
absence of synergetic effect between the bimetallic Pt and Pd. However, the
activity results revealed the presence of the additional effect from the bimetallic
combination of PtPd.
The transition metal catalysts used in hydrodearomatization, the role of
34 Catalysis

preparation, the nature of the metal precursor and support and the ultimate
dispersion of the active metal phase and their bearing on the catalytic data
were carefully reviewed by Krylov et aZ.32

3 Industrial Aspects

The aim of this section is to illustrate the importance of aromatic saturation in

the refining industry. There were a number of commercial processes having
aromatic saturation as their major objective before the growing interest in
removal of aromatics in diesel began in 1991. For example, aromatic satura-
tion is used in the production of kerosene and jet fuel for smoke point
i m p r ~ v e r n e n t . ' ~ ~A- ' ~
high
~ smoke point due to a low aromatic content
improves the quality of a flame, producing a greater flame without smoke and
d e p 0 ~ i t s .A
l ~high
~ smoke point reduces the effects of the radiation from the
jet flame on exposed mechanical parts in a jet engine.
The removal of aromatics is essential in the production of lubricants and
solvents to both control the technical performance of the product and the
impact on health and environment. A low aromatic content improves the
viscosity index (VI) of engine oil. The lower the VI, the lower the variation of
the viscosity with temperature.126
In 1993 the European Community decided to label lubricants based on the
DMDS extractable content of the lubricant according to the Institute of
Petroleum method IP 346. The polyaromatics in the lubricant are extracted in
to a DMDS phase and the 3% limit for the DMDS extractable content is based
on a correlation with skin cancer in skin painting tests on mice. 127
In the production of food/medical grade oils, a complete reduction of
aromatics according to the demands in the FDA, DAB or BS pharmacopoeia
is needed. The production of medical white oil represents the most severe
process condition used in hydrorefining. The first extraction stage and the first
hydrotreating stage remove the major part of the nitrogen, sulfur and the
aromatics. The intermediate product will meet the demands on the less refined
product technical white oil. A low space velocity, high pressure and noble
metal catalyst is needed in the second hydrotreating stage to overcome the
thermodynamic limitations for the reduction of the remaining aromatics in the
medical white oil. The production routes for lubricants and food/medical
grade oil by extraction and acid/clay treatment have gradually been replaced
by catalytic hydroprocessing routes. 128-130
It is an established practice in fuel refining to pretreat FCC feed stocks. One
of the main objectives in the hydrotreating of FCC-feed stock is to reduce
sulfur to minimize sulfur oxide release during regeneration of the catalyst and
to meet the sulfur specification of the products. A more severe hydrotreating of
the FCC-feed and a change of the catalyst from a CoMo catalyst to a catalyst
containing NiMoP, a higher pressure, and a lower space velocity will increase
the reduction of the nitrogen and aromatic content in the FCC-feed. The
hydrogenation of aromatic and nitrogen components in FCC feed stocks
I :Catalytic Hydrodearomat iza t ion 35

Table 3 Swedish and Californian diesel specijications

Sweden
Class Class I Class 11 Class 111 California
>50 000 bpsd
Density, kgm-3 800-820 800-820 800-830 830-860
Sulfur, ppm 10 50 500 500
Nitrogen, ppm 10
Aromatics, vol% 5 10 25 10
Cetane index 50 47 47
Cetane number 48
IBP, "C 180 180 180 170-215
FBP, "C 300 310 330 305-350

decreases the coke deposited on the catalyst and improves the selectivity to
more valuable products.1279131-132
Aromatic saturation is also desired in residue desulfurization for transporta-
tion fuels and in hydrocracking to increase the hydrogedcarbon ratio. Hydro-
genation of aromatics is desired in the hydrotreating of straight run gas oil to
improve the cetane number in diesel, and is even more necessary because the
use of other low quality sources of various diesel feedstocks as straight run gas
oil, visbreaker gas oil, coker gas oil and light cycle oil is increasing.133
The Swedish (1991) and the California (1993) authorities were the first to
introduce legislation limiting the aromatic content in diesel. Table 3 shows the
Swedish and Californian diesel specifications. The motivation for the legisla-
tion is that the reduction of the aromatic content and sulfur content results in
reduced particulate and NO, emissions from the diesel engine.
The specifications for fuel oil and diesel will become even more stringent for
Europe and USA. 134-135 Asian countries are already moving towards similar
tighter specifications.136
Changes in fuel specifications have been the dominant force for the develop-
ment and introduction of new catalysts and processes for hydrotreating.
Several new processing schemes have been introduced since 1991. Stricter
specifications will continue to require improvements in performance.
As highlighted above, thermodynamic considerations will limit the use of
higher reaction temperatures in deep hydrogenation of aromatics. In current
commercial processes for deep hydrogenation of aromatics, a two-stage
process is used. In the first stage the sulfur and nitrogen contents are reduced
by using a NiMo catalyst on alumina. Some aromatic saturation does also
occur during this first step, but the main objective in the first step is to reduce
sulfur and nitrogen. This allows for the use of a noble-metal catalyst at low
reaction temperatures in the second stage after an intermediate gas separation
and stripping in between the two stages.137Examples of licensors of this two-
stage technology are Shell, Topsoe, Lummus-Criterion and IFP. 1339136~138-140

An option with the Synsat process from Criterion-Lummus is to remove the

H2S and NH3 containing by-product gases within a single reactor. The Synsat
36 Catalysis
Recycle gas
Fresh Feed ~ Make-upH2

Recvcle

Gas to
VapodLiquid
Separation and

Product to stripping

Reactor 1ene;th

Figure 2 (a) SynSat reactor; (b) temperature and hydrogen partial pressure proJles

reactor, shown in Figure 2, also includes an optional counter-current gas flow

in the bottom catalyst bed to further reduce the H2S content, increase the
hydrogen partial pressure and maintain the temperature profile. 38
The catalysts commonly used in the second stage for aromatic saturation is
a sulfur-resistant Pd-Pt, noble-metal catalyst on an acidic zeolite. Much
attention has been focused on ways to increase the sulfur tolerance of noble
metal catalysts. 3 l4
339

A comparative in 1992 by Cooper et al. shows that a two-stage

operation with an inter-stage stripper and sulfur-tolerant noble metal catalyst
is the optimum for deep aromatic saturation.
It has to be mentioned that diesel meeting the tightening specifications can
also be obtained by hydrocracking or mild hydrocracking where the catalyst
also contains an acidic function as well as the hydrogenating-dehydrogenating
function.143The acidic function introduces a shift in boiling range and a ring
opening. The ring opening results in a further improvement of the cetane
number after a prior saturation of the aromatic ring. Hydrocracking is outside
1: Catalytic Hydrodearomatization 37

the scope of the present paper but there are some processes for deep aromatic
saturation including an option for ring opening, boiling range shift or/and a
cold flow improvement, e.g. the Akzo-Fina CFI and the SynShift
processes.

4 Summary and Conclusion

In this paper we have reviewed the literature regarding the state of aromatic
hydrogenation processes including the kinetic, thermodynamic, catalytic chem-
istry and industrial aspects. It is possible to produce a diesel fuel with a low
aromatic content, high cetane number, uncoloured and with a low sulfur
content. The low sulfur content is a necessity since the effective dearomatiza-
tion catalysts are sensitive to sulfur. In the recent years several solutions to the
severe sulfur deactivation of the dearomatization catalyst have been presented.
However, the sulfur tolerance has to be further increased.
The interesting temperatures are around 340 "C. At higher temperatures, the
equilibrium limits the yield. At 370 "C, uncatalytic hydrogen donor reactions
are possible and aromatics are formed from hydrogenated products. Higher
temperatures can be used, depending on the hydrogen partial pressure. The
higher the pressure the higher the temperature that can be used. If a more
active catalyst is found, a lower temperature could be used, making it possible
to use lower hydrogen partial pressure. This would lead to large savings in the
production of low aromatic compounds.
In the near future, it would be of interest to develop more basic knowledge
on the industrial process. This will reduce the cost for dearomatization. There
is a need for experiments with more industrial relevant model compounds and
to find equilibrium data for model compounds under industrial conditions.
There is also a need for experiments with industrial feeds, e.g. feedstocks to
FCC and light cycle oils from FCC that can be used as diesel fuel. This could
achieve a valuable increase of the cetane number, especially in the USA. Other
interesting oils are base oils for lube stock.
The sulfur resistance by using a zeolite carrier has been demonstrated.
However, it is of great interest to increase this resistance or to develop
completely new concepts since most feedstocks do contain significant levels of
sulfur. Deep desufurization before dearomatization is costly.

The need for more knowledge of selective hydrogenation

1 benzene --+ cyclohexene (not cyclohexane).
2 competitive reduction of benzene in gasoline by hydrogenation of a light
fraction from catalytic reformer to reduce benzene in gasoline.
3 hydrogenation of specific aromatic compounds in competition with other
aromatics in the feed.
4 developing catalysts with a high hydrogenation activity while at the same
time maintaining strong resistance to poisoning of sulfur in the form of
hydrogen sulfide and benzothiophenes.
38 Catalysis

5 !studying the influence of possible poisons like hydrogen sulfide, ammonia,

and water on the kinetic of hydrodehydroaromatization on one ring and
I

two ring and multiple aromatic model compounds (the major portion of the
aromatic content in diesel feedstocks) in the production of low aromatic
diesel fuels.
6 more research to develop both sulfur- and nitrogen-resistant catalysts,
because in industrial feeds, several heteroaromatics are present.
7 studying new methods for hydrogenation of aromatics like under super-
zritical conditions.

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