Note: Descriptions are shown in the official language in which they were submitted.
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A PROCESS FOR PRESULPHIDING HYDROCARBON
CONVERSION CATALYSTS
This invention relates to a process for
" presulphurizing or presulphiding hydrocarbon conversion
catalysts, presulphurized catalysts and their use in
hydrocarbon conversion processes.
It is well known that it is often desirable to employ
the step of "presulphiding" or "presulphurizing" of the
metals forming part of the composition of certain
catalysts for refining and/or hydroconverting
hydrocarbons, either before they are used initially,
i.e., fresh catalysts, or before they are re-used
following regeneration. Hydrocarbon conversion
catalysts, such as hydrotreating, hydrocracking and tail-
gas treating catalysts are typically subjected to such a
"presulphiding step".
A hydrotreating catalyst may be defined as any
catalyst composition which may be employed to catalyze
the hydrogenation of hydrocarbon feedstocks, and most
particularly to hydrogenate particular components of the
feed stock, such as sulphur-, nitrogen- and metals-
containing organo-compounds and unsaturates. A
hydrocracking catalyst may be defined as any catalyst
composition which may be employed to crack large and
complex petroleum derived molecules to attain smaller
molecules with the concomitant addition of hydrogen to
the molecules. A tail gas catalyst may be defined as any
catalyst composition which may be employed to catalyze
the conversion of hazardous effluent gas streams to less
harmful products, and most particularly to convert oxides
of sulphur to hydrogen sulphide which can be recovered
and readily converted to elemental sulphur. A reduced
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catalyst may be defined as any catalyst composition that
contains a metal in the reduced state such as, for
example, an olefin hydrogenation catalyst. Such metals
are typically reduced with a reducing agent such as, for
example, hydrogen or formic acid. The metals on these
reduced catalysts may be fully reduced or partially
reduced.
Catalyst compositions for hydrogenation catalysts are
well known and several are commercially available.
Typically, the active phase of the catalyst is based on
at least one metal of group VIII, VIB, IVB, IIB or IB of
the Periodic Table of the Elements. In general, the
hydrogenation catalysts contain at least one element
selected from Pt, Pd, Ru, Ir, Rh, Os, Fe, Co, Ni, Cu, Mo,
W, Ti Hg, Ag or Au supported usually on a support such as
alumina, silica, silica-alumina and carbon.
Catalyst compositions for hydrotreating and/or
hydrocracking or tail gas treating are well known and
several are commercially available. Metal oxide
catalysts which come within this definition include
cobalt-molybdenum, nickel-tungsten, and nickel-molybdenum
supported usually on alumina, silica and silica-alumina,
including zeolite, carriers. Also, other transition
metal element catalysts may be employed for these
purposes. In general, catalysts containing at least one
element selected from V, Cr, Mn, Re, Co, Ni, Cu, Zn, Mo,
W, Rh, Ru, Os, Ir, Pd, Pt, Ag, Au, Cd, Sn, Sb, Bi and Te
have been disclosed as suitable for these purposes.
For maximum effectiveness these metal oxide catalysts
are converted at least in part to metal sulphides. The
metal oxide catalysts can be sulphided in the reactor by
contact at elevated temperatures with hydrogen sulphide
or a sulphur-containing oil or feed stock ("in-situ").
However, it is advantageous to the user to be
supplied with metal oxide catalysts having sulphur, as an
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element or in the form of an organo-sulphur compound,
incorporated therein. These presulphurized catalysts can
be loaded into a reactor and brought up to reaction
conditions in the presence of hydrogen~causing the
sulphur or sulphur compound to react with hydrogen and
the metal oxides thereby converting them into sulphides
without any additional process steps being needed. These
presulphurized catalysts provide an economic advantage to
the plant operator and avoid many of the hazards such as
flammability and toxicity, which the plant operator
encounters when using hydrogen sulphide, liquid
sulphides, organic polysulphides and/or mercaptans to
sulphide the catalysts.
Several methods of presulphurizing metal oxide
catalysts are known. Hydrotreating catalysts have been
presulphurized by incorporating sulphur compounds into a
porous catalyst prior to hydrotreating a hydrocarbon
feedstock. For example, U.S. patent No. 4,530,917
discloses a method of presulphurizing a hydrotreating
catalyst with organic polysulphides. U.S. patent
No. 4,177,136 discloses a method of presulphurizing a
catalyst by treating the catalyst with elemental sulphur.
Hydrogen is then used as a reducing agent to convert the
elemental sulphur to hydrogen sulphide in situ.
U.S. patent No. 4,089,930 discloses the pretreatment of a
catalyst with elemental sulphur in the presence of
hydrogen. U.S. patent No. 4,943,547 discloses a method
of presulphurizing a hydrotreating catalyst by subliming
elemental sulphur into the pores of the catalyst then
heating the sulphur-catalyst mixture to a temperature
above the melting point of sulphur in the presence of
hydrogen. The catalyst is activated with hydrogen.
Published PCT application No. WO 93/02793 discloses a
method of presulphurizing a catalyst where elemental
sulphur is incorporated in a porous catalyst and at the
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same time or subsequently treating the catalyst with a
liquid olefinic hydrocarbon.
However, these ex-situ presulphurized catalysts must
be subjected to a separate activation step prior to
contact with the hydrocarbon feed in a hydrocarbon
processing reactor.
Therefore, it is an object of the present invention
to prepare an activated, presulphurized or presulphided
catalyst, either fresh or regenerated, without the
requirement for a separate activation treatment prior to
contact with the hydrocarbon feed in the reactor.
Therefore, in accordance with the present invention,
there is provided a process for presulphurizing porous
particles of a sulphidable catalyst containing at least
one metal or metal oxide, which comprises
(a) impregnating the catalyst with an inorganic
polysulphide solution to obtain a sulphur-incorporated
catalyst in which at least a portion of the sulphide or
sulphur is incorporated in the pores of the catalyst; and
(b) heating the sulphur-incorporated catalyst in the
presence of a non-oxidizing atmosphere.
The present invention further provides a
presulphurized catalyst obtainable by a process according
to the invention.
As used in this specification, the term "inorganic
polysulphide" refers to polysulphide ions having the
general formula S(x)2- where x is an integer greater
than 2, i.e. x is an integer having a value of at
least 3, preferably from 3 to 9, and more preferably from
3 to 5, and the "inorganic" terminology, in this context
refers to the nature of the polysulphide moiety rather
than to the counterion, which may be organic. As used
herein, the term "inorganic polysulphide solution" refers
to a solution containing inorganic polysulphides. As
used in this specification, the terms "metal(s)-", "metal
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oxide(s)-" and "metal sulphide(s)-" containing catalysts
include catalyst precursors that are subsequently used as
actual catalysts. Further, the term "metal(s)" includes
metals) in partially oxidized form. The term "metal
oxide(s)" includes metal oxides) in partially reduced
form. The term "metal sulphide(s)" includes metal
sulphides) that are partially sulphided as well as
totally sulphided metals. The above terms include in
part other components such as carbides, borides,
nitrides, oxyhalides, alkoxides and alcoholates.
In the present invention, a presulphidable metal- or
metal oxide-containing catalyst is impregnated with an
inorganic polysulphide solution to presulphurize the
presulphidable metal or metal oxide catalyst at a
temperature and for a time effective to cause
incorporation of the sulphide or sulphur into the pores
of the catalyst. The catalyst is heated following
impregnation under non-oxidizing conditions for a time
sufficient to fix the incorporated sulphide or sulphur
onto the catalyst.
The catalysts referred to herein as "sulphidable
metal oxide catalyst(s)" can be catalyst precursors that
are used as actual catalysts while in the sulphided form
and not in the oxide form. Since the preparative
technique of the instant invention can be applied to
regenerated catalysts which may have the metal sulphide
not completely converted to the oxides, "sulphidable
metal oxide catalyst(s)" also refers to these catalysts
which have part of their metals in the sulphided state.
In a preferred embodiment, prior to impregnation with
the inorganic polysulphide solution, the metal or metal
oxide catalyst particles or pellets are hydrated to
equilibrium with air in order to reduce the initial
exotherm.
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In carrying out the process of the present invention,
porous catalyst particles are contacted and reacted with
an inorganic polysulphide solution under conditions which
cause the sulphide or sulphur compounds to be
incorporated into the pores of the catalyst by
impregnation. The inorganic polysulphide-incorporated or
sulphur compound-incorporated catalysts will be referred
to as "sulphur-incorporated catalysts".
The inorganic polysulphide solution is typically
prepared by dissolving elemental sulphur in an aqueous
ammonium {or ammonium derivative, i.e., tetramethyl
ammonium, tetraethyl ammonium, etc.) sulphide solution.
Preferred polysulphides include inorganic polysulphides
of general formula S{x)2- wherein x is an integer greater
than 2, preferably from 3 to 9 and more preferably from 3
to 5, such as, for example, S{3)2-, S{4)2-, S{5)2-
S{6)2- and mixtures thereof.
The inorganic polysulphide solution is a red solution
in which a dark colouring denotes a long chain
polysulphide and a lighter colouring denotes a shorter
chain polysulphide. The inorganic polysulphide solution
thus prepared is used to impregnate the catalyst
particles using a pore volume impregnation method or by
incipient wetness such that the pores of the catalyst are
filled without exceeding the volume of the catalyst. The
amounts of sulphur used in the instant process will
depend upon the amounts of catalytic metal present in the
catalyst that needs to be converted to the sulphide. For
example, a catalyst containing molybdenum would require
two moles of sulphur or mono-sulphur compounds to convert
each mole of molybdenum to molybdenum disulphide, with
similar determinations being made for other metals. On
regenerated catalysts, existing sulphur levels may be
factored into the calculations for the amounts of sulphur
required.
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The amount of sulphur typically present in the
inorganic polysulphide solution in the present process is
in the range of from 5 percent by weight to 50 percent by
weight, based on the total weight of the solution.
Higher concentrations of sulphur can be obtained by
increasing the concentration of the starting ammonium
sulphide solution. The inorganic polysulphide solution
will generally have a ratio of sulphur to sulphide by
weight in the range from 2:1 to 5:1, and preferably in
the range from 2:1 to 3:1. The amount of sulphur in the
inorganic polysulphide solution is generally such that
the amount of sulphur impregnated onto the catalyst
particles is typically an amount sufficient to provide
for stoichiometric conversion of the metal components
from the oxide form to the sulphide form and is generally
in the range of from 2 percent by weight to 15 percent by
weight, and preferably from 4 percent by weight to
12 percent by weight, based on the total weight of the
sulphurized catalyst.
It has been found that the addition of
presulphurizing sulphur in amounts down to about 50
percent of the stoichiometric requirement results in
catalysts having adequate hydrodenitrification activity,
which is an important property of hydrotreating and first
stage hydrocracking catalysts. Thus, the amount of
presulphurizing sulphur used for incorporation into the
catalyst will typically be in the range from 0.2 to 1.5
times the stoichiometric amount, and preferably from 0.4
to 1.2 times the stoichiometric amount.
For hydrotreating/hydrocracking and tail gas treating
catalysts containing Group VIB and/or Group VIII metals
the amount of presulphurizing sulphur employed is
typically 1% to 15% by weight of the catalyst charged,
and preferably, the amount of presulphurizing sulphur
employed is 4o to 12% by weight of the catalyst charged.
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The sulphur impregnation step will typically be
carried out at a temperature in the range from 0 °C to
30 °C or higher, up to 60 °C. The lower temperature
limit is fixed by the freezing point of the inorganic
polysulphide solution under the specific conditions of
impregnation, whereas the upper temperature limit is
fixed primarily by decomposition of the inorganic
polysulphide solution to volatile compounds and elemental
sulphur.
Following impregnation of the catalyst particles with
the inorganic polysulphide solution, the sulphur-
incorporated catalyst is subjected to a heat treatment in
the presence of a flowing non-oxidizing gas such as, for
example, nitrogen, carbon dioxide, argon, helium and
mixtures thereof, at a temperature sufficient to drive
out most of the residual pore volume water and to fix the
sulphur on the catalyst. The heat treatment of the
sulphur-incorporated catalyst is preferably carried out
using a ramped temperature procedure in which the
sulphur-incorporated catalyst is first heated to a
temperature in the range of from 50 °C to 150 °C,
preferably 120 °C, to drive out most of the pore volume
water. The catalyst is then ramped to a final hold
temperature in the range of from 120 °C to 400 °C, and
preferably from 230 °C to 350 °C, to fix the incorporated
sulphur onto the catalyst. Following this heat
treatment, the catalyst is cooled to room (ambient)
temperature and rehydrated with a water saturated non-
oxidizing gas. The resulting catalyst is stable to
handling in air.
The presulphurized or presulphided catalyst of the
instant invention is then loaded into, for example, a
hydrotreating and/or hydrocracking reactor or tail gas
reactor, the reactor is heated up to operating (e. g.
hydrotreating and/or hydrocracking or tail gas treating)
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conditions, and the catalyst is then immediately
contacted with a hydrocarbonaceous feedstock, without the
need for an extended activation of the catalyst with
hydrogen prior to contact of the catalyst with the
hydrocarbonaceous feedstock. While not wishing to be
bound by any particular theory, it is believed that the
extended activation period with hydrogen generally
required for ex-situ presulphided catalysts is not
necessary for catalysts presulphided according to the
present invention because, in the present process, most
of the sulphur has already reacted with the metal or
metal oxides to form metal sulphides, or alternatively,
the sulphur is fixed in the pores of the catalyst to such
an extent that it does not leave the pores of the
catalyst prior to being converted to the sulphide.
The process of the present invention is further
applicable to the sulphurizing of spent catalysts which
have been oxy-regenerated. After a conventional oxy-
regeneration process, an oxy-regenerated catalyst may be
presulphurized as would fresh catalyst in the manner set
forth above.
The present process is particularly suitable for
application to hydrotreating and/or hydrocracking or tail
gas treating catalysts. These catalysts typically
comprise Group VIB and/or Group VIII metals supported on
porous supports such as alumina, silica, silica-alumina
and zeolites. The materials are well defined in the art
and can be prepared by techniques described therein, such
as in U.S. patent No. 4,530,911 and U.S. patent
No. 4,520,128. Preferred hydrotreating and/or
hydrocracking or tail gas treating catalysts will contain
a group VIB metal selected from molybdenum, tungsten and
mixtures thereof and a Group VIII metal selected from
nickel, cobalt and mixtures thereof supported on alumina.
Versatile hydrotreating and/or hydrocracking catalysts
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which show good activity under various reactor conditions
are alumina-supported nickel-molybdenum and cobalt-
molybdenum catalysts. Phosphorus is sometimes added as a
promoter. A versatile tail gas treating catalyst which
shows good activity under various reactor conditions is
an alumina-supported cobalt-molybdenum catalyst.
The ex-situ presulphurization method of this
invention allows the hydrotreating, hydrocracking and/or
tail gas treating reactors to be started up more quickly
by providing for immediate contact with the
hydrocarbonaceous feedstock in the reactor and
eliminating the extended activation step with hydrogen
which is necessary for conventional ex-situ
presulphurized catalysts.
Thus, the present invention further provides a
process for converting a hydrocarbonaceous feedstock
(i.e., a hydrocarbon conversion process) which comprises
contacting the feedstock with hydrogen at elevated
temperature in the presence of a presulphurized catalyst
according to the invention.
Hydrotreating conditions comprise temperatures in the
range from 100 °C to 425 °C and pressures above
40 atmospheres (4.05 MPa). The total pressure will
typically be in the range from 400 to 2500 psig (2.76 to
17.23 MPa). The hydrogen partial pressure will typically
be in the range from 200 to 2200 psig (1.38 to
15.17 MPa). The hydrogen feed rate will typically be in
the range from 200 to 10,000 standard cubic feet per
barrel ("SCF/BBL"). The feedstock rate will typically
have a liquid hourly space velocity ("LHSV") in the range
from 0.1 to 15.
Hydrocracking conditions comprise temperatures in the
range from 200 °C to 500 °C and pressures above
atmospheres (4.05 MPa). The total pressure will
35 typically be in the range from 400 to 3000 psig (2.76 to
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20.68 MPa). The hydrogen partial pressure will typically
be in the range from 300 to 2600 psig (2.07 to
17.93 MPa). The hydrogen feed rate will typically be in
the range from 1000 to 10,000 standard cubic feet per
barrel ("SCF/BBL"). The feedstock rate will typically
have a liquid hourly space velocity ("LHSV") in the range
from 0.1 to 15. First stage hydrocrackers, which carry
out considerable hydrotreating of the feedstock may
operate at higher temperatures than hydrotreaters and at
lower temperatures than second stage hydrocrackers.
The hydrocarbonaceous feedstocks to be hydrotreated
or hydrocracked in the present process can vary within a
wide boiling range. They include lighter fractions such
as kerosine fractions as well as heavier fractions such
as gas oils, coker gas oils, vacuum gas oils, deasphalted
oils, long and short residues, catalytically cracked
cycle oils, thermally or catalytically cracked gas oils,
and syncrudes, optionally originating from tar sands,
shale oils, residue upgrading processes or biomass.
Combinations of various hydrocarbon oils may also be
employed.
Tail gas treatment reactors typically operate at
temperatures in the range from 200 °C to 400 °C and at
atmospheric pressure (101.3 kPa). About 0.5-5% vol. of
the tail gas fed to the reactor will comprise hydrogen.
Standard gaseous hourly space velocities of the tail gas
through the reactor are in the range from 500 to
10,000 hr-1. There are several ways the subject catalysts
can be started up in a tail gas treatment reactor. Claus
unit feed or tail gas can be used to start up the subject
catalysts. Supplemental hydrogen, as required, may be
provided by a gas burner operating at a substoichiometric
ratio in order to produce hydrogen.
The invention will be described by the following
examples which are provided for illustrative purposes.
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Prena_rat; on of Tnoraani ~ pol ~r~ml rah; r3~ ~r,~ "t; .,r
An inorganic polysulphide solution for use in the
following examples was prepared by adding 42 grams of
elemental sulphur to a vigorously stirred solution of
ammonium sulphide (150 millilitres, 22 %wt.). The
elemental sulphur immediately began to dissolve and the
resulting solution became red-orange. The mixture was
stirred until all of the sulphur was dissolved. The
actual sulphur content of the solution was 30 %wt, and
the sulphur to sulphide weight ratio in the solution was
3Ø
example 1
A commercial hydrotreating catalyst having the
properties listed below was used to prepare the
presulphurized catalysts.
Table A: Catalyst Properties
Nickel 3.0 owt
Molybdenum 13.0 owt
Phosphorus 3.5 %wt
Support gamma alumina
Surface Area, m2/g 162
Water Pore Vol., cc/g 0.47
Size 1/16 inch trilobes
A 50 gram sample of the above catalyst was hydrated
to equilibrium with air. The hydrated catalyst was then
impregnated with 28.0 millilitres of the above inorganic
polysulphide solution. This solution was added dropwise
to an agitated bed of catalyst pellets contained in a
nitrogen purged (0.5 litres/minute) three hundred
millilitre 3N round bottomed flask, using a syringe pump
apparatus. The stand on which the round bottomed flask
was attached was vibrated using an FMC vibrating table,
with the amplitude of vibration set so as to create a
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tumbling bed of catalyst pellets. The resulting black
pellets were then heated from room temperature to 121 °C
(250 °F) for one hour. The catalyst was then ramped to
the final hold temperature of 260 °C (500 °F) and held
for one hour. The final sulphur level was 9.3% by weight
of the total catalyst. The sulphur content of the
catalyst was analyzed using LECO corporation SC-
432 carbon-sulphur analyzer. The properties of the
catalyst are listed in Table 1 below.
COn'~a_ra_t i vP Example A
The commercial hydrotreating catalyst described in
Example 1 above was subjected to the following in-situ
sulphiding procedure.
A sample of the catalyst was crushed and sieved to
15-45 mesh, loaded into a testing unit having a set
pressure of sulphiding gas (5% H2S/95% H2) of
1 atmosphere and a flow rate 45 litres/hour. The
temperature was then ramped from room temperature up to
204 °C at 0.5 °C per minute and held at that temperature
for two hours. The temperature was then increased to
371 °C at a rate of 0.5 °C per minute and held at that
temperature for one hour and then cooled to room
temperature. Thereafter, the unit was switched to a pure
hydrogen flow and target rates and pressures established,
and then hydrocarbon feed was introduced. The final
sulphur level was 8.8o by weight of the total catalyst.
The sulphur content of the catalyst was analyzed using
LECO corporation SC-432 carbon-sulphur analyzer. The
properties of the catalyst are listed in Table 1 below.
Cata first Testing
The catalyst sulphided in Example 1 above was used to
hydrotreat a catalytically-cracked heavy gas oil (CCHGO)
in a trickle-flow reactor. A sample of the catalyst was
crushed and sieved to a 16-45 mesh, diluted with silicon
carbide and loaded into a trickle-flow reactor tube. The
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reactor tube was pressured to 1100 psig (7.6 MPa) with
hydrogen at a flow rate of 45 litres per hour. The
reactor was then heated to 93 °C and a CCHGO feed was
passed over the catalyst at a liquid hourly space
velocity (LHSV) of 1.5. The temperature was ramped at a
rate of 0.5 °C per hour up to 332 °C and then held for a
period of sixty hours. Samples were then collected and
analyzed to determine the hydrogenation,
hydrodenitrification and hydrodesulphurization
activities. Rate constants are reported relative to
Comparative Example A.
Comparative Example A was tested in a manner similar
to Example 1 above, except that since the catalyst was
sulphided by an in-situ sulphiding method, the catalyst
was not unloaded from the reactor following sulphiding.
The results are presented in Table 1 below.
As can be seen in Table 1, a presulphiding method
according to the invention which utilizes an inorganic
polysulphide solution is an effective means for
incorporating sulphur into a hydrotreating catalyst
(Example 1).
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Table 1
Heat
Sulphur Temp wt% Sulphur
Ex. # Source °C Sulphur Reten.l Hydro2 HDS2 HDN2
1 In- 121 9.3 90% 0.89 0.72 0.86
organic
Poly-
sulphide
Comp. 5% 371 8.8 NM 1.0 1.0 1.0
Ex. A H2S/H2
NM = Not Measured
1 Reported as o of sulphur remaining relative to
sulphur loaded onto catalyst
2 Relative to H2S/H2 sulphided catalyst
Exa ple 2
Z-763 Ni-W/Ultrastable Y zeolite based hydrocracking
catalyst, available from Zeolyst International Inc., was
presulphurized according to the procedure set forth
below.
A 100 gram sample of the above catalyst was hydrated
to equilibrium with air. The hydrated catalyst was then
impregnated with 23.4 millilitres of the above inorganic
polysulphide solution diluted to the water pore volume of
38.6 millilitres. This solution was added dropwise to an
agitated bed of catalyst pellets contained in a nitrogen
purged (0.5 litres/minute) three hundred millilitre 3N
round bottomed flask, using a syringe pump apparatus.
The stand on which the round bottomed flask was attached
was vibrated using an FMC vibrating table, with the
amplitude of vibration set so as to create a tumbling bed
of catalyst pellets. The resulting black pellets were
then heated from room temperature to 150 °C for one hour.
The catalyst was then ramped to the final hold
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temperature of 343 °C and held for one hour. After
cooling to room temperature, the air sensitive catalyst
was rehydrated with water using a water saturated
nitrogen stream so that the catalyst could be safely
handled in air for reactor loading. The final sulphur
level was 7.480 by weight of the total catalyst. The
sulphur content of the catalyst was analyzed using LECO
corporation SC-432 carbon-sulphur analyzer. The
properties of the catalyst are listed in Table 2 below.
Comparative Example B
The commercial hydrocracking catalyst described in
Example 2 above was subjected to the following in-situ
sulphiding procedure.
A sample of the catalyst was loaded into a testing
unit having a set pressure of sulphiding gas
(5o H2S/95% H2) of 350 psig (2.4 MPa) and a flow rate set
to give a gas hourly space velocity (GHSV) of 1500 (e. g.,
for 40 millilitres of catalyst, the flow rate is 60
litres/hour). The temperature was then ramped from room
temperature up to 150 °C in one-half hour and then from
150 °C to 370 °C over a six hour period. The temperature
was then held at 370 °C for two hours and then lowered to
150 °C. Thereafter, the unit was switched to a pure
hydrogen flow and target rates and pressures established,
and then hydrocarbon feed was introduced. The final
sulphur level was 5.45% by weight of the total catalyst.
The sulphur content of the catalyst was analyzed using
LECO corporation SC-432 carbon-sulphur analyzer.
The properties of the catalyst are listed in Table 2
below.
Cata yst Testing
The catalysts sulphided in Example 2 and Comparative
Example B above were used to hydrocrack a hydrotreated
catalytically-cracked light gas oil in a trickle-flow
reactor. A sample of the catalyst was crushed and sieved
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to a 16-45 mesh, diluted with silicon carbide and loaded
into a trickle-flow reactor tube. The reactor tube was
pressured to 1500 psig (10.34 MPa) with hydrogen. The
reactor was then heated to 150 °C and a hydrotreated
catalytically-cracked light gas oil feed was passed over
the catalyst at a liquid hourly space velocity (LHSV) of
6Ø The hydrogen to feed ratio in the reactor tube was
6500 standard cubic feet per barrel (SCF/BBL). The
temperature was ramped at a rate of 22 °C per day for
four days and at a rate of 6 °C per day for five days up
to a temperature of 260 °C. The temperature was then
adjusted to obtain a target conversion of 12 wt% of
190+ °C in feed. The results are presented in Table 2
below.
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_ 18 _
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SUBSTITUTE SHEET (RULE 26)
CA 02258000 1998-12-09
WO 97/48488 PCT/EP97/03130
_ I9 _
As can be seen in Table 2, the sulphur retention of a
catalyst presulphided according to the invention, in
which an inorganic polysulphide solution is utilized
(Example 2), is 96%, indicating that essentially all of
the sulphur remains on the catalyst after the heating
step. In addition, the hydrocracking activity of the
catalyst in Example 2 is equivalent to that of a
hydrocracking catalyst presulphided using a conventional
in-situ presulphiding method (Comparative Example B).
SUBSTITUTE SHEET (RULE 26)
