CA2358901C - Hydroprocessing using bulk multimetallic catalysts - Google Patents

Abstract

Hydrotreating a petroleum feedstream comprised of at least 50 wt. % of an atmospheric distillation distillate boiling range product stream, preferably hydrodesulfurization of raw virgin petroleum distillates, using a bulk multimetallic catalyst comprised of at least one Group VIII non-noble metal and at least two Group VIB metal wherein the ratio of Group VIB metal to Group VIII metal is from about 10:1 to 1:10.

Description

~'CT/US 0 0 ~ 0 0 9 8 0 PAGE 1- lP : ~. ,»;G Z~O~
CROSS RFFFRFNC~ TO RFhATPD APPLICATIONS
This is a continuation-in-part of USSN 09/231,156 which was filed on January 15, 1999, which is a continuation-in-part of USSN 08/900,389 which was filed on July 15, 1997.
This invention relates to the hydrotreating, preferably hydrodesulfurization, hydrodenitrogenation, and combinations thereof, using a bulk multimetallic catalyst comprised of at least one Group VIII non-noble metal and at least two Group VIB metal wherein the ratio of Group VIB metal to Group VIII metal is from about 10:1 to 1:10.
As the supply of low sulfur, low nitrogen crudes decrease, refineries are - processing crudes with greater sulfur and nitrogen contents at the same time that environmental regulations are mandating lower levels of these heteroatoms in products. Consequently, a need exists for increasingly efficient desulfurization and denitrogenation catalysts.
A family of compounds related to hydrotalcites, e.g., ammonium nickel molybdate, has been prepared as an approach to improved hydrotreating catalysts. Whereas X-ray diffraction analysis has shown that hydrotalcites are composed of layered phases with positively charged sheets and exchangeable anions located in the galleries between the sheets, the related ammonium nickel molybdate phase has molybdate anions in interlayer galleries bonded to nickel AMENDED SIiE~T

~C1'/US 0 0 ~ 0 0 g 8 0 PAGE 2- ~PEA/US ~ ~ ~"JG ZOOD
oxyhydroxide sheets. See, for example, Levin, D., Soled, S. L., and Ying, J.
Y., Crystal Structure of an Ammonium Nickel Molybdate prepared by Chemical Precipitation, Inorganic Chemistry, Vol. 35, No. 14, p. 4191-4197 (1996). The preparation of such materials also has been reported by Teichner and Astier, Appl. Catal. 72, 321-29 ( 1991 ); Ann. Chim. Fr. 12, 337-43 ( 1987), and C. R.
Acad. Sci. 304 (II), #11, 563-6 (1987) and Mazzocchia, Solid State Ionics, 63-(1993) 731-35.
Consequently, a need exists for increasingly efficient desulfurization and denitrogenation catalysts.
In accordance with this invention there is provided a process for hydrotreating raw virgin petroleum distillates, which process comprises contacting a feedstock comprised of at least about SO wt.% raw virgin distillate, at hydrotreating conditions, with a bulk multimetallic catalyst comprised of at least one Group VIII non-noble metal and at least two Group VIB metals and wherein the ratio of Group VIB metal to Group VIII non-noble metal is from r-_ '~..., about 10:1 to about 1:10.
In a preferred embodiment of the present invention the Group VIII non-noble metal is selected from Ni and Co and the Group VIB metals are selected from Mo and W.

IPEAIUS ~ ~ AUG 2000 In another preferred embodiment of the present invention two Group VIB
metals are present as Mo and W and the ratio of Mo to W is about 9:1 to about 1:9.
In yet another preferred embodiment of the present invention the bulk multimetallic is represented by the formula:
~~b ~~~c ~d ~z wherein X is one or more Group VIII non-noble metals, and the molar ratio of b:
(c+d) is 0.5/1 to 3/1, preferably 0.75/1 to 1.5/1, more preferably 0.75/1 to 1.25/1.
In still another preferred embodiment of the present invention the molar ratio of c:d is preferably >0.01/1, more preferably >0.1/1, still more preferably 1/10 to 10/1, still more preferably 113 to 3/1, most preferably substantially equimolar amounts of Mo and W, e.g., 2/3 to 3/2; and z = [2b + 6 (c+d))/2.
In another preferred embodiment of the present invention the bulk catalyst is essentially amorphous and has a unique X-ray diffraction pattern showing crystalline peaks at d = 2.53 Angstroms and d = 1.70 Angstroms.
In still another preferred embodiment of the present invention the Group w__ VIII non-noble metal is nickel.
Figure 1 is the X-ray diffraction pattern of a Ni-Moo.sWo.s-~
compound prepared by boiling precipitation before calcining (Curve A) and after calcining at 400°C (Curve B). Note that the patterns for both the precursor and the decomposition product of the precursor are quite similar with the two peaks at essentially the same place. The ordinate is relative intensity; the abscissa is two theta (degrees).

~P~AIU~ i 4 AUG 200A

Figure 2 shows the X-ray diffraction patterns, by CuKa radiation (~,=1.5405A), of Ni-Mo,_X-Wx-O precursors wherein curve A is Mo0,gW0.l~
curve B is Mo0.7W0.3~ cur'i'e C is Mop.5W0.5~ curve D is Mo0.3W0.7~ curve E
is MoO,1 W0.9~ and curve F is MoOW 1. The ordinate and abscissa are as described for Figure 1.
Figure 3 is a plot of HDS activity for the catalysts of examples 20 to 24 hereof.
Figure 4 is a plot of the HDN activity for the catalysts of examples 20 and 24 hereof.
The invention is based in part on the discovery that molybdenum in a nickel-molybdenum oxide phase may be partially substituted by tungsten. The resulting phase is an essentially ammonia-free, substantially amorphous oxide which upon sulfidation pro~rides enhanced hydroprocessing activity relative to the unsubstituted Ni-Mo phase. The invention is also based in part on the discovery of catalysts containing at least one Group VIII non-noble metal and at least two Group VIB metals, wherein the ratio of Group VIB metal to Group VIII non-noble metal ranges from about 10:1 to about 1:10.
The bulk multimetallic catalyst composition used in the practice of the present invention can be used in virtually all hydroprocessing processes to treat a plurality of feeds under wide-ranging reaction conditions such as temperatures of from 200 to 450°C, hydrogen pressures of from 5 to 300 bar, liquid hourly space velocities of from 0.05 to 10 h-' and hydrogen treat gas rates of from 35.6 to 1780 m3/m3 (200 to 10000 SCFB). The term "hydroprocessing" encompasses all processes in which a hydrocarbon feed is reacted with hydrogen at the temperatures and pressures noted above, and include hydrodemetallation, hydrodewaxing, hydrotreating, hydrogenation, hydrodesulfurization, AMENDED SHEET

~TI!!S 00/ 00 980 PAGE 4-a- ~~~~S j 'fit h°iUG ZOOO
hydrodenitrogenation, hydrodearomatization, hydroisomerization, and hydrocracking including selective hydrocracking. Depending on the type of hydroprocessing and the reaction conditions, the products of hydroprocessing may show improved viscosities, viscosity indices, saturates content, low temperature properties, volatilities and depolarization. It is to be understood that hydroprocessing of the present invention can be practiced in one or more reaction zones and can be practiced in either countercurrent flow or cocurrent AMENDED SHEhl i~TII~S 00/ 00 g80 IPEA,/(j~ ~ :x ,°~UG 2000 flow mode. By countercurrent flow mode we mean a process mode wherein the feedstream flows countercurrent to the flow of hydrogen-containing treat gas.
The hydroprocessing reactor can also be operated in any suitable catalyst-bed arrangement mode. For example, it can be a fixed bed, slurry bed, or ebulating bed.
The hydrocarbon feedstocks which are typically subjected to hydrotreating herein will typically boil at a temperature above 150°C.
The feedstocks can contain a substantial amount of nitrogen, e.g. at least 10 wppm nitrogen, and even greater than 500 wppm, in the form of organic nitrogen .-, compounds. The feeds can also have a significant~sulfur content, ranging from about 0.1 wt.% to 3 wt.%, or higher. If desired, the feeds can be treated in a known or conventional manner to reduce the sulfur and/or nitrogen content thereof.
Feedstocks of interest to the present invention are those that are comprised of at least about 50 wt.% of the distillate boiling range product from atmospheric distillation unit. Preferably the feedstock contains at least about 50 wt.% raw virgin petroleum distillate. The remainder of the feedstock, other than the atmospheric distillation product can be cracked distillate feedstock. Such -- cracked feedstock are typically product streams from a coker or fluid catalytic cracker. Streams from an atmospheric distillation unit are raw virgin streams in that they have not undergone any further processing and typically have a total sulfur content of about 0.5 - 2 wt% and total nitrogen content up to about 500 wppm.
This invention is operable over a range of conditions consistent with the intended objectives in terms of product quality improvement and consistent with any downstream process with which this invention is combined in either a common or sequential reactor assembly. It is understood that hydrogen is an AMENDED SHEET

(>
essential component of the process. -this invention is commonly operated at a temperature of 500 - 800 °F (260 - 426.6°C), preferably 575 -700 °F (301.6 -371.1 °C). Operating pressure includes 100 - 1000 psig, preferably 200 -psig, and more preferably 300 - 500 psig at gas rates of 500 - I 0,000 SCF/B, preferably 750 - 5000 SCF/B. The feed rate may be varied over the range 0.1 -100 LSHV, preferably 0.3 - 5 LSHV.
The hydrotreating catalyst used in the practice of the present invention is a bulk multimetallic catalyst comprised of at least one Group VIII non-noble metal and at least two Group VIB metals and wherein the ratio of Group VIB
metal to Group VIII non-noble metal is ti-om about 10:1 to about 1:10. It is preferred that the catalyst be a bulk trimetallic catalyst comprised of one Group VIII non-noble metal, preferably Ni or Co and the two Group VIB metals Mo and W. It is preferred that the ratio of Mo to W be about 9: I to about 1:9.
The preferred bulk trimetallic catalyst compositions used in the practice of the present invention is represented by the formula:
(X)b (Mo)~ (~'~')a ~~
wherein X is a Group VIII non-noble metal, the molar ratio of b: (c+d) is 0.5/1 to 3/1, preferably 0.75/1 to 1.5/1, more preferably 0.75/1 to 1.25/1;
The molar ratio of c:d is preferably >0.01/l, more preferably >0.1/I, still more preferably 1 / 10 to 10/ I , still more preferably 1 /3 to 3/ I , most preferably substantially equimolar amounts of Mo and W, e.g., 2/3 to 3/2; and z = [2b + 6 (~+d)~/2 The essentially amorphous material has a unique X-ray diffraction pattern showing crystalline peaks at d = 2.53 Angstroms and d = 1.70 Angstroms.

The mixed metal oxide is readily produced by the decomposition ol~ a precursor having the formula:
(NHa)~ ~X)n ~Mo)~ (w)a ~Z
wherein the molar ratio of a:b is <_ I.0/l, preferably 0-l: and b, c, and d, are as defined above, and z = [a + 2b + 6 (c+d)~/?. The precursor has similar peaks at d = 2.53 and 1.70 Angstroms.
Decomposition of the precursor may be effected at elevated temperatures, e.g., temperatures of at least about 300°C, preferably about 300-450°C, in a suitable atmosphere, e.g., inerts such as nitrogen, argon, or steam, until decomposition is substantially complete, i.e., the ammonium is substantially completely driven off. Substantially complete decomposition can be readily established by thermogravimetric analysis (TGA), i.e., flattening of the weight change curve.
The catalyst compositions used in the practice of the present invention can be prepared by any suitable means. One such means is a method wherein not all of the metals are in solution. Generally, the contacting of the metal components in the presence of the protic liquid comprises mixing the metal component and subsequently reacting the resulting mixture. It is essential to the solid route that at least one metal components is added at least partly in the solid state during the mixing step and that the metal of at least one of the metal components which have been added at least partly in the solid state, remains at least partly in the solid state during the mixing and reaction step. "Metal"
in this context does not mean the metal in its metallic form but present in a metal compound, such as the metal component as initially applied or as present in the bulk catalyst composition.

Generally, during the mixing step either at least one metal component is added at least partly in the solid state and at least one metal component is added in the solute state, or all metal components are added at least partly in the solid state, wherein at least one of the metals of the metal components which are added at least partly in the solid state remains at least partly in the solid state during the entire process of the solid route. 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 this metal component in the erotic liquid. That a metal component is added "at least partly in the solid state" means that at least part of the metal component is added as solid metal component and, optionally, another part of the metal component is added as a solution of this metal component in the erotic liquid. A typical example is a suspension of a metal component in a erotic liquid in which the metal is at least partly present as a solid, and optionally partly dissolved in the erotic liquid.
To obtain a bulk catalyst composition with high catalytic activity, it is therefore preferred that the metal components, which are at least partly in the solid state during contacting, are porous metal components. It is desired that the total pore volume and pore size distribution of these metal components is approximately the same as those of conventional hydrotreating catalysts.
Conventional hydrotreating catalysts generally have a pore volume of 0.05 - ~
ml/g, preferably of 0.1 - 4 ml/g, more preferably of 0.1 - 3 ml/g and most preferably of 0.1 - 2 ml/g determined by nitrogen adsorption. Pores with a diameter smaller than 1 nm are generally not present in conventional hydrotreating catalysts. Further, conventional hydrotreating catalysts have generally a surface area of at least 10 m'/g and more preferably of at least ~0 m'/g and most preferably of at least 100 m'/g, determined via the B.E.T.
method.
For instance, nickel carbonate can be chosen which has a total pore volume of c) 0.19 - 0.39 ml/g and preferably of0.24 - 0.35 ml/g determined by nitrogen adsorption and a surface area of l ~0 - 400 m''/g and more preferably of 200 -m~/g determined by the B.E.T. method. Furthermore these metal components should have a median particle diameter of at least 50 nm, more preferably at least 100 nm, and preferably not more than X000 ym and more preferably not more than 3000 Vim. Even more preferably, the median particle diameter lies in the range of 0.1 - 50 ~m and most preferably in the range of 0.5 - 50 Vim. For instance, by choosing a metal component which is added at least partly in the solid state and which has a large median particle diameter, the other metal components wil~only react with the outer layer of the large metal component particle. In this case, so-called "core-shell" structured bulk catalyst particles are obtained.
An appropriate morphology and texture of the metal component can either be achieved by applying suitable preformed metal components or by preparing these metal components by the above-described precipitation under such conditions that a suitable morphology and texture is obtained. A proper selection of appropriate precipitation conditions can be made by routine experimentation.
As has been set out above, to retain the morphology and texture of the metal components which are added at least partly in the solid state, it is essential that the metal of the metal component at least partly remains in the solid state during the whole process of this solid route. It is noted again that it is essential that in no case should the amount of solid metals during the process of the solid route becomes zero. The presence of solid metal comprising particles can easily be detected by visual inspection at least if the diameter of the solid particles in which the metals are comprised is larger than the wavelength of visible light.
Of course, methods such as quasi-elastic light scattering (QELS) or near forward scattering which are known to the skilled person can also be used to ensure that in no point in time of the process of the solid route, all metals are in the solute state.
The protic liquid to be applied in the solid or solution route of this invention for preparing catalyst can be any erotic liquid. Examples include water, carboxylic acids, and alcohols such as methanol or ethanol. Preferably, a liquid comprising water such as mixtures of an alcohol and water and more preferably water is used as erotic liquid in this solid route. Also different erotic liquids can be applied simultaneously in the solid route. For instance, it is possible to add a suspension of a metal component in ethanol to an aqueous solution of another metal component.
The Group VIB metal generally comprises chromium, molybdenum, tungsten, or mixtures thereof: Suitable Group VIII non-noble metals are, e.g., iron, cobalt, nickel, or mixtures thereof. Preferably, a combination of metal components comprising nickel, molybdenum and tungsten or nickel, cobalt, molybdenum and tungsten is applied in the process of the solid route. If the erotic liquid is water, suitable nickel components which are at least partly in the solid state during contacting comprise water-insoluble nickel components such as nickel carbonate, nickel hydroxide, nickel phosphate, nickel phosphite, nickel formate, nickel sulfide, nickel molybdate, nickel tungstate, nickel oxide, nickel alloys such as nickel-molybdenum alloys, Raney nickel, or mixtures thereof.
Suitable molybdenum components, which are at least partly in the solid state during contacting, comprise water-insoluble molybdenum components such as molybdenum (di- and tri) oxide, molybdenum carbide, molybdenum nitride, aluminum molybdate, molybdic acid (e.g. H,MoO.~), molybdenum sulfide, or mixtures thereof. Finally, suitable tungsten components which are at least partly in the solid state during contacting comprise tungsten di- and trioxide, tungsten CA 02358901 2001-06-28 0 O ~ D G g s ~
PAGE 11- IPEA/C~S I 4 AUG 2Q~~
sulfide (WS2 and WS3), tungsten carbide, tungstic acid (e.g. H2WO4 - H20, H2W4~13 - 9H20), tungsten nitride, aluminum tungstate (also meta-, or polytungstate) or mixtures thereof. These components are generally commercially available or can be prepared by, e.g., precipitation. e.g., nickel carbonate can be prepared from a nickel chloride, sulfate, or nitrate solution by adding an appropriate amount of sodium carbonate. It is generally known to the skilled person 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, O, and/or H
besides the metal, are preferred because they are less detrimental to the environment. Nickel carbonate is a preferred metal component to be added at least partly in the solid state because when nickel carbonate is applied, C02 evolves and positively influences the pH of the reaction mixture. Further, due to the transformation of carbonate into CO2, the carbonate does not end up in the wastewater.
Preferred nickel components which are added in the solute state are water-soluble nickel components, e.g. nickel nitrate, nickel sulfate, nickel acetate, nickel chloride, or mixtures thereof. Preferred molybdenum and tungsten components which are added in the solute state are water-soluble molybdenum and tungsten components such as alkali metal or ammonium molybdate (also peroxo-, di-, tri-, tetra-, hepta-, octa-, or tetradecamolybdate), Mo-P heteropolyanion compounds, Wo-Si heteropolyanion compounds, W-P
heteropolyanion compounds, W-Si heteropolyanion compounds, Ni-Mo-W
heteropolyanion compounds, Co-Mo-W heteropolyanion compounds, alkali metal or ammonium tungstates (also meta-, para-, hexa-, or polytungstate), or mixtures thereof.

I?
Preferred combinations of metal components are nickel carbonate, tungstic acid and molybdenum oxide. Another preferred combination is nickel carbonate, ammonium dimolybdate and ammonium metatungstate. It is within the scope of the skilled person to select further suitable combinations of metal components. It must be noted that nickel carbonate always comprises a certain amount of hydroxy-groups. It is preferred that the amount of hydroxy-groups present in the nickel carbonate be high.
An alternative method of preparing the catalysts used in the practice of the present invention is to prepare the bulk catalyst composition by a process comprising reacting in a reaction mixture a Group VIII non-noble metal component in solution and a Group VIB metal component in solution to obtain a precipitate. As in the case of the solid route, preferably, one Group VIII
non-noble metal component is reacted with two Group VIB metal components.
The molar ratio of Group VIB metals to Group VIII non-noble metals applied in the process of the solution route is preferably the same as described for the solid route. Suitable Group VIB and Group VIII non-noble metal components are, e.g. those water-soluble nickel, molybdenum and tungsten components described above for the solid route. Further Group VIII non-noble metal components are, e.g., cobalt or iron components. Further Group VIB metal components are, e.g.
chromium components. The metal components can be added to the reaction mixture in solution, suspension or as such. If soluble salts are added as such, they will dissolve in the reaction mixture and subsequently be precipitated.
Suitable Group VIB metal salts which are soluble in water are ammonium salts such as ammonium dimolybdate, ammonium tri-, tetra- hepta-, octa-. and tetradeca- molybdate. ammonium para-, meta-, hexa-, and polytungstate, alkali metal salts, silicic acid salts of Group VIB metals such as molybdic silicic acid, molybdic silicic tungstic acid, tungstic acid. metatungstic acid, pertungstic acid, heteropolyanion compounds of Mo-P, Mo-Si. W-P, and W-Si. It is also possible to add Group VIB metal-containing compounds which are not in solution at the time of addition, but where solution is effected in the reaction mixture.
Examples of these compounds are metal compounds which contain so much crystal water that upon temperature increase they will dissolve in their own metal water. Further, non-soluble metal salts may be added in suspension or as such, and solution is effected in the reaction mixture. Suitable non-soluble metals salts are heteropolyanion compounds of Co-Mo-W (moderately soluble in cold water), heteropolyanion compounds of Ni-Mo-W (moderately soluble in cold water).
The reaction mixture is reacted to obtain a precipitate. Precipitation is effected by adding a Group VIII non-noble metal salt solution at a temperature and pH at which the Group VIII non-noble metal and the Group \/IB metal precipitate, adding a compound which complexes the metals and releases the metals for precipitation upon temperature increase or pH change or adding a Group VIB metal salt solution at a temperature and pH at which the Group VIII
non-noble metal and Group VIB metal precipitate, changing the temperature, changing the pH, or lowering the amount of the solvent. The precipitate obtained with this process appears to have high catalytic activity. In contrast to the conventional hydroprocessing catalysts, which usually comprise a carrier impregnated with Group VIII non-noble metals and Group VIB metals, said precipitate can be used without a support. Unsupported catalyst compositions are usually referred to as bulk catalysts. Changing the pH can be done by adding base or acid to the reaction mixture, or adding compounds, which decompose upon temperature, increase into hydroxide ions or Ht ions that respectively increase or decrease the pH. Examples of compounds that decompose upon temperature increase and thereby Increase or decrease the pH are urea.
nitrites, ammonium cyanate, ammonium hydroxide, and ammonium carbonate.

i~C1'IUS 00/ 00 9gp.
PAGE 14- ~PE~~ ; :~ n~G 200 In an illustrative process according to the solution route, solutions of ammonium salts of a Group VIB metal are made and a solution of a Group VIII
non-noble metal nitrate is made. Both solutions are heated to a temperature of approximately 90°C. Ammonium hydroxide is added to the Group VIB metal solution. The Group VIII non-noble metal solution is added to the Group VIB
metal solution and direct precipitation of the Group VIB and Group VIII
non-noble metal components occurs. This process can also be conducted at lower temperature andlor decreased pressure or higher temperature and/or (.,.",, increased pressure.
In another illustrative process according to the solution route, a Group VIB metal salt, a Group VIII metal salt, and ammonium hydroxide are mixed in solution together and heated so that ammonia is driven off and the pH is lowered to a pH at which precipitation occurs. For instance when nickel, molybdenum, and tungsten components are applied, precipitation typically occurs at a pH
below 7.
Independently from whether the solid or solution route is chosen the resulting bulk catalyst composition preferably comprises and more preferably consists essentially of bulk catalyst particles having the characteristics of the bulk catalyst particles described under the heading "Catalyst compositions of the invention."
The bulk catalyst composition can generally be directly shaped into hydroprocessing particles. If the amount of liquid of the bulk catalyst composition is so high that it cannot be directly subjected to a shaping step, a solid liquid separation can be performed before shaping. Optionally the bulk catalyst composition, either as such or after solid liquid separation, can be calcined before shaping.
AMENDED SHEET

PAGE 15- ,PS~US ~ ~ AJG ZOOO
The median diameter of the bulk catalyst particles is at least 50 nm, more preferably at least 100 nm, and preferably not more than 5000 p.m and more preferably not more than 3000 pm. Even more preferably, the median particle diameter lies in the range of 0.1 - SO p.m and most preferably in the range of 0.5-SO~,m.
If a binder material is used in the preparation of the catalyst composition it can be any material that is conventionally applied as a binder in hydroprocessing catalysts. Examples include silica, silica-alumina, such as conventional silica-alumina, silica-coated alumina and alumina-coated silica, alumina such as (pseudo)boehmite, or gibbsite, titania, zirconia, cationic clays or anionic clays such as saponite, bentonite, kaoline, sepiolite or hydrotalcite, or mixtures thereof. Preferred binders are silica, silica-alumina, alumina, titanic, zirconia, or mixtures thereof. These binders may be applied as such or after peptization.
It is also possible to apply precursors of these binders that, during the process of the invention are converted into any of the above-described binders. Suitable precursors are, a 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, aluminum and/or silicon (to prepare a cationic clay and/or anionic clay), chlorohydrol, aluminum sulfate, or mixtures thereof.
If desired, the binder material may be composited with a Group VIB
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 binder material with any of these metals may be carried out by impregnation of the solid binder with these materials. The person skilled in the art knows suitable impregnation techniques. If the binder is AfNEIVDED SHEET

peptized, it is also possible to carry out the peptization in the presence ofCJroup VIB and/or Group VIII non-noble metal components.
If alumina is applied as binder, the surface area preferably lies in the range of 100 - 400 m~/g, and more preferably 1 ~0 - 3 SO m'/g, measured by the B.E.T. method. The pore volume of the alumina is preferably in the range of 0.5 - l.~ ml/g measured by nitrogen adsorption.
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. Therefore, the amount of binder material to be added in the process of the invention generally depends on the desired activity of the final catalyst composition. Binder amounts tcom 0 - 95 wt.% of the total composition can be suitable, depending on the envisaged catalytic application. However, to take advantage of the resulting unusual high activity of the composition of the present invention, binder amounts to be added are generally in the range of 0.5 - 75 wt.% of the total composition.
The catalyst composition can be directly shaped. Shaping comprises extrusion, pelletizing, beading, and/or spray drying. It must be noted that if the catalyst composition is to be applied in slurry type reactors, fluidized beds, moving beds, expanded beds, or ebullating beds, spray drying or beading is generally applied for fixed bed applications, generally, the catalyst composition is extruded, pelletized and/or beaded. In the latter case, prior to or during the shaping step, any additives that are conventionally used to facilitate shaping can be added. These additives may comprise aluminum stearate, surfactants, graphite or mixtures thereof. These additives can be added at anv stage prior to the shaping step. Further, when alumina is used as a binder. it may be desirable to add acids prior to the shaping step such as nitric acid to increase the mechanical strength of the extrudates.
It is preferred that a binder material is added prior to the shaping step.
Further, it is preferred that the shaping step is carried out in the presence of a liquid, such as water. Preferably, the amount of liquid in the extrusion mixture, expressed as LOI is in the range of 20 - 80%.
The resulting shaped catalyst composition can, after an optional drying step, be optionally calcined. Calcination however is not essential to the process of the invention. If a calcination is carried out in the process of the invention, it can be done at a temperature of, e.g., from 100° - 600°C and preferably 350° to 500°C for a time varying from 0 5 to 48 hours. The drying of the shaped particles is generally carried out at temperatures above 100°C.
In a preferred embodiment of the invention, the catalyst composition is subjected to spray drying, (flash) drying, milling, kneading, or combinations thereof prior to shaping. These additional process steps can be conducted either before or after a binder is added, after solid-liquid separation, before or after calcination and subsequent to xe-wetting. It is believed that by applying any of the above-described techniques of spray drying, (flash) drying, milling, kneading, or combinations thereof; the degree of mixing between the bulk catalyst composition and the binder material is improved. This applies to both cases where the binder material is added before or after the application of any of the above-described methods. However, it is generally preferred to add the binder material prior to spray drying and/or any alternative technique. If the binder is added subsequent to spray drying and/or any alternative technique, the resulting composition is preferably thoroughly mixed by any conventional technique prior to shaping. An advantage of; e.g., spray drying is that no wastewater streams are obtained when this technique is applied.
Furthermore, a cracking component may be added during catalyst preparation. The cracking component may serve as an isomerization enhancer.
'l'he cracking component can be any conventional cracking component such as cationic clays, anionic clays, zeolites such as ZSM-~, (ultra-stable) zeolite Y.
zeolite X, ALPO's, SAPO's, amorphous cracking components such as silica-alumina, or mixtures thereof. It will be clear that some materials may act as a binder and a cracking component at the same time. For instance, silica-alumina may have at the same time a cracking and a binding function.
If desired, the cracking component may be composited with a Group VIB
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 be carried out by impregnation of the cracking component with these materials.
The cracking component, which can comprise about 0-80 wt.%, based on the total weight of the catalyst, can be added at anv stage of the process of the present invention prior to the shaping step. However, it is preferred to add the cracking component during the compositing step (ii) with the binder.
Generally, it depends on the envisaged catalytic application of the final catalyst composition which of the above-described cracking components is added. A zeolite is preferably added if the resulting composition shall be applied in hydrocracking or fluid catalytic cracking. Other cracking components such as silica-alumina or cationic clays are preferably added if the final catalyst composition shall be used in hydrotreating applications. fihe amount of cracking material that is added depends on the desired activity of the final composition and the application envisaged and thus may vary icom 0 - 80 wt.°,%, based on the total weight of the catalyst composition.
If desired, further materials can be added in addition to the Illetal components already added. ~~hese materials include any material that is added during conventional hydroprocessing catalyst preparation. Suitable examples are phosphorus compounds, boron compounds, fluorine-containing compounds, additional transition metals, rare earth metals, tillers, or mixtures thereof.
Suitable phosphorus compounds include ammonium phosphate, phosphoric acid, or organic phosphorus compounds. Phosphorus 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 compounds can also be used for peptization. For instance, the binder can be peptized by contacting the binder with phosphoric acid or with a mixture of phosphoric and nitric acid.
Suitable additional transition metals are, e.g., rhenium, ruthenium, rhodium, iridium, chromium, vanadium, iron, cobalt, platinum, palladium.
cobalt, nickel, molybdenum, or tungsten. Nickel, molybdenum ,and tungsten can be applied in the form of any of the water-insoluble nickel. molybdenum and/or tungsten components that are described above for the solid route. 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. It is, e.g., possible to impregnate the final catalyst composition with an impregnation solution comprising any of these metals.
The processes of the present invention for preparing the bulk catalyst compositions may further comprise a sultidation step. Sultidation is generally i°~1/~500~ 00 gS0 PAGE 20- ~~~~~ ~ ~ AUG 2OOO
carried out by contacting the catalyst composition or precursors thereof with a sulfur containing compound such as elementary sulfiu, hydrogen sulfide or polysulfides. The sulfidation can generally be carried out subsequently to the preparation of the bulk catalyst composition but prior to the addition of a binder material, and/or subsequently to the addition of the binder material but prior to subjecting the catalyst composition to spray drying and/or any alternative method, and/or subsequently to subjecting the composition to spray drying and/or any alternative method but prior to shaping, and/or subsequently to shaping the catalyst composition. It is preferred that the sulfidation is not carried r-~
out prior to any process step that reverts the obtained metal sulfides into their oxides. Such process steps are, e.g., calcination or spray drying or any other high temperature treatment in the presence of oxygen. Consequently, if the catalyst composition is subjected to spray drying and/or any alternative technique, the sulfidation should be carried out subsequent to the application of any of these methods.
Additionally to, or instead of, a sulfidation step, the bulk catalyst composition may be prepared from at least one metal sulfide. If, e.g. the solid route is applied in step (i), the bulk catalyst component can be prepared form nickel sulfide and/or molybdenum sulfide and/or tungsten sulfide.
If the catalyst composition is used in a fixed bed processes, the sulfidation is preferably carried out subsequent to the shaping step and, if applied, subsequent to the last calcination step. Preferably, the sulfidation is carried out ex situ, i.e., the sulfidation is carried out in a separate reactor prior to loading the sulfided catalyst composition into the hydroprocessing unit. Furthermore, it is preferred that the catalyst composition is both sulfided ex situ and in situ.
One or more of the reaction zones may contain a conventional hydrodesulfiuization.
AMENDEp SHEET

PAGE 21- ~~~~ j i BUG 2000 catalyst. Suitable conventional hydrodesulfurization catalysts for use in the present invention includes those that are comprised of at least one Group VIII
metal, preferably Fe, Co or Ni, more preferably Co and/or Ni, and most preferably Co; and at least one Group VI metal, preferably Mo or W, more preferably Mo, on a relatively high surface area support material, preferably alumina. Other suitable hydrodesulfurization catalyst supports include zeolites, amorphous silica-alumina, and titania-alumina Noble metal catalysts can also be employed, preferably when the noble metal is selected from Pd and Pt. It is within the scope of the present invention that more than one type of hydrodesulfurization catalyst be used in the same reaction vessel. The Group VIII metal is typically present in an amount ranging from about 2 to 20 wt.%, preferably from about 4 to 12%. The Group VI metal will typically be present in an amount ranging from about S to 50 wt.%, preferably from about 10 to 40 wt.%, and more preferably from about 20 to 30 wt.%. All metal weight percents are on support. By "on support" we mean that the percents are based on the weight of the support. For example, if the support were to weigh 100 g. then wt.% Group VIII metal would mean that 20 g. of Group VIII metal was on the ,..
support.
It has been found that in this case, the bulk catalyst particles are sintering-resistant. Thus the active surface area of the bulk catalyst particles is maintained during use. The molar ratio of Group VIB to Group VIII non-noble metals ranges generally from 10:1 - 1:10 and preferably from 3:1 - 1:3. In the case of a core-shell structured particle, these ratios of course apply to the metals contained in the shell. If more than one Group VIB metal is contained in the bulk catalyst particles, the ratio of the different Group VIB metals is generally not critical. The same holds when more than one Group VIII non-noble metal is applied. In the case where molybdenum and tungsten are present as Group VIB
metals, the molybenumaungsten ratio preferably lies in the range of 9:1 -1:9.
Preferably the Group VIII non-noble metal comprises nickel and/or cobalt. It is M~NDE~D SHEEI

~'Gl"IUS 00~ 00 980 PAGE 22- ~~~~ ~ ~ hIUG ZOOO
further preferred that the Group VIB metal comprises a combination of molybdenum and tungsten. Preferably, combinations of nickel/molybdenum/tungsten and cobaltlmolybdenum/tungsten and nickeUcobalt/molybdenum/tungsten are used. These types of precipitates appear to be sinter-resistant. Thus, the active surface area of the precipitate is retained during use. The metals are preferably present as oxidic compounds of the corresponding metals, or if the catalyst composition has been sulfided, sulfidic compounds of the corresponding metals.
Preferably the particles have a surface area of at least 50 m2/g and more preferably of at least 100 m2/g measured via the B.E.T. method. It is furthermore preferred that the particles comprise 50 - 100 wt.%, and even more preferably 70 - 100 wt.% of at least one Group VIII non-noble metal and at least one Group VIB metal, based on the total weight of the particles, calculated as metal oxides. The amount of Group VIB and Group VIII non-noble metals can easily be determined via TEM-EDX.
It is desired that the pore size distribution of the particles is approximately ,.3 the same as the one of conventional hydrotreating catalysts. More in particular, these particles have preferably 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 0.1 ml/g determined by nitrogen adsorption. Preferably, pores smaller than 1 nm are not present. Furthermore these particles preferably have a median diameter of at least 50 nm, more preferably at least 100 nm, and preferably not more than ~m and more preferably not more than 3000 pm. Even more preferably, the median particle diameter lies in the range of 0.1 - 50 H.m and most preferably in the range of 0 5 - 50 pm.
AAAENDE~ SHEEI

~T'/l~S 0 0 ~ 0 0 9 8 0 PAGE 23- 'P~~~ ~ ~1 I~UG ZOOO
The surface area of the catalyst composition preferably is at least 40 m2/g, more preferably at least 80 m2/g and most preferably at least 120 m2/g. The total pore volume of the catalyst composition is preferably at least 0.05 ml/g and more preferably at least O 1 ml/g as determined by water porosimetry. To obtain catalyst compositions with high mechanical strength, it may be desirable that the catalyst composition of the invention has a low macroporosity.
It was found that the bulk catalyst particles have a characteristic X-ray diffraction pattern which differs from catalysts obtained by co-mixing and ~~' conventional hydroprocessing catalysts obtained by impregnation. The X-ray diffraction pattern of the bulk catalyst particles comprises, and preferably essentially consists of, peaks characteristic to the reacted metal components.
If, e.g., nickel hydroxy-carbonate has been contacted with a molybdenum and tungsten component as described above, the resulting bulk catalyst particles are characterized by an X-ray diffraction pattern which comprises peaks at d values of (4.09 A), 2.83 A, 2.53 ~, 2.32 A, 2.23 A, 1.70 ~, (1.54 A), 1.47 t~. Values in brackets indicate that the corresponding peaks are rather broad and/or have a low intensity or are not distinguished at all. The term "the X-ray diffraction pattern essentially consists of " these peaks means that apart from these peaks, there are essentially no further peaks contained in the diffraction pattern. The precipitate for catalyst obtained by the solution route has a characteristic X-ray diffraction pattern which differs from catalyst obtained by co-mixing and conventional hydroprocessing catalysts obtained by impregnation. For instance the X-ray diffraction pattern of a Ni-Mo-W precipitate as prepared by the solution route has peaks at d values of 2.52 ~, 1.72 ~ and 1.46 ~.
Also as previously stated, the catalyst composition may comprise conventional hydroprocessing catalysts. The binder materials and cracking components of the conventional hydroprocessing catalyst generally comprise any of the above-described binder materials and cracking components. The 1~~D SHEET

hydrogenation metals of the conventional hvdroprocessing catalyst gcnerallv 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 catalysts. These catalysts can be in the spent, regenerated, or fresh state.
As will be clear from the above, it is possible to add the Group VIII non-noble metal containing compound and the Group VIB metal-containing compound in various ways, at various temperatures and pHs. in solution, in suspension, and as such, simultaneously and sequentially.
The precursor compound can also be readily prepared by one of several methods, including a variation of the boiling decomposition method used by Teichner and Astier in which a tungsten compound is added to the initial mixture of a molybdenum salt, a nickel salt and ammonium hydroxide. Direct precipitation and pH controlled precipitation may also be used to prepare the precursor compound. In all cases, however, water soluble salts of nickel, molybdenum and tungsten are employed.
Preferably, the molybdenum and tungsten salts are ammonium compounds, e.g., ammonium molybdate, ammonium metatungstate, while the nickel salt may be the nitrate or hydrated nitrates.
The decomposed precursor can be sulfided or pre-sultided by a variety of known methods. For example, the decomposition product can be contacted with a gas comprising HAS and hydrogen, e.g., I O% H~S/H~, at elevated temperatures for a period of time sufficient to sulfide the decomposition product, usually at the point of HAS breakthrough in the exit gas. Sult7ding can also be effected.
in situ, by passing a typical feedstock containin~~ sulfur over the decomposition product.
Process conditions applicable for the use of the catalysts described herein may vary widely depending on the feedstock to be treated. 'thus, as the boiling point of the feed increases, the severity of the conditions will also increase. The following table serves to illustrate typical conditions for a range of feeds.
FEED TYPICAL TEMP. PRESS, SPACE H~ GAS RATE
BOILING C BAR VELOCITY SCF/B
RANGE C V/V/HR

naphtha 25-210 100-37010-60 0.5-10 100-2,000 diesel 170-350 200-40015-110 0.5-4 500-6,000 heavy 325-475 260-43015-170 0.3-2 1000-6,000 gas oil tube 290-550 200-4506-210 0.2-5 100-10,000 oil residuum10-50%>~75 340-45065-1100 0.1-1 2,000-10,000 -The following examples will serve to illustrate, but not limit. this invention.
Example 1 Preparation of NH4-Ni-Mo-O Phase (boiling decomposition as per Teichner and Astier procedure):
In a 1 liter flask, 26.~ g ammonium molybdate (0.15 moles Mo) and X3.6 g nickel nitrate hexahydrate (0.15 moles Ni) were dissolved in 300 cc of water so that the resulting pH equaled 4.3. To this solution, a concentrated NHq.OH
solution was added. At first, a precipitate formed which on further addition of NH40H dissolved to give a clear blue solution with a pH of 8.3, and additional NH40H (~250cc) was added until a pH of 10 was reached. The solution was heated to 90°C for 3 h during which ammonia gas evolved and a Green ~TNSOO~ 00 Sao PAGE 26- lpEAIUS ~ 4 AUG Z00~
precipitate formed. The final pH lay between 6.8 and 7. The suspension was cooled to room temperature, filtered, washed with water and dried at 120°C
overnight. About 18.68 of material was obtained. The sample analyzed for Ni at 26.6 wt.% and Mo at 34 wt.%. The X-ray diffraction spectra of the phase matches the pattern reported by Teichner.
Exam I~e 2 Preparation of NH4-Ni-Mo.SW.s-O by boiling decomposition:
In a 1 liter flask, 13.2 g ammonium molybdate (0.075 moles Mo), 18.7 g ammonium metatungstate (.075 moles W) and 43.6 g nickel nitrate hexahydrate (0.15 moles Ni) were dissolved in 300cc of water so that the resulting pH
equaled 4.3. To this solution, a concentrated NH40H solution (~600cc) was added until the pH reached 10. At this point, some precipitate remained. The solution was refluxed at ~ 100°C for 3 h. During this heating, the precipitate dissolved to give a clear blue solution and on further heating, a green precipitate formed. The heating was continued until the pH reached between 6.8 and 7.
The suspension was cooled to room temperature, filtered, washed with water and dried at 120°C overnight. 18 grams of material is obtained. The X-ray diffraction spectra of the phase is given in Figure 1 showing an amorphous background with the two largest peaks at d=2.53 and 1.70.
Example 3 Preparation of NH4-Ni-Mo,SW.S-O by direct precipitation:
In a 1 liter flask, 17.65 g of ammonium molybdate (0.1 mole Mo) and 24.60 g of ammonium metatungstate (0.1 mole W) were dissolved in 800 cc of water giving a solution pH of ~5.2. To this solution 0.4 moles of NH40H (~30 cc) was added, raising the pH to ~9.8 (solution A). This solution was warmed to 90°C.
A second solution was prepared by adding 58.2 g of nickel nitrate, (0.2 moles Ni) which was dissolved in SO cc of water (solution B) and maintained at 90°C.
ffl SHEET

pCTILfS ~ 0 ~ 00 980 ' PAGE 27- ~P~S 1 't ~U~' ZOOO
This solution was added dropwise at a rate of 7 cc/min into the ammonium molybdate/ammonium metatungstate solution. A precipitate begins to form after 1/4 of the solution was added. This suspension which was at a pH ~6.5 was stirred for 30 minutes while the temperature was maintained at 90°C.
The material was filtered hot, washed with hot water, and dried at 120°C.
Approximately 38 g of material was recovered.
Preparation of NH4-Ni-Mo.5W.5-O by controlled pH
precipitation:
Two solutions were prepared with the same amounts of nickel, tungsten, molybdenum and ammonium hydroxide are described in Example 3 (solutions A
and B) except that each solution contained about 700 cc of water. The two solutions were added into a separate vessel initially containing 400 cc of water held at 90°C. Solution B (the acidic solution) was pumped into the vessel at a constant rate of ~l5cc/min, while solution A is added through a separate pump which is under feedback PC control and set to maintain the pH at 6.5. On mixing the two solutions a precipitate forms. The slurry was stirred at 90°C for 30 minutes, filtered hot, washed with hot water, and dried at 120°C.
~ Catalytic Evaluation Using Dibenzothiophene (DBT):
1.5-2 g of the catalysts of Examples 1-4 were placed in a quartz boat which was in turn inserted into a horizontal quartz tube and placed into a Lindberg furnace.
The temperature was raised to 370°C in about one hour with N2 flowing at 50 cc/m, and the flow continued for 1.5 h at 370°C. N2 was switched off and 10%
H2SIH2 then added to the reactor at 20 cc/m, the temperature increased to 400°C, and held there for 2 hours. The heat was then shut off and the catalyst cooled in flowing H2S/H2 to 70°C, at which point this flow was discontinued AMfNDCD SHEET

and N2 was added. At room temperature. the quartz tube was removed and the material transferred into a N~ purged glove box. Catalysts were evaluated in a 300cc modified Carbem~ 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 a layer of mullite beads. 100 cc of liquid feed. containing ~ wt% dibenzothiophene in decalin was added to the autoclave. A hydrogen flow of 100 cc/min was passed through the reactor and the pressure was maintained at 31 SOkPa using a back pressure regulator. The temperature was raised to 350°C at ~-6 deg/min and run until either ~0%
DBT
was converted or until 7 hours was reached. A small aliquot of product was removed every 30 minutes and analyzed by GC. Rate constants for the overall conversion as well as the conversion to the reaction products biphenyl (BP) and cvclohexylbenzene (CHB) were calculated as described by M. Daage and R. R.
Chianelli [J. Cat. 149, 414-27 ( 1994)) and are shown in Table 1. As described in that article, higlLSelectivities to cyclohexylbenzene relative to BP during the desulfurization reaction are a good indication of a catalyst with high hydrodenitrogenation activity, whereas high selectivities of BP relative to CHB
indicates a catalyst with high hydrodesulfurization activity.
The results show that partial substitution of tungsten for molybdenum results in catalysts that are substantially higher for DBT conversion. A standard supported Ni-Mo on A1203 catalyst is also shown for comparison. The high CHB/BP ratio suggests that the catalysts are active for HDN.
Table 1. Comparison of Activity in DBT Conversion Tests With Tungsten Addition by Different Preparation Schemes htotal W CHB/BP ~aO

catalyst preparation technique example 350C 350C
#

NH,~-Ni-Mo-O , boiling decompositionI IU6 ~ 10.-1 i NH4-Ni-Mo.5W.5-Uboiiingdecomposition? 171 10,2 ~

NH4-Ni-Mo.SW'.5-Udirectprccipitation.~ 167 12,.1 NH4-Ni-1~lo.Sl~'.S-Ocontrolled pH -t 181 12,p preparation Ni,Mo/A1~03 impregnation 129 6.4 A series of catalysts were prepared in accordance with the general preparation scheme of example 2 (i.e.. boiling decomposition) but varying the Mo and W
relative ratios by changing the amount of ammonium molybdate and ammonium metatungstate added to the solutions. Decomposition was effected as described in Example ~. The catalysts so prepared are shown in Table 2 along with their catalytic activities for DBT measured as described in Example ~.
Table 2. Comparison of Activity in DBT Conversion Tests with Variation in Relative W and Mo content ammonium ammonium nickel KtotalCHB/BP
Catalyst Sample molybdate metatungstatenitrate ~ lad 350C
(g) (g) hexahydrate350C
(g) NH4-NiW-O 18983-970 36.95 .13.62 128 11.3 ~

NH4-NiMo.l 18983-1252.65 33.62 43.62 132 14.1 W.g-U

NH4-NiMo.3 18983-1017.94 '_5.87 43.62 154 I 1.6 W.TO

NH4-NiMo.SW.S'O18357-10913.17 18.74 43.62 171 10.3 NH4-NiMo.7W_3-O18983-9518.54 11.09 43.62 IS8 II.S
~

NH4-NiMo_9W.1-O18983-9223.83 3.69 43.62 141 IO.S

The data show that the most active catalyst contains an approximately equimolar mixture of tungsten and molybdenum.
Examlhe 77 A series of catalysts were prepared as described in Example 3 (direct precipitation) in which equimolar mixtures of Mo and W were precipitated but the nickel content was varied. Decomposition was effected as described in Example ~. The catalysts so prepared are shown in Table 3 along with their catalytic activities for DBT measured as described in example ~.
Table 3. Variation ofNickel Content in NH4-Ni-Mo,SW,j-O Catalysts ammonium ammonium nickel Ktotal CHB/BP
(a7 molybdate metatungstatenitrate- 350C C~ 350C

Catalyst Sample (g) (g) hexahydrate (g) NH4-Ni0.75Mo.5W.5-O19086-I1017.65 24.6 43.65 171 13.0 NH4-NiI,OMo.5W.5-O19086-8217.65 24.6 58.2 167 12.4 NH4-Ni1,25Mo.5VJ,5-O19086-Ill17.65 24.6 73.75 174 I1.0 NH4-NiI.5Mo.5W.5-019086-11217.65 24.6 87.3 148 9.55 Catalytic performance does not change substantially with variations in Ni tTOm 0.75 to 1.5, although K appears to go through a maximum at about 1.25 Ni.
A series of catalysts were prepared in which the quantity of NH~OH used in the preparation was varied. The catalysts were prepared in accordance to the procedure described in Example 3 except that the amount of NH40H in solution A was varied to change to NH40H/Ni molar ratio when the two solutions were mixed. Decomposition was effected as described in Example ~. The catalysts so prepared are shown in Table 4 along with their catalytic activities for DBT
measured as described in Example ~.
Table 4. Variation in NH40H Addition to Preparation Catalyst ammonium ammonium nickel cm3 KtotalKCHB
NH40H/Ni Sample molybdatemetatungstatenitrate cone ~a% /BP
mole ratio (g) (g) hexahydrateNH40H 350C (a~
(g) 350C

1:2 19086-9617.65 24.6 43.65 6.8 102 10.5 l:l 19086-9717.65 24.6 58.2 14 137 10.4 2:1 19086-8217.65 24.6 72.75 30 167 12.4 3:1 19086-10417.65 24.6 87.3 41 164 ( 1.4 4:1 19086-10617.65 24.6 87.3 55 161 12.1 While decomposition ofthe precursor compound will drive off most, if not all, of the ammonium portion of the precursor, the preparation of the precursor and the catalytic utility of the decomposition product can be affected by the amount of NH40H employed. Thus, the effectiveness of the decomposition product as a catalyst is enhanced when the NH40H/Ni ratio in the preparation of the precursor compound is from about 1:1 to about 4:1, preferably about 1.5:1 to about 4:1, and more preferably about 2:1 to about 4:1. While not wishing to be bound by any particular theory or mechanism, there is some evidence the NH40H/Ni ratio causes the Ni-M-W-O phase to change in the decomposition product.
Example 9 The catalysts of examples 1 and ? were compared against standard supported Ni-Mo catalysts for the conversion of a LSADO (low sulfur auto diesel oil feed).
This feed contained 510 wppm sulfur, 50 wppm nitrogen, and 30.6% aromatics with a gravity of 39.8° API. The catalysts were tested at 304°C.
650 psig of H~, and 1850 SCFB/B of H~. The relative activities of the different catalysts are summarized in Table ~.
Table 5. Relative Hvdrotreatina Activities on LSADO Feed wClIUS 00~ 00 980 Catalyst Relative VolumetricRelative Volumetric HDS Activi HDN Activi Ni-Mo/A1203 1 1 NH4-NiMo-O 0.25 0.50 NH4-Ni 1,pMo,5W,5-O 1.4 2.05 The Ni-Mo/A1203 catalyst is a standard HDN/HDS catalyst, the NH4-Ni-Mo phase is the bulk phase with no tungsten, and the NH4-Nil,oMo,5W,5-O is the bulk phase with partial substitution of W for Mo. The NH4-NiMo-O catalyst is also r representative of known compounds. The catalyst of this invention is illustrated by NH4-Nil,oMoo.swo.s-O and the data show the clear advantage of ammonium nickel tungsten molybdate for HDN/HDS activity.
Preparation of a bulk catalyst composition according to the solid route:
l8.lkg-ammonium dimolybdate (15.33kg Mo03) are dissolved in 575 liters water. Subsequently 28.Skg ammonium metatungstate (24 69kg W03) is added to the solution. The resulting solution is preheated up to 90°C. 26.Skg NiC03 ' -., (49.7% Ni) powder is mixed with water and the resulting paste is added to the ammonium dimolybdate/ammonium metatungstate solution. The resulting mixture is reacted for 7 hours at 89°C.
Preparation of a bulk catalyst composition according to the solution route:
In a 1-liter flask, 13.2 g ammonium molybdate (0.075 moles Mo), 18.7 g ammonium metatungstate (0.075 moles W) and 43.6 g nickel nitrate hexahydrate (0.15 moles Ni) were dissolved in 300 ml water so that the resulting pH
equaled AMENDED SHEET

PAGE 33- [ PS ~ ~ jy U G 2000 4.3. To this solution, a concentrated NH40H solution (about 600 ml) was added until the pH reached 10. At this point, some precipitate remained. The solution was refluxed at 100°C for 3 hours. During this heating, the precipitate dissolved to give a clear blue solution and on further heating, a green precipitate formed.
The heating was continued until the pH reached a value between 6.8 and 7Ø
The suspension was cooled to room temperature, filtered, washed with water and dried at 120°C overnight. 18 grams of material were obtained.
__ 657g of a NiMo-W bulk catalyst composition obtained according to the procedure described in Example 10 was added to 1362 g of an aqueous slurry containing 125g of alumina (prepared by precipitation of sodium aluminate and aluminum sulfate). The resulting Ni-Mo-W bulk catalyst - alumina composition was subsequently mixed at 80°C until an LOI of 31 % was obtained. The resulting composition was subsequently extruded and the extrudates were dried at 120.C for about 90 minutes and subsequently calcined at 385°C for one hour in air.
Examyle 13 (,~~le 21105981 The process of Example 10 was repeated except that instead of the alumina suspension, a silica sol containing 10 wt.% silica were applied.
Examyle 14 sample 21105911 657g of a Ni-Mo-W bulk catalyst composition obtained according to the procedure described in Example 10 was added to 510g of a boehmite paste containing 125g boehmite. The rebuffing paste was mixed at 60°C to obtain an AMENDS SHEE'~

rtr~~u~ a a ~ a a y ~s a PAGE 34- ~~~ ~ i ~ nUG 2OOO
LOI of 42%. The resulting composition was extruded, dried and calcined as described in Example 12.
The procedure described in Example 10 was repeated except that alumina is present during the preparation of the bulk catalyst composition. To 755g of the resulting dried Ni-Mo-W bulk catalyst - alumina composition containing 60g alumina, 461 g water and a small amount of nitric acid were added. The resulting mixture was mixed at 70°C while evaporating water until an LOI of 34%
was obtained. The resulting composition was extruded, dried and calcined as described in Example 12.
Examyle 16 Ammonium molybdate, ammonium tungsten and/or ammonium chromate are dissolved and combined in a first reactor. The temperature is increased to 90°C.
The Group VIII salt is dissolved in a second reactor and heated to 90°C.
Ammonium hydroxide is added to the first reactor to form a basic solution. The Group VIII metal solution is added to the first dropwise with stirring in 20 minutes. After 30 minutes, the precipitate is filtered and washed. The precipitate is dried overnight at 120°C and calcined at 385°C.
Example 17 The precipitation method of Example 16 was used to prepare a precipitate from ammonium dimolybdate, ammonium meta tungstate and Fe(III(N03)3 ~ 9 H20 in 98% yield comprising 41.2 wt.% Fe203, 21.3 wt.% Mo03, and 36.9 wt.% W03.
The surface area of the precipitate was 76 m2/g. The pore volume as measured up to 60 nm by BET using the adsorption curve was 0.147 ml/g.
AMENDED SHEEZ

PAGE 35- I PEAIUS i ~ ~ iJ G ZOOO
Exam In a 18 The precipitation method of Example 16 was used to prepare a precipitate from Ni(C03)2~6H20, (NH4)6Mo~024~4H20, and (NH4)zCr20~ in 87.7% yield comprising 52.2 wt.% NiO, 29.4 wt.% Mo03, and 16.6 wt.% Cr203, The surface area of the precipitate was 199 m2/g. The pore volume as measured up to 60 nm by BET using the adsorption curve was 0.276 ml/g.
The precipitation method of Example 16 was used to prepare a precipitate from Ni(C03)2~6H20, (NH4)6H2W120ao, and (NH~)2Cr20~ in 87.7% yield comprising 44.0 wt.% NiO, 42.4 wt.% W03, and 11.8 wt.% Cr203, The surface area of the precipitate was 199 mz/g. The pore volume as measured up to 60 nm by BET
using the adsorption curve was 0.245 ml/g.
Hvdrotreatin~ Ra, w Virgin Petroleum Distillates The activity advantage and the strong pressure response of bulk multimetallic Ni-Mo-W catalysts of the present invention, referred to herein as "BMCat,"
over '~' conventional bimetallic Group VIII/Group VIB bimetallic hydrotreating catalysts for HDS and HDN is demonstrated below through hydrotreating of a European raw virgin feed, raw virgin distillate designated FS-9593.
Comparison between the activity of the BMCat and a conventional supported CoMo on alumina/silica catalyst, commercially available as KF756 from Akzo Nobel, has been obtained between 150 and 400 psig. Selected feedstock properties are listed in Table 6. Results are found in Tables 7, 8 and 9.
Table 6. Analytical Summary for 100% Virgin Distillate (FS-9593) AMENDED SHEET

' PAGE 36- ~~~~5 ~ 4 A U G Z~~~
Test Name Results) Sulfur in Oils 9320 m Nitro en b Antek 79 m Gravi 35.4 API

5.0 wt.% 398 F 203 C

50.0 wt.% 561 F 294 C

95.0 wt.% 656 F 347 C

A reactor was charged with 6 cc of a Co substituted BMCat (Coo,3Ni1,2Moo,5Wo.s) which was diluted to 8 cc using denstone. After liquid phase sulfiding the catalyst was used to process a raw virgin distillate (Table 6) in a pressure range of 150 - 400 psig. The lineout liquid products were analyzed for sulfur by X-ray and for nitrogen by Antek. Comparison of Example 20 with Example 23 reveals that the bulk trimetallic catalyst of the present invention has a much stronger pressure response than the conventional bimetallic KF756 catalyst.
T'he procedure of Example 20 was repeated except that the cobalt level of the BMCat was 0.4 wt.% instead of 0.3 wt.%. Comparison of Example 21 with Example 23 again reveals that the BMCat of the present invention have much stronger pressure response than the conventional bimetallic KF756 catalyst.
The procedure of Example 20 was repeated except that the 0.75 wt.% Co was used instead of 0.3 wt.%. Comparison of Example 22 with Example 23 again AMENDED SHEEI

iiCl'/l~S 0 0 / 0 0 9 8 0 PAGE 3T- ~~~~ ~ ~ BUG ZDOQ
reveals that the BMCat of the present invention have much stronger pressure response than the conventional bimetallic KF756 catalyst.
The procedure of Example 20 was repeated except that only the conventional bimetallic KF756 catalyst comprised of CoMo/A1203 was charged in the reactor.
Comparison of Example 23 with Example 20, 21 and 22 reveals that the BMCat of the present invention have much stronger pressure response than the conventional bimetallic KF756 catalyst.
Table 7. Comparison of KF756 and BMCats at 150 psig. Virgin Distillate (FS-9593) (S = 9320 ppm, N = 79 ppm). 330°C, 150 psig, 1.0 LHSV, TGR
= 2000 SCFB.
Product 1.5-orderHDS RVA Product HDN RVA
S~ k ~ to N ~3~ to KF756 m RT-601 m Exam le ~'S6 177 8 6.5 100 53 3 100 Exam le BMA" 210 2 5.8 89 39 2 175 -' Exam le Co0.3 BMCat 251 18 5.3 82 39 5 175 Exam le Co0.4 BMCat 336 4 4.1 63 46 2 130 Example Co0.75 BMCat376 (14) 4.4 68 47 (4) 125 22 I [ I

( 1 ) The value in parentheses is the standard deviation. Product sulfurs are averages of a few balances after activity lineout.
(2) k~s = LHSV*( 11SQRT[S] - 1/SQRT[S]p)* 100.
(3) The value in parentheses is the standard deviation. Product nitrogens are not lined out values.
Table 8. Comparison of BMCats with KF756 for HDS and HDN at Different Process Pressures. Virgin Distillate (FS-9593) (S = 9320 ppm, N = 79 ppm). 330°C, 1.0 LHSV, TGR = 2000 SCFB.
AMENDED SHEET

~CTlUS00~00980 PAGE 38- ~~S~S I 4 ,BUG 2000 HDS HDN Relative Relative to 1CF756 t 5 Hi Pressure, 150 250 400 150 250 400 psig Exam le Co0.3-BMCat 81 130 300 170 350 432 Exam le Co0.4-BMCat 68 93 200 162 230 380 Exam le Co0.75-BMCat 63 98 200 125 325 400 Example BMCat (powder)89 ~ - ~ - ~ 175 ~ - -23 ~ ~

( 1 ) 1.5-order volumetric rate constants.
(2) 1 st-order volumetric rate constants.
(3) Based on the data prior to lineout.
A reactor was charged with 6 cc of a BMCat having a composition Ni,.sMoo.swo.s (his is the base composition for the bulk multimetallic catalysts used in these examples where there no cobalt substitution) which was diluted to 8 cc using denstone. After liquid phase sulfiding the catalyst was used to process raw virgin distillate (FS-9593, Table 6) at a pressure of 150 psig.
The lineout liquid products were analyzed for sulfur by X-ray and for nitrogen by Antek. The results were presented in Table 7 and 8 for comparison with KF756 and other BMCats. Plots (Figure 3 and 4) of HDS and HDN activities verses reator hydrogen pressure provide a performance projection of BMCats of the present invention at moderate hydrogen pressure.
AMENDED SHEET

Claims (20)

CLAIMS:

1. A hydroprocessing process, comprising:
contacting a feedstock, at hydroprocessing conditions, with a bulk multimetallic catalyst comprised of at least one Group VIII non-noble metal and at least two Group VIB metals and wherein the ratio of Group VIB metal to Group VIII non-noble metal is from about 10:1 to about 1:10.

2. The process of claim 1 wherein the Group VIII non-noble metal is selected from Ni and Co and the Group VIB metals are selected from Mo and W.

3. The process of claim 1 wherein two Group VIB metals are present as Mo and W and the ratio of Mo to W is about 9:1 to about 1:9.

4. The process of claim 1 wherein the bulk multimetallic is represented by the formula:
(X)b (Mo)c (W)d O z wherein X is a Group VIII non-noble metal, and the molar ratio of b: (c+d) is 0.5/1 to 3/1.

5. The process of claim 3 wherein the molar ratio of b:(c+d) is 0.75/1 to 1.5/1.

6. The process of claim 3 wherein the molar ratio of c:d is >0.01/1.

7. The process of claim 1 further comprising the step of sulfiding a multimetallic oxide precursor in order to form the bulk multimetallic catalysts, wherein the precursor is essentially an amorphous material having a unique X-ray diffraction pattern showing crystalline peaks at d = 2.53 Angstroms and d =
1.70 Angstroms.

8. The process of claim 1 wherein the feedstock comprises at least one of naphtha, diesel, heavy gas oil, Tube oil, and residuum virgin distillates.

PAGE 40-a-

9. The process of claim 8 wherein the feedstock is naphtha boiling in the range of 25°C to 210°C, and the hydroprocessing conditions include a reaction temperature of 100°C to 370°C, a pressure of 10 Bar to 60 Bar, a space velocity of 0.5 to 10 V/VBr, and a hydrogen gas treat rate of 100 to 2,000 SCF/B.

10. The process of claim 8 wherein the feedstock is diesel boiling in the range of 170°C to 350°C, and the hydroprocessing conditions include a reaction temperature of 200°C to 400°C, a pressure of 15 Bar to 110 Bar, a space velocity of 0.5 V/V/Hr to 4 V/V/Hr, and a hydrogen gas treat rate of 500 SCF/B
to 6,000 SCF/B.

11. The process of claim 8 wherein the feedstock is heavy gas oil boiling in the range of 325°C to 475°C, and wherein the hydroprocessing conditions include a reaction temperature of 260°C to 430°C, a pressure of 15 Bar to 170 Bar, a space velocity of 0.3 V/V/Hr to 2 V/V/Hr, and a hydrogen gas treat rate of 1,000 SCF/B to 6,000 SCF/B.

12. The process of claim 8 wherein the feedstock is a lubricating oil boiling in the range of 290°C to 550°C, and wherein the hydroprocessing conditions include a reaction temperature of 200°C to 450°C, a pressure of 6 Bar and 210 Bar, a space velocity of 0.2 V/V/Hr to 5 V/VHr, and a hydrogen gas treat rate of 100 SCF/B to 10,000 SCF/B.

13. The process of claim 8 wherein the feedstock is a residuum having a 10% to 50% boiling range of 575°C, and wherein the hydroprocessing conditions include a reaction temperature of 340°C to 450°C, a pressure of 65 Bar to 1100 Bar, a space velocity of 0.1 V/V/Hr to 1 V/V/Hr, and a hydrogen gas treat rate of 2,000 to 10,000 SCF/B.

-PAGE40-b-

14. The process of claim 1 wherein the bulk multimetallic catalyst is in the form of particles having a median diameter of at least 50 nm, a surface area of at least 10 m2/gm, a pore volume ranging from 0.05 to 5 m1/g, and an absence of pores smaller than 1 nm.

15. The process of claim 14 wherein the bulk multimetallic catalyst particle has a core-shell structure.

16. The process of claim 1 further comprising forming a hydrotreated product.

17. The process of claim 16 further comprising contacting at least one of the feedstock and hydroprocessed product with a catalytically effective amount of a second catalyst under catalytic conversion conditions.

18. The process of claim 17 wherein the second catalyst is at least one of a hydroprocessing catalyst, a cracking catalyst, and an isomerization catalyst.

19. The process of claim 18 wherein the second catalyst is present in at least one of (i) a first reaction zone or zones upstream of the bulk multimetallic catalyst;
(ii) a second reaction zone or zones containing the bulk multimetallic catalyst; and (iii) a third reaction zone or zones downstream of the bulk multimetallic catalyst.

20. The process of claim 1 wherein the bulk multimetallic catalyst is a sulfided catalyst.