U.S. patent application number 17/176252 was filed with the patent office on 2021-06-03 for nickel containing mixed metal-oxide/carbon bulk hydroprocessing catalysts and their application.
The applicant listed for this patent is ALBEMARLE EUROPE SPRL. Invention is credited to JACOB ARIE BERGWERFF, SONA EIJSBOUTS-SPICKOVA, RONALD JAN HUIBERTS, WILHELMUS CLEMENS JOZEF VEERMAN.
Application Number | 20210162378 17/176252 |
Document ID | / |
Family ID | 1000005399947 |
Filed Date | 2021-06-03 |
United States Patent
Application |
20210162378 |
Kind Code |
A1 |
BERGWERFF; JACOB ARIE ; et
al. |
June 3, 2021 |
NICKEL CONTAINING MIXED METAL-OXIDE/CARBON BULK HYDROPROCESSING
CATALYSTS AND THEIR APPLICATION
Abstract
The current invention relates a process for making and using a
bulk catalyst precursor (i.e. no support material is added as such)
comprising Ni and Mo and/or W and an organic component, wherein the
molar ratio of C:(Mo+W) ranges from 1.5 to 10. The bulk catalyst
precursor is prepared from a mixture of metal-precursors with an
organic agent. The organic agent is partly decomposed to form a
mixed metal-oxide/C phase which is in effect the bulk catalyst
precursor. This bulk catalyst precursor (i) is effectively
insoluble in water (ii) does not have any appreciable pore volume
or surface area and (iii) does not contain a (nano)crystalline
metal-oxide phase as characterized by XRD.
Inventors: |
BERGWERFF; JACOB ARIE;
(AMSTERDAM, NL) ; VEERMAN; WILHELMUS CLEMENS JOZEF;
(VOLENDAM, NL) ; HUIBERTS; RONALD JAN; (PURMEREND,
NL) ; EIJSBOUTS-SPICKOVA; SONA; (NIEUWKUIJK,
NL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ALBEMARLE EUROPE SPRL |
Louvain-La-Neuve |
|
BE |
|
|
Family ID: |
1000005399947 |
Appl. No.: |
17/176252 |
Filed: |
February 16, 2021 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
16074628 |
Aug 1, 2018 |
10953389 |
|
|
PCT/EP2017/052122 |
Feb 1, 2017 |
|
|
|
17176252 |
|
|
|
|
62289707 |
Feb 1, 2016 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B01J 31/0202 20130101;
B01J 35/006 20130101; B01J 37/04 20130101; B01J 31/34 20130101;
B01J 37/0236 20130101; B01J 31/04 20130101; B01J 35/1009 20130101;
B01J 23/8885 20130101; B01J 23/888 20130101; B01J 37/20 20130101;
B01J 37/0009 20130101; B01J 35/1014 20130101; B01J 23/883 20130101;
B01J 35/0013 20130101; B01J 35/02 20130101; B01J 37/084 20130101;
B01J 31/2208 20130101; C10G 45/08 20130101; C10G 2300/202 20130101;
B01J 27/0515 20130101; B01J 35/002 20130101 |
International
Class: |
B01J 27/051 20060101
B01J027/051; B01J 35/10 20060101 B01J035/10; B01J 35/00 20060101
B01J035/00; B01J 37/08 20060101 B01J037/08; C10G 45/08 20060101
C10G045/08; B01J 31/02 20060101 B01J031/02; B01J 31/22 20060101
B01J031/22; B01J 37/04 20060101 B01J037/04; B01J 37/00 20060101
B01J037/00; B01J 23/888 20060101 B01J023/888; B01J 31/04 20060101
B01J031/04; B01J 23/883 20060101 B01J023/883; B01J 37/20 20060101
B01J037/20; B01J 35/02 20060101 B01J035/02; B01J 31/34 20060101
B01J031/34 |
Claims
1. A process for hydroprocessing of a hydrocarbon feedstock
comprising sulphur and nitrogen containing organic compounds
comprising the step of contacting the hydrocarbon feedstock with a
NiW, NiMo or NiMoW oxidic bulk catalyst obtained from a NiW, NiMo
or NiMoW bulk catalyst precursor composition comprising nickel
oxide, and molybdenum oxide or tungsten oxide or mixtures thereof,
and an organic component prepared from an organic additive, wherein
the total amount of molybdenum oxide and tungsten oxide is at least
30 wt %, the molar ratio of nickel to molybdenum plus tungsten is
higher than 0.05, the molar ratio of carbon to molybdenum plus
tungsten is between 1.5 and 10; and wherein the organic additive is
selected from Acetic acid, Aspartic acid, Citric acid, Formic acid,
Fumaric acid, Gluconic acid, Glutamic acid, Glyoxylic acid,
Ketoglutaric acid, Maleic acid, Malic acid, Oxaloacetic acid,
Propionic acid, Pyruvic acid, Succinic acid, Fructose, Glucose,
Lactose, Saccharose, Sorbitol, Xylitol, Serine and mixtures thereof
where the bulk catalyst precursor further comprises Ni-crystals
detected by transmission electron microscopy technique (TEM), the
catalyst comprising a minimum metal loading of 2.0 moles of
molybdenum plus tungsten per liter reactor, wherein the molar ratio
of nickel to molybdenum plus tungsten is higher than 0.05, a molar
ratio of carbon to molybdenum plus tungsten between 1.5 and 10.
2. The process of claim 1 wherein the catalyst further comprises a
peak at 45.degree. 2 theta in the XRD pattern recorded using X-ray
radiation with a wavelength of 1.54 .ANG..
3. The process of claim 1 wherein the catalyst further comprises
Ni-crystals detected by transmission electron microscopy technique
(TEM).
4. The process according to claim 1 wherein the catalyst comprises
an inorganic binder comprising silica, silica-alumina, alumina,
titania, titania-coated alumina, zirconia, bentonite, attapulgite,
or mixtures thereof.
5. The process of claim 1 wherein the metal loading of molybdenum
plus tungsten per liter reactor is between 3.0 and 7.0.
6. The process of claim 1 wherein the molar ratio of carbon to
molybdenum plus tungsten between 1.5 and 7.0.
7. The process of claim 1 wherein the molar ratio of nickel to
molybdenum plus tungsten is between 0.10 and 1.05.
8. The process of claim 1 wherein the molar ratio of nickel to
molybdenum plus tungsten is between 0.20 and 0.75.
9. A process for the manufacture of a mixed metal oxide organic
phase catalyst precursor, the process comprising: a. forming a
solution in protic liquid of one or more soluble metal compounds
comprising nickel and molybdenum or tungsten or mixtures thereof
and one or more organic compound, wherein the molar ratio of nickel
to molybdenum plus tungsten is higher than 0.05; b. evaporating the
protic liquid; c. partially decomposing the metal-organic phase to
form the mixed metal oxide organic phase catalyst precursor wherein
the molar ratio of carbon to molybdenum plus tungsten is between
1.5 and 10; i. wherein the one or more organic compound is Acetic
acid, Aspartic acid, Citric acid, Formic acid, Fumaric acid,
Gluconic acid, Glutamic acid, Glyoxylic acid, Ketoglutaric acid,
Maleic acid, Malic acid, Oxaloacetic acid, Propionic acid, Pyruvic
acid, Succinic acid, Fructose, Glucose, Lactose, Saccharose,
Sorbitol, Xylitol, Serine and mixtures thereof. wherein the
resulting catalyst precursor is a NiW, NiMo or NiMoW bulk catalyst
precursor composition comprising nickel oxide, and molybdenum oxide
or tungsten oxide or mixtures thereof, and an organic component
prepared from an organic additive, wherein the total amount of
molybdenum oxide and tungsten oxide is at least 30 wt %, the molar
ratio of nickel to molybdenum plus tungsten is higher than 0.05;
wherein the bulk catalyst precursor further comprises Ni-crystals
detected by transmission electron microscopy technique (TEM)
10. The process of claim 9 wherein the one or more organic compound
is an organic acid or a sugar.
11. A process for the manufacture of a sulphidic catalyst
comprising sulphiding the bulk catalyst of claim 9.
12. The process of claim 9 wherein the shaping of the bulk catalyst
precursor comprises forming an extrudate with an inorganic binder
and water and then drying the extrudates at a temperature of at
least 120.degree. C.
13. A process for the manufacture of an oxidic catalyst comprising
shaping of the bulk catalyst precursor of claim 9.
Description
REFERENCE TO RELATED APPLICATIONS
[0001] This application is a division of U.S. application Ser. No.
16/074,628, filed on Aug. 1, 2018, which is the National Stage of
International Patent Application No. PCT/EP2017/052122 filed on
Feb. 1, 2017, which in turn claims the benefit of U.S. Provisional
Patent Application No. 62/289,707, filed on Feb. 1, 2016, the
disclosures of which are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] This invention generally relates to a nickel containing bulk
catalyst for hydroprocessing. The catalysts are prepared by a
method wherein reagents containing Group VIII and Group VIB metals,
such as metal salts are mixed with at least one organic acid,
polyol or sugar. The resulting mixture is heat treated and then
sulfided. The catalysts can be used for hydroprocessing,
particularly hydrodesulfurization and hydrodenitrogenation, of
hydrocarbon feedstocks.
BACKGROUND OF THE INVENTION
[0003] The hydroprocessing of hydrocarbon feedstocks generally
encompasses all processes in which a hydrocarbon feedstock is
reacted with hydrogen in the presence of a catalyst and under
hydroprocessing conditions, typically, at elevated temperature and
elevated pressure. The term hydroprocessing includes, but is not
limited to, processes such as hydrogenation, hydrodesulfurization,
hydrodenitrogenation, hydrodemetallization, hydrodearomatization,
hydrodeoxygenation, hydroisomerization, hydrodewaxing,
hydrocracking and mild hydrocracking.
[0004] In general, conventional hydroprocessing catalysts are
composed of a carrier (or support) with a Group VIB metal component
and a Group VIII non-noble metal component deposited thereon. Such
catalysts may be prepared by impregnating a carrier with aqueous
solutions of compounds of the desired metals, followed by one or
more drying and/or calcination steps.
[0005] Alternative techniques for the preparation of the
"supported" catalysts are described in U.S. Pat. No.
4,113,605--where inter alia nickel carbonate is reacted with
MoO.sub.3 to form crystalline nickel molybdate, which is
subsequently mixed and extruded with alumina--and in German Patent
No. DE 3029266, where nickel carbonate is mixed with WO.sub.3 and
the resulting composition is mixed with alumina impregnated with
compounds such as nickel nitrate and ammonium tungstate.
[0006] A significant amount of attention has recently been directed
to the provision of catalysts, which can be applied without a
carrier, generally referred to as bulk catalysts. WO 99/03578
describes a method for the preparation of bulk hydroprocessing
catalysts compositions comprising bulk metal oxide particles having
one Group VIII non-noble metal and two Group VIB metals by reacting
and co-precipitating nickel, molybdenum, and tungsten compounds in
the absence of sulfides.
[0007] WO 00/41810 describes a method for the preparation of a
hydroprocessing catalyst comprising bulk metal oxide particles
wherein one or more Group VIII non-noble metal and two or more
Group VIB metals are reacted in a protic liquid, wherein the metal
compounds are at least partly in the solid state during the
reaction and where eventually a solid comprising a
(nano)crystalline mixed metal oxide phase characterized by a
specific XRD pattern is obtained. It also discloses producing the
hydroprocessing catalyst in a convenient form for use in a
hydroprocessing process by shaping, for example by extrusion, and
by compositing the obtained bulk metal oxide particles with small
quantities of further materials, for example binder material, to
facilitate shaping and to provide mechanical strength to a shaped
catalyst.
[0008] U.S. Pat. No. 7,951,746 Patent describes a method of
preparation of an amorphous bulk catalyst precursor and eventual
catalyst comprising (i) cobalt and molybdenum or tungsten (ii) an
amorphous precursor (iii) having 20-60 wt % of a carbon containing
compound based on an organic complexing acid and (iv) having a
surface area of 16 m.sup.2/g or less.
[0009] U.S. Pat. No. 6,566,296 claims a process for preparing a
catalyst composition by combining a group VIII non-noble metal
component and a least two group VIB metal components and an organic
additive at any stage in the preparation. The molar ratio of the
organic additive to the total amount of group VIII and group VIB
components is at least 0.01. Examples describe the preparation of a
NiMoW oxidic catalyst with di-ethyleneglycol added during the
shaping of the catalyst or by post-impregnation. Again, a solid
catalyst is obtained comprising a (nano)crystalline mixed metal
oxide phase as characterized by the presence of specific peaks in
its XRD pattern.
[0010] Although the bulk catalyst compositions described above have
an excellent hydroprocessing activity, there exists a continuous
need in the art to develop novel bulk catalyst compositions with
further improved hydroprocessing activity, in particular, in
hydrodesulfurisation (HDS), as well as hydrodenitrogenation (HDN),
and hydrogenation of particular target hydrocarbon feedstocks, such
as diesel and vacuum gas oil (VGO).
SUMMARY OF THE INVENTION
[0011] Accordingly, one aspect of the current invention is a bulk
catalyst precursor (i.e. no support material is added as such)
comprising Ni and Mo and/or W and an organic component, wherein the
molar ratio of C:(Mo+W) ranges from 1.5 to 10. The bulk catalyst
precursor is prepared from a mixture of metal-precursors with an
organic agent. The organic agent is partly decomposed to form a
mixed metal-oxide/C phase which is in effect the bulk catalyst
precursor. This bulk catalyst precursor (i) is effectively
insoluble in water (ii) does not have any appreciable pore volume
or surface area and (iii) does not contain a (nano)crystalline
metal-oxide phase as characterized by XRD. A bulk catalyst is made
from the bulk catalyst precursor. After conventional liquid phase
sulfidation, the active sufidic bulk catalyst is formed which has a
very high activity in different hydroprocessing applications. After
sulfidation of the oxidic catalyst, it is possible that the
sulfidic catalyst (i) shows surface area as measured via N.sub.2
physisorption and hexane adsorption (ii) loses some of its C during
sulfidation.
[0012] In one embodiment it is disclosed a bulk catalyst precursor
composition comprising Nickel, Molybdenum and/or Tungsten, and an
organic component, wherein the amount of molybdenum oxide plus
tungsten oxide is at least 30 wt %, wherein the molar ratio of
C:(Mo+W) ranges from 1.5 to 10. The ratio of Ni:(Mo+W) is at least
0.05.
[0013] In another embodiment, a bulk catalyst is provided that is
obtained by shaping the bulk catalyst precursor by any method known
in the art, such as extrusion, pelletizing, and/or beading. The
bulk catalyst is characterized by a minimum metal loading of 2.0
moles of molybdenum plus tungsten per liter reactor, wherein the
molar ratio of nickel to molybdenum plus tungsten is higher than
0.05 and the molar ratio of carbon to molybdenum plus tungsten is
between 1.5 and 10. The MoO.sub.3+WO.sub.3 loading of this bulk
catalyst is higher than what is typically applied in supported
hydroprocessing catalysts. In another embodiment, a sulfided
catalyst is provided that is formed by sulfiding the above bulk
catalyst composition.
[0014] In another embodiment, the method for preparing a bulk
catalyst precursor is disclosed. The method includes combining at
least one Ni compound and at least one Group VIB metal compound
with at least one organic agent, thereby forming a solution. The
solution is then evaporated and dried. The drying can be carried
out by using commonly available drying methods such as
spray-drying, freeze drying, or plate drying, etc. The dried
material is then subjected to a further heat treatment at about
300.degree. C. to about 500.degree. C. to form a bulk catalyst
precursor, which can be shaped by any method known in the art to
obtain a bulk catalyst. The bulk catalyst is then sulfided under
sulfiding conditions to produce a sulfided catalyst.
[0015] In another embodiment, a method for hydroprocessing a
hydrocarbon feedstock is provided. The method includes contacting
said feedstock with a sulfided bulk catalyst, the sulfided bulk
catalyst formed by sulfiding the bulk catalyst as described
above.
[0016] In accordance with another aspect of the invention there is
provided a process for the hydroprocessing of a hydrocarbon
feedstock wherein the feedstock is contacted under hydroprocessing
conditions with the aforementioned bulk catalyst composition. The
bulk catalyst composition according to this invention can be used
in virtually all hydroprocessing processes to treat a plurality of
feedstocks under wide-ranging reaction conditions, including but
not limited to pre-treating a feedstock prior to it being
hydrocracked, pre-treating a feedstock prior to it being
catalytically cracked or treating a feedstock to generate a
transportation fuel with a specific maximum sulphur concentration.
Generally, these reaction conditions comprise a temperature in the
range from about 200.degree. to about 450.degree. C., hydrogen
pressures in the range from about 5 to about 300 Bar, liquid hourly
space velocities (LHSV) in the range from about 0.1 to about 10
h.sup.-1 and H.sub.2/oil ratios in the range from about 50 to about
2000 Nl/l. However, it is preferred to employ the catalyst of the
present invention in the hydroprocessing of, and more particularly,
the hydrodesulfurisation (HDS), hydrodenitrogenation (HDN) and
hydrodearomatization (HDA) of feedstocks comprising a diesel oil or
a vacuum gas oil under conditions at least comprising liquid hourly
space velocities (LHSV) in the range from about 0.1 to about 10
h.sup.-1 and H.sub.2/oil ratios in the range from about 50 to about
2000 Nl/l. The bulk catalyst precursor composition has been found
to show improved hydrodesulfurisation activity in applications
ranging from 30 to 80 bar in treating a host of different
Distillate feed streams. It is fully expected that the bulk
catalyst precursor of the invention will have advantages in other
hydroprocessing application such as the treatment of VGO fractions
and in a broader pressure range as well.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] FIG. 1 XRD patterns of bulk catalyst precursors 1-A to 1-D
according to the invention, Comparative bulk catalyst precursor 1-E
and Comparative bulk catalyst 1-E.
[0018] FIG. 2 TEM image of bulk catalyst precursor 1-A at high
magnification.
[0019] FIG. 3 TEM image of bulk catalyst precursor 1-B at high
magnification.
[0020] FIG. 4 TEM image of bulk catalyst precursor 1-C at high
magnification.
[0021] FIG. 5 XRD patterns of bulk catalyst precursor 2-A according
to the invention and a comparative bulk catalyst precursor 2-B.
[0022] FIG. 6 XRD patterns of bulk catalyst precursor 3-A according
to the invention and a comparative bulk catalyst precursor 3-B.
[0023] FIG. 7 XRD patterns of bulk catalysts 4-A and 4-B according
to the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0024] It has been found that a bulk catalyst precursor (i.e. no
support material is added as such) comprising Ni and Mo and/or W
and an organic phase, wherein the molar ratio of C:(Mo+W) is
between 1.5 and 10, which (i) is effectively insoluble in water
(ii) does not have any appreciable pore volume or surface area and
(iii) does not exhibit the presence of a a (nano)crystalline
metal-oxide phase as evidenced by XRD have many advantages over
corresponding bulk catalysts prepared differently.
[0025] The preparation method described in this patent differs from
the one used for the bulk catalysts in the prior art. The bulk
catalyst precursor is prepared via drying of a NiW, a NiMo or NiMoW
solution containing an organic agent followed by decomposition at
high T resulting in a mostly amorphous NiMo/W--C phase, which
constitutes the bulk catalyst precursor. The bulk catalyst
precursors of the invention are characterized by the absence of a
crystalline metal-oxide phase. As can be derived from the prior
art, a (nano)crystalline metal-oxide phase is generally observed in
bulk catalyst precursors, as evident from the presence of specific
peaks in the XRD patterns of these materials.
[0026] The absence of a support material in bulk catalysts makes
that it is extremely difficult to keep the metal oxide phase
well-dispersed in this type of system. During precipitation or heat
treatment processes, (nano)crystalline metal-oxide phases are
therefore generally formed. Despite the high concentration of
metal-oxides in the bulk catalyst precursors of the invention, such
a crystalline phase is surprisingly absent. It can be envisaged
that in the bulk catalysts precursors of the invention, the
carbonaceous phase that remains after the thermal treatment acts as
a dispersing agent for the metal-oxide phase, resulting in the
prevention of the formation of a crystalline metal-oxide phase.
[0027] Without wanting to be bound to any theory, it can be
speculated that the absence of any crystalline metal-oxide phases
in the oxidic catalyst precursor are indicative of a good
dispersion of the metal-oxide phase, resulting in a catalyst with a
high amount of active sites when the oxidic phase is converted to
the active metal-sulfides. Higher activity is observed for the
newly invented catalyst versus the catalyst prepared via the
methods of the prior art discussed in this case.
[0028] The solid catalyst precursor is obtained by evaporation to
dryness of a solution containing metal-precursors. This allows for
complete flexibility in the catalyst composition: most if not all
metal precursors that are present in the solution end up in the
bulk catalyst precursor. In precipitation of a certain metal-oxide
phase, which is generally done in preparation of other bulk
catalysts known in the prior art, on the other hand, the
composition is defined by the stoichiometry of that insoluble
phase. For example, the Ni:(Mo+W) ratio of the catalyst can be
readily adjusted in the catalysts of the invention. In general a
Ni:(Mo+W) ratio between 0.20 and 0.75 is applied in hydroprocessing
applications, as the amount of Ni is sufficient for the formation
of MoS.sub.2 and/or WS.sub.2 crystallites that are completely
decorated with Ni-atoms that act as a promotor of the active phase.
However, in some cases a lower ratio may be preferred as this
results in lower costs. A higher Ni:(Mo+W) ratio than 0.75 would
generally result in the formation of a separate Ni-sulfide phase in
the final catalyst, which is applied in certain cases where the
functionality of the Ni-sulfide phases is desired.
[0029] Avoiding a precipitation process removes the need to deal
with a metal-contaminated solvent after filtration. For commercial
production of catalysts, this is not a trivial advantage.
[0030] It was found that for bulk catalysts prepared with the
process described below, formation of metallic Ni-crystals can be
observed in the mixed metal-oxide/C phase that forms the bulk
catalyst precursor upon heat treatment using X-ray Diffraction
(XRD) or transmission electron microscopy (TEM). Characteristic
peaks of Ni(0) may be observed in the XRD pattern of the bulk
catalyst precursor at 45.degree. and 52.degree. 2theta which are
indicative of the presence of metallic Ni(0) crystals. It cannot be
excluded that C is present, dissolved in the Ni lattice, as the
formation of such a NiC.sub.x phase does not result in a markedly
different XRD pattern. For sake of simplicity, in the following,
the Ni(0) or NiC.sub.x crystals will be referred to as Ni-crystals.
As a result of the formation of Ni-crystals in the bulk catalyst
precursor, Ni-sulfide crystals will be present in the sulfided
catalyst. These Ni-crystals are formed under the conditions that
are present during heat treatment at a temperature >350.degree.
C. as a step in the preparation of the catalyst precursor. The
decomposition of the organics during heat treatment results in a
reductive environment, which together with the temperature leads to
the reduction of the Ni-oxide phase and the formation of the
Ni-crystals. Although the resulting bulk catalyst precursor does
not contain any crystalline metal-oxide phase, it may therefore not
be completely amorphous. In the XRD pattern of bulk catalyst
precursors of the invention calcined at a temperature
>350.degree. C., the presence of a peak at 45.degree. 2theta can
be observed that can be attributed to the presence of Ni-crystals.
A distinguishing feature of this type of catalysts is that when the
Ni-crystals are formed, their particle size distribution is very
well-defined and the crystals are homogeneously distributed
throughout the catalyst precursor phase, as can be observed with
electron microscopy. The characteristic high dispersion of the
Ni-crystals indicates that the carbon matrix that is formed is an
effective dispersing agent for the active phase. In the same way as
the Ni-crystals are kept separated during catalyst preparation, the
mixed Ni(Mo/W)-sulfide crystallites in the active catalyst are
envisaged to remain well dispersed as well.
[0031] At the same time, the NiMo, NiMoW and NiW composition
results in an improved activity even in conditions where normally
CoMo-catalysts are being applied. It is shown that this type of
catalyst can also be made by using a polyol or sugar instead of a
complexing acid.
[0032] The various embodiments relating to these findings are
described below in further detail.
Preparation of the Bulk Catalyst Precursor and Bulk Catalyst
[0033] The general process involves the following steps. First,
intimate mixing of organic agents and metal precursors. Ideally
metal-organic complexes are being formed, but this is not required.
In practice this is achieved by making a solution of
metal-precursors and the organic compounds. The preferred solvent
is water. Second, removal of the solvent that is used in step 1.
This can be done via thermal drying in a static oven, by
spray-drying or in any other device, but also via freeze drying or
vacuum drying. Third, partial decomposition of the metal-organic
phase to form the mixed metal-oxide/carbon phase which constitutes
the bulk catalyst precursor. This is brought about by a thermal
treatment, in practice under inert atmosphere (e.g. nitrogen or
steam), but air may also be used as long as complete combustion of
the organics is prevented. During this treatment the C:O and C:H
ratio of the organic phase will increase and the material will
become more carbonaceous. This could also be brought about by a
chemical reaction, i.e. treatment with e.g. sulphuric acid. Fourth,
shaping of the catalyst precursor to obtain the bulk catalyst. This
can be done via extrusion, pelletizing, beading, compacting or any
other suitable method known in the art. Fifth, sulfidation of the
bulk catalyst to form the sulfidic bulk catalyst. This can be done
in-situ in the reactor or ex-situ by any known method. While the
above lays out the preferred order, other orders of carrying out
the process are envisioned. For example, you can shape the
precursor prior to decomposition and you can also carry out
sulfidation prior to shaping.
[0034] The first step of the process is to create a solution
containing the Group VIII metal, Group VIB metal, and organic
agent. It is preferred that both the Group VIII compound and the
Group VIB compound are added in an appropriate predetermined
concentration to yield the desired molar ratios. It is desired to
have a molar ratio of Ni:(Mo+W) that can vary from 0.05 to 1.05. It
is more preferable to have a Ni:(Mo+W) ratio of 0.10-1.05, in
particular, while a Ni:(Mo+W) of 0.20-0.75 is most preferred. Group
VIII and Group VIB metal reagents and organic agent are mixed with
a protic liquid. The mixture is then often heated and constantly
stirred for about 1 hour until a clear solution is created. The
heating step is only necessary when a reaction of the metal
precursors is required to allow for their dissolution. Although it
is desired to form a clear solution in which all components are
completely dissolved for the sake of having an optimal homogeneity
throughout the catalyst, the presence of a small amount of
unreacted starting materials or a precipitate that is formed after
reaction of the starting materials can still be acceptable.
[0035] The preferred Group VIII metal is Ni. The preferred Group
VIB metals are Mo and W. Non-limiting examples of suitable Ni
precursor compounds include carbonates and acetates and mixtures
thereof, including, nickel carbonate, nickel hydroxy carbonate,
nickel acetate, nickel citrate, nickel hydroxides, nickel oxide,
nickel nitrate, nickel sulphate and mixtures thereof. Preferred
molybdenum and tungsten precursor compounds include Molybdenum
oxide, molybdic acid, ammonium molybdates, phosphomolybdates,
silicomolybdates, Mo-acetylacetonates, Na-molybdates, Tungstic
acid, ammonium tungstates, phosphotungstates, silicotungstates,
Na-tungstates, and mixtures thereof.
[0036] The organics that can be used in the preparation are
carbohydrates (molecules, not necessarily of biological origin that
at least contain C, H and O). The organics can be a mixture of
different molecules. The wt % C in the total of organic molecules
is typically lower than about 50%. The organic molecules contain at
least 2 oxygen atoms. The organic molecules can be introduced as
separate compounds but may also be introduced via the counterion of
the metal-salts. Non-limiting examples of organic additives or
agents suitable for use herein include Acetic acid, Aspartic acid,
Citric acid, Formic acid, Fumaric acid, Gluconic acid, Glutamic
acid, Glyoxylic acid, Ketoglutaric acid, Maleic acid, Malic acid,
Oxaloacetic acid, Propionic acid, Pyruvic acid, Succinic acid,
Fructose, Glucose, Lactose, Saccharose, Sorbitol, Xylitol, Serine
and mixtures thereof. In any event, the organic additive is added
in an amount that results in a molar ratio of C:(Mo+W) of between
1.5 and 10 in the bulk catalyst precursor.
[0037] The solvent can be any solvent which does not interfere with
the reactions of the metal compounds. Examples of solvents include
protic liquids such as water, and alcohols such as methanol,
ethanol or mixtures thereof. Preferred protic liquids are mixtures
of water and other protic liquids, such as mixtures of an alcohol
and water, and a more preferred protic liquid is water alone.
[0038] It will be evident that different protic liquids can be
applied simultaneously in the process. For instance, it is possible
to add a suspension of a metal compound in ethanol to an aqueous
solution of another metal compound. In some cases, a metal compound
can be used which dissolves in its own water of crystallization.
The water of crystallization serves as protic liquid in this
case.
[0039] The second step in the process for preparing the catalysts
is a drying step. The drying step is used to remove water, or any
other solvent that is used in the preparation of the initial
solution, from the mixture. In the drying step, decomposition of
the organic agent generally does not take place. It is within the
scope of this invention that the heating and/or drying can be
performed in multiple steps according to a heating profile. The
heating or drying step can be performed by any known method in the
art. In particular, the drying step can be carried out by
convective drying using hot gas, for instance in a tray dryer or by
spray-drying. Alternatively, drying can be done by contact drying,
for instance using a rotating disc dryer, paddle dryer or a scraped
heat exchanger. Drying via micro-wave heating, freeze-drying or
vacuum drying are other options. Spray-drying typically is carried
out at an outlet temperature in the range of about 100.degree. to
about 200.degree. C. and preferably about 120.degree. to about
180.degree. C.
[0040] The third step in the process for preparing the catalysts is
partial decomposition of the metal-organic phase. The dried
catalyst precursor is subjected to a further heating stage or
calcination step. This additional heating stage can be carried out
at a temperature from about 300.degree. C. to about 500.degree. C.
for an effective amount of time. This effective amount of time will
range from about 1 second to about 24 hours, preferably from about
1 minute to about 5 hours. The heating (including possible
decomposition) can be carried out in the presence of a flowing
oxygen-containing gas such as air, a flowing inert gas such as
nitrogen, or a combination of oxygen-containing and inert gases.
The time, temperature and conditions for this step are selected
such that there is only partial decomposition of the organic
additive. A significant amount of carbon is still present after the
heat treatment step and the C:(Mo+W) atomic ratio in the bulk
catalyst precursor is at least 1.5. The C:O and C:H ratio of the
organic phase formed after the decomposition step is generally
lower than that of the organic agent added in the first step. In
general, it is found that a higher temperature results in a lower
activity of the catalyst. Nevertheless, it can be preferred to
carry out the calcination at a higher T because the obtained
carbonaceous phase formed at higher temperature is more refractory,
has a higher C:O and C:H ratio and is more stable under
hydroprocessing conditions. As explained, Ni-crystals may be formed
during this step in the preparation. Besides metal-oxides and an
ill-defined organic phase, metallic Ni-crystals may be present
after the thermal treatment. Nevertheless, the material that is
formed after the partial decomposition step will be referred to as
a mixed metal oxide/C phase. In practice, the drying and
decomposition steps may be carried out in a single process
step.
[0041] After this step, the bulk catalyst precursor is obtained
which typically has the following compositional properties:
[0042] MoO.sub.3+WO.sub.3 wt % between 30-85 wt %
[0043] Ni:(Mo+W) molar ratio higher than 0.05
[0044] A molar ratio of C:(Mo+W) between 1.5 and 10.
[0045] A BET-SA as measured by N.sub.2 physisorption of <40
m.sup.2/g
[0046] The fourth step in the process for preparing the catalysts
is a shaping step. A bulk catalyst precursor composition, obtained
after heating, can be directly formed into shapes suitable for a
desired catalytic end use to yield the bulk catalyst. Shaping can
also occur prior to the second heating/calcination step. Shaping
comprises extrusion, pelletizing, beading and/or spray-drying. It
must be noted that if the bulk catalyst composition is to be
applied in slurry-type reactors, fluidized beds, moving beds, or
expanded beds, generally spray-drying or beading is applied. For
fixed bed or ebullating bed applications, generally the bulk
catalyst composition is extruded, pelletized and/or beaded. In the
case of extrusion, pelletization or beading, at any stage prior to
or during the shaping step, any additives which are conventionally
used to facilitate shaping can be added. These additives may
comprise aluminium stearate, surfactants, graphite, starch, methyl
cellulose, bentonite, attapulgite, polyethylene glycols,
polyethylene oxides, or mixtures thereof.
[0047] To prepare bulk catalyst extrudates, the bulk catalyst
precursor can be mixed with an inorganic additive and water and
extruded in the presence of an organic extrusion aid. The binder
materials to be applied may be any materials conventionally applied
as binders in hydroprocessing catalysts. Examples are silica,
silica-alumina, such as conventional silica-alumina, silica-coated
alumina and alumina-coated silica, aluminas such as
(pseudo)boehmite, or gibbsite, titania, titania-coated alumina,
zirconia, cationic clays or anionic clays such as saponite,
bentonite, attapulgite, kaolin, sepiolite or hydrotalcite, or
mixtures thereof. Preferred binders are silica, silica-alumina,
alumina, titania, titania-coated alumina, zirconia, bentonite,
attapulgite, or mixtures thereof. These binders may be applied as
such or after peptization. In some cases the bulk catalyst
precursor is milled to obtain a smaller particle size which helps
to achieve higher compacted bulk density (CBD) in a fixed bed
reactor. This could be beneficial to obtain high metal loadings per
reactor volume and it could also increase the strength of the
compacted particles. The resulting extrudates are dried at
120.degree. C. or subjected to a further heat treatment at a
temperature lower than the temperatures used during the step 2 (the
drying step) in the preparation.
[0048] Binder materials may already be added during or after step 1
(the preparation of the solution) or step 2 (the drying step) in
the preparation. This may be preferred to enable a better
distribution of the binder materials throughout the catalyst
extrudates. It is understood that these binder materials are not
considered to be part of the bulk catalysts precursor, as they are
solely added to provide integrity and strength to the catalyst and
do not contribute to the activity of the catalyst.
[0049] The shaped material that is obtained after step 4 is
referred to as the bulk catalyst characterized by:
[0050] Ni:(Mo+W) molar ratio higher than 0.05
[0051] A molar ratio of C:(Mo+W) between 1.5 and 10.
[0052] A minimum metal loading of 2.0 moles (Mo+W)/liter reactor
volume
[0053] The process optionally may comprise a sulfidation step (step
5). Sulfidation generally is carried out by contacting the bulk
catalyst precursor, directly after its preparation or after any one
of process steps, with a sulfur-containing compound such as
elementary sulfur, hydrogen sulfide, dimethyl disulfide (DMDS), or
organic or inorganic polysulfides. The sulfidation step can be
carried out in the liquid and the gas phase. The sulfidation can be
carried out subsequent to the preparation of the bulk catalyst
composition. It is preferred that the sulfidation is not carried
out prior to any process step by which the obtained metal sulfides
revert to their oxides. Such process steps are, e.g., a thermal
treatment or spray-drying or any other high-temperature treatment
if carried out under an oxygen-containing atmosphere. Consequently,
if the bulk catalyst composition is subjected to spray-drying
and/or any alternative technique or to a thermal treatment under an
oxygen-containing atmosphere, the sulfidation preferably is carried
out subsequent to the application of any of these methods. Of
course, if these steps are carried out under an inert atmosphere,
sulfidation can also be carried out prior to these steps. If the
bulk catalyst composition is used in fixed bed processes, the
sulfidation preferably is carried out subsequent to the shaping
step and, if applied, subsequent to the last thermal treatment in
an oxidizing atmosphere.
[0054] The sulfidation can generally be carried out in situ and/or
ex situ. Preferably, the sulfidation is carried out in situ, i.e.
the sulfidation is carried out in the hydroprocessing reactor after
the oxidic bulk catalyst composition being loaded into the
hydroprocessing unit.
[0055] The bulk catalyst composition according to the invention is
particularly useful for hydroprocessing hydrocarbon feedstocks.
Accordingly, the invention relates to a process for hydroprocessing
a hydrocarbon feedstock, said process comprising contacting a
hydrocarbon feedstock under hydroprocessing conditions with a
catalyst composition comprising a metal oxide/C phase that
comprises at least one Group VIII non-noble metal, at least one
Group VIB metal and optionally Ni-crystals.
Characterization of the Bulk Catalyst Precursor and Bulk
Catalysts
[0056] N.sub.2 adsorption isotherms of the catalysts were obtained
using a Micromeretics Gemini-V analyzer. Samples were subjected to
120.degree. C. and vacuum as a pre-treatment before the
measurements. Values for the surface area were obtained using the
so-called Brunauer-Ernett-Teller (BET) method the value will be
referred to as SA-BET in the following text.
[0057] The composition of the bulk catalyst precursors or the bulk
catalysts was determined using X-ray fluroscence (XRF) and a
separate measurement of the C-content. The C-content was determined
on the catalyst precursor using a combustion method and detection
of the amount of CO.sub.2 formed per quantity of sample. Before the
XRF measurement, the catalyst precursor was subjected to a
calcination treatment, typically to 600.degree. C. in such a way
that any organics were removed and a metal-oxide phase is obtained.
At the same time the weight loss during this calcination procedure
was measured. Using the weight loss during calcination
(LOI600.degree. C.), and the metal composition of the metal oxide
obtained after calcination as determined by XRF [MeO.sub.x (wt %
XRF)], the actual composition of the bulk catalyst precursor or the
bulk catalyst was calculated using Equation 1.
MeO.sub.x (wt %)=(100%-LOI600.degree. C.)*MeO.sub.x (wt % XRF)
Equation 1
[0058] The X-ray diffraction measurements were performed in a Q-Q
Bragg-Brentano geometry using a Bruker D8Advance diffractometer
that was equipped with a Cu anode (using X-ray radiation with a
wavelength of 1.54 .ANG.) and a LYNXEYE detector. The sample was
measured from 4-70.0.degree. 2q with a step size of 0.05.degree. 2q
using fixed divergence- and anti-scatter slits of 0.5.degree.. It
is known in the art that the presence of any crystalline
metal-oxide phases with the relevant compositions (i.e. containing
Ni and Mo and or W), will result in the presence of at least one
peak in the XRD pattern in the range of 10-40.degree. 2 theta.
[0059] The broadness of a peak in XRD patterns is a function of the
average crystallite size of the phase that is being observed. The
Scherrer equation as presented in Equation 2 is commonly used to
derive a crystallite size (.tau.) from the broadness (.beta., the
Full Width at Half Maximum, or FWHM in radians) of a peak at
position .theta. in a XRD pattern (A. L. Patterson, Phys. Rev. 56,
978 1939). A value of 0.9 is often used for the dimensionless shape
factor K, while .alpha. is the wavelength of the X-rays used: in
this case 1.54 .ANG.. It can easily be derived that for a
crystalline phase with a reflection at 40.degree. 2theta, a crystal
size of 5 nm will result in a FWHM of 2.degree. 2theta. For
crystals smaller than 5 nm, the peak width will be even
broader.
.tau. = K .alpha. .beta. cos .theta. : Equation 2 ##EQU00001##
[0060] For this purpose, a crystalline metal-oxide phase is present
when the crystal size of the metal-oxide crystalline domains is
larger than 5 nm. Hence, when it is stated that any crystalline
metal-oxide phases are absent in the catalyst precursors of the
invention, it is meant that the XRD pattern of catalyst precursor
of the invention does not show any peak with a FWHM of smaller than
2.degree. 2 theta in the range of 10-40.degree. 2 theta.
[0061] The XRD patterns of the NiW, NiMo bulk catalyst precursors
1-A to 1-D and (comparative) NiMoW bulk catalyst precursor 1-E and
the catalyst that is formed from this precursor are presented in
FIG. 1. It can be seen that for bulk catalyst precursors of the
invention, the XRD patterns show either no peaks, showing that the
material is almost amorphous (bulk catalyst precursor 1-A and 1-D),
some very broad peaks with a full width at half the maximum (FWHM)
of more than 2.degree. 2theta that can be attributed to the
carbon-phase that is formed (bulk catalyst precursors 1-B and 1-C)
and/or sharp peaks located at 2 theta=45.degree. and 52.degree.
that can be attributed to Ni-crystals being formed during the
partial decomposition step (bulk catalyst precursors 1-B and 1-C).
The XRD patterns of other bulk catalyst precursors of the invention
(2-A and 3-A) are presented in FIGS. 5 and 6, while the XRD
patterns of bulk catalysts 4-A and 4-B of the invention are
presented in FIG. 7. None of the XRD patterns of bulk catalyst
precursors or bulk catalysts of the invention exhibit any peaks
with a FWHM of smaller than 2.degree. 2 theta in the range of
10-40.degree. 2 theta. This indicates that no crystalline
metal-oxide phase is present in these samples.
[0062] The XRD patterns of the NiMoW comparative bulk catalyst 1-E
and its precursor show peaks, of which the ones with highest
intensity are located at 2 theta=36.degree. and 54.degree.
corresponding the formation of a distorted NiWO.sub.4 phase. The
FWHM of these peaks is smaller than 2.degree. 2 theta, indicating
the presence of a crystalline metal-oxide phase according to the
definition explained above. This is in line with what has been
generally shown in the prior art for bulk hydroprocessing catalysts
with NiMo/W compositions prepared via precipitation.
Use in Hydroprocessing of the Invention
[0063] The catalyst composition according to the invention can be
used in virtually all hydroprocessing processes to treat a
plurality of feeds under wide-ranging reaction conditions such as
temperatures of from 200 to 450.degree. C., hydrogen pressures of
from 5 to 300 bar, liquid hourly space velocities of from 0.05 to
10 h.sup.-1 and hydrogen treat gas rates of from about 50 to about
2000 m.sup.3/m.sup.3 (280 to 11236 SCF/B). The term hydroprocessing
used in the context of this invention encompasses all processes in
which a hydrocarbon feedstock is reacted with hydrogen at the
temperatures and pressures noted above, and including
hydrogenation, hydrodesulfurization, hydrodenitrogenation,
hydrodemetallization, hydrodearomatization, hydrodeoxygenation,
hydroisomerization, hydrodewaxing, hydrotreating, hydrofinishing
and hydrocracking.
[0064] The catalyst composition of the invention is particularly
effective for the removal of nitrogen and sulfur from a hydrocarbon
feed. Accordingly, in a preferred embodiment, the catalyst of the
invention is used to remove sulfur, nitrogen, or a combination of
sulfur and nitrogen, from hydrocarbon feedstocks. The contacting of
the hydrocarbon feedstock with the catalyst composition occurs in
the presence of a hydrogen-containing treat gas, and the reaction
is operated under effective hydroprocessing conditions. The
contacting of the hydrocarbon feedstock with the catalyst
composition produces a hydrocarbon product that has less nitrogen,
sulfur, or both, compared to the feedstock.
[0065] The hydrocarbon feedstock is a material comprising hydrogen
and carbon. A wide range of petroleum and chemical hydrocarbon
feedstocks can be hydroprocessed in accordance with the present
invention. Hydrocarbon feedstocks include those obtained or derived
from crude petroleum oil, from tar sands, from coal liquefaction,
from shale oil and from hydrocarbon synthesis. The catalyst
composition of the present invention is particularly effective for
removing sulfur, nitrogen or a combination of sulfur and nitrogen
from hydrocarbon feedstocks. Hydrocarbon feedstocks indeed often
contain nitrogen and sulfur contaminants, often in the form of
sulfur and/or nitrogen-containing organic compounds. Nitrogen
contaminants may be basic or non-basic.
EXAMPLES
[0066] The following examples will serve to illustrate but not
limit this invention.
[0067] Example 1 set out to compare NiMo/W bulk catalyst precursors
prepared according to the invention vs. NiMoW bulk catalyst known
in the art and supported NiMo-reference catalyst in high P (80 bar)
hydrotreating of an HGO feed.
[0068] A first bulk catalyst precursor was created according to the
embodiments discussed above. In a beaker glass, 17.01 g D-sorbitol
(.gtoreq.98 wt %) was dissolved in 100 ml water without heating.
When the solution was clear, 10.59 g of ammonium heptamolybdate
(81.5 wt % MoO.sub.3) was added, resulting in a clear solution.
Next, 9.00 g acetic acid (96 wt % acetic acid) was added and 7.47 g
Nickel acetate (23.6 wt % Ni). A green clear solution was obtained.
This solution was heated to 85.degree. C. for one hour while
evaporation of water was prevented by placing a watch glass on top
of the beaker. The solution remained clear. This solution was
transferred to a porcelain dish and placed in an oven at
120.degree. C. for 14 hours under ambient conditions. After drying,
a dark green solid was obtained. This material was placed in a
rotary calciner and heated to 325.degree. C. under a nitrogen flow
with a ramp rate of 5.degree. C./min and a hold time of 4 hours.
The composition of the resulting material and the surface area as
observed by nitrogen physisorption are presented in Table 1. The
XRD pattern of this bulk catalyst precursor is presented in FIG. 1.
TEM imaging was carried out on this bulk catalyst precursor. A
characteristic image at a high magnification is presented as FIG.
2. This was bulk catalyst precursor 1-A.
[0069] A second bulk catalyst precursor was created according to
the embodiments discussed above. In a beaker glass, 26.14 g of
Nickel acetate (23.58 wt % Ni) was dissolved in 30.34 g of an
aqueous gluconic acid solution (50 wt % gluconic acid) without
heating. The resulting mixture was heated to 60.degree. C. for 15
minutes resulting in a clear solution. Next, 24.64 g of ammonium
metatungstate (94.10 wt % WO.sub.3) was added while the temperature
of the solution was kept at 60.degree. C. Again a clear solution
was obtained. This solution was transferred to a porcelain dish and
placed in an oven at 120.degree. C. for 14 hours under ambient
conditions. After drying, a dark green solid was obtained. This
material was placed in a rotary calciner and heated to 400.degree.
C. under a nitrogen flow with a ramp rate of 5.degree. C./min and a
hold time of 4 hours. The composition of the resulting material and
the surface area as observed by nitrogen physisorption are
presented in Table 1. The XRD pattern of this bulk catalyst
precursor is presented in FIG. 1. TEM imaging was carried out on
this bulk catalyst precursor. A characteristic image at a high
magnification is presented as FIG. 3. This was bulk catalyst
precursor 1-B.
[0070] A third bulk catalyst precursor was created according to the
embodiments discussed above. In a beaker glass, 2.49 g of Nickel
acetate (23.6 wt % Ni) was dissolved in 30.34 g of an aqueous
gluconic acid solution (50 wt % gluconic acid) without heating. The
resulting mixture was heated to 60.degree. C. for 15 minutes
resulting in a clear solution. Next, 24.64 g of ammonium
metatungstate (94.1 wt % WO.sub.3) was added while the temperature
of the solution was kept at 60.degree. C. Again a clear solution
was obtained. This solution was transferred to a porcelain dish and
placed in an oven at 120.degree. C. for 14 hours under ambient
conditions. After drying, a dark green solid was obtained. This
material was placed in a rotary calciner and heated to 400.degree.
C. under a nitrogen flow with a ramp rate of 5.degree. C./min and a
hold time of 4 hours. The composition of the resulting material and
the surface area as observed by nitrogen physisorption are
presented in Table 1. The XRD pattern of this bulk catalyst
precursor is presented in FIG. 1. TEM imaging was carried out on
this catalyst precursor. A characteristic image at a high
magnification is presented as FIG. 4. This was bulk catalyst
precursor 1-C.
[0071] A fourth bulk catalyst precursor was created according to
the embodiments discussed above. In a beaker glass, 16.38 g .alpha.
D-glucose (anhydrous, 96%) was dissolved in 120 ml water. After the
glucose was dissolved, 10.59 g ammonium heptamolybdate (81.5 wt %
MoO.sub.3) was added. Next, 9.00 g of acetic acid (96 wt % acetic
acid) and 7.47 g Nickel acetate (23.6 wt % Ni) was added. The
solution was heated to 85.degree. C. for one hour, while
evaporation of water is prevented by placing a watch glass on top
of the beaker. The resulting solution still contained a small
amount of solid material. In a second beaker glass, 16.83 g .alpha.
D-glucose (anhydrous, 96%) was dissolved in 120 ml water. After the
glucose was dissolved, 10.59 g ammonium heptamolybdate (81.5 wt %
MoO.sub.3) was added. Next, 9.00 g of acetic acid (96 wt % acetic
acid) and 7.47 g Nickel acetate (23.6 wt % Ni) was added. The
resulting solution contained a small amount of solid material of
unknown origin. The content of both beakers was combined in a
porcelain dish and placed in an oven at 120.degree. C. for 14 hours
under ambient conditions. After drying, a dark green solid was
obtained. This material was placed in a rotary calciner and heated
to 325.degree. C. under a nitrogen flow with a ramp rate of
5.degree. C./min and a hold time of 4 hours. The composition of the
resulting material and the surface area as observed by nitrogen
physisorption are presented in Table 1. The XRD pattern of this
bulk catalyst precursor is presented in FIG. 1. This was bulk
catalyst precursor 1-D.
[0072] A comparative catalyst was made according to teachings known
in the art. A NiMoW bulk catalyst was prepared following the
teachings of U.S. Pat. No. 6,566,296. In a reactor 755 g of Nickel
hydroxy-carbonate (Containing 70.0 wt % Ni) was slurried in 500 ml
water. The temperature was raised to 60.degree. C. and 90 g
molybdic acid (90 wt % MoO.sub.3) was added. Next 137 g tungstic
acid (70.31 wt % W) was added. This mixture was allowed to react
for sufficient time for complete reaction of the starting
materials. The resulting slurry was filtered to obtain the
precipitate. This is comparative bulk catalyst precursor 1-E. The
XRD pattern of this material is presented in FIG. 1. 597 g of the
obtained solid was mixed with 241.85 g boehmite and 24.37 g of 65%
HNO.sub.3 and kneaded to obtain a homogeneous mixture. The water
content in the extrusion mix was adjusted (by heating or water
addition) in order to obtain an extrudable mix, as known to a
person skilled in the art. The mix was extruded using apertures of
1.5 mm diameter and the extrudates were dried for one hour at
120.degree. C. The resulting material was placed in a rotary
calciner and heated to 385.degree. C. under air flow with a ramp
rate of 5.degree. C./min and a hold time of 1 hour. The resulting
material had the following composition as determined by XRF:
WO.sub.3 (31.4 wt %), NiO (31.3 wt %), MoO.sub.3 (20.6) and
Al.sub.2O.sub.3 (15.6 wt %). The SA-BET of this material as
measured using N.sub.2 physisorption was larger than 120 m.sup.2/g.
Although part of this SA originates from the Al.sub.2O.sub.3, the
low concentration of this component cannot account for this high
SA. This means that the metal-oxide bulk catalyst precursor 1-E
also has a significant SA-BET. Subsequently, 4.4 grams diethylene
glycol was weighed and diluted with water of a sufficient volume to
carry out a pore volume impregnation on the extrudates. The
resulting solution was added to 50 g of the above mentioned
calcined extrudates. Impregnation was done for approximately 30
minutes at 120.degree. C. in a closed container under regular
mixing. Next, the extrudates were heated while rotating until the
extrudates reached a temperature of 90.degree. C., as a sign that
the material was dry and all water had evaporated. The composition
of the resulting material and the surface area as observed by
nitrogen physisorption are presented in Table 1. The XRD pattern of
this catalyst is presented in FIG. 1 as well. This is Comparative
bulk catalyst 1-E.
[0073] As a second comparative catalyst, a supported
NiMo--Al.sub.2O.sub.3 catalyst that is a commercial catalyst for
high P hydrotreating of distillate feeds was included in the
testing. The composition and the surface area of this catalyst as
observed by nitrogen physisorption are presented in Table 1. This
is Comparative catalyst 1-F.
[0074] From the data in Table 1, it can be observed that the SA of
the bulk catalysts precursors 1-A to 1-D is very small, in all
cases smaller than can be measured using the N.sub.2 physisorption
method. For comparative catalyst 1-E and 1-F on the other hand, a
high SA is observed.
TABLE-US-00001 TABLE 1 Composition and SA-BET as determined by
N.sub.2 physisorption of bulk catalyst precursors (b.c.p) 1-A-1-D
and comparative catalysts 1-E and 1-F. Compar- ative Compar- bulk
itive b.c.p. b.c.p. b.c.p. b.c.p. catalyst catalyst 1-A 1-B 1-C 1-D
1-E 1-F NiO (wt %) 12.4 21.3 2.4 11.7 27.1 3.3 CoO (wt %) MoO3 (wt
%) 47.6 44.6 17.9 20.0 WO3 (wt %) 63.1 74.7 27.2 Ni:(Mo + W) 0.50
1.05 0.10 0.50 1.50 0.32 C (wt %) 29.4 13.9 15.7 29.2 3.9 n.a.
C:(Mo + W) 7.4 4.3 4.1 7.9 1.3 n.a. LOI 600.degree. C. 40.0 15.6
22.9 43.9 13.3 17.2 (wt %) SA-BET <5 <5 <5 <5 126 121
(m.sup.2/g)
[0075] Bulk catalyst precursors 1-A-1-D according to the invention
are characterized by the presence of a significant amount of carbon
and a molar ratio of C:(Mo+W) of at least 4. Furthermore, in
contrast to comparative catalysts 1-E and 1-F, the surface area of
the catalysts according to the invention is always smaller than 5
m.sup.2/g. The XRD pattern of bulk catalyst precursors 1-A-1-D
according to the invention, the precursor to Comparative bulk
catalyst 1-E and the Comparative bulk catalyst 1-E are presented in
FIG. 1. The patterns of Comparative bulk catalyst precursor 1-E and
Comparative bulk catalyst 1-E show the most intense peaks at 2
theta=36.degree. and 54.degree.. These peaks can be attributed to
the presence of a distorted nano-crystalline NiWO.sub.4 phase. No
peaks with a FWHM smaller than 2.degree. 2 theta are present in the
2 theta range of 10-40.degree. of the XRD pattern of the bulk
catalyst precursors 1-A to 1-D according to the invention. The
sharp peaks (the FWHM is smaller than 1.degree. 2 theta) that are
observed at 45 and 52 degrees 2 theta in the pattern of catalysts
1-A and 1-B can be attributed to Ni-crystals being formed and are
not the result of any crystalline metal-oxide phase.
[0076] In the TEM images of bulk catalyst precursors 1-A, 1-B and
1-C as presented in FIG. 2-4, the presence of Ni-crystals was also
clearly observed. A general feature of bulk catalyst precursor of
the invention is that the Ni-crystals that are formed are very well
dispersed in the sense that (i) the spatial distribution of the
particle throughout the sample is very homogeneous and (ii) the
particles size distribution is extremely narrow. As can be seen in
FIG. 2, in bulk catalyst precursor 1-A, the Ni-crystals are small
(<5 nm in diameter) and the concentration is low. For this
reason, no peaks are observed in the corresponding XRD pattern,
despite the presence of a crystalline Ni-phase. Hence, the absence
of any peaks in the XRD pattern does not mean that no Ni-crystals
are present in the bulk catalyst precursors. The presence of
Ni-crystals in the TEM-micrographs (FIGS. 3 and 4) is even more
pronounced in bulk catalyst precursors 1-B and 1-C.
[0077] Testing Procedure: The bulk catalyst precursors and the
Comparative catalysts were sized to a sieve fraction of 125-300
.mu.m and loaded in a reactor with 0.9 ml volume. The test unit
used for performance testing allowed for the side-by-side testing
of different catalysts at identical processing conditions
(temperature, pressure, feed and H.sub.2/oil ratio), while the LHSV
can be adjusted for each catalyst, e.g. via the catalyst intake.
The catalysts were pre-sulfided using a 2.5 wt % DMDS spiked LGO
feed that was fed over the catalyst at a LHSV of 3.0 at 45 bar and
with a H2/oil ratio of 300 nl/l. The T program that was used during
pre-sulfiding is given in Table 2. The catalytic activity of the
catalysts was evaluated at 80 bar pressure, 341.degree. C. and a
H.sub.2/oil ratio of 500 nl/l in processing an HGO with feed
characteristics as presented in Table 3.
TABLE-US-00002 TABLE 2 Pre-sulfidation T-protocol used for the
activation of bulk catalyst precursors 1-A - 1-D and comparative
catalysts 1-E and 1-F. Start T (.degree. C.) End T (.degree. C.)
Time (h) Step 1 21 21 24 Step 2 21 150 3 Step 3 150 250 10 Step 4
250 250 14 Step 5 250 345 19 Step 6 345 345 12
TABLE-US-00003 TABLE 3 Properties of the HGO feed used for
performance testing of bulk catalyst precursors 1-A - 1-D and
comparative catalysts 1-E and 1-F. S-content (ppmwt) 14773
N-content (ppmwt) 542 Density at 15.degree. C. (g/ml) 0.8981
Initial boiling point (.degree. C.) 208 Boiling point at 50 wt %
(.degree. C.) 355 Boiling point at 90 wt % (.degree. C.) 416
Boiling point at 95 wt % (.degree. C.) 431
[0078] The volume and weight of the catalysts in the different
reactors and the S and N content of the resulting product at
different reaction conditions is given in Table 4. The catalyst
intake is presented in grams on dry basis (g, d.b.). This means the
weight of the bulk catalyst precursor or the catalyst after
calcination at 600.degree. C. in air. First of all, it can be
observed that all bulk catalyst precursors are more active than
Comparative catalyst 1-F, the commercial NiMo/Al.sub.2O.sub.3
catalyst. At a LHSV of 2.0, the Comparative catalyst 1-F was able
to produce a product with 762 ppm S and 52 ppm N. Bulk catalyst
precursors 1-A to 1-D and the Comparative bulk catalyst 1-E are
able to produce a product with a lower concentration of N at a LHSV
of 2.4, which indicates that the relative volumetric activity of
these catalysts is at least 20% higher than Comparative catalyst
1-F. Furthermore, it can be seen that the bulk catalyst precursors
1-A-1-D of the invention are considerably more active in terms of
HDN activity than the Comparative bulk catalyst 1-E. At a LHSV of
2.4, the comparative catalysts 1-E was able to produce a product
with 50 ppm N, while the catalysts of the invention produce a
product with 28 ppm N or less. In a number of hydroprocessing
applications, such as hydrocracking pretreat and FCC pretreat
treatment of typically vacuum gasoil type feed, the removal of
nitrogen is the primary objective. In these operations, the bulk
catalyst precursors of the invention all have a considerable
advantage over Comparative catalyst 1-E. The high activity of bulk
catalyst precursors 1-A to 1-D of the invention vs. the comparative
catalysts is surprising considering the low SA-BET of these
catalysts.
TABLE-US-00004 TABLE 4 Catalyst intake and observed conversion for
bulk catalyst precursors 1-A-1-D and comparative catalysts 1-E and
1-F in a 80 bar test processing HGO. Com- Com- para- para- b.c.p.
b.c.p. b.c.p. b.c.p. tive tive 1-A 1-B 1-C 1-D 1-E 1-F intake
volume 0.45 0.45 0.45 0.45 0.45 0.90 (ml) intake weight 0.28 0.72
0.39 0.27 0.60 0.81 (g, d.b.) LHSV 4.0 4.0 4.0 4.0 4.0 --
(ml.sub.feed * ml.sub.catalyst.sup.-1 * h.sup.-1) S (ppmwt) 1044
224 3813 1207 1420 -- N (ppmwt) 64 36 99 78 138 -- LHSV 2.4 2.4 2.4
2.4 2.4 2.0 (ml.sub.feed * ml.sub.catalyst.sup.-1 * h.sup.-1) S
(ppmwt) 281 35 1592 406 689 762 N (ppmwt) 6 +213 28 9 50 52
[0079] Example 2 set out to compare a NiW bulk catalyst precursor
prepared according to the invention vs. a CoMo bulk catalyst
precursor known in the art and a supported CoMo-reference catalyst
in low P (30 bar) hydroprocessing of a LGO feed. In a beaker glass,
12.44 g Ni acetate (23.6 wt % Ni) was dissolved in 30.34 g of a
gluconic acid solution (containing 50 wt % D-gluconic acid) at
ambient T. 24.64 g of ammonium meta tungstate (94.1 wt % WO.sub.3)
was added and the solution was heated to 70.degree. C. under
constant stirring, resulting in a clear solution. This solution was
dried in a static oven at 120.degree. C. for 5 hours. The resulting
brown-greenish solid was placed in a rotary calciner and heated to
400.degree. C. under nitrogen flow with a ramp rate of 5.degree.
C./min and a hold time of 4 hours. The composition of the resulting
material and the surface area as observed by nitrogen physisorption
are presented in Table 5. The XRD pattern of this bulk catalyst
precursor is presented in FIG. 5. This is bulk catalyst precursor
2-A .
[0080] Next, two comparative catalysts were prepared. First, a
comparative CoMo bulk catalyst precursor was prepared by the
following process, as disclosed in U.S. Pat. No. 7,951,746. In a
beaker glass, 25.74 g Cobalt acetate (23.7 wt % Co) was dissolved
in 165 ml of a glyoxylic acid solution (50 wt % glyoxylic acid) at
ambient temperature. 36.38 g ammonium heptamolybdate (81.5 wt %
MoO.sub.3) was added and the solution was heated to 80.degree. C.
under constant stirring. When the T reaches around 60.degree. C.,
the reaction of the ammonium heptamolybdate is rather vigorous and
the formation of foam is observed. After an hour stirring at
80.degree. C., a solution is obtained that is almost clear, but
still contains a minor amount of solid material. The resulting
mixture was dried overnight in a static oven at 120.degree. C. The
darkly colored solid was placed in a rotary calciner and heated to
325.degree. C. under a flow of dry air with a ramp rate of
5.degree. C./min and a hold time of 4 hours. The composition of the
resulting material and the surface area as observed by nitrogen
physisorption are presented in Table 5. The XRD pattern of this
bulk catalyst precursor is presented in FIG. 5. This is Comparative
bulk catalyst precursor 2-B.
[0081] A supported CoMo--Al.sub.2O.sub.3 catalyst was prepared by
impregnation of a CoMo-solution onto a commercial Al.sub.2O.sub.3
support used for the preparation of hydrotreating catalysts. The
.gamma.-Al.sub.2O.sub.3 extrudates have a SA-BET of 267 m.sup.2/g,
a mean pore diameter as determined by N.sub.2 desorption of 8 nm
and a pore volume as determined by N.sub.2 physisorption of 0.78
ml/g. A Co.sub.3.sup.2+[Co.sub.2Mo.sub.10O.sub.38H.sub.4].sup.6-
solution was prepared with a metal loading comparable to commercial
CoMo--Al.sub.2O.sub.3 catalysts using a method for making the
impregnation solution as published in an article in Langmuir 2013,
29, 207-215. The impregnation solution was prepared by mixing 180.0
g MoO.sub.3 (100%) with 0.80 l water in a beaker glass.
Subsequently, 612.5 g of a H.sub.2O.sub.2 solution was added (30 wt
% H.sub.2O.sub.2) and the suspension was heated to 40.degree. C.
After about 2 hours stirring at 40.degree. C., a clear solution is
obtained. To this solution, 79.9 g of CoCO.sub.3 (46 wt % Co) was
added in small portions in a period of 45 minutes., The resulting
mixture was heated to 90.degree. C. and was allowed to react for 2
hours. The solution was divided over 9 autoclaves containing 50 ml
of solution each, which were heated under autogenic pressure to
150.degree. C., where they were kept for 2 hours. The resulting
solution was spray-dried using a bench top spray-dryer of the type
Buchi Mini Spraydryer B-290 equipped with inert loop B295. During
spray-drying, the inlet temperature was 180.degree. C. and the
outlet temperature 100-110.degree. C. The solution was supplied to
the spray-dryer with a throughput of approximately 200 ml/hour. The
obtained powder was re-dissolved in water to obtain the
impregnation solution. The final catalyst was obtained by pore
volume impregnation of this solution onto the alumina carrier,
whereby the solution volume and concentration were adjusted to
arrive at the desired composition of the final catalyst. The final
catalyst contained 23.81% MoO.sub.3 and 6.16% CoO as determined by
XRF after calcination at 600.degree. C. This composition is in line
with the composition of commercial CoMo--Al.sub.2O.sub.3 catalysts
that are generally applied in this application. The composition of
the resulting material and the surface area as observed by nitrogen
physisorption are presented in Table 5. This is Comparative
catalyst 2-C.
[0082] From the data in Table 5, it can be observed that the SA of
the bulk catalyst precursor 2-A is smaller than can be measured
using the N.sub.2 physisorption method. For the Comparative bulk
catalyst precursor 2-B the SA is extremely low, while for
Comparative catalyst 2-C a high SA is observed.
[0083] In FIG. 5, the XRD patterns of bulk catalyst precursor 2-A
and Comparative bulk catalyst precursor 2-B are presented. No peaks
in the range of 10-40.degree. 2 theta are observed in the XRD
pattern of either bulk catalyst precursor indicative of an absence
of any (nano)crystalline metal-oxide phase. It can be observed that
in the XRD pattern of bulk catalyst precursor 2-A, a sharp peak is
present at about 45.degree. 2 theta, which can be attributed to the
presence of Ni-crystals. This peak is absent In Comparative bulk
catalyst precursor 2-B.
TABLE-US-00005 TABLE 5 Composition and SA-BET as determined by
N.sub.2 physisorption of bulk catalyst precursor 2-A, comparative
bulk catalyst precursor 2-B and comparative catalyst 2-C.
Comparative Comparative b.c.p. 2-A 2-B 2-C NiO (wt %) 11.1 CoO (wt
%) 14.8 5.6 MoO3 (wt %) 56.9 21.6 WO3 (wt %) 68.7 C (wt %) 16.0
18.9 0.0 C:(Mo + W) 4.5 4.0 0.0 LOI 600.degree. C. (wt %) 20.3 28.4
9.4 SA-BET (m.sup.2/g)) <5 6.2 220
[0084] The bulk catalyst precursors and the supported catalyst were
sized to a sieve fraction of 125-300 .mu.m and loaded in a reactor
with 0.9 ml volume. The test unit used for performance testing
allowed for the side-by-side testing of different catalysts at
identical processing conditions. The catalysts were pre-sulfided
using a 2.5 wt % DMDS spiked LGO feed that was fed over the
catalyst at a LHSV of 3.0 at 30 bar and with a H2/oil ratio of 300
nl/l. The T program that was used during pre-sulfiding is given in
Table 6. The catalytic activity of the catalysts was evaluated at
30 bar pressure, 350.degree. C. and a H2/oil ratio of 200 nl/l in
processing an LGO with feed characteristics as presented in Table
7.
TABLE-US-00006 TABLE 6 Pre-sulfidation T-protocol used for the
activation of samples 2-A - 2-C. Start T (.degree. C.) End T
(.degree. C.) Time (h) Step 1 21 21 24.0 Step 2 21 250 7.3 Step 3
250 250 8.2 Step 4 250 320 3.5 Step 5 320 320 5.0
TABLE-US-00007 TABLE 7 Properties of the LGO feed used for
performance testing of samples 2-A - 2-C. S-content (ppmwt) 12467
N-content (ppmwt) 146 Density at 15.degree. C. (g/ml) 0.850 Initial
boiling point (.degree. C.) 131 Boiling point at 50 wt % (.degree.
C.) 309 Boiling point at 90 wt % (.degree. C.) 383 Boiling point at
95 wt % (.degree. C.) 402
[0085] The volume and weight of the samples in the different
reactors and the S content of the resulting product at different
reaction conditions is given in Table 8. It can be observed that
the HDS activity of the NiW bulk catalyst catalyst precursor 2-A is
significantly higher than the activities of the Comparative CoMo
bulk catalyst precursor 2-B and the Comparative
CoMo--Al.sub.2O.sub.3 catalyst 2-C. The NiW bulk catalyst precursor
2-A manages to reach a lower S value (12 ppm) at a LHSV of 1.5 than
the Comparative CoMo bulk catalyst precursor 2-B at a LHSV of 1.2
(89 ppm) and the Comparative supported catalyst 2-C (240 ppm) at a
LHSV of 1.5. Since normally catalysts with a CoMo composition are
being applied in low P hydroprocessing of Distillate feeds, this is
a surprising finding.
TABLE-US-00008 TABLE 8 Catalyst intake, LHSV applied and observed
conversion for bulk catalyst precursor 2-A, comparative bulk
catalyst precursor 2-B and comparative catalyst 2-C in a 30 bar
test processing LGO. Comparative Comparative b.c.p. 2-A 2-8 2-C
intake volume (ml) 0.90 0.90 0.90 intake weight (g, d.b.) 1.19 0.73
0.66 LHSV (ml.sub.feed*ml.sub.catalyst.sup.-1*h.sup.-1) 1.5 1.2 1.5
S (ppmwt) 12 89 240 N (ppmwt) <3 10 64
[0086] Example 3 set out to compare a NiMoW bulk catalyst precursor
prepared according to the invention vs. a CoMo bulk catalyst
precursor using the exact same preparation method in medium P (45
bar) processing of a LGO feed. In a beaker glass, 12.44 g Nickel
acetate (23.6 wt % Ni) was dissolved in 30.34 g of a gluconic acid
solution (50 wt % D-gluconic acid) at ambient T. 12.32 g of
ammonium meta tungstate (94.1 wt % WO.sub.3) and 8.83 g of
ammoniumheptamolybdate (81.5 wt % MoO.sub.3) was added and the
solution was heated to 70.degree. C. under constant stirring and
kept at this temperature, while preventing the evaporation of water
for one hour. The resulting solution was dried in a static oven at
120.degree. C. for 5 hours. The resulting solid was placed in a
rotary calciner and heated to 400.degree. C. under nitrogen flow
with a ramp rate of 5.degree. C./min and a hold time of 4 hours.
The composition of the resulting material and the surface area as
observed by nitrogen physisorption are presented in Table 9. The
XRD pattern of this bulk catalyst precursor is presented in FIG. 6.
This is bulk catalyst precursor 3-A .
[0087] A comparative CoMo bulk catalyst precursor was prepared by
the same method. In a beaker glass, 12.45 g Cobalt acetate (23.7 wt
% Co) was dissolved in 30.34 g of a gluconic acid solution (50 wt %
D-gluconic acid) at ambient T. 17.66 g of ammonium heptamolybdate
(81.5 wt % Mo) was added and the solution was heated to 70.degree.
C. under constant stirring. The resulting solution was dried
overnight in a static oven at 120.degree. C. for 5 hours. The
resulting solid was placed in a rotary calciner and heated to
400.degree. C. under nitrogen flow with a ramp rate of 5.degree.
C./min and a hold time of 4 hours. The composition of the resulting
material and the surface area as observed by nitrogen physisorption
are presented in Table 9. The XRD pattern of this bulk catalyst
precursor is presented in FIG. 6. The resulting material is
Comparative bulk catalyst precursor 3-B.
[0088] From the data in Table 9, can be observed that the SA of
both catalysts is smaller than can be measured using the N.sub.2
physisorption method. In FIG. 6, the XRD patterns of bulk catalyst
precursor 3-A and Comparative bulk catalyst precursor 3-B are
presented. No peaks in the range of 10-40.degree. 2 theta are
observed in the XRD pattern of either bulk catalyst precursor
indicative of the absence of any (nano)crystalline metal-oxide
phase. It can be observed that in the XRD pattern of bulk catalyst
precursor 3-A, a sharp peak is present at about 45.degree. 2 theta
which can be attributed to the presence of Ni-crystals. This peak
is absent In Comparative bulk catalyst precursor 3-B.
TABLE-US-00009 TABLE 9 Composition and SA-BET as determined by
N.sub.2 physisorption of bulk catalyst precursors 3-A and 3-B.
Comparitive b.c.p. 3-A 3-B NiO (wt %) 14.2 -- CoO (wt %) -- 15.0
MoO3 (wt %) 41.1 57.8 WO3 (wt %) 22.0 -- C (wt %) 20.0 22.5 C:(Mo +
W) 4.4 4.7 LOI 600.degree. C. (wt %) 22.7 27.2 SA (m.sup.2/g) <5
<5
[0089] Testing Procedure: The bulk catalyst precursors were sized
to a sieve fraction of 125-300 .mu.m and loaded in a reactor with
0.9 ml volume. The test unit used for performance testing allowed
for the side-by-side testing of different catalysts at identical
processing conditions. The samples were pre-sulfided using a 2.5 wt
% DMDS spiked LGO feed that was fed over the catalyst at a LHSV of
3.0 at 45 bar and with a H.sub.2/oil ratio of 300 nl/l. The T
program that was used during pre-sulfiding is given in Table 10.
The catalytic activity of the catalysts was evaluated at 45 bar
pressure, 350.degree. C. and a H.sub.2/oil ratio of 300 nl/l in
processing an LGO with feed characteristics as presented in Table
11.
TABLE-US-00010 TABLE 10 Pre-sulfidation T-protocol used for the
activation of samples 3-A and 3-B. Start T (.degree. C.) End T
(.degree. C.) Time (h) Step 1 21 21 3.0 Step 2 21 250 7.7 Step 3
250 250 14.3 Step 4 250 320 3.5 Step 5 320 320 27.5
TABLE-US-00011 TABLE 11 Properties of the LGO feed used for
performance testing of samples 3-A and 3-B. S-content (ppmwt) 10961
N-content (ppmwt) 199 Density at 15.degree. C. (g/ml) 0.8587
Initial boiling point (.degree. C.) 139 Boiling point at 50 wt %
(.degree. C.) 315 Boiling point at 90 wt % (.degree. C.) 382
Boiling point at 95 wt % (.degree. C.) 400
[0090] The volume and weight of the bulk catalyst precursors in the
different reactors, the space velocity that was applied and the N
and S content of the resulting product at different reaction
conditions is given in Table 12. It can be observed that the HDS
and HDN activity of the NiMoW bulk catalyst precursor 3-A is
significantly higher than that of the Comparative bulk CoMo
catalyst precursor 3-B. For example, bulk catalyst precursor 3-A
manages to reach significantly lower S values (39 ppm) at a LHSV of
3.0 than Comparative bulk catalyst precursor 3-B (72 ppm) at a LHSV
of 2.0. This implies that bulk catalyst precursor 3-A of the
invention has a volumetric HDS-activity of more than 150% vs.
Comparative bulk catalyst precursor 3-B. This is a surprising
finding, as for this type of conditions (medium P hydrotreating of
distillate feeds), catalysts with CoMo compositions are generally
applied.
TABLE-US-00012 TABLE 12 Catalyst intake, LHSV applied and observed
conversion for bulk catalyst precursors 3- A and 3-B in a 45 bar
test processing LGO. Comparitive b.c.p. 3-A 3-B intake volume (ml)
0.90 0.90 intake weight (g, d.b.) 0.73 0.50 LHSV
(ml.sub.feed*ml.sub.catalyst.sup.-1*h.sup.-1) 3.0 3.0 S (ppmwt) 39
336 N (ppmwt) <3 7 LHSV
(ml.sub.feed*ml.sub.catalyst.sup.-1*h.sup.-1) 2.0 2.0 S (ppmwt) 13
72 N (ppmwt) <3 <3
[0091] Example 4 set out to illustrate the shaping of bulk catalyst
precursors of the invention to form bulk catalysts of the invention
and their application in high pressure hydroprocessing. In a beaker
glass, 134.66 g Nickel hydroxy carbonate (48.4 wt % Ni) was
slurried in 300 ml water and heated to 75.degree. C. After
approximately 30 minutes, 217.78 g of MoO.sub.3 (100 wt %
MoO.sub.3) was added in small portions: the formation of CO.sub.2
is observed by the formation of bubbles. The temperature was
increased to 90.degree. C. and the mixture was allowed to react for
2 hours, while evaporation of water was prevented by placing a lid
on the beaker. Subsequently, 400 g of a 50 wt % gluconic acid
solution was added. A clear intensely dark blue-green solution was
obtained. This solution was dried overnight in a static oven at
120.degree. C. for 5 hours. The resulting solid was placed in a
rotary calciner and heated to 450.degree. C. under nitrogen flow
with a ramp rate of 5.degree. C./min and a hold time of 4 hours.
This is bulk catalyst precursor 4-A.
[0092] In a beaker glass, 80.79 g Nickel hydroxy carbonate (48.4 wt
% Ni) was slurried in 300 ml water and heated to 75.degree. C.
After approximately 30 minutes, 130.67 g of MoO.sub.3 (100 wt %
MoO.sub.3) was added in small portions: the formation of CO.sub.2
is observed by the formation of bubbles. The temperature was
increased to 90.degree. C. and the mixture was allowed to react for
2 hours, while evaporation of water was prevented by placing a lid
on the beaker. Subsequently, 400 g of a 50 wt % gluconic acid
solution was added. A clear intensely dark blue-green solution was
obtained. This solution was dried overnight in a static oven at
120.degree. C. for 5 hours. The resulting solid was placed in a
rotary calciner and heated to 350.degree. C. under nitrogen flow
with a ramp rate of 5.degree. C./min and a hold time of 4 hours.
This is bulk catalyst precursor 4-B.
[0093] The bulk catalyst precursors were milled using a ball-mill
and subsequently wet-mixed with approximately 5 wt % percent of an
oxidic binder material (based on the total weight of the catalyst
composition). The water content of the mixture was adjusted in
order to obtain an extrudable mix, and the mixture was subsequently
extruded. The resulting solid cylindrical extrudates were dried at
120.degree. C. for 16 hours (overnight). In this way, bulk
catalysts 4-A and 4-B were obtained. These catalysts show
sufficiently high strength and low abrasion to be loaded in a
commercial fixed bed hydrotreating reactor. The XRD patterns of
these bulk catalysts are presented in FIG. 7.
[0094] The composition of bulk catalysts 4-A and 4-B and the
surface area as observed by nitrogen physisorption of the
extrudates are presented in Table 13. It can be observed that both
bulk catalysts show a very low or no SA-BET. In the XRD patterns in
FIG. 7, it can be observed that peaks are present at 45.degree. and
52.degree. 2 theta, indicating the presence of Ni-crystals in these
bulk catalysts. No peaks are observed in the range of 10-40.degree.
2 theta, showing that no nano-crystalline metal-oxide phase is
present in these bulk catalysts.
TABLE-US-00013 TABLE 13 Composition, SA-BET as determined by
N.sub.2 physisorption of bulk catalysts 4-A and 4-B. Bulk catalyst
Bulk catalyst 4-A 4-B Ni:(Mo + W) 0.75 0.75 MoO3 (wt %) 55.7 47.2 C
(wt %) 13.3 18.4 Oxidic binder (wt %) 2.6 2.5 C:(Mo + W) 2.9 4.7 SA
(m.sup.2/g) 11 <5
[0095] The bulk catalyst extrudates were sized and sieved to remove
extrudates with a length over diameter ratio larger than about 2.5.
The sized extrudates were subsequently loaded in a reactor with 10
ml volume. The test unit used for performance testing allowed for
the side-by-side testing of different catalysts at identical
processing conditions. The catalysts were pre-sulfided using a 2.5
wt % DMDS spiked LGO feed that was fed over the catalyst at a LHSV
of 3.0 at 45 bar and with a H.sub.2/oil ratio of 300 nl/l. The T
program that was used during pre-sulfiding is given in Table 14.
The catalytic activity of the catalysts was evaluated at 80 bar
pressure, 290.degree. C. and a H.sub.2/oil ratio of 500 nl/l in
processing an LGO/LCO blend with feed characteristics as presented
in Table 15. The catalyst was exposed to the LGO/LCO blend at
reaction condition for approximately 8 days.
TABLE-US-00014 TABLE 14 Pre-sulfidation T-protocol used for the
activation of samples 4-A and 4-B. Start T (.degree. C.) End T
(.degree. C.) Time (h) Step 1 25 25 3.5 Step 2 25 250 22.5 Step 3
250 250 12.0 Step 4 250 345 19.0 Step 5 345 345 12.0
TABLE-US-00015 TABLE 15 Properties of the LGO/LCO blended feed used
for performance testing of samples 4-A and 4-B. S-content (ppmwt)
15977 N-content (ppmwt) 441 Density at 15.degree. C. (g/ml) 0.8787
Initial boiling point (.degree. C.) 74 Boiling point at 50 wt %
(.degree. C.) 277 Boiling point at 90 wt % (.degree. C.) 352
Boiling point at 95 wt % (.degree. C.) 370
[0096] The volume and weight of the bulk catalysts in the different
reactors, the space velocity that was applied and the N and S
content of the resulting product is given in Table 16. It can be
observed that the HDS and HDN activity of bulk catalyst 4-B is
significantly higher than that of bulk catalyst 4-B, since lower S
and N values are obtained at the same reaction conditions.
TABLE-US-00016 TABLE 16 Catalyst intake, LHSV applied and observed
conversion for bulk catalysts 4-A and 4-B in a 80 bar test
processing a LGO/LCO blend. Bulk Catalyst Bulk Catalyst 4-A 4-B
intake volume (ml) 10 10 intake weight (g, d.b.) 13.40 10.50 Mo
loading (mole Moil Rx) 6.0 4.7 LHSV
(ml.sub.feed*ml.sub.catalyst.sup.-1*h.sup.-1) 1.9 1.9 S (ppmwt)
3626 2627 N (ppmwt) 128 61
[0097] After the performance test, the spent catalysts were removed
from the reactor and unloaded in white oil. Subsequently, the spent
catalysts were washed with toluene using Soxhlet extraction
equipment to remove any feed remaining in the catalyst pores. After
this treatment, any residual toluene was removed by evaporation.
N.sub.2 physisorption was carried out on the spent catalysts and
the C-content was determined. Results of the analysis on spent
catalysts are presented in Table 17.
[0098] The spent catalyst analysis illustrates that the carbon
content of the catalyst can be reduced during application, as is
the case for bulk catalyst 4-B, where the C:(Mo+W) molar ratio has
decreased from 4.7 to 2.1. Apparently, some fraction of the organic
phase is removed under reaction conditions. This is a surprising
finding as in general in hydroprocessing, carbon is deposited on
the catalyst in the form of coke and the carbon content of the
spent catalyst is higher than that of the fresh catalyst. Moreover,
for catalyst 4-B, the SA-BET of the spent catalyst is significantly
higher than in the fresh bulk catalyst. However, generally a
constant SA, or a decrease in SA is observed due to catalysts
deactivation, when comparing the spent catalysts with the fresh
catalyst.
TABLE-US-00017 TABLE 17 Carbon content and SA-BET of spent bulk
catalysts 4-A and 4-B. Spent Catalyst Spent Catalyst 4-A 4-B C (wt
%) 10.7 8.0 C:(Mo + W) 2.8 2.1 SA-BET (m.sup.2/g) 12 57
* * * * *