BACKGROUND OF THE INVENTION
[0001] This invention relates to the use of a catalyst slurry for hydrotreating heavy fossil
fuel feedstocks such as vacuum gas oils or heavy gas oils. High catalyst activity
is maintained by circulating the catalyst between a hydrotreating zone and a hydrogen
stripping reactivation zone.
[0002] The petroleum industry employs hydrotreating to process heavy vacuum gas oils, particularly
coker gas oils, in order to improve their quality as fluid catalytic cracker (FCC)
feeds. Hydrotreating accomplishes the saturation of multi-ring aromatic compounds
to one-ring aromatics or completely saturated naphthenes. This is necessary to assure
low coke and high gasoline yields in the cat cracker. Multi-ring aromatics cannot
be cracked effectively to mogas and heating oil products, whereas partially hydrogenated
aromatics or naphthenes can be cracked to premium products. Hydrotreating is further
capable of removing sulfur and nitrogen which is detrimental to the cracking process.
[0003] Hydrotreating employs catalysts that tend to become poisoned by organic nitrogen
compounds in the feed. Such compounds become adsorbed onto the catalyst and tie up
needed hydrogenation sites due to the slow kinetics or turnover for hydrodenitrogenation.
Higher temperatures may be utilized to overcome this problem. However, at high temperatures
thermodynamic equilibrium tends to favor the preservation of undesirable multi-ring
aromatic compounds.
[0004] It is an object of the present invention to circumvent both the kinetic and equilibrium
limts encountered in conventional hydrotreating processes which employ fixed bed catalysts.
It is a further object of the present invention to provide an improved hydrotreating
process employing a catalyst slurry. It is a still further object of the present invention
to accomplish reactivation of the catalyst employed in the present process by hydrogen
stripping the catalyst in an essentially continuous cyclic process.
[0005] In comparison to the present process, hydrogen stripping with a conventional fixed
bed reactor has been found to provide only a temporary gain in catalyst activity,
which gain is quickly lost in a few days. Therefore, frequent and expensive shut downs
would be required for hydrogen stripping to be effective in a fixed bed hydrotreating
process.
[0006] Hydrotreating processes utilizing a slurry of dispersed catalysts in admixture with
a hydrocarbon oil are generally known. For example, Patent No. 4,557,821 to Lopez
et al discloses hydrotreating a heavy oil employing a circulating slurry catalyst.
Other patents disclosing slurry hydrotreating include U.S. Patent Nos. 3,297,563;
2,912,375; and 2,700,015.
[0007] Various problems in operating the slurry processes disclosed in the prior art have
apparently hindered commercialization. For example, according to the process disclosed
in Patents Nos. 4,557,821; 2,912,375 and 2,700,015, it is necessary to reactivate
the catalyst by air oxidation. However, air oxidation is expensive since depressurization
of the catalyst environment between the hydrotreating reactor and the reactivator,
requiring expensive lock hoppers, is necessary before combusting off the contaminants
on the catalyst. Furthermore, expensive equipment is necessary to avoid air contamination
and possible explosions.
BRIEF DESCRIPTION OF THE INVENTION
[0008] The present invention is directed to a method of maintaining high catalyst activity
in a slurry hydrotreating process for heavy fossil fuels wherein a hydrotreating catalyst
of small particle size is contacted with heavy petroleum or synfuel stocks for hydrogenation
of heavy aromatics and removal of nitrogen and sulfur. The catalyst is circulated
between a hydrotreating reaction zone and hydrogen stripping reactivation zone.
[0009] These and other objects are accomplished according to our invention, which comprises:
(1) reacting the heavy fossil fuel in a hydrotreating zone with hydrogen in the presence
of a hydrotreating catalyst;
(2) separating the catalyst from the product of the hydrotreating zone;
(3) reactivating the catalyst in a reactivation zone by subjecting the same to hydrogen
stripping; and
(4) recycling the reactivated catalyst to the hydrotreating zone.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The process of the invention will be more clearly understood upon reference to the
detailed discussion below upon reference to Fig. 1 (Sole Fig.) which shows a schematic
diagram of one process scheme according to this invention comprising a slurry hydrotreating
step and hydrogen reactivation stripping step.
DETAILED DESCRIPTION OF THE INVENTION
[0011] Applicants' process is directed to a slurry hydrotreating process in which the catalyst
used in a hydrotreating zone is reactivated by hydrogen stripping in a cyclic, preferably
continuous process.
[0012] The catalyst is reactivated in a separate reactivation zone and recycled back to
the hydrotreating zone. In addition, fresh or reactivated (regenerated) catalyst
can be continually added while aged or deactivated catalyst can be purged or reactivated.
Because the catalyst is being regularly reactivated according the present process,
the slurry hydrotreating step can be operated at more severe conditions (which otherwise
tend to deactivate the catalyst) than used in conventional fixed bed hydrotreating.
A conventional fixed bed hydrotreater typically operates for about 1 or 2 years before
it is necessary to shut it down in order to replace the catalyst. An advantage of
the present slurry process in combination with catalyst reactivation is increased
activity of the catalyst compared to a fixed bed.
[0013] It is noted that the permanent deactivation of the catalyst which occurs in conventional
fixed bed hydrotreating is reduced in the present hydrotreating process by hydrogen
reactivation. This permanent deactivation is believed to occur by the presence of
coking, resulting from polymerization reactions and metal deactivation, caused by
the presence of organic metal compounds present in the feedstocks. These polymerization
reactions are prevented by periodic hydrogen reactivation which strips adsorbed feed
from the catalyst.
[0014] The slurry hydrotreating process of this invention can be used to treat various feeds
including fossil fuels such as heavy catalytic cracking cycle oils (HCCO), coker gas
oils, and vacuum gas oils (VGO) which contain significant concentrations of multi-ring
and polar aromatics, particularly large asphaltenic molecules. Similar gas oils derived
from petroleum, coal, bitumen, tar sands, or shale oil are suitable feeds.
[0015] Suitable feeds for processing according to the present invention include those gas
oil fractions which are distilled in the range of 500 to 1200°F, preferably in the
650 to 1100°F range. Above 1200°F it is difficult or impossible to strip all of the
feed off the catalyst with hydrogen and the catalyst tends to coke up. Also, the presence
of concarbon and asphaltenes deactivate the catalyst. The feed should not be such
that more than 10% boils above 1050°F. The nitrogen content is normally greater than
1500 ppm. The 3+ ring aromatics content of the feed will generally represent 25% or
more by weight. Polar aromatics are generally 5% or more by weight and concarbon constitutes
1% or more by weight.
[0016] Suitable catalysts for use in the present process are well known in the art and include,
but are not limited to, molybdenum (Mo) sulfides, mixtures of transition metal sulfides
such as Ni, No, Co, Fe, W, Mn, and the like. Typical catalysts include NiMo, CoMo,
or CoNiMo combinations. In general sulfides of Group VII metals are suitable. (The
Periodic Table of Elements referred to herein is given in
Handbook of Chemistry and Physics, published by the Chemical Rubber Publishing Company, Cleveland, Ohio, 45th Edition,
1964.) These catalyst materials can be unsupported or supported on inorganic oxides
such as alumina, silica, titania, silica alumina, silica magnesia and mixtures thereof.
Zeolites such as USY or acid micro supports such as aluminated CAB-O-SIL can be suitably
composited with these supports. Catalysts formed in-situ from soluble precursors such
as Ni and Mo naphthenate or salts of phosphomolybdic acids are suitable.
[0017] In general the catalyst material may range in diameter from 1 µ to 1/8 inch. Preferably,
the catalyst particles are 1 to 400 µ in diameter so that intra particle diffusion
limitations are minimized or eliminated during hydrotreating.
[0018] In supported catalysts, transition metals such as Mo are suitably present at a weight
percent of 5 to 30%, preferably 10 to 20%. Promoter metals such as Ni and/or Co are
typically present in the amount of 1 to 15%. The surface area is suitably about 80
to 400 m²/g, preferably 150 to 300 m²/g.
[0019] Methods of preparing the catalyst are well known. Typically, the alumina support
is formed by precipitating alumina in hydrous form from a mixture of acidic reagents
in an alkaline aqueous aluminate solution. A slurry is formed upon precipitation of
the hydrous alumina. This slurry is concentrated and generally spray dried to provide
a catalyst support or carrier. The carrier is then impregnated with catalytic metals
and subsequently calcined. For example, suitable reagents and conditions for preparing
the support are disclosed in U.S. patents Nos. 3,770,617 and 3,531,398, herein incorporated
by reference. To prepare catalysts up to 200 microns in average diameter, spray drying
is generally the preferred method of obtaining the final form of the catalyst particle.
To prepare larger size catalysts, for example about 1/32 to 1/8 inch in average diameter,
extruding is commonly used to form the catalyst. To produce catalyst particles in
the range of 200 µ to 1/32 inch, the oil drop method is preferred. The well known
oil drop method comprises forming an alumina hydrosol by any of the teachings taught
in the prior art, for example by reacting aluminum with hydrochloric acid, combining
the hydrosol with a suitable gelling agent and dropping the resultant mixture into
an oil bath until hydrogel spheres are formed. The spheres are then continuously withdrawn
from the oil bath, washed, dried, and calcined. This treatment converts the alumina
hydrogel to corresponding crystalline gamma alumina particles. They are then impregnated
with catalytic metals as with spray dried particles. See for example, U.S. Patents
Nos. 3,745,112 and 2,620,314.
[0020] Referring to FIG. 1, a feed stream 1, consisting for example of gas oil feed, is
introduced into a slurry hydrotreating reactor 2. Before being passed to this reactor,
the feedstream is typically mixed with a hydrogen containing gas in stream 3 and heated
to a reaction temperature in a furnace or preheater 4. A make-up hydrogen stream 30
may be introduced into the hydrogen stream 3, which in turn may be either combined
with the feed stream or alternatively mixed in the hydrotreating reactor 2. The hydrotreating
reactor contains a catalyst in the form of a slurry at a solids weight percent of
about 10 to 70 percent, preferably 40 to 60 percent. In the embodiment shown in the
figure, the feed enters through the bottom of the reactor and bubbles up through an
ebulating or fluidized bed.
[0021] Depending on the size of the catalyst particles, the hydrotreating reactor may have
filters at the entrance and/or exit orifices to keep the catalyst particles in the
reactor. Alternatively, the reactor may have a flare (increasing diameter) configuration
such that when the reactor is kept at minimum fluidization velocity, the catalyst
particles are prevented from escaping through an upper exit orifice.
[0022] Although a single slurry hydrotreating reactor may be used in the present process,
it is preferred for greater efficiencies that the slurry hydrotreating process be
operated in two or more stages, as disclosed in copending U.S. Application No. 414,175,
hereby incorporated by reference. Accordingly, a high temperature stage may be followed
by one or more low temperature stages. For example, a two stage process might process
fresh feed in a 760°F stage and process the product from the first stage in a 720°F
stage. Alternatively, several stages can be operated at successively lower temperatures,
such as a 780°F stage followed by a 740°F stage followed by a 700°F stage. Such an
arrangement provides fast reaction rates in the first stage and lower equilibrium
multi-ring aromatics levels (hence greater kinetic driving forces) in the final stage
or stages. Staging is especially advantageous in the present slurry process as compared
to a fixed bed process because the initial stages can be operated at higher temperatures,
heat transfer is better and diffusion does not limit reaction rates.
[0023] Referring again to FIG. 1, an effluent from the hydrotreating reactor 2, containing
liquids and gases and substantially no catalyst solids, is passed via stream 5 through
a cooler 6 and introduced into a gas-liquid separator or disengaging means 7 where
the hydrogen gas along with ammonia and hydrogen sulfide by-products from the hydrotreating
reactions may be separated from the liquid product in stream 8. The separated gases
in stream 11 are recycled via compressor 10 back for reuse in the hydrogen stream
3. The recycled gas is usually passed through a scrubber to remove hydrogen sul fide
and ammonia because of their inhibiting effects on the kinetics of hydrotreating and
also to reduce corrosion in the recycle circuit.
[0024] In many cases, the liquid product in stream 8 is given a light caustic wash to assure
complete removal of hydrogen sulfide. Small quantities of hydrogen sulfide, if left
in the product, will oxidize to free sulfur upon exposure to the air, and may cause
the product to exceed pollution or corrosion specifications.
[0025] In order to reactivate the catalyst in the hydrotreating reactor 2, an exit stream
containing catalyst solids is removed from the reactor as stream 12 and enters a separator
14, which may be a filter, vacuum flash, centrifuge, or the like to divide the effluent
into a catalyst stream 15 and a liquid stream 16 for recycle via pump 17 to the hydrotreating
reactor 2.
[0026] The catalyst stream 15 from separator 14 comprises suitably 30 to 60 percent catalyst.
Optionally this catalyst stream may be diluted with a lighter liquid such as naphtha
to fluidize the catalyst and aid in the transport of the catalyst, while permitting
easy separation by distillation and recycle. In any case, the catalyst material is
transported to the stripper reactor or reactivator 20. A hydrogen stream 22, preferably
heated in heater 21, is introduced into reactivator 20 where the catalyst is hydrogen
stripped. The reactivator yields a reactivated catalyst stream 23 for recycle back
to the hydrotreating reactor 2. Spent catalyst may be purged from stream 23 via line
24 and fresh make-up catalyst introduced via line 18 into the feed stream. The reactivated
catalyst from the reactivator 20 is suitably returned to the hydrotreating reactor
2 at a rate of about 0.05 to 0.50 lbs reactivated catalyst to lbs gas oil feed, preferably
0.1 to 0.3.
[0027] The reactivator 20 also yields a top gas stream 25 which is subsequently passed through
cooler 26, gas-liquid separator 27 and via stream 13 combined with the hydrogen recycle
stream 11. Off gas may be purged via line 29. Stripped liquids from the separator
27 may be returned to the hydrotreater reactor 2 via stream 28.
[0028] The process conditions in the process depend to some extent on the particular feed
being treated. The hydrotreating zone of the reactor is suitably at a temperature
of about 650 to 780°F, preferably 675 to 750°F and at a pressure of 800 to 4000 psig,
preferably 1500 to 2500 psig. The hydrogen treat gas rate is 1500 to 10,000 SCF/B,
preferably 2500 to 5000 SCF/B. The space velocity or holding time (WHSV, lb/lb of
catalyst-hr) is suitably 0.2 to 5.0, preferably 0.5 to 2.0.
[0029] The reactivating zone is suitably maintained at a temperature of about 650 to 780°F,
preferably 675 to 750°F, and a pressure of about 800 to 4000 psig, preferably 1500
to 2500. The strip rate (SCF/ lb catalyst-hr) is suitably about 0.03 to 7, preferably
0.15 to 1.5.
EXAMPLE 1
[0030] To illustrate a slurry hydrotreating process, according to the first step of the
present invention, the following experiment was conducted. A commercial hydrotreating
catalyst, KF-840, was crushed and screened to 32/42 mesh size. Catalyst properties
are shown in Table I. This crushed catalyst was then sulfided overnight using a 10%
H₂S in H₂ gas blend. A 10.3 gram sample of the presulfided catalyst was added to a
300 cc stirred autoclave reactor along with 100 cc's of a heavy feed blend comprised
of heavy vacuum gas oils, heavy coker gas oils, coker bottoms and heavy cat cracked
cycle oil. Properties of the feed are listed in Table II.
Table I
Catalyst Properties |
NiO, Wt% |
3.8 |
MoO₃, Wt% |
19.1 |
P₂O₅, Wt% |
6.4 |
Surface Area, m²/gm |
175 |
Pore/volume, cm³/gm |
0.38 |
Table II
Feedstock Properties |
Sulfur, Wt% |
1.63 |
Nitrogen, Wt% |
0.39 |
Carbon, Wt% |
87.63 |
Hydrogen, Wt% |
9.60 |
Gravity, °API |
9.2 |
Wt% Aromatics by HPLC |
|
Saturates |
26 |
1 Ring |
9 |
2 Ring |
10 |
3+ Ring |
43 |
Polar Aromatics |
12 |
GC Distillation, °F |
|
5% |
665 |
20% |
753 |
50% |
882 |
80% |
1004 |
95% |
1150 |
[0031] The autoclave was heated to 720°F under 1200 psig hydrogen pressure. The autoclave
was operated in a gas flow thru mode so that hydrogen treat gas was added continuously
while gaseous products were taken off. Hydrogen was added over the course of the run
so that the initial hydrogen charge plus make-up hydrogen was equivalent to 3500 SCF/B
of liquid charged to the autoclave. After two hours at reaction conditions, the autoclave
was quenched or cooled quickly to stop reactions. The autoclave reactor was de-pressured
and the catalyst was filtered from the liquid products. These products were then analyzed
to determine the extent of HDS (hydrodesulfurization), HDN (hydrodenitrogenation),
and aromatics hydrogenation. The results are shown in Table III below.
[0032] In another run, at a higher catalyst loading, a 30.9 gram of the same presulfided
catalyst was added to a 300 cc sample stirred autoclave reactor along with 100 cc's
of the same heavy feed blend. The autoclave was run as the same conditions as in the
previous experiment. The results of this run are also shown in Table III.
Table III
Slurry Catalyst Loading and Product Quality |
Feed Properties |
Fresh, Sulfided Catalyst |
Fresh, Sulfided Catalyst |
Slurry Catalyst Loading Wt% Catalyst on FF. |
0 |
10.5 |
31.5 |
Slurry Product Quality |
|
|
|
Wt% Sulfur |
1.63 |
0.32 |
0.10 |
Wt% Nitrogen |
0.39 |
0.22 |
0.093 |
Wt% Sats + 1R AR |
34 |
55 |
66 |
Wt% 3+ R AR & Polars |
55 |
28 |
18 |
Wt% Polar AR |
12 |
4.1 |
1.2 |
[0033] From these results, it can be concluded that the fresh catalyst slurry was very effective
for removing organic sulfur and organic nitrogen compounds from the heavy feed blend.
With only 10% catalyst on fresh feed (FF), only 20% of the organic sulfur, 55% of
the organic nitrogen, and half the 3+ ring aromatics contained in the raw feed remained.
Only a third of the heaviest, polar aromatic compounds remained. With a higher catalyst
loading, 31% on fresh feed, even higher levels of contaminant removal were obtained.
Only 6% of the organic sulfur, a fourth of the organic nitrogen, and a third of the
heavy aromatics remained. Polar aromatics were reduced to 10% of the feed value.
EXAMPLE 2
[0034] To illustrate the second step of the invention, involving hydrogen catalyst reactivation,
the following experiment was conducted. Catalyst discharged from an autoclave experiment
at the same conditions of the first two runs of Example 1 was stripped with an H₂S/H₂
blend for 18 hours at 650°F. After hydrogen stripping, the catalyst discharged from
the first autoclave pass was laden with 3.6% "coke" or adsorbed hydrocarbons. A 32.0
gm sample of this coke laden catalyst, containing 30.9 gms of the NiMo/alumina catalyst
was charged to a 300 cc autoclave with 100 cc's of the same feed used in Experiment
1. The autoclave was run at the same conditions as Experiment 1. The catalyst was
filtered from the products and hydrogen stripped again for use in a subsequent run.
This procedure was repeated until the product analyses had leveled off. Product analyses
are shown in Table IV.
[0035] Catalyst discharged from an autoclave run at the same conditions as in Experiment
1 was filtered and charged to the autoclave with the same feed as the previous runs.
The same filtered catalyst was recycled in the autoclave several times in order to
line out catalyst performance. The results of these runs are shown below.
Table IV
Slurry Catalyst Loading and Product Quality |
Recycled, Hydrogen Stripped Catalyst |
Recycled, Filtered Catalyst |
Slurry Catalyst Loading Wt% Catalyst on FF |
31.5 |
31.5 |
Slurry Product Quality |
|
|
Wt% Sulfur |
0.10 |
0.12 |
Wt% Nitrogen |
0.093 |
0.18 |
Wt% Sats + 1R AR |
64 |
61 |
Wt% 3+ R AR & Polars |
18 |
23 |
Wt% Polar AR |
1.2 |
2.7 |
[0036] From the above results, it can be concluded that the recycled catalyst was still
highly active for nitrogen and sulfur removal, as well as aromatics hydrogenation.
Although, catalyst activity for HDN and heavy aromatics removal were diminished somewhat,
hydrogen stripping restored catalyst to nearly fresh activity.
EXAMPLE 3
[0037] To further illustrate a hydrogen stripping catalyst reactivation process, the following
experiment was conducted. Another lot of the same commercial catalyst used in the
previous experiments was used in a fixed bed reactor for several hundred hours on
oil. Prior to discharging, the catalyst was stripped with hydrogen at 700°F for several
hours. After the catalyst was discharged from a fixed bed reactor, a portion of it
was crushed and screened to 32/42 mesh size. This catalyst was laden with 21.2% coke
or adsorbed hydrocarbons. A 39.2 gram sample of this coked catalyst, containing 30.9
grams of NiMo/alumina catalyst, was charged to the autoclave with the same feed as
the previous examples. The catalyst was filtered from the products and recycled in
an autoclave run several times in order to line-out catalyst performance. The results
of these runs with the hydrogen stripped, aged catalyst and the filtered, aged catalyst
are shown in Table IV.
Table IV
Slurry Catalyst Loading and Product Quality |
Hydrogen Stripped, Aged Catalyst |
Recycled, Filtered, Aged Catalyst |
Slurry Catalyst Loading Wt% Catalyst on FF |
31.5 |
31.5 |
Slurry Product Quality |
|
|
Wt% Sulfur |
0.20 |
0.25 |
Wt% Nitrogen |
0.14 |
0.27 |
Wt% Sats + 1R AR |
62 |
56 |
Wt% 3+ R AR & Polars |
25 |
29 |
Wt% Polar AR |
3.6 |
5.2 |
[0038] From the above results, it can be concluded that although the hydrogen stripped catalyst
was less active than fresh, it was substantially more active than the catalyst which
was recycled without hydrogen stripping. On the other hand, without hydrogen stripping,
the aged catalyst lost much of its activity.
[0039] The process of the invention has been described generally and by way of example
with reference to particular embodiments for purposes of clarity and illustration
only. It will be apparent to those skilled in the art from the foregoing that various
modifications of the process illustrated herein can be made without departure from
the spirit and scope of the invention.
[0040] US 414,175 (United States' patent application serial number 414,175) referred to
herein corresponds with European patent application No. entitled "Slurry Hydroprocessing
Staged Process" filed on or about the same date as the present patent application
and which describes and claims a process for the hydrotreating of a hydrocarbonaceous
material to improve the quality of the hydrotreated product for use as a feed to a
catalytic cracking unit, comprising:
(1) contacting the hydrocarbonaceous material feed with hydrogen in a relatively high
temperature first hydrotreating zone in the presence of a hydrotreating catalyst slurry
such that substantial hydrodenitrogenation and aromatics saturation of the feed is
carried out, and wherein multi-ring aromatics are saturated in preference to either
single-ring aromatics or saturates;
(2) contacting the effluent from the first hydrotreating zone in the presence of
a hydrotreating catalyst slurry with further hydrogen in a relatively low temperature
second hydrotreating zone; and
(3) separating catalyst and a gaseous mixture comprising hydrogen from the product
of the second hydrotreating zone to yield a hydrotreated product.
1. A process for hydrotreating a heavy fossil fuel to hydrogenate heavy aromatics
and remove sulfur, the process comprising:
reacting the heavy fossil fuel in a hydrotreating zone with hydrogen in the presence
of a non-noble metal containing hydrotreating catalyst;
separating the catalyst from the product of the hydrotreating zone;
reactivating the catalyst in a reactivating zone, separate from the hydrotreating
zone, by hydrogen stripping; and
recycling the reactivated catalyst to the hydrotreating zone.
2. The process of claim 1 wherein the reactivating zone is at a temperature of from
about 650 to 780°F (343.3 to 415.6°C) and a pressure of from about 800 to 4000 psig
(5.516 to 275.8 MPa) e.g., from 1500 to 2500 psig (10.343 to 17.238 MPa).
3. The process of claim 1 or claim 2 wherein the hydrotreating zone is at a temperature
of from about 650 to 780°F (343.3 to 415.6°C) and a pressure of from about 800 to
4000 psig (5.516 to 275.8 MPa).
4. The process of any one of claims 1 to 3 wherein the heavy fossil fuel is a product
of a petroleum, coal, shale oil, bitumen, tar sand, or synfuel conversion process,
and may be selected from a heavy catalytic cracking cycle oil, coker gas oil, or vacuum
gas oil.
5. The process of any one of claims 1 to 4 wherein the heavy fossil fuel is distilled
in the range of from 500 to 120°F (260 to 648.9°C).
6. The process of any one of claims 1 to 5 wherein the reaction of the fuel with hydrogen
is effected in a plurality of staged hydrotreating zones.
7. The process of any one of claims 1 to 6 wherein the catalyst is comprised of molybdenum
sulfide, and the catalyst may further comprise nickel and/or cobalt.
8. The process of any one of claims 1 to 7 wherein the catalyst is supported on an
inorganic oxide material, and wherein the inorganic oxide material may be selected
from a group consisting of alumina, silica, titania, silica-alumina, silica-magnesia,
and mixtures thereof.
9. The process of any one of claims 1 to 8 wherein the average diameter of the catalyst
particles is in the range of from 10 µm to 1/8 inch (3.175 mm), e.g., from 10 to 400
µm.
10. The process of any one of claims 1 to 9 wherein the surface area of the catalyst
is in the range of from 80 to 400 m²/g.
11. The process of any one of claims 1 to 10 wherein the stripping rate is 0.15 to
7 SCF/lb cat-hr (9.364 to 436.975 liter hydrogen-containing strip gas per kg catalyst
per hour).
12. The process of any one of claims 1 to 11 wherein catalyst is circulated at a rate
of 0.1 to 0.3 kg of reactivated catalyst per kg of feed.
13. The process of any one of claims 1 to 12 where in the catalyst is reactivated
by hydrogen-stripping in a cyclic, continuous process.