Title of Invention

A MIXED METAL CATALYST ITS PREPARATION AND USE

Abstract A process for preparing a catalyst composition The present invention relates to a process for preparing a catalyst composition comprising bulk catalyst particles comprising at least one Group VIII non-noble metal and at least two Group VIB metals, which process comprises combining and reacting at least one Group VIII non-noble metal component with at least two Group VIB metal components in the presence of a protic liquid, with at least one of the metal components remaining at least partly in the solid state during the entire process.
Full Text A MIXED METAL CATALYST COMPOSITION, ITS PREPARATION AND USE
Held of the invention
The invention relates to a process for the preparation of a mixed metal catalyst composition comprising bulk catalyst particles comprising at least one Group VIII non-noble metal and at least two Group VIB metals, to the catalyst composition obtainable by said process, and to the use of said composilion as catalyst in hydroprocessing applications.
Background nf thft jpventlnn
In the hydroprocessing of hydrocarbon feedstocks, the feedstocks are hydrotreated and/or hydrocracked in the presence of hydrogen. Hydroprocessing encompasses all processes in which a hydrocarbon feed is reacted with hydrogen at elevated temperature and elevated pressure including processes such as hydrogenation, hydrodesulphurization, hydrodenitrogenation, hydrodemetallization, hydro-dearomatization, hydroisomerization, hydroduwaxing, hydrocracking. and hydrocracking under mild pressure conditions, which is commonly referred to as mild hydrocracking.
In general, hydroprocessing catalysts are composed of a carrier with a Group VIB metal component and a Group VIII non-noble metal component deposited thereon. Generally, such catalysts are prepared by impregnating a carrier with aqueous solutions of compounds of the metals in question, followed by one or more drying and calcination steps. Such a catalyst preparation process is described, e.g., in US 2,873,257 and EP 0469675.
An alternative technique for the preparation of the above catalysts is described in US 4,113,605, where, e.g., nickel carbonate is reacted with, e.g., MoOj to form crystalline nickel moiybdate, which is subsequently mixed and extruded with alumina.

amorphous sulphide comprising iron as Group VIII non-nobie metal and a metat selected from molybdenum, tungsten or mixtures thereof as Group VIB metal, as well as a polydentate ligand such as ethylene diamine in both references the catalyst is prepared via co-precipitation of water-soluble sources of one Group VIM non-noble metal and two Group VIB metals in the presence of sulphides. The precipitate is isolated, dried, and calcined. All process steps have to be performed in an inert atmosphere, which means that sophisticated techniques are required to carry out this process. Further, due to this co-precipitation technique there are huge amounts of waste water.
It is therefore a further object of the present invention to provide a process which is technically simple and robust and which does nol require any handling under an inert atmosphere during the preparation of the catafyst and in which huge amounts of waste water can be avoided.
US 3,678,124 discloses oxtdic bulk catalysts to be used in oxidative dehydrogenation of paraffin hydrocarbons. The catalysts are prepared by co-precipitating water-soluble components of the corresponding metals. Again, the co-precipitation technique results in huge amounts of waste water.
The catalyst of US 4,153,578 is a Raney rickel catalyst to be used for the hydrogenation of butyrte diol. The catalyst is prepared by contacting Raney nickel optionally containing, e.g., tungsten with a molybilenum component in the presence of water. Molybdenum is adsorbed on the Raney nickel by stirring the resulting suspension at room temperature.
Finally, in non-prepubfished international patent aoplication WO 9903578, catalysts are prepared by co-precipitating certain amounts of a nickel, molybdenum, and tungsten source in the absence of sulphides.
Summary of the jnventiqn
It has now been found that all the above objectives can be met by a process which
comprises combining and reacting at least one Group VIII non-noble metal component

with at least two Group V1B metal components in the presence of a protic liquid, with at least one of the metal components remaining at least partly in the solid state during the entire process.
Another aspect of the present invention is a novel catalyst composition.
A further aspect of the present invention is the u;;e of the above composition for the hydreprocesstng of a hydrocarbon feedstock.
Detailed description of the invention
Process, of the invention
(A) Preparation of bulk catalyst particles
The present invention is directed to a process fur preparing a catalyst composition
comprising bulk catalyst particles comprising at least one Group VIII non-nobie metal
and at least two Group VIB metals, which process comprises combining and reacting at
least one Group VIII non-noble metal component with at least two Group VIB metal
components in the presence of a protic liquid, with at least one of the metal
components remaining at least partly in the solid state during the entire process.
It is thus essential to the process af the invention that at least one metal component remains at least partly in the solid state during the entire process of the invention. This process comprises combining and reacting the metal components. More in particular, it comprises adding the metal components to each other and simultaneously and/or thereafter reacting them. It is consequently essentia to the process of the invention that at least one metal component is added at least partly in the solid state and that this metal component remains at least partly in the solid state during the entire reaction. The term "at least partly in the solid state" in this context means that at least part of the metal component is present as a solid metal component and, optionally, another part of the metal component is present as a solution of this metal component in the protic liquid. A typical example of this is a suspension of a metal component in a protic liquid

with at least two Group VIB metal components in (lie presence of a pratic liquid, with at least one of the metal components remaining at least partly in the solid state during the entire process.
Another aspect of the present invention is a navel catalyst composition.
A further aspect of the present invention is the use of the above composition for the hydroprocessing of a hydrocarbon feedstock.
Detailed description of the invention
Process of Ifru invention
(A) Preparation of bulk catalyst particles
The present invention is directed to a process for preparing a catalyst composition
comprising bulk catalyst particles comprising at least one Group Vlli non-noble metal
and at least two Group VIB metals, which process comprises combining and reacting at
least one Group Vlli non-nobte metal component with at least two Group VIB metal
components in the presence of a protic liquid, with at least one of the metal
components remaining at least partly in the solid state during the entire process.
It is thus essential to the process of the invention that at least one metal component remains at least partly in the solid state during the entire process of the invention. This process comprises combining and reacting the metal components. More in particular, it comprises adding the metal components to each other and simultaneously and/or thereafter reacting them. It is consequently essential to the process of the invention that at least one metal component is added at least party in the solid state and that this metal component remains at least partly in the solid state during the entire reaction. The term "at least partly in the solid state" in this ccmtext means that at least part of the metal component is present as a solid metal component and, optionally, another part of the metal component is present as a solution of this metal component in the protic liquid. A typical example of this is a suspension of a metal component in a protic liquid

in which the metal is at least partly present as a solid, and optionally partly dissolved in the protic liquid.
It is possible to first prepare a suspension of a metal component in the protic liquid and to add, simultaneously or one after the other, sa(utton(s) and/or further suspension^} comprising dissolved and/or suspended metal component(s) in the protic liquid. It is also possible to first combine solutions either simultaneously or one after the other and to subsequently add further suspension(s) and optionally solution(s) either simultaneously or one after the other.
In all these cases, a suspension comprising a metal component can be prepared by suspending a solid metal component in the protic Ikjuid.
However, it is also possible to prepare the suspension by (cojprecipitating one or mere metal components. The resulting suspension can tie applied as such in the process of the invention, i.e. further metal components in solution, in slurry orper se are added to the resulting suspension. The resulting suspension can also be applied after solid-liquid separation and/or after optionally being dried and/or after optionally being thermally treated and/or after optionally being wetted or reslurried in the protic liquid. Instead of a suspension of a metal component, a metal component in the wetted or dry state can be used.
It must be noted that the above process alternatives are only some examples to illustrate the addition of the metal components to the reaction mixture. Generally, all orders of addition are possible. Preferably, all Group Vlfl non-noble metal components are combined simultaneously and all Group VIE; metal components are combined simultaneously and the resulting two mixtures are subsequently combined.
As long as at least one metal component is at least partly in the solid state during the process of the invention, the number of metal components which are at least partly in the solid state is not critical. Thus it is possible fors.ll metal components to be combined in the process of the invention to be applied at least partly in the solid state. Alternatively, a metal component which is at least partly in solid state can be combined with a metal component which is in the solute state. E.g., one of the metal components

is added at least partly in the solid state and at [east two and preferably two metal components are added in the solute state, in another embodiment, two metal components are added at least partly in the solid state and at .east one and preferably one metal component is added in the solute state.
That a metal component is added "in the solute state" means that the whole amount of this metal component is added as a solution of thi:3 metal component in the protic liquid.
Without wishing to be bound by any theory. Applicant believes that the metal components which are added during the process of the invention interreact at least in part: the protic liquid is responsible for the transport of dissolved metal components. Due to this transport, the metal components come: into contact with each other and can react. It is believed that this reaction can even teke place if all metal components are virtually completely in the solid state. Due to the presence of the protic liquid, a smal) fraction of metal components may still dissolve and consequently react as described above. The presence of a protic liquid during thi; process of the present invention is therefore considered essential.
The reaction can be monitored by conventional techniques such as IR spectroscopy or Raman spectroscopy. The reaction is indicated in this case by signal changes. In some cases, it is also possible to monitor the reaction by monitoring the pH of the reaction mixture. The reaction in this case is indicated by pH change. Further, the completeness of the reaction can be monitored by X-ray diffraction. This will be described in more detail under the heading "Catalyst composition of Ihe invention."
It will be clear that it is not suitable to first pre-sare a solution comprising all metal components necessary for the preparation of a certain catalyst composition and to subsequently coprecipitate these components. Nor is it suitable for the process of the invention to add metal components at least partly in the solid state and to choose the process conditions, such as temperature, pH or smount of protic liquid, in such a way that all added metal components are present completely in the solute state at least at some stage. On the contrary, as has been set out above, at least one of the metal

components which is added at least partly in the sciid state must remain at least partly in the solid state during the entire reaction step-Preferably, at least 1 wt%, even more preferably at least 10 wt%, and still more preferably at least 15 wt% of a metal component is added in the solid state during the process of the invention, based on the total weight of all Group VtB and Group VIII non-noble metal components, calculated as metal oxides. When it is desired to obtain a high yield, i.e., a high amount of the final catal/st composition, the use of metal components of which a high amount remains in the solid state during the process of the invention may be the preferred method. In that case, low amounts of metal components remain dissolved in the mother liquid and the amount of metal components ending up in the waste water during the subsequent solid-liquid separation is decreased. Any loss of metal components can be avoided completely if thu mother liquid resulting from solid-liquid separation is recycled in the process of the present invention. It is noted that it is a particular advantage of the process of the present invention that compared to a catalyst preparation based on a co-precipitation process, the amount of waste water can be considerably reduced.
Depending on the reactivity of the metal components, preferably at least 0.01 wt%, more preferably at least 0.05 wt%, and most preferably at least 0.1 wt% of ail metal components initially employed in the process of the invention is added as a solution, based on the total weight of all metal components, calculated as metal oxides. In this way, proper contacting of the metal components is ensured. If the reactivity of a particular metal component to be added is low, it is recommended to add a high amount of this metal component as solution.
The protic liquid to be applied in the process of the present invention can be any pratic liquid. Examples are water, carboxylic acids, and alcohols such as methanol, ethanol or mixtures thereof. Preferably, a liquid comprising water, such as mixtures of an alcohol and water and more preferably water, is used as protic liquid in the process of the present invention. Also different protic liquids can be applied simultaneously in the process of the invention. For instance, it is possible to add a suspension of a metal

component in ethanol to an aqueous solution of another metal component, in some cases, a metal component can be used which dissolves in its own crystal water. The crystal water serves as protic liquid In this case. Of course, a protic liquid must be chosen which does not interfere with the reaction.
At least one Group VIII non-noble metal component and at least two Group VIB metal components are applied in the process of the invention. Suitable Group VIB metals include chromium, molybdenum, tungsten, or rnixlures thereof, with a combination of molybdenum and tungsten being most preferred. 'Suitable Group VIM non-noble metals include iron, cobalt, nickel, or mixtures thereof, preferably cobalt and/or nickel. Preferably, a combination of metal components comprising nickel, molybdenum, and tungsten or nickel, cobalt, molybdenum, and tungsten, or coPalt, molybdenum, and tungsten is applied in the process of the invention.
It is preferred that nickel and cobalt make up at least 50 wt% of the total of Group VIM non-noble metal components, calculated as oxides, more preferably at least 70 wt%, still more preferably at least 90 wt%. It may be especially preferred for the Group Vlii non-noble metal component to consist essentially of nickel and/or cobalt.
It is preferred that molybdenum and tungsten make up at least 50 vut% of trie total of Group VIB metal components, calculated as trioxktes, more preferably at least 70 wt%, still more preferably at least 90 vrt%. It may be eBpecially preferred for the Group Vie metal component to consist essentially of molybdenum and tungsten.
The molar ratio of Group V!B to Group VIII non-noble metals applied in the process of the invention generally ranges from 10:1 -1:10 and preferably from 3:1 -1:3. The molar ratio of the different Group VIB metals to one another generally is not critical. The same holds when more than one Group VIII non-noble metal is applied. When molybdenum and tungsten are applied as Group VIB metals, the molybenum:tungsten molar ratio preferably lies in the range of 9:1 -1:19, more preferably 3:1 -1.9. most preferably 3:1 -1:6.

If the protic liquid is water, the solubility of the Group VIII non-noble metal components and Group VIB metal components which are at leE.st partly in the solid state during the process of the invention generally is less than 0.05 mol/{100 ml water at 18°C).
If the protic liquid is water, suitable Group VIII nori-nable metal components which are at least partly in the solid state during the process of the invention comprise Group VIII non-noble metal components with a low solubility in water such as citrates, oxalates, carbonates, hydroxy-carbonates, hydroxides, phosphates, phosphides, sulphides, aluminates, molybdates, tungstates, oxides, or mixtures thereof. Preferably. Group VIII non-noble metal components which are at least partly in the solid state during the process of the invention comprise, and more preferably consist essentially of, oxalates, carbonates, hydroxy-carbonates, hydroxides, phosphates, molybdates, tungstates, oxides, or mixtures thereof, with hydroxy-carbonates and carbonates being most preferred. Generally, the molar ratio between the hydroxy groups and the carbonate groups in the hydroxy-carbanate lies in the ranjie of 0 - 4, preferably 0-2, more preferably 0 -1 and most preferably 0.1 - 0.3. Mosl preferably, the Group VIII non-noble metal component which is at least partly in the stolid state during the process of the invention is a Group VIII non-noble metal salt.
If the protic liquid is water, suitable nickel and cobalt components which are at least partly in the solid state during the process of thu invention comprise water-insotuble nickel or cobalt components such as oxalate:;, citrates, aluminates, carbonates. hydroxy-carbonates, hydroxides, molybdates. phosphates, phosphides, sulphides, tungstates, oxides, or mixtures thereof of nickel aid/or cobalt. Preferably, the nickel or cobalt component comprises, and more preferably consists essentially, of oxalates, citrates, carbonates, hydroxy-carbonates, hyoroxides, molybdates, phosphates, tungstates, oxides, or mixtures thereof of nickel anaVor cobalt, with nickel and/or cobalt hydraxy-carbonate, nickel and/or cobalt hydroxidu, nickel and/or cobalt carbonate, or mixtures thereof being most preferred. Generally, the molar ratio between the hydroxy groups and the carbonate groups in the nickel or cobalt or nickel-cobalt hydroxy-carbanate lies in the range of 0 - 4, preferably 0-2, more preferably 0 - 1 and most preferably 0.1 - 0.8. Suitable iron components whi:h are at least partly in the solid state

are iron(ll) citrate, iron carbonate, hydroxy-carbonate, hydroxide, phosphate, phosphide, sulphide, oxide, or mixtures thereof, with iron(ll) citrate, iron carbonate, hydroxy-carbonate, hydroxide, phosphate, phosphide, oxide, or mixtures thereof being preferred.
If the protic liquid is water, suitable Group VIB metal components which are at least partly in the solid slate during contacting comprise Group VIB metal components with a low solubility in water, such as di- and trioxides, carbides, nitrides, aluminium sails, acids, sulphides, or mixtures thereof. Preferred Group VIB metal components which are at (east partly in the solid state during contacting comprise, and preferably consist essentially of, di-and trioxides, acids, or mixtures thereof.
Suitable molybdenum components which are at least partly in the solid state during the process of the invention comprise water-insoluble molybdenum components such as molybdenum di- and trioxide. molybdenum sulphide, molybdenum carbide, molybdenum nitride, aluminium molybdate, molybdic acids {e.g. H,MoO«), ammonium phcsphomolybdate, or mixtures thereof, with molybdic acid and molybdenum di- and trioxide being preferred
Finally, suitable tungsten components which are a* least partly in the solid state during the process of the invention comprise water-insoluble tungsten compounds, such as tungsten di- and trioxide, tungsten sulphide (WS2 and WS3), tungsten carbide, ortho-tungstic acid (H3W(VHjO), tungsten nitride, aluminium tungstate (also meta- or polytungstate), ammonium phosphotungstate,: or inixtures thereof, with ortho-tungstic acid and tungsten di- and trioxide being preferred.
AH the above components generally are commercially available or can be prepared by, e.g., precipitation. E.g., nickel hydroxy-carbonate can be prepared from a nickel chloride, sulphate, or nitrate solution by adding an appropriate amount of sodium carbonate. It is generally known to the skilled oerson to choose the precipitation conditions in such a way as to obtain the desired morphology and texture.

In general, metal components which mainly contain C, 0 and/or H beside the metal are preferred because they are less detrimental to the environment. Group VIII non-noble metal carbonates and hydroxy-carbonate are preferred metal components to be added at least partly in the solid state because when carbonate or hydroxy-carbonate is applied, COz evolves and positively influences the pH of the reaction mixture. Further, because the carbonate is transformed into COj and does not end up in the waste water, it is possible to recycle the waste water. Further, in this case no washing step is necessary to remove undesired anions from the resulting bulk catalyst particles.
Preferred Group VIII non-noble metal components to be added in the solute state comprise water-soluble Group VIII non-noble meta saits, such as nitrates, sulphates, acetates, chlorides, formates, hypophosphites and nixtures thereof. Examples include water-soluble nickel anchor cobalt components, e.g., water-soluble nickel and/or cobalt salts such as nitrates, sulphates, acetates, chlorides, formates, or mixtures thereof of nickel and/or cobalt as well as nickel hypophosphiie. Suitable iron components to be added in the solute state comprise iron acetate, choride, formate, nitrate, sulphate, or mixtures thereof.
Suitable Group V1B metal components to be added in the solute state include water-soluble Group V1B metal salts such as normal ammonium or alkali metal monomolybdates and tungstates as well as wster-sotuble isopoly-compounds of molybdenum and tungsten, such as metatungstic acid, or water-soluble heteropoly compounds of molybdenum or tungsten further comprising, e.g.. P, Si, Ni, or Co or combinations thereof. Suitable water-soluble isopoty- and heteropoly compounds are given in Molybdenum ChemicaJs, Chemical data seres. Bulletin Cdb-14, February 1969 and in Molybdenum Chemiggls, Chemical data series, Bulletin Cdb-12a-revised, November 1969. Suitable water-soluble chromium compounds are, e.g., normal chromates, isopolychromates and ammonium chromium sulphate.
Preferred combinations of metal components are a Group VIII non-noble metal hydroxy-carbonate and/or carbonate, such as nickel or cobalt hydroxy-carbonate and/or carbonate, with a Group V!8 metal oxide and/or a Group VIB acid, such as the

combination of tungstic acid and molybdenum oxide, or the combination of molybdenum trioxide and tungsten trioxide, or a Group Vlll hydroxy-carbonate and/ar carbonate, such as nickel or cobalt hydroxy carbonate and/or carbonate, with Group VIB metal salts, such as ammonium dimolybdatu, ammonium heptamolybdate, and ammonium metatungstate. It is within the capabiiity of the skilled person to select further suitable combinations of metal components.
It has been found that the morphology and the texture of the metal component or components which remain at least partly in the solid state during the process of the invention can be retained during the process of the present invention. Consequently, by applying metal component particles with a certain morphology and texture, the morphology and the texture of the bulk catalyst particles contained in the final catalyst composition can be controlled at least to some extent. "Morphology and texture" in the sense of the present invention refer to pore volume, pore size distribution, surface area, particle form and particle size. The "bulk catalyst particles" contained in the final catalyst composition will be described under the heading "Catalyst composition of the present invention."
Generally the surface area of the oxidic bulk catalyst particles is at least 60%, preferably at least 70%, and more preferably at least 80% of the surface area of the metal component which remains at least partly in the solid state during the process of the invention. The surface area is expressed in thi:; case as surface area per weight of this metai component, calculated as metal oxide. Further, the median pore diameter (determined by nitrogen adsorption) of the oxidic tiuik catalyst particles generally is at least 40% and preferably at least 50% of the median pore diameter of the metal component which remains at least partly in the solid state dunng the process of the invention. Furthermore, the pore volume {deternrned by nitrogen adsorption) in the oxidic catalyst particles generally is at least 40% and preferably at least S0% of the pore volume of the metal component which remains at least partly in the solid state during the process of the invention, with the pore volume being expressed in volume of pares per weight of this metal component, calculated as metal oxide.

The retainment of the particle size generally is dependent on the extent of mechanical damage undergone by the axidic bulk catalyst particles during processing, especially during steps such as mixing or kneading. The particle diameter can be retained to a high extent if these treatments are short and gentle. In this case, the median particle diameter of the axidic bulk catalyst particles generally is at least 80% and preferably at least 90% of the median partide diameter of the metal component which remains al least partly in the solid state during the process of the invention. The particle size can also be affected by treatments such as spray-dryir.g, especially if further materials are present. It is within the capability of the skilled person to select suitable conditions in order to control the particle size distribution during such treatments.
When a metal component which is added at least partly in the solid state and which has a large median particle diameter is selected, it is thought that the other metal components will only react with the outer layer of the large metal component particle. In this case, so-called "core-shell" structured bulk catalyst particles result.
An appropriate morphology and texture of the metal oomponent(s) can be achieved either by applying suitable preformed metal components or by preparing these metal components by means of the above-described precipitation or re-crystallization or any other technique known by the skilled person under such conditions that a suitable morphology and texture are obtained. A proper selection of appropriate precipitation conditions can be made by routine experimentation
To obtain a final catalyst composition with high catalytic activity, it is preferred that the metal component or components which are at teasi partfy in the solid state during the process of the invention are porous metal components. It is desired that the total pore volume and the pore size distribution of these metal components are similar to those of conventional hydroprocessing catalysts. Conventional hydroprocessing catalysts generally have a pore volume of 0.05 - 5 ml/g, preferably of 0.1 - 4 mi/g, more preferably of 0.1 - 3 ml/g, and most preferably of 0.1 - 2 ml/g, as determined by mercury or water porosimetry. Further, conventional hydroptocessing catalysts generally have a

surface area of at least 10 mJ/g, more preferably of at least 50 rrr/g, and most preferably of at least 100 m*/g. as determined via the B.E.T. method.
The median particle diameter of the metal component or components which are at least partly in the solid state during the process of the invention preferably is in the range of at least 0.5 jim, more preferably at least 1 urn, most preferably at least 2 p, but preferably not more than 5000 jjm, more preferably not more than 1000 ^im, even more preferably not more than 500 urn. and most preferably not more than 150 fim. Even more preferably, the median particle diameter lies in the range of 1 • 150nm and most preferably in the range of 2- 150 |im. Generally, the smaller the particle size of the metal components, the higher their reactivity. Therefore, metal components with particle sizes below the preferred lower limits are ir principle a preferred embodiment of the present invention. However, for health, safety, and environmental reasons, the handling of such small particles requires special precautions.
In the following, preferred process conditions during the combination of the metal components and the (subsequent) reaction step will be described: a) combination of the metal components:
The process conditions during the combination of the metal components generally are not critical. It is possible to add all components at ambient temperature at their natural pK (if a suspension or solution is applied). Generally, it is of course preferred to Keep the temperature of the metal components to be added below the atmospheric boiling point of the reaction mixture to ensure easy handling of the components during the addition. However, if desired, also temperatures above the atmospheric boiling point of the reaction mixture or different pH values can be applied. If the reaction step is carried out at increased temperature, the suspensions and optionally solutions which are added to the reaction mixture generally can be pre-heated to an increased temperature which can be equai to the reaction temperature.
As has been mentioned above, the addition of one or more metal components can also be carried out while already combined metal components react with each other. In this case, the combination of the metal components and the reaction thereof overlap and constitute a single process step.

bj reaction step:
During and/or after their addition, the metal comoonents generally are agitated at a
certain temperature far a certain period of time to allow the reaction to take pface. The
reaction temperature preferably is in the range of Q° - 30Q°C. more preferably 50° -
300°C, even more preferably 70° - 200°C, and rrost preferably in the range of 70° -
18Q°C. If the temperature is below the atmospheric: boiling point of the reaction mixture.
the process generally is carried out at atmospheric pressure. Above this temperature,
the reaction generally is carried out at increased pressure, preferably in an autoclave
and/or static mixer.
Generally, the mixture is kept at its natural pH during the reaction step. The pH
preferably is in the range of 0 -12, more preferably in the range of 1 - 10, and even
more preferably in the range of 3 - 8. As has beei set out above, care must.be taken
that the pH and the temperature are chosen in such a way that not all the metals are
dissolved during the reaction step.
The reaction time generally lies in the range of 1 minute to several days, more
preferably in the range of 1 minute to 24 hours, and most preferably in the range of 5
minutes to 20 hours. As has been mentioned above, the reaction time depends on the
temperature.
After the reaction step, if necessary, the solid can be separated from the liquid, e.g., via filtration.
The process of the present invention can be carried out both as a batch process and as a continuous process.
If so desired, a material selected from the group of binder materials, conventional hydroprocessing catafysts, cracking components, or mixtures thereof can be added during the above-described preparation of the bulk catalyst particles or to the particles after their preparation, as will be elucidated below. Details in respect of these materials are given below in chapter (B).

For this process embodiment, the following options are available: the Group VIB and Group VIII non-noble metal components can generally be combined with any of the above materials either prior to or during the reaction of the metal components. They can, e.g., be added to the material either simultaneously or one after the other. Alternatively, the Group VIB and Group VIII non-noble metal components can be combined as described above, and subsequently a material can be added to the combined metal components. It is further possibles to combine part of the Group VIB and Group Vlll non-noble metal components either simultaneously or one after the other, to subsequently add the material, and to finally add the rest of the Group VIB and Group Vlll non-noble metal components either simultaneously or one after the other. For instance, a Group VIB or Group Vlll non-nobl>! metal component which is at least partly in the solid state during the process of the invention can be first mixed and if desired shaped with the material and, subsequently, further Group VIB and/or Group Vtll non-noble metal components) can be added to the optionally shaped mixture. However, it is also possible to combine the material with Group VIB and Group Vlll non-noble metal components) in the salute state .and to subsequently add a metal component at least partly in the solid state. Finally, simultaneous addition of the metal components and the material is possible.
As stated above, the material to be added during the preparation of the bulk catalyst particles can be a binder material. Binder material according to the present invention means a binder and/or a precursor thereof. If a precursor is added in the form of a solution, care must be taken that the binder is converted to the solid state during the process of the invention. This can be done by adjusting the pH conditions in such a way that precipitation of the binder occurs. Suitable conditions for the precipitation of the binder are known to the skilled person and need no further explanation. If the amount of liquid of the resulting catalyst composition is too high, optionally a solid-liquid separation can be carried out.
Additionally, further materials such as phosphorus-containing compounds, boron-containing compounds, silicon-containing compounds, fluorine-containing compounds, additional transition metals, rare earth metals, or mixtures thereof can be added during

the preparation of the buik catalyst particles in a similar way to that described for the above materials. Details in respect of these further materials are given below.
It is noted that irrespective of whether any of the above (further) materials are added during the preparation of the particles, the particles resulting from the process described above under (A) will be denoted as "hulk catalyst particles" in the present invention.
(S) Subsequent process steps
Preferably, the bulk catalyst particles either as such or comprising any of the above
(further) materials are subjected to one or mare oi the following process steps of
(i) compositing with a material selected from the group of binder materials, conventional
hydroprocessing catalysts, cracking components, or mixtures thereof,
(ii) spray-drying, (flash) drying, milling, kneading, slurry-mixing, dry or wet mixing, or
combinations thereof,
(iii) shaping,
(iv) drying and/or thermally treating, and
(v) sulphidtng.
These process steps will be explained in more derail in the following:
Process step (i)
The material can be added in the dry state, either thermally treated or not, in the wetted
and/or suspended state and/or as a solution.
The material can be added during the preparation of the bulk catalyst particles (see above), subsequent to the preparation of the bulk catalyst composition but prior to any step (ii) and/or during and/or subsequent to any step (ii) but prior to any shaping step
m.
Preferably, the material is added subsequent tci the preparation of the bulk catalyst particles and prior to spray-drying or any alternative technique, or, if spray-drying or the

alternative techniques are not applied, prior to shaping. Optionally, the bulk catalyst composition prepared as described above can be subjected to a solid-liquid separation before being composited with the material- After solid-liquid separation, optionally, a washing step can be included. Further, it is possible to thermally treat the bulk catalyst composition after an optional solid-liquid separation and drying step and prior to its being composited with the material.
In all the above-described process alternatives, the term "compositing the bulk catalyst composition with a material" means that the material is added to the bulk catalyst composition or vies versa and the resulting composition is mixed. Mixing is preferably done in the presence of a liquid ("wet mixing"). Tris improves the mechanics) strength of the final catalyst composition.
It has been found that compositing the bulk catalyst particles with the material and/or incorporating the material during the preparation of the bulk catalyst particles leads to bulk catalyst compositions of particularly high mechanical strength, in particular if the median particle size of the bulk catalyst particles is in the range of at least 0.5pm, more preferably at least 1 pjn, most preferably at least 2 jim, but preferably not more than 5000 urn, more preferably not more than 1000um, even more preferably not more than 500 jim, and most preferably not more than 150 um. Even more preferably, the median particle diameter lies in the range of 1 - 150 um arid most preferably in the range of 2-150 um.
The compositing of the bulk catalyst particles with, the material results in bulk catalyst particles embedded in this material or wee versa. Normally, the morphology of the bulk catalyst particles is essentially maintained in the resulting catalyst composition.
As stated above, the material may be selected from a binder materia), a conventional hydroprocessing catalyst, a cracking component, or mixtures thereof. These materials will be described in more detail below.

The binder materials to be applied may be any materials conventionally applied as binders in hydraprocessing catalysts. Examples are silica, silica-alumina, such as conventional siiica-alumina, silica-coated alumina and alumina-coated silica, alumina such as (pseudo)boehmite, or gibbsite, titania, titania-coated alumina, zirconia, cationic clays or anionic clays such as saponite, bentonitd, kaolin, sepiolite or hydrotalcite, or mixtures thereof. Preferred binders are silica, silica-alumina, alumina, titania, titania-coated alumina, zirconia, bentonite, or mixtures thereof. These binders may be applied as such or after peptization.
It is also possible to apply precursors of these binders which during the process of the invention are converted into any of the above-described binders. Suitable precursors are, e.g., alkali metal aluminates (to obtain an alumina binder), water glass (to obtain a silica binder), a mixture of alkali metal aluminates and water glass (to obtain a silica-alumina binder), a mixture of sources of a di-, tri - and/or tetravalent metal such as a mixture of water-soluble salts of magnesium, aluminium and/or silicon (to prepare a cationic clay and/or anionic day), aluminium chlorohydrol, aluminium sulphate, aluminium nitrate, aluminium chloride, or mixtures thereof.
If desired, the binder material may be composited with a Group VIB metal-containing compound and/or a Group VIII nan-noble metal-containing compound, prior to being composited with the bulk catalyst composition anilOT prior to being added during the preparation thereof. Compositing the binder material with any of these metal-containing compounds may be carried out by impregnation of the binder with these materials. Suitable impregnation techniques are known to the person skilled in the art. If the binder is peptized, it is also possible to carry out Hie peptization in the presence of Group VIB and/or Group VIII non-noble metal containing compounds.
If alumina is applied as binder, the surface area of the alumina generally lies in the range of 50 - 600 m2/g and preferably 10Q - 450 m*/g, as measured by the B.E.T. method. The pare volume of the alumina preferably is in the range of 0.1 -1.5 ml/g, as measured by nitrogen adsorption. Before the characterization of the alumina, it is thermally treated at 600nC for 1 hour.

Generally, the binder material to be added in the process of the invention has less catalytic activity than the bulk catalyst composition or no catalytic activity at all. Consequently, by adding a binder material, the activity of the bulk catalyst composition may be reduced. Furthermore, the addition of binder material leads to a considerable increase in the mechanical strength of the final catalyst composition. Therefore, the amount of binder material to be added in the process of the invention generally depends on the desired activity and/or desired mechanical strength of the final catalyst composition. Binder amounts from 0 - 95 wt% of the total composition can be suitable, depending on the envisaged catalytic application. However, to take advantage of the resulting unusually high activity of the composition of the present invention, the binder amounts to be added generally are in the range of 0 - 75 wt% of the total composition, preferably 0-50 wt%, mare preferably 0 - 30 wt%.
Conventional hydroprocessing catalysts are, e.g., conventional hydrodesulphurization, hydrodenitrogenation, or hydracracking catalysts. These catalysts can be added in the used, regenerated, fresh, or sulphided stata. If desired, the conventional hydroprocessing catalyst may be milled or treated in any other conventional way before being applied in the process of the invention.
A. cracking component according to the present invention is any conventional cracking component such as cationic clays, anionic ciays, ciystalline cracking components such as zeolites, e.g. ZSM-5, (ultra-stable) zeolite Y, zsolite X. ALPOs, SAPOs, MCM-41, amorphous cracking components such as silica-alumina, or mixtures thereof. It will be dear that some materials may act as binder and cracking component at the same time. For instance, silica-alumina may have a cracking and a binding function at the same time.
If desired, the cracking component may be compos.ted with a Group V1B metal and/or a Group VIII non-noble metal prior to being composited with the bulk catalyst composition and/or prior to being added during the preparation thereof. Compositing the cracking component with any of these metals may take the 'orm of impregnation of the cracking component with these materials.

Generally, it depends on the envisaged catalytc application of the final catalyst composition which of the above-described cracking components, if any, is added. A crystalline cracking component is preferably added if the resulting composition is to be applied in hydrocracking. Other cracking components such as silica-alumina or cadonic clays are preferably added if the final catalyst composition is to be used in hydrotreating applications or mild hydrocracking. The amount cf cracking material which is added depends an the desired activity of the final composition and the application envisaged, and thus may vary from 0 to 90 wt%, based on the total weight of the catalyst composition.
Optionally, further materials, such as phosphoms-containing compounds, boron-containing compounds, silicon-containing compourds, fluorine-containing compounds, additional transition metal compounds, rare ear:h metal compounds, or mixtures thereof, may be incorporated into the catalyst composition.
As phosphorus-containing compounds may be applied ammonium phosphate, phosphoric acid or organic phosphorus-containing compounds. Phosphorus-containing compounds can be added at any stage of the process of the present invention prior to the shaping step and/or subsequent to the shaping step. If the binder material is peptized, phosphorus-containing compounds can also be used for peptization. For instance, an alumina binder can be peptized by being contacted with phosphoric acid or with a mixture of phosphoric acid and nitric acid.
As boron-containing compounds may be applied, e.g., boric acid or heteropoly compounds of boron with molybdenum and/or tungsten and as fluorine-containing compounds may be applied, e.g., ammonium fluoride. Typical silicon-containing compounds are water glass, silica gel, tetraethylortrtosiiicate or heteropoly compounds of silicon with molybdenum and/or tungsten. Further, compounds such as fluorosilicic acid, fiuoroboric acid, difluorophosphoric acid or lexafluorophosphoric acid may be applied if a combination of F with Si. B and P, respectively, is desired.

Suitable additional transition metals are, e.g., rhenium, manganese, ruthenium, rhodium, iridium, chromium, vanadium, iron, pla:inum, palladium, titanium, zirconium, niobium, cobalt, nickel, molybdenum, or tungsten. These metals can be added at any stage of the process of the present invention prior to the shaping step. Apart from adding these metals during the process of the invention, it is also possible to composite the final catalyst composition therewith. Thus i: is possible to impregnate the final catalyst composition with an impregnation solution comprising any of these metals.
Process step (ii)
The bulk catalyst particles optionally comprising any of the above (further) materials can be subjected to spray-drying, (flash) drying, milling, kneading, slurry-mixing, dry or wet mixing, or combinations thereof, with a combination of wet mixing and kneading or slurry mixing and spray-drying being preferred.
These techniques can be applied either before or after any of the above (further) materials are added (if at ail), after solid-liquid separation, before or after a thermal treatment, and subsequent to re-wetting.
Preferably, the bufk catalyst particles are both composited with any of the above materials and subjected to any of the above techniques. It is believed that by applying any of the above-described techniques of spray-di-ying, (flash) drying, milling, kneading, slurry-mixing, dry or wet mixing, or combinations Ihereof, the degree of mixing between the bulk catalyst composition and any of the above materials is improved. This applies to cases where the materia! is added before as well as after the application of any of the above-described methods. However, it is generally preferred to add the material prior to step (ii). If the material Is added subsequent to step (ii), the resulting composition preferably is thoroughly mixed by any conventional technique prior to any further process steps such as shaping. An advantage of, e.g., spray-drying is that no waste water streams are obtained when this technique is applied.
Spray-drying typically is carried out at an outlel temperature in the range of 100° -200°C and preferably 120° - 180°C.

Dry mixing means mixing the bulk catalyst particles in the dry state with any of the above materials in the dry state. Wet mixing, e.g., comprises mixing the wet filter cake comprising the bulk catalyst particles and optionally any of the above materials as powders or wet filter cake to form a homogenous paste thereof.
Process step (iii)
If so desired, the bulk catalyst optionally comprising any of the above (further) materials may be shaped optionally after step (ti) having been applied. Shaping comprises extrusion, palletizing, beading and/or spray-dryinci. It must be noted that if the catalyst composition is to be applied in slurry-type reactors, fiuidized beds, moving beds, or expanded beds, generally spray-drying or beading is applied. For fixed bed or ebullating bed applications, generally the catalyst composition is extruded, peiletized and/or beaded, in the Jatter case, 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, polyethylene glycols, polyethylene oxides, or mixtures thereof. Further, when alumina is used as binder, it may be desirable to add acids such as nitric acid prior to the shaping step to increase the mechanical strength of the extrudates.
If the shaping comprises extrusion, beading and/or spray-drying, it is preferred that the shaping step is carried out in the presence of a liquid, such as water. Preferably, for extrusion and/or beading, the amount of liquid in the shaping mixture, expressed as LOI. is in the range of 20 - 80%.
If so desired, coaxial extrusion of any of the above materials with the bulk catalyst particles, optionally comprising any of the above materials, may be applied. More in particuiar, two mixtures can be co-extruded, in .vhich case the bulk catalyst particles optionally comprising any of the above materiE.ls are present in the inner extrusion medium while any of the above materials without the bulk catalyst particles is present in the outer extrusion medium or wee versa.

Step (iv)
After an optional drying step, preferably above 100DC, the resulting shaped catalyst composition may be thermally treated if desired. A thermal treatment, however, is not essential to the process of the invention. A "thermal treatment" according to the present invention refers to a treatment performed at a temperature of, e.g., from 100° - 600*C, preferably from 150° to 550aC, more preferably 150°C - 4508C, for a time varying from 0.5 to 48 hours in an inert gas such as nitrogen, cr in an oxygen-containing gas, such as air or pure oxygen. The thermal treatment can be earned out in the presence of water steam.
In all the above process steps the amount of liquid must be controlled. If, e.g., prior to subjecting the catalyst composition to spray-drying the amount of liquid is too low, additional liquid must be added. If, on the other hand, e.g., prior to extrusion of the catalyst composition the amount of liquid is too high, the amount of liquid must be reduced by, e.g., solid-liquid separation via, e.g., filtration, decantation, or evaporation and, if necessary, the resulting material can be dried and subsequently re-wetted to a certain extent. For all the above process steps, it is within the scope of the skilled person to control the amount of liquid appropriately
Process step (v)
The process of the present invention may further comprise a sulphidation step. Suiphidation generally is carried out by contacting the bulk catalyst particles directly after their preparation or after any one of process steps (i) - (iv) with a sulphur-containing compound such as elementary sulphur, hydrogen sulphide, DMDS, or polysulphides. The sulphidation step can be carried out in the liquid and the gaseous phase. The suiphidation can be earned out subsequent to the preparation of the bulk catalyst composition but prior to step (i) and/or subsequent to step (i) but prior to step (ii) and/or subsequent to step (ii) but prior to step (iii) and/or subsequent to step (lii) but prior to step (iv) and/or subsequent to step (iv). It is preferred that the sulphidation is not carried out prior to any process step by which the obtained metal sulphides revert to their oxides. Such process steps are, e.g.. a thermal treatment or spray-drying or any other high-temperature treatment if carried DUI under an oxygen-containing

atmosphere. Consequently, if the catalyst composition is subjected to spray-drying and/or any alternative technique or to a thermal treatment under an oxygen-containing atmosphere, the sulphidation preferably is carried out subsequent to the application of any of these methods. Of course, if these methods are applied under an inert atmosphere, sulphidation can also be carried out prior to these methods.
if the catalyst composition is used in fixed bed procsisses, the sulphidation preferably is carried out subsequent to the shaping step and, if applied, subsequent to the last thermal treatment in an oxidizing atmosphere.
The sulphidation can generally be carried out in situ and/or ex situ. Preferably, the sulphidation is carried out ex situ, i.e. the sulphidation is carried out in a separate reactor prior to the sulphided catalyst composition being loaded into the hydroprocessing unit. Furthermore, it is preferreo that the catalyst composition is sulphided both ex situ and in situ.
A preferred process of the present invention comprises the fallowing successive process steps of preparing the bulk catalyst particle:: as described above, slurry mixing the obtained bulk catalyst particles with, e.g., a binder, spray drying the resulting composition, rewetting, kneading, extrusion, drying, calcining and sulphiding. Another preferred process embodiment comprises the following successive steps of preparing the bulk catalyst particles as described above, isolating the particles via nttration, wet mixing the fitter cake with a material, such as a binder, kneading, extrusion, drying, calcining and sulphiding.
Catalyst composition of thq invention
The invention further pertains to a catalyst composition obtainable by the above-described process. Preferably, the invention pertains to a catalyst composition obtainable by process step (A) and optionally one or more of process steps B(i) - (iv) described above.
In a preferred embodiment, the invention pertains to a catalyst composition obtainable by the above-described process wherein the morphology of the metal component(s)

which are at least partly in the solid state during ;he process is retained in the catalyst composition. This retention of morphology is described in detail under the heading "Process of the present invention."
(a) oxidic catalyst composition
Furthermore, the invention pertains to a catalyst composition comprising bulk catalyst particles which comprise at least one Group VIM non-noble metal and at least two Group VIB metals, wherein the metals are preseit in the catalyst composition in their oxidic state, and wherein the characteristic full width at half maximum does not exceed 2.5° when the Group VIB metals are molybdenum, tungsten, and, optionally, chromium, or does not exceed 4.0° when the Group VIB metals are molybdenum and chromium or tungsten and chromium.
As described in the chapter "characterization me:hods", the characteristic full width at half maximum is determined on the basis of tha peak located at 26= 53.6° {±0.7°) (when the Group VIB metals are molybdenum, tungsten and optionally chromium or when the Group VIB metals are tungsten and chromium) or at 29 = 63.5° (±0.6°) (when the Group VIB metais are molybdenum and chrorrium).
Preferably, the characteristic full width at half maximum does not exceed 2.2°, more preferably 2.0°, still more preferably 1.8°, and most preferably it does not exceed 1.6° {when the Group VIB metals are molybdenum, tungsten, and, optionally, chromium) or it does not exceed 3.5°, more preferably 3.0°, still more preferably 2.5°, and most preferably 2.0° (when the Group VIB metals are molybdenum and chromium or tungsten and chromium).
Preferably, the X-ray diffraction pattern shows two peaks at the positions 29 = 38.7° (±0.6°) and 40.8° (+0.7°) (these peaks will be referred to as doublet P) and/or two peaks at the positions 28 = 61.1" (±1.5°) and 64.T1 (±1.2°) {these peaks will be referred to as doublet Q} when the Group VIB metals are molybdenum, tungsten, and, optionally, chromium.

From the characteristic full width at half maximum of the oxidic catalyst compositions of the present invention and, optionaily. the presence of at least one of the two doublets P and Q, it can be deduced that the microstructure of the catalyst of the present invention differs from that of corresponding catalysts prepared via co-precipitation as described in WO 9903578 or US 3,678,124.
Typical X-ray diffraction patterns are described in the examples.
The X-ray diffraction pattern of the bulk catalyst particles preferably does not contain any peaks characteristic to the metal components ta be reacted. Of course, if desired, it is also possible to choose the amounts of metal components in such a way as to obtain bulk catalyst particles characterized by an X-ray diffraction pattern still comprising one or more peaks characteristic to at least one of these metal components. If, e.g., a high amount of the metal component which is at least partly in the solid state during the process of the invention is added, or if this metal component is added in the form of large particles, small amounts of this metal eom|>onent may be traced in the X-ray diffraction pattern of the resulting bulk catalyst partides.
The molar ratio of Group VIB to Group VIII non-noble metals generally ranges from 10:1-1:10 and preferably from 3:1 -1:3. In lha casie of a core-shell structured particle, these ratios of course apply to the metals contained in the shell. The ratio of the different Group VIB metais to one another generally is not critical. The same holds when more than one Group Vlll non-noble metal is applied. In cases where molybdenum and tungsten are present as Group VIB metals, the molybenum:tungsten ratio preferably lies in the range of 9:1 -1:19, more preferably 3:1 -1:9, most preferably 3:1 -1:6.
The bulk catalyst particles comprise at least one Group Vlll non-noble metal component and at least two Group VIB metal comoonents. Suitable Group VIB metals include chromium, molybdenum, tungsten, or mixlures thereof, with a combination of molybdenum and tungsten being most preferred. Suitable Group Vlll non-noble metals include iron, cobalt, nickel, or mixtures thereof, preferably nickel and/or cobalt.

Preferably, a combination of metals comprising nickel, molybdenum, and tungsten or nickel, cobalt, molybdenum, and tungsten, or cobalt, molybdenum, and tungsten is contained in the bulk catalyst particles of the inveniion.
It is preferred that nickel and cobalt make up at least 50 wt% of the total of Group Vlll non-noble metal components, calculated as oxides, more preferably at least 70 wt%, still more preferably at least 90 wt%. It may be especially preferred for the Group Vlll non-noble metal component to consist essentially of nickel and/or cobait.
It is preferred that molybdenum and tungsten make up at least 50 wt% of the total of Group VIB metal components, calculated as dioxides, more preferably at least 70 wt%, still more preferably at least 90 wt%. It may be especially preferred for the Group VIB metal component to consist essentially of molybdenum and tungsten.
Preferably, the oxidic bulk catalyst particles comprised in these catalyst compositions have a B. E. T. surface area of at least 10 m2/g, more preferably of at least 50 m2/g, and most preferably of at least 80 m2/g, as measured via the B.E.T. method.
If during the preparation of the bulk catalyst particles none of the above (further) materials, such as a binder material, a cracking component or a conventional hydroprocessing catalyst, have been added, the bulk catalyst particles will comprise about 100 wt% of Group VIB and Group Vlll non-noble metals. If any of the above materials have been added during the preparation of the bulk catalyst particles, they will preferably comprise 30 - 100 wt%, more p-eferably 50 - 100 wt%, and most preferably 70 -100 wt% of the Group VIB and Group Vlll non-noble metals, the balance being any of the above-mentioned (further) materials. The amount of Group VIB and Group Vlll non-noble metals can be determined vis TEM-EDX, AAS or ICP.
The median pore diameter (50% of the pore volume is below said diameter, the other 50% above it) of the oxidic bulk catalyst partic.es preferably is 3 - 25 nm, more preferably 5 -15 nm (determined by N2 adsorption).

The total pore volume of the oxidic bulk catalyst particles preferably is at least 0.05 ml/g and more preferably at least 0.1 ml/g. as determined by N, adsorption.
It is desired that the pore size distribution of the bu'k catalyst particles is approximately the same as that of conventional hydroprocessing catalysts. More in particular, the bulk catalyst particles preferably have a median pore diameter of 3 - 25 nm, as determined by nitrogen adsorption, a pore volume of 0.05 - 5 ml/g, more preferably of 0,1 - 4 ml/g, still more preferably of 0.1 - 3 ml/g, and most preferably of 0.1 - 2 ml/g. as determined by nitrogen adsorption.
Furthermore, these bulk catalyst particles preferably have a median particle size in the range of at least 0.5 urn, more preferably at least 1 ^m, most preferably at least 2 nm, but preferably not more than 5000 jim. more prefeiably not more than 1000 jim, even more preferably not more than 500 fim, and most preferably not more than 150 ym. Even more preferably, the median particle diameter lies in the range of 1 - 150[im and most preferably in the range of 2 -150 jim.
As has been mentioned above, if so desired, it is possible to prepare core-shell structured bulk catalyst particles using the process of the invention. In these particles. at least one of the metals is anisotropically distributed in the bulk catalyst particles. The concentration of a metal, the metal component of which is at least partly in the solid state during the process of the invention, generally is higher in the inner part, i.e., the core of the final bulk catalyst particles, than in the outer part. i.e. the shell of the final bulk catalyst particles. Generally, the concentration of this metal in the shell of the final bulk catalyst particles is at most 95% and in most cases at most 90% of the concentration of this metal in the core of the final bulk catalyst particles. Further, it has been found that the metal of a metal component which is applied in the solute state during the process of the invention is also anisotropically distributed in the final bulk catalyst particles. More in particular, the concentration of this metal in the core of the final bulk catalyst particles generally is lower than the concentration of this metal in the shell. Stiil more in particular, the concentration of tris metal in the core of the final bulk catalyst particles is at most 80% and frequently at most 70% and often at most 60% of

the concentration of this metal in the shell. It must be noted that the above-described anisotropic metal distributions, if any. can be found in the catalyst composition of the invention irrespective of whether the catalyst conposition has been thermally treated and/or sulphided. In the above cases, the shell generally has a thickness of 10 - 1,0.0.0. nm.
Though the above anisotropic metal distribution can be achieved with the process of the invention, the Group VIB and Group VIII non-noble metals generally are homogeneously distributed in the bulk catalyst, particles. This embodiment generally is preferred.
Preferably, the catalyst composition additionally comprises a suitable binder material. Suitable binder materials preferably are those described above. The particles generally are embedded in the binder material, which functions as a glue to hold the particles together. Preferably, the particles are homogeneously distributed within the binder. The presence of the binder generally leads to an increased mechanical strength of the final catalyst composition. Generally, the catalyst composition of the invention has a mechanical strength, expressed as side crush strength, of at least 1 lbs/mm and preferably of at least 3 lbs/mm (measured an exta dates with a diameter of 1 - 2 mm).
The amount of binder depends, int. al., on (he desired activity of the catalyst composition. Binder amounts from 0 - 95 wt% of I he total composition can be suitable, depending on the envisaged catalytic application. However, to take advantage of the unusually high activity of the composition of the. present invention, the binder amounts generally are in the range of 0 - 75 wt% of the total composition, preferably 0 - 50 wt%, more preferably 0-30 wt%.
If desired, the catalyst composition may comprise a suitable cracking component. Suitable cracking components preferably are those described above. The amount of cracking component preferably is in the range of 0 - 90 wt%, based on the total weight of the catalyst composition.

Moreover, the catalyst composition may comprise conventional hydroprocessing catalysts. The conventional hydroprocessing catalyst generally comprises any of (he above-described binder materials and cracking components. The hydrogenation metals of the conventional hydroprocessing catalyst generally comprise Group VIB and Group VIII non-noble metals such as combinations of nickel or cobalt with molybdenum or tungsten. Suitable conventional hydroprocessing catalysts are. e.g., hydrotreating or hydrocracking catalysts. These catalysts can be in the used, regenerated, fresh, or sulphided state.
Furthermore, the catalyst composition may comprise any further material which is conventionally present in hydroprocessing catalysts such as phosphorus-containing compounds, boron-containing compounds, silicon-containing compounds, fluorine-containing compounds, additional transition mettils, rare earth metals, or mixtures thereof. Details in respect of these further materials are given above. The transition or rare earth metals generally are present in the oxidic: form when the catalyst composition has been thermally treated in an oxidizing atmosphere and/or in the sulphided form when the catalyst composition has been sulphided.
To obtain catalyst compositions with high mechanical strength, it may be desirable for the catalyst composition of the invention to have a low macroporosity. Preferably, less than 30% of the pore volume of the catalyst composition is in pores with a diameter higher than 100 nm (determined by mercury intrusion, contact angle: 130°), more preferably less than 20%.
The oxidic catalyst composition of the present invention generally comprises 10 -100 wt%, preferably 25 -100 wt%, more preferably 45 -100 wt% and most preferably 65 -
100 wt% of Group VIB and Group VIII non-noble metals, based on the total weight of the catalyst composition, calculated as metal oxideii.
It is noted that a catalyst prepared via stepwise impregnation with Group VIB and Group Vilt non-nobie metal solutions on an alumina carrier as described in JP

09000929 does not comprise any bulk catalyst particles and thus has a morphology which is completely different from that of the present invention.
(b} sulphided catalyst composition
If so desired, the catalyst composition of the p.-esent Invention can be sulphided. Consequently, the present invention further pertains to a catalyst composition comprising sulphidic bulk catalyst particles which comprise at least one Group VIII non-nabie metal and at least two Group VIB metals ami wherein the degree of sulphidation under conditions of use does not exceed 90%.
Furthermore the present invention pertains to a catalyst composition comprising sulphidic bulk catalyst particles which comprise at l«3ast one Group Vlll non-noble metal and at least two Group VIB metals and wherein the degree of sulphidation under conditions of use does not exceed 30% and wherein the catalyst composition does not comprise sulphided farms of a compound of the formula N^MOjWaO,, with b/(c+d) being in the range of 0.75 - 1.5 or even Q.5 -3 and c/d b-aing in the range of 0.1 -10 or even being equal to or greater than 0.01, and z = [2ti+6(c+d)]/2, or wherein the catalyst composition even does not comprise any sulphided forms of nickel molybdate in which at least a portion but less than alt of the molybdenum is replaced by tungsten, as disclosed in non-prepublished international patent application WO 9903578.
It will be clear that the above sulphided catalyst composition may comprise any of the above-described (further) materials.
The present invention further pertains to a shaped and sulphided catalyst composition
comprising
0) sulphidic bulk catalyst particles comprising at least one Group Vlll non-noble metal
and at least two Group VIB metals, wherein the degree of sulphidation under conditions
of use does not exceed 90% and
(ii) a material selected from the group of binder materials, conventional
hydroprocessing catalysts, cracking components, o- mixtures thereof.

It is essential that the degree of sulphidation of :he sulphidic bulk catalyst particles under conditions of use does not exceed 90%. Preferably, the degree of sulphidation under conditions of use is in the range of 10 - 90%, more preferably of 20 - 90%, and most preferably of 40 - 90%, The degree of sulphidation is determined as described in the chapter "characterization methods."
If conventional sulphidation techniques are applied in the process of the present invention, the degree of sulphidation of the sulphidic bulk catalyst particles prior to use is essentially identical to the degree of sulphidation under conditions of use. However, if very specific sulphidation techniques are applied, it might be that the degree of sulphidation prior to the use of the catalyst is higher than during the use thereof, as during use part of the sulphides or elemental sulphur is removed from the catalyst. In this case the degree of sulphidation is the one thjit results during use of the catalyst and not prior thereto. The conditions of use are those described below in the chapter "use according to the invention." That the catalyst is "under conditions of use" means that it is subjected to these conditions for a time period long enough for the catalyst to reach equilibrium with its reaction environment.
It is further preferred that the catalyst composition cf the present invention is essentially free of Group VIII non-noble metal disulphides. More in particular, the Group Vlll non-noble metals are preferably present as (GroupVIII non-noble metal^S,, with x/y being in the range of 0.5 -1.5
It is noted that the sulphidic catalyst compositions of the present invention have a much better catalytic performance than catalysts comprising one Group Vlll non-noble metal and only one Group VIB metal.
The shaped and sulphided catalyst particles may have many different shapes. Suitable shapes include spheres, cylinders, rings, and symmetric or asymmetric polylobes, for instance tri- and quadrulobes. Particles resulting from extrusion, beading or pilling usually have a diameter in the range of 0.2 to 10 mn, and their length likewise is in the range of 0.5 to 20 mm. Particles resulting from spcay-drying generally have a median particle diameter in the range of 1 jim -100 jim.

Details about the binder materials, cracking components, conventional ftydropracessing catalysts, and any further materials as well as 1he amounts thereof are given above. Further, details in respect af the Group VIII non-roble metals and the Group VIB metals contained in the sulphided catalyst compositions and the amounts thereof are given above.
It is noted that the core-shell structure described above for the oxidic catalyst composition is not destroyed by sulphidation. i.e., the sulphided catalyst compositions may also comprise this core-shell structure.
It is further noted that the sulphided catalysts a-e at least partly crystalline materials, i.e., the X-ray diffraction pattern of the sulphidic bulk catalyst particles generally comprises several crystalline peaks characteristic to the Group Vlll non-noble metal and Group VIB metal sulphides.
As for the oxidic catalyst composition, preferably, less than 30% of the pore volume of the sulphidic catalyst composition is in pores with a diameter higher than 100 nm (determined by mercury intrusion, contact angle: 130°), more preferably less than 20%.
Generally, the median particle diameters of the sulphidic bulk catalyst particles are identical to those given above for the oxidic bulk catalyst particles.
use according to thft inyqr1*10"
The catalyst composition according to the indention can be used in virtually all hydroprocessing processes to treat a plurality of feeds under wide-ranging reaction conditions, e.g., at temperatures in the range of 20Qq to 450°C, hydrogen pressures in
the range of 5 to 300 bar, and space velocities (LHSV) in the range of 0.05 to 10 h'\ The term " hydroprocessing" in this context encompasses all processes in which a hydrocarbon feed is reacted with hydrogen at elevated temperature and elevated pressure, including processes such as hydrogenation, hydrodesulphurization.

hydrodenitragenation, hydrodemetallization, hydradearomatization, hydroisomerization, hydrodewaxing, hydrocrackrng, and hydrocracking under mild pressure conditions, which is commonly referred to as mild hydrocracking. The catalyst composition of the invention is particularly suitable for hydrotreating hydrocarbon feedstocks. Such hydrotreating processes comprise, e.g., hydrodesiulphurization. hydrodenitragenation, and hydradearomatization of hydrocarbon feedstocks. Suitable feedstocks are, e.g., middle distillates, kero, naphtha, vacuum gas oil!., and heavy gas oils. Conventional process conditions can be applied, such as temperatures in the range of 250M50°C, pressures in the range of 5-250 bar, space velocities In the range of 0,1-10 h'\ and Hj/oil ratios in the range of 50-2000 Nl/l.
Characterization methods
1. Side crush strength determination
First, the length of, e.g., an extrudate particle was measured, and then the extrudate particle was subjected to compressive loading (25 lbs in 8.6 sec.) by a movable piston. The force required to crush the particle was measured. The procedure was repeated with at least 40 extrudate particles and the average was calculated as force (lbs) per unit length (mm). The method preferably was applied to shaped particles with a length not exceeding 7 mm.
2. Pore volume via N2 adsorption
The N; adsorption measurement was carried out as described in the Ph.D. dissertation of J.C.P. Broekhoff (Delft University of Technology 1969).
3. Amount of added solid metal components
Qualitative determination: The presence of solid metal components during the process of the invention can easily be detected by visual inspection at least if the metal components are present in the form of particles with a diameter larger than the wavelength of visible light. Of course, methods : uch as quasi-elastic light scattering (QELS) or near-forward scattering, which are known to the skilled person, can also be used to verify that at no point in time during the process of the invention all metals will be in the salute state.

Quantitative determination: if the metal components which are added at least partly in the solid state are added as suspensions), the amount of solid metal components added during the process of the invention can be determined by filtration of the suspension(s) to be added under the conditions which are applied during the addition (temperature, pH. pressure, amount of liquid), in such a way that all solid material contained in the suspensian(s) is collected as solid filter cake. From the weight of the solid and dried filter cake, the weight of the solid metal components can be determined by standard techniques. Of course, if apart from solid metal components further solid components, such as a solid binder, are present in the filter cake, the weight of this solid and dried binder must be subtracted from trie weight of the solid and dried filter cake.
The amount of solid metal components in the fiter cake can also be determined by standard techniques such as atomic absorption spectroscopy (AAS), XRF, wet chemical analysis, orlCP.
if the metal components which are added at least partly in the solid state are added in the wetted or dry state, a filtration generally is net possible. In this case, the weight of the solid metal components is considered equal to the weight of the corresponding initially employed metal components, on a dry basis. The total weight of all metal components is the amount of all metal components initially employed, on a dry basis, calculated as metal oxides.
4. Characteristic full width at half maximum
The characteristic full width at half maximum of fre oxidic catalysts was determined on
the basis of the X-ray diffraction pattern of the catalysts using a linear background:
{a) if the Group V1B metals are molybdenum and tungsten: the characteristic fuil width
at half maximum, is the full width at half maximum (in terms of 26) of the peak at 28 =
53.6° (±0.7°)
(b) if the Group VlB metals are molybdenum and chromium: the characteristic fulf width
at half maximum is the full width at half maximum {in terms of 29) of the peak at 29 =
63.5C (±0.6°)

(c) if the Group V1B metals are tungsten and chromium: the characteristic full width at
half maximum is the full width at half maximum (in t=rms of 26) of the peak at 29 = 53.6°
(±0.7-)
(d) if the Group VIB metals are molybdenum, tungsten, and chromium: the
characteristic full width at half maximum is the full width at half maximum {in temis of
26) of the peak at 29 = 53.6° (±0.7°).
For the determination of the X-ray diffraction pattern, a standard powder diffractometer
(e.g., Philips PW10S0) equipped with a graphite monochromator can be used. The
measurement conditions can, e.g., be chosen as follows:
X-ray generator settings: 40 W and 40 mA
wavelength: 1.5418 angstroms
divergence and anti-scatter slits: 1°
detector slit 0.2 mm,
step size: 0.04 ("29)
time/step: 20 seconds.
5. Degree of sulphidatlon
Any sulphur contained in the sulphidic bulk catalyst composition was oxidized in an oxygen flow by heating in an induction oven, ""he resulting sulphur dioxide was analyzed using an infrared cell with a detection system based on the IR characteristics of the sulphur dioxide. To obtain the amount of sulphur the signals relating to sulphur dioxide are compared to those obtained on calibration with well-known standards. The degree of sulphidation is then calculated as the ratio between the amount of sulphur contained in the sulphidic bulk catalyst particles and the amount of sulphur that would be present in Hie bulk catalyst particles if all Group VIB and Group Vtll non-noble metals were present in tine form of their disulphides.
It will be clear to the skilled person that the catalyst the degree of sulphidation of which is to be measured is to be handled under an inert atmosphere prior to the determination of the degree of sulphidation.
The invention will be further illustrated by the following Examples:

Example 1
17.65 g of ammonium heptamolybdate (NH«)eMo,0M*4HiO (0.1 mole Mo, ex. Aldrich)
and 24.60 g of ammonium metatungstate (NH4),H2W,jO« (0.1 mole W, ex. Strem
Chemical) were dissolved in 800 ml water, giving a solution with a pH of about 5.2 at
room temperature. The solution was subsequently leated to 90°C (solution A).
3S.3 g of nickel hydroxycarbonate 2NiC03*3Ni{OH)I*4HI0 (0.3 mole Ni, ex. Aldrich)
were suspended in 200 ml of water, and this suspension was heated to 90°C
(suspension B). The nickel hydroxycarbonate had a 8. E. T. surface area of239 mVg
(= 376 mz/g NiO), a pore volume of 0.39 crn'/g (= 0.62 cm2/g NiO) (measured by
nitrogen adsorption), a median pore diameter of 6.1! nm, and a median particle diameter
of 11.1 micrometer.
Then suspension B was added to solution A in 10 minutes, and the resulting suspension was maintained at 90°C for a period of 18 - 20 hours with continuous stirring. At the end of this time, the suspension was filtered. The resulting solid was dried at 120°C for 4 hours and subsequently calcined at 400°C. The yield was about 92 %, based on the calculated weight of all metal components having been converted to their oxides.
The oxtdic bulk catalyst particles had a B. E. T. surface area of 167 mVg (= 486 m2/g NiO = 128% of the corresponding surface area of the nickel hydroxycarbonate), a pore voiume of 0.13 cm3/g (= 0.39 cm3/g NiO = 63% of the pore voiume of the nickel hydroxycarbonate), a median pore diameter of 3.4 nm (= 55% of the median pore diameter of the nickel hydroxycarbonate), and a median particle diameter of 10.6 micrometer (= 95% of the median partide diameter of the nickel hydroxycarbonate).
The X-ray diffraction pattern obtained after the calcination step is shown in Figure 1. The characteristic full width at half maximum was determined to be 1.38° (on the basis of the peak at 29 = 53.82°).

Subsequently, the catalyst was sulphided: 1.5 - 7. g of the catalyst were placed in a quartz boat, which was inserted into a horizontal ouartz tube and placed in a Lindberg furnace. The temperature was raised to 370°C in iibout one hour with nitrogen flowing at 50 ml/min, and the How continued for 1.5 h at 370°C. Nitrogen was switched off, and 10% H2S/Hj was then added to the reactor at 20 ml/min. The temperature was increased to 400°C and held there for 2 hours. The heat was then shut off and the catalyst was cooled in flowing H2S/Hj to 70°C, at which point this flow was discontinued and the catalyst was cooled to room temperature under nitrogen.
The sulphided catalyst was evaluated in a 300 ml modified Carbeny batch reactor designed for constant hydrogen flow. The catalyst was pilled and sized to 20/40 mesh and one gram was loaded into a stainless steel basket, sandwiched between layers of muliite beads. 100 ml of liquid feed, containing 5 wt% of dibenzothiophene (DBT) in decaline, were added to the autoclave. A hydrogen flow of 100 ml/min was passed through the reactor, and the pressure was maintained at 3150 kPa using a back¬pressure regufator. The temperature was raised to 350°C at 5 - 6°C/min, and the test was run until either 50% of the DBT had been converted or 7 hours had passed. A small aliquot of product was removed every ?IQ minutes and analyzed by gas chromatography (GC). Rate constants for the overall conversion were calculated as described by M. Oaage and R. R. Chianelti O-CataL 149, 414 - 427 (1994)).
The total DBT conversion (expressed as rate constant) at 350°C (&„&) was measured to be 138*10" molecules/(g*s).
Comparative Example A
A catalyst was prepared as described in Example 1, except that only one Group VIB metal component was applied: a catalyst was prepared as in Example 1 using 35.3 g of ammonium heptamoh/bdate (NH4)aMor03/4HI0 (i).2 mole Mo) and 35.3 g of nickel hydroxycarbonate 2NiCOj*3Ni(OH)j'4H20 (0.3 mole Ni). The yield was about 85%. based on the calculated weight of ail metal components having been converted to their oxides. The catalyst was sulphided and tested as described in Example 1. The total

DBT conversion (expressed as rate constant) al 350°C (!,„,) was measured to be 95.2*10" molecules/(g*s) and was thus significant!/ below that of Example 1.
Comparative Example B
A catalyst was prepared as described in Example; 1, except that only one Group VIB metal component was used: a catalyst was prepared as in Example 1 using 49.2 g of ammonium metatungstate (NH,)8HIW,!011i (0.2 mole W) and 35.3 g of nickel hydroxycarbonate 2NiCCV3Ni(OHy4HiO {0.3 mole Ni). The yield was about 90%, based on the calculated weight of all metal components having been converted to their oxides. The catalyst was sulphided and tested an described in Example 1. The total DBT conversion (expressed as rate constant) al 350°C (X,^) was measured to be 107*10ia molecules/(g*s) and was thus significantly below that of Example 1.
Example 2
28.8 g of Mo03 (0.2 mole Mo, ex. Aldrich) and 50.3 g of tungstic acid H,WO« (0.2 mole W, ex. Aldrich) were slurried in 800 ml of water (suspension A) and heated to 90°C. 70.6 g of nickel hydroxycarbonate 2NiCO3'3Ni(OH)i*4H20 (0.6 mole of Ni, ax. Aldrich) were suspended in 200 ml of water and heated to 90°C (suspension B). Suspension B was added to suspension A in 60 minutes, and the resulting mixture was maintained at 90°C for a period of 18 hours with continuous stining. At the end of this time, the suspension was filtered and the resulting solid was dried at 120°C for 4 - 3 hours and calcined at 400°C. The yield was about 99%, based on the calculated weight of all metal components having been converted to itieir oxides. The oxidic bulk catalyst particles had a B. E. T. surface area of 139 m2/g (= 374 m2/g NiO = 99% of the corresponding surface area of the nickel hydroxycarbonate), a pore volume of 0.13 cm3/g (= 0.35 cm3/g NiO = 56% of the pore volume of the nickel hydroxycarbonate), a median pore diameter of 2.7 nm {= 60% of the median pore diameter of the nickel hydroxycarbonate), and ;t median particle diameter of 14.5 micrometer (= 131% of the median particle diametesr of the nickel hydroxycartjonate)
The X-ray diffraction pattern of the oxidic bulk catalyst particles comprised peaks at 29 = 23.95 {very broad), 30.72 (very broad), 35.72, 38.76, 40.93, 53.80, 61.67. and 64.23°.

The characteristic full width at half maximum was determined to be 1.60" for the calcined catalyst composition (determined on the basis of the peak at 26 = 53.80°).
The catalyst was sulphided and the catalytic perfcrmance was tested as described in Example 1. The total conversion at 350°C (X„,w) was measured to be 144*1 Q1B molecules/(g*s).
The degree of sutphidation under conditions of use was 62%.
Example 3
The preparation of Example 2 was repeated, except that instead of H^WO, (NH^HjWuO^ was used. The yield was about 96%, based on the calculated weight of all metal components having been converted to ther oxides.
Example 4
Example 2 was repeated with different amounts of nickel. The yields and the characteristic full width at half maximum (determined on the basis of the peaks in the range 28 = 53.66 - 53.92°) are given in the following Table:

Molar amounts of metais added [mole] yfcsld" characteristic full width at half maximum in degrees 2fi for the calcined samples
Ni Mo W '


1.0 0.5 0.5 96 1.47
1.25 0.5 0.5 100 1.50
1.5 0.5 0.5 99 1.60
2.0 0.5 0.5 99 1.32
'(based on the calculated weight of all metal components having been converted to their oxides) [%]

Example 5
Example 4 was repeated with different molybderum : tungsten ratios.
The yields and the characteristic full widths at half maximum (determined on the basis of the peaks in the range 28 = 53.30 - 53.94°} ate given in the following Table;

Molar amounts of metals added [mole] yield' characteristic full width at half maximum in degrees 2S for the calcined samples
Ni Mo W


15 0.7 0.3 97 1.29
1.5 0.5 0.5 99 1.60
1.5 0.3 0.7 98 1.06
1.5 0.1 0.9 98 1.11
"(based on the calculated weight of all metal components having been converted to their oxides) [%]
Example 6
A catalyst composition was prepared in a manner analogous to the procedure described in Example 1. The resulting rnixtu-e was spray-dried. The spray-dried powder contained 43.5 wt% NiO, 20,1 wt% MoO-„ and 34.7 wt% W03. The pore volume of the spray-dried bulk catalyst particles was 0.14 ml/g, measured by nitrogen adsorption, and the B. E. T. surface area was 171 rn^g.
The bulk catalyst particles were wet-mixed with :!0 wt% of an alumina binder, based on the total weight of the catalyst composition. The water content of the mixture was adjusted in order to obtain an extrudabie mix, and the mixture was subsequently extruded. After extrusion, the extnjdate was dried at 12a°C and calcined at 385°C. The resulting catalyst composition had a B. E. T. surface area of 202 m2/g, a pore volume measured by mercury porosimetry of 0.25 rnl/g, and a sice crush strength of 5.4 lbs/mm.

Part of the resulting catalyst was sulphided using a SRGO {straight run gas oil) spiked with DMDS (dimethyl disuiphide) to obtain a total S content of 2.5 wt% S at 30 bar (LHSV = 4 hr1, H:oil = 200). The catalyst temperature was increased from room temperature to 320°C, using a ramp of 0.5°C/min. and kept at 320°C for 10 hours. The samples were then cooled down to room temperature.
The degree of sulphidation of the sulphided cata yst composition under conditions of use was determined to be 52%
Another part of the catalyst was sulphided witi a DMDS spiked feed. The thus sulphided catalyst was then tested with LCCO (light cracked cycle oil). The relative volume activity in hydrodenitrogenation was measured to be 281, compared to a commercially available alumina supported nickel and molybdenum-containing catalyst.
Example 7
A catalyst composition was prepared in a msinner analogous to the procedure described in Example 1. After the reaction was completed, peptized alumina (15 wt%, based on the total weight of the catalyst composition) was co-slurried with the bulk catalyst particles and the sJuny was spray-dried. The resulting catalyst contained 13.2 wt% AljOj, 33.9 wt% NiO, 20.5 wt% Mo03 and 30.2 wt% W03. The pore volume of the oxidic catalyst composition was 0.17 ml/g. measured by nitrogen adsorption, and the B. E. T. surface area was 114 rrrVg. The spray-dried particles were mixed with an amount of water as required to form an extrudable mix. The resulting mixture was extruded and the resulting extrudates were dried at 120°C and calcined at 385*0. The resulting catalyst composition had a B. E. "". surface area of 133 m2/g, a pore volume measured by mercury porasimetry of 0.24 ml/g, and a side crush strength of 5.3 lbs/mm.
Part of the resulting catalyst was sulphided using a mixture of 10 vol% H,S in H, at atmospheric pressure (GHSV (gas hourly space velocity) = ca. 8700 rWm'^hr"1). The catalyst temperature was increased from room temperature to 400°C. using a ramp of

6BC/rrrrn, and kept at 400°C for 2 hours. The sample was then coaled down to roam temperature in the H2S/HZ mixture.
The degree of sulphidation of the sulphided catalyst composition under conditions of use was determined to be 64%.
Another part of the catalyst was sulphided with a DMDS spiked feed. The thus sulphided catalyst was then tested with LCCO {light cracked cycle oil). The relative volume activity in hydrodenitrogenation was nieasured to be 235, compared to a commercially available alumina supported nickel and molybdenum-containing catalyst.


WE CLAIM:
1. A process for preparing a catalyst composition comprising bulk catalyst particles comprising at least one Group VIII non-noble metal and at least two Group VIB metals, which process comprises combining and reacting at least one Group VIII non-noble metal component with at least two Group VIB metal components in the presence of aprotic liquid, with at least one of the metal components remaining at least partly in the solid state during the entire process.
2. The process as claimed in claim 1, wherein at least one of the metal components is at least partly in the solid state and at least one of the metal components is in the solute state during the combination of the metal components.
3. The process as claimed in claim 1, wherein all metal components are at least partly in the solid state during the combination of the metal components.
4. The process as claimed in any one of the preceding claims, wherein the protic liquid comprises water.
5. The process as claimed in any one of the preceding claims, wherein the Group VIII non-noble metal comprises cobalt, nickel, iron, or mixtures thereof.
6. The process as claimed in any one of the preceding claims, wherein the Group VIB metals comprise at least two of chromium, molybdenum or tungsten.

7. The process as claimed in claim 5 or 6, wherein the group VIB metal and the Group VIII non-noble metal comprise nickel and/or cobalt, molybdenum, and tungsten.
8. The process as claimed in any one of the preceding claims, wherein a material selected from the group of binder materials, conventional hydroprocessing catalysts, cracking components, or mixtures thereof is added during the combining and/or reacting of the metal components,
9. The process of any one of the preceding claims, wherein the bulk catalyst particles are subjected to one or more of the following process steps:
(i) compositing with a material selected from the group of binder materials, conventional hydroprocessing catalysts, cracking components, or mixtures thereof,
(ii) spray-drying, (flash) drying, milling, kneading, slurry-mixing, dry or wet mixing, or combinations thereof,
(iii) shaping,
(iv) drying and/or thermally treating, and (v) sulphiding.
10. A catalyst composition obtainable by the process as claimed in any one of the preceding
claims.
11. A catalyst composition comprising bulk catalyst particles which comprise at least one Group
VII non-noble metal and at least two Group VIB metals, wherein the metals are present in the
catalyst composition in their oxidic state, and wherein the characteristic full width at half
maximum does not exceed 2.5° when the Group VIB metals are molybdenum, tungsten, and,

optionally, chromium, or does not exceed 4.0° when the Group VIB metals are molybdenum and chromium or tungsten and chromium.
12. The catalyst composition as claimed in claim 11, wherein the characteristic full width at half
maximum does not exceed 2.0° when the Group VIB metals are molybdenum, tungsten, and,
optionally, chromium, or does not exceed 3.0° when the Group VIB metals are molybdenum and
chromium tungsten and chromium.
13. The composition as claimed in claim 12, wherein the degree of sulphidation under
conditions of use does not exceed 90%.
14. A hydro processing process for a hydrocarbon feed stock wherein catalyst composition as
claimed in any one of claims 10 to 13 is used.


Documents:

in-pct-2001-0997-che abstract.pdf

in-pct-2001-0997-che assignment.pdf

in-pct-2001-0997-che claims-duplicate.pdf

in-pct-2001-0997-che claims.pdf

in-pct-2001-0997-che correspondence-others.pdf

in-pct-2001-0997-che correspondence-po.pdf

in-pct-2001-0997-che description (complete)-duplicate.pdf

in-pct-2001-0997-che description (complete).pdf

in-pct-2001-0997-che drawings.pdf

in-pct-2001-0997-che form-1.pdf

in-pct-2001-0997-che form-19.pdf

in-pct-2001-0997-che form-26.pdf

in-pct-2001-0997-che form-3.pdf

in-pct-2001-0997-che form-5.pdf

in-pct-2001-0997-che form-6.pdf

in-pct-2001-0997-che petition.pdf


Patent Number 223714
Indian Patent Application Number IN/PCT/2001/997/CHE
PG Journal Number 47/2008
Publication Date 21-Nov-2008
Grant Date 19-Sep-2008
Date of Filing 13-Jul-2001
Name of Patentee ALBEMARLE NETHERLANDS B.V.
Applicant Address STATIONSPLEIN 4, 3818 LE AMERSFOORT
Inventors:
# Inventor's Name Inventor's Address
1 EIJSBOUTS, SONJA Goudenregenstraat 1, NL-5253 BE Nieuwkuijk
2 OOGJEN, BOB, GERARDUS Galopstraat 36, NL-1326 RR Almere
3 HOMAN FREE, HARMANNUS, WILLEM Pastoorakker 35, NL-3871 MN Hoevelaken
4 CERFONTAIN, MARINUS BRUCE S. Louisweg 99, NL-1034 WR Amsterdam
5 RILEY, KENNETH, LLOYD 1259 Rodney Drive, Baton Rouge, LA 70808-5874
6 SOLED, STUART LEON 21 Cooks Cross Road, Pittstown, NJ 08867
7 MISEO, SABATO 770 County Road 579, Pittstown, NJ 08867
PCT International Classification Number B01J37/02
PCT International Application Number PCT/EP00/00355
PCT International Filing date 2000-01-13
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 09/231,118 1999-01-15 U.S.A.
2 09/231,125 1999-01-15 U.S.A.